JPS6253955A - Production of alkoxycarbamoyl aromatic carboxylic acid - Google Patents

Abstract

PURPOSE:To readily obtain a compound useful as a monomer for aromatic polyamides in high yield and selectivity, by reacting an aromatic aminocarboxylic acid with carbon monoxide and an alcohol in the presence of an oxidizing agent and catalyst. CONSTITUTION:An aromatic aminocarboxylic acid expressed by formula I (Ar is bifunctional aromatic group) is reacted with carbon monoxide and an alcohol expressed by the formula ROH (R is aliphatic or aromatic and aliphatic group) in the presence of an oxidizing agent, e.g. molecular oxygen, and a catalyst consisting of a platinum group metal or a compound containing the platinum group metal, e.g. palladium or rhodium, and bromine, iodine or a compound containing the bromine or iodine at 120-250 deg.C under 20-300kg/cm<2> pressure to afford the aimed compound expressed by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) 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.

BACKGROUND OF THE INVENTION Alkoxycarbamoyl aromatic carboxylic acids are important as monomers for aromatic polyamides, and traditionally this compound was produced by the reaction of an aromatic aminocarboxylic acid with a chloroformic acid ester (U.S. Pat. 3rd, 55th
No. 8,571).

(Problems to be Solved by the Invention) The conventional method described above has the disadvantage that phosgene, which is highly toxic and highly corrosive, must be used in order to produce chloroformic acid ester. Therefore, there has been a desire for a method that can easily produce alkoxycarbamoyl aromatic carboxylic acids without using phosgene or the like.

(Means and effects for solving the problem) Therefore, the present inventors have conducted intensive studies to develop a method for easily producing alkoxycarbamoyl aromatic acid and rubonic acid. We have discovered a catalyst system that can directly urethanize the amino groups of aromatic aminocarboxylic acids with -carbon oxide and alcohols without side reactions caused by carbonic acid or carboxyl groups, and thereby produce the desired alkoxycarbamoyl. It was discovered for the first time that aromatic carboxylic acids can be produced with high yield and high selectivity, and the present invention was completed. This catalyst system is based on an unsubstituted aromatic amine previously discovered by the present inventors and an aromatic amine having a substituent other than a carboxyl group, such as an alkyl group, an N,N-dialkylamino group, etc.
Those capable of converting grade amino compounds into urethanes with high yield and high selectivity (for example, JP-A-58-110554, JP-A-5
No. 9-106452), it was surprising that these catalyst systems were able to urethanize aromatic aminocarboxylic acids without side reactions of carboxyl groups.

That is, the present invention provides an oxidizing agent and at least one selected from a platinum group metal or a compound containing a platinum group metal;
In the presence of a catalyst consisting of at least one selected from bromine, iodine, or a compound containing these, formula (1) % formula % (1) (wherein Ar represents a divalent aromatic group) Reacting an aromatic 7-minocarboxylic acid represented by carbon monoxide and an alcohol represented by the formula (■) ROH, (II) (wherein R represents an aliphatic group or an araliphatic group) A method for producing an alkoxycarbamoyl aromatic carboxylic acid represented by the characteristic formula (III) (wherein Ar is a divalent aromatic group and R is an aliphatic group or an araliphatic group) It is.

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, and these elements may be in a metallic state or may be components forming a compound. In addition, these catalyst components include, for example, activated carbon, graphite, silica, alumina, silica-alumina, silica titania, titania, zirconia, barisim sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, polymers, ion exchange resins, zeolites. , molecular sieve, magpsium silicate, magnesia, or the like.

Examples of platinum group elements in the metallic state include metals such as palladium, rhodium, platinum, ruthenium, iridium, and osmium, these metal blacks, and catalyst components containing these metal ions on the above-mentioned carrier, and then hydrogen or formaldehyde hydrazide, and alloys or intermetallic compounds containing these metals. Further, the alloy or intermetallic compound may be one of these platinum group metