JPH0558426B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a new method for producing alkoxycarbamoyl aromatic carboxylic acids. More specifically, the present invention relates to a method for producing an alkoxycarbamoyl aromatic carboxylic acid by reacting an aromatic aminocarboxylic acid with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent. (Prior art) Alkoxycarbamoyl aromatic carboxylic acid is
It is important as a monomer for aromatic polyamides, and previously this compound was produced by the reaction of aromatic aminocarboxylic acids with chloroformic acid esters (US Pat. No. 3,558,571). (Problems to be Solved by the Invention) The above-mentioned conventional method had the disadvantage that highly toxic and highly corrosive phosgene had to be used in order to produce chloroformic acid ester. Therefore, a method for easily producing alkoxycarbamoyl aromatic carboxylic acids without using phosgene or the like has been desired. (Means and Effects for Solving the Problems) Therefore, the present inventors have conducted intensive studies to develop a method for easily producing alkoxycarbamoyl aromatic carboxylic acids, and have found that We have discovered a catalyst system that can directly urethanize the amino groups of aromatic aminocarboxylic acids with carbon monoxide and alcohols without side reactions caused by carboxyl groups, and thereby create the desired alkoxycarbamoyl aromatic aroma. The present inventors discovered for the first time that group carboxylic acids can be produced with high yield and high selectivity, leading to the completion of the present invention. This catalyst system uses unsubstituted aromatic primary amines and substituents other than carboxyl groups previously discovered by the present inventors, such as alkyl groups, N,N-
Those that can convert aromatic primary amino compounds having dialkylamino groups etc. into urethanes in high yield and high selectivity (for example, JP-A-58-110554, JP-A-59-
No. 106452), it was surprising that these catalyst systems were able to urethanize aromatic aminocarboxylic acids without side reactions of carboxyl groups. That is, in the presence of a catalyst comprising an oxidizing agent and at least one selected from a platinum group metal or a compound containing a platinum group metal, and at least one selected from bromine, iodine, or a compound containing these. The aromatic aminocarboxylic acid represented by the formula () H ₂ N−Ar−COOH () (in the formula, Ar represents a divalent aromatic group) is combined with carbon monoxide and the formula () ROH () ( In the formula, R represents an aliphatic group or an aromatic aliphatic group.) Formula () characterized by reacting with an alcohol represented by (In the formula, Ar represents a divalent aromatic group, and R represents an aliphatic group or an araliphatic group.) The present invention provides a method for producing an alkoxycarbamoyl aromatic carboxylic acid represented by the following formula. The platinum group metals and compounds containing platinum group metals used in the present invention are particularly suitable if they contain at least one element selected from platinum group elements such as palladium, rhodium, platinum, ruthenium, iridium, and osmium. There is no limitation, these elements may be in a metallic state,
It may be a component that forms a compound. In addition, these catalyst components include, for example, activated carbon, graphite, silica, alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, polymers, ion exchange resins, It may be supported on a carrier such as zeolite, molecular sieve, magnesium silicate, or magnesia. As platinum group elements in the metallic state, for example, metals such as palladium, rhodium, platinum, ruthenium, iridium and osmium;
Catalytic components containing these metal ions are supported on the above-mentioned carrier and then reduced with hydrogen, formaldehyde, hydrazine, etc., and alloys or intermetallic compounds containing these metals are used. In addition, alloys or intermetallic compounds are
These platinum group metals may be used together, or other elements such as selenium, tellurium, sulfur, antimony, bismuth, copper, silver, gold, zinc,
It may contain tin, vanadium, iron, cobalt, nickel, mercury, lead, thallium, chromium, molybdenum, tungsten, and the like. On the other hand, examples of compounds containing platinum group elements include halides, sulfates, nitrates, phosphates,
Inorganic salts such as borates, organic acid salts such as acetates, oxalates, formates, cyanides, hydroxides, oxides, sulfides, nitro groups, cyano metal salts and ammonia containing groups, halogens, anions such as oxalate ions,
Examples include metal complex compounds such as salts or complexes containing amines, phosphines, carbon monoxide, and chelate ligands, and organometallic compounds having organic ligands or organic groups. Among these catalyst components, those containing palladium or rhodium or both are preferable, such as Pd black;
Pd-C, Pd- _Al2O3 , Pd- _SiO2 , _Pd - _TiO2 ,
Supported palladium catalysts such as Pd- _ZrO2 , Pd- _BaSO4 , Pd- _CaCO3 , Pd-asbestos, Pd-zeolite, Pd-molecular sieve; Pd-Pb,
Pd-Se, Pd-Te, Pd-Hg, Pd-Tl, Pd-P,
Pd-Cu, Pd-Ag, Pd-Fe, Pd-Co, Pd-Ni,
Alloys or intermetallic compounds such as Pd-Rh, and these alloys or intermetallic compounds supported on the above-mentioned supports; PdCl ₂ , PdBr ₂ , PdI ₂ , Pd
(NO ₃ ) ₂ , PdSO ₄ and other inorganic salts; Pd
(OCOCH ₃ ) ₂ , organic acid salts such as palladium oxalate; Pd(CN) ₂ ; PdO; PdS; M ₂ [PdX ₄ ], M ₂
Palladate salts represented by [PdX ₆ ] (M represents an alkali metal or ammonium ion, and X represents a nitro group, cyano group, or halogen); [Pd(NH ₃ ) ₄ ]X ₂ , [Pd(en ) ₂ ] Palladium ammine complexes such as X ₂ (X has the same meaning as above and en represents ethylenediamine); PdCl ₂
(PhCN) ₂ , PdCl ₂ (PR ₃ ) ₂ , Pd(CO) (PR ₃ ) ₃ , Pd
(PPh ₃ ) ₄ , PdCl(R) (PPh ₃ ) ₂ , Pd (C ₂ H ₄ )
Complex compounds such as (PPh ₃ ) ₂ , Pd(C ₃ H ₅ ) ₂ or organometallic compounds (R represents an organic group, Ph represents a phenyl group); chelate ligands such as Pd(acac) ₂ complex compounds (acac represents acetylacetone); Rh black; supported rhodium catalysts similar to Pd;
Rh alloys or intermetallic compounds similar to Pd and those supported on carriers; RhCl ₃ and hydrates, RhBr ₃ and hydrates, RhI ₃ and hydrates,
Inorganic salts such as Rh( _SO4 ) ₃ and hydrates; _Rh2
(OCOCH ₃ ) ₄ , Rh ₂ O ₃ , RhO ₂ ; M ₃ [RhX ₆ ] and hydrate (M and X have the same meanings as above);
Rhodium ammine complexes such as [Rh( _NH3 ) ₅ ] _X3 , [Rh(en) ₃ ] _X3 , etc.; rhodium carbonyl clusters such as _Rh4 (CO) ₁₂ , _Rh6 (CO) ₁₆ ; RhCl
(CO) ₂ ] ₂ , RhCl ₃ (PR ₃ ) ₃ , RhCl (PPh ₃ ) ₃ , RhX
Complex compounds or organometallic compounds such as (CO)L ₂ (X has the same meaning as above, L is a ligand consisting of an organic phosphorus compound and an organic arsenic compound), RhH (CO) (PPh ₃ ) ₃ , etc. can be mentioned. In the reaction of the present invention, one type of these platinum group metals or compounds containing platinum group metals may be used, or two or more types may be used as a mixture, and there are no particular restrictions on the amount used. However, it is generally desirable that the amount of the platinum group metal-containing component is in the range of 0.0001 to 50 mol % equivalent relative to the aromatic aminocarboxylic acid. Bromine molecules, iodine molecules, or compounds containing bromine or iodine, which are another important catalyst component used in the present invention, may be organic or inorganic. or metal halides that are iodine, onium halide compounds or compounds that can produce these compounds in a reaction system, oxoacids of halogens or their salts, complex compounds containing halogen ions, organic halides, interhalogen compounds, etc. is preferably used. Examples of metal halides include alkali metals, alkaline earth metals, copper, silver, zinc, cadmium, mercury, aluminum, gallium, thallium, germanium, tin, lead, antimony, bismuth, titanium, zirconium, vanadium, and niobium. , tantalum, tellurium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rare earth metals, and other halides are used. Particularly preferred are alkali metal and alkaline earth metal bromides or iodides. Examples of alkali metal and alkaline earth metal bromides or iodides include lithium bromide, sodium bromide, rubidium bromide, cesium bromide, magnesium bromide, strontium bromide,
Combining a single metal such as barium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, etc. with a single halogen Compounds; double salts such as magnesium potassium bromide; potassium bromide fluoride, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium iodine chloride bromide, rubidium iodine bromide, potassium iodine bromide, iodine bromide Examples include polyhalides such as cesium and rubidium iodine bromide. An onium halide compound is a compound containing an element with a lone pair of electrons, in which a proton or other cationic reagent binds to these lone pairs, and the element with a lone pair of electrons forms a covalent bond with a valence of 1. is increased to become a cation, and has a halogen anion as a counter ion. Examples of such onium compounds include ammonium compounds ([R ¹ R ² R ³ R ^{4 N} ]X), phosphonium compounds ([R ¹ R ² R ³ R ^{4 P} ] R ³ R ⁴ As ^] X) ^, stibonium compounds ([ ^{R 1 R 2 R 3 R 4 Sb} ] ³ S ]X ), oxysulfonium compounds ⁽ [ ^{R 1 R 2 R 3 S ( O} )] ^3Te ]X) ^, stannonium compounds ([ ^R1R2R3Sn ]X) ^{, and iodonium compounds ([R1R2I ] X} ). Here, R ¹ , R ² , R ³ , and R ⁴ represent hydrogen or a group selected from an aliphatic group, an aromatic group, an aliphatic group, and an araliphatic group, and each may be the same, In some cases, it may also be a constituent element of a ring containing an element having a lone pair of electrons. Also, X
represents a halogen selected from Br and I. Of course, it may be a compound having two or more such onium groups in its molecule, or it may be a polymer containing such onium groups in its main chain or side chain. Such halogenated onium compounds, which are onium compounds whose anion is a halogen, include amines or nitrogen-containing compounds, phosphine compounds, arsine compounds, stibine compounds, oxy compounds,
It is easily obtained by reaction with sulfide compounds, sulfoxide compounds, selenide compounds, telluride compounds, etc. These can be produced outside the reaction system, or they can be produced within the reaction system. You may let them. Of course, it may be produced by another method, or may be produced within the reaction system by another method. Among these, preferred are halogenated ammonium compounds, halogenated phosphonium compounds,
Among the halogenated anthonium compounds and halogenated sulfonium compounds, particularly preferred are halogenated ammonium compounds and halogenated phosphonium compounds. Halogenated ammonium compounds can be easily obtained by reacting a corresponding nitrogen-containing compound with hydrogen halide, or by reacting a nitrogen-containing compound with an alkyl halide or an aryl halide. For example, ammonia; primary amine;
Examples include amines such as secondary amines and tertiary amines; hydroxylamines; hydrazines; hydrazones; amino acids; oximes; imidoesters; amides and various nitrogen-containing heterocyclic compounds. Halogen oxoacids and their salts refer to halogen oxyacids and their salts with positive oxidation numbers of 1, 3, 5, and 7, and specifically include hypobromous acid, bromate acid, and perbromate acid. , hypoiodic acid, iodic acid, iodic acid, orthoperiodic acid, metaperiodic acid, and salts of these acids. The cations of the salts may be of any kind, such as ammonium ions and various metal ions, but alkali metal ions and alkaline earth metal ions are particularly preferred. The halogen-containing complex compound may contain either a cationic or anionic halogen, such as polyhalogenated halogenated salts such as ammonium dichlorobromate and tetramethylammonium tetrabromoiodate; Metal halides such as potassium iodotellurate, tetraethylammonium tetraiodomercurate, potassium tetraiodobismuthate, sodium tetrabromocuprate, cesium tetrabromoferrate, barium hexaiodostannate, potassium tetraiodolearate, potassium hexabromotellurate, etc. ; Complexes having compounds such as octate (N, N-dimethylformamide) lanthanum triiodide, iodopentaammine chromium triiodide, and bis(2,2'-bipyridine) copper diiodide are used. In addition, organic halides have the general formula R ⁶ (X)m (wherein R ⁶ is an m-valent organic group, X is Br or I,
m represents an integer of 1 or more. ), and when m is 2 or more, X
may be different halogen species. Further, halogen X is a heteroatom other than carbon, such as nitrogen,
It may be combined with phosphorus, oxygen, sulfur, selenium, etc. Such organic halides include, for example, aliphatic mono- and polyhalides such as methyl halide, ethyl halide, methylene halide, haloform, and tetrahalogenmethane;
Aromatic mono- and polyhalides such as halogenbenzene, dihalogenbenzene (each isomer), iodosobenzene, iodoxybenzene; Alicyclic halides such as halogenated cyclohexane and halogenated cyclobutane; halogenated benzyl,
Aroaliphatic halides such as halogenated phenethyl; heterocyclic halides such as halogenated furan, halogenated tetrahydrofuran, halogenated thiophene, halogenated imidazole, and halogenated piperidine; acids such as halogenated acetyl and halogenated benzoyl Halides: N-halides such as N-halogensuccinimide, N-halogenalkylamine, N-halogenacetamide, and N-halogenbenzamide are preferably used. Furthermore, these organic groups can be substituted with various substituents, such as nitro groups, lower alkyl groups, cyano groups, alkoxy groups, aryloxy groups, aromatic groups, sulfoxide groups, sulfone groups, carbonyl groups, ester groups, amide groups, etc. or may have an unsaturated group. Moreover, an iodine molecule can also be used as the bromine molecule. Further, as a compound containing bromine or iodine, hydrogen halides such as hydrogen bromide and hydrogen iodide, or hydrohalic acid can also be used. Note that when using an organic halide, bromine molecule, or iodine molecule, it is also a preferable method to further add a basic substance. Such bromine, iodine, or compounds containing these may be used alone or in combination of two or more. Among bromine, iodine, or compounds containing these used in the method of the present invention, those containing iodine are particularly preferred catalyst components. The amount of bromine, iodine, or a compound containing these used in the reaction of the present invention is usually in the range of 0.001 to 10,000 times the amount of the metal element in the platinum group element-containing component used. It is preferable to The aromatic aminocarboxylic acid used as a raw material in the present invention has an amino group and a carboxyl group represented by the general formula () H ₂ N-Ar-COOH () (wherein, Ar represents a divalent aromatic group). Any group may be used as long as the group is directly bonded to the aromatic nucleus. Examples of such aromatic aminocarboxylic acids include aminobenzoic acid (each isomer),
Aminonaphthalenecarboxylic acid (each isomer), aminoanthracenecarboxylic acid (each isomer), aminopyridinecarboxylic acid (each isomer), aminoquinolinecarboxylic acid (each isomer), aminofurancarboxylic acid (each isomer) ), and the following general expression () (In the formula, A is a simple chemical bond or -O-, -
S-, -SO ₂ -, -CO-, CONH-, -COO-, -
2 selected from C(R ¹ )(R ² )- and -N(R ¹ )-
A valent group, and R ¹ and R ² represent H, an aliphatic group, or an alicyclic group. Examples include compounds (isomers) in which an amino group and a carboxyl group are bonded to the diphenyl compound represented by the following formula. Furthermore, in these aromatic aminocarboxylic acids, at least one hydrogen on the aromatic ring may be substituted with another substituent, such as a halogen atom, a nitro group, a cyano group, an alkyl group, an alicyclic group, an aromatic group, or an aralkyl group. may be substituted with a group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, etc. Particularly preferred among these aromatic aminocarboxylic acids are m- and p-aminobenzoic acid,
1-amino-naphthalene-4-carboxylic acid, 1-
Amino-naphthalene-5-carboxylic acid, 2-amino-naphthalene-6-carboxylic acid, p-(4-amino-phenyl)benzoic acid, p-(4-amino-
p-(4-amino-phenylcarbamoyl)benzoic acid, and N-(4-amino-phenyl)terephthalic monoamide. The alcohols used in the present invention include monohydric or polyhydric alcohols. Such alcohols include, for example, those having 1 to 20 carbon atoms.
Examples include linear or branched monovalent or polyvalent alkanols and alkenols, monovalent or polyvalent cycloalkanols and cycloalkenols, and aralkyl alcohols. Furthermore, these alcohols have other substituents, such as halogen atoms,
It may contain a cyano group, an alkoxy group, a sulfoxide group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, and the like. In the present invention, monohydric alcohols are particularly preferred. Specific examples of such alcohols include methanol, ethanol, propanol (each isomer),
Butanol (each isomer), pentanol (each isomer), hexanol (each isomer), heptanol (each isomer), octanol (each isomer), nonyl alcohol (each isomer), decyl alcohol (each isomer) ), undecyl alcohol (each isomer), lauryl alcohol (each isomer), tridecyl alcohol (each isomer), tetradecyl alcohol (each isomer), pentadecyl alcohol (each isomer)
Aliphatic alcohols such as; cycloalkanols such as cyclohexanol and cycloheptanol; ethylene glycol monomethyl ether,
Alkylene glycol monoethers such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; benzyl alcohol, etc. Aralkyl alcohol and the like are used. As the oxidizing agent used in the present invention, ordinary oxidizing agents can be used, but preferred are molecular oxygen, organic nitro compounds, or mixtures thereof. This molecular oxygen may be pure oxygen or a substance containing oxygen, which may be air, or may be air or other gases that do not inhibit the reaction of pure oxygen, such as inert gases such as nitrogen, argon, helium, and carbon dioxide. It may be diluted by adding gas. In some cases, it may also contain gases such as hydrogen, carbon monoxide, hydrocarbons, and halogenated hydrocarbons. Further, the organic nitro compound may be any one of alicyclic, aliphatic, and aromatic nitro compounds. Preferred are aromatic nitro compounds such as nitrobenzene, particularly preferred are
It is an aromatic nitrocarboxylic acid that has the same skeleton structure as the raw material aromatic aminocarboxylic acid. In this case, the raw aromatic aminocarboxylic acid and the aromatic nitrocarboxylic acid can be reacted to produce an alkoxycarbamoyl aromatic carboxylic acid having the same structure. Among the oxidizing agents, molecular oxygen is particularly preferred. Molecular oxygen may be used in less or more than equivalent amounts, but mixtures of oxygen/carbon monoxide or oxygen/alcohols should be used outside the explosive limits. In the method of the present invention, it is preferable to use an equivalent or more amount of alcohol so that it also serves as a reaction solvent, or other solvents that do not adversely affect the reaction can also be used. Examples of such solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, tetralin, and decalin; and aromatic solvents such as benzene, toluene, xylene, and mesitylene. Nitriles such as acetonitrile and benzonitrile; Sulfones such as sulfolane, methylsulfolane and dimethylsulfolane; tetrahydrofuran, 1,4-dioxane, 1,2-
Ethers such as dimethoxyethane; acetone,
Ketones such as methyl ethyl ketone; Esters such as ethyl acetate and ethyl benzoate; N,N-
Examples include amides such as dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphoramide. Furthermore, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromonaphthalene; chlorhexane, chlorocyclohexane, trichlorotrifluoroethane, methylene chloride, and tetrachloride. Halogenated aliphatic hydrocarbons such as carbon or halogenated aliphatic hydrocarbons are also used as solvents. In the urethanization reaction of the present invention, other additives can be added to the reaction system as necessary in order to carry out the reaction more efficiently. Suitable examples of such additives include zeolites, orthoesters, ketals, acetals, enol ethers, and trialkylorthoborates. Further, the reaction of the present invention is usually carried out at a temperature range of 80 to 300°C, preferably 120 to 250°C. Also,
Reaction pressure is 1~500Kg/ ^cm2 , preferably 20~300Kg/cm2
Kg/cm ² , and the reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually several minutes to several hours. The reaction of the present invention can be carried out either batchwise or continuously, in which reaction components are continuously supplied and a reaction solution is continuously drawn out. (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 5.56 g (40 mmol) of para-aminobenzoic acid and 60 ml of ethanol were placed in a stirred autoclave with an internal volume of 200 ml.
ml, palladium black 42.4mg (0.4mg atom), and sodium iodide 120mg (0.8mmol), and after replacing the system with carbon monoxide, the carbon monoxide was 70Kg/
cm ² , then increase the total pressure by injecting air.
It was set to 100Kg/ ^cm2 . After reacting for 1 hour at 160-170°C with stirring, the reaction mixture was cooled and filtered to obtain a pale yellow solution. Analysis of this solution revealed that the reaction rate of para-aminobenzoic acid was 98%, and that para-ethoxycarbamoylbenzoic acid was produced with a yield of 95% and selectivity of 97%. The yellow solid obtained by distilling ethanol off from this reaction solution was washed with dilute hydrochloric acid and water, and then recrystallized from a mixed solvent of ethanol and water to produce white needle-like crystals (melting point 198-200°C). 6.8 g of paraethoxycarbamoylbenzoic acid was obtained. In addition, when sodium iodide was not used, the urethanization reaction hardly proceeded. Example 2 The reaction was carried out in the same manner as in Example 1 except that meta-aminobenzoic acid was used instead of para-aminobenzoic acid. As a result, the reaction rate of meta-aminobenzoic acid was 96%, and meta-ethoxycarbamoylbenzoic acid was recovered. It was generated with a rate of 92% and a selectivity of 96%. Example 3 The reaction was carried out in the same manner as in Example 1 except that methanol was used instead of ethanol. As a result, the reaction rate of para-aminobenzoic acid was 97%, and the yield of para-methoxycarbamoylbenzoic acid was 94%. It was generated with a selectivity of 97%. Example 4 Example 1 except that 1-aminonaphthalenecarboxylic acid-5 is used instead of para-aminobenzoic acid.
The reaction rate of 1-aminonaphthalenecarboxylic acid-5 was 93%,
1-Ethoxycarbamoylnaphthalenecarboxylic acid-5 was produced in a yield of 88% and a selectivity of 95%. Examples 5 to 13 Table 1 shows the results of producing para-ethoxycarbamoylbenzoic acid from para-aminobenzoic acid in the same manner as in Example 1 except for changing the catalyst system. In these Examples, 40 mmol of para-aminobenzoic acid, 60 ml of ethanol, 0.5 mg atom of a platinum group metal or a compound containing a platinum group element, and 0.8 mmol of bromine, iodine, or a compound containing these were used. Note that the % display of the catalyst used in these Examples indicates the weight % of the supported catalyst component. Pd
-Te/C is obtained by co-supporting palladium chloride and tellurium dioxide on activated carbon at a molar ratio of 10:3.
It is hydrogen-reduced at 350℃.

[Table] Example 14 30 mmol of para-aminobenzoic acid and 15 m of para-nitrobenzoic acid were placed in a stirred autoclave with an internal volume of 200 ml.
mol, methanol 60ml, palladium chloride 0.5m
After adding 1.5 mmol of potassium iodide and replacing the inside of the system with carbon monoxide, 130 kg/cm ² of carbon monoxide was introduced under pressure. The reaction was carried out at 170 to 180°C for 3 hours while stirring. Analysis of the reaction solution revealed that the reaction rates of para-aminobenzoic acid and para-nitrobenzoic acid were 30% and 38%, respectively, and 11 mmol of para-methoxycarbamoylbenzoic acid was produced. (Effects of the Invention) According to the present invention, as is clear from the examples,
Alkoxycarbamoyl aromatic carboxylic acids can be easily produced with high yield and high selectivity.

Claims (1)

[Scope of Claims] 1. Presence of a catalyst consisting of an oxidizing agent and at least one selected from a platinum group metal or a compound containing a platinum group metal, and at least one selected from bromine, iodine, or a compound containing these. Below, an aromatic aminocarboxylic acid represented by the formula () H ₂ N−Ar−COOH () (in the formula, Ar represents a divalent aromatic group) is combined with carbon monoxide and the formula () ROH () (In the formula, R represents an aliphatic group or an aromatic aliphatic group.) Formula () characterized by reacting with an alcohol represented by (In the formula, Ar represents a divalent aromatic group, and R represents an aliphatic group or an araliphatic group.) A method for producing an alkoxycarbamoyl aromatic carboxylic acid represented by the following. 2. The method according to claim 1, wherein the oxidizing agent is molecular oxygen. 3. The method according to claim 1 or 2, wherein the platinum group metal and the compound containing the platinum group metal are palladium, rhodium, a palladium compound, and a rhodium compound. 4 The compound containing bromine or iodine is an alkali metal or alkaline earth metal halide,
The claim is at least one selected from onium halide compounds or compounds capable of producing these compounds in a reaction system, halogen oxoacids or salts thereof, complex compounds having halogen ions, and organic halides. The method according to any one of paragraphs 1 to 3. 5. The method according to claim 1, wherein at least one selected from palladium or a compound containing palladium and at least one selected from iodine or a compound containing iodine are used as the catalyst. 6. The method according to any one of claims 1 to 5, wherein the aromatic aminocarboxylic acid is m- or p-aminobenzoic acid.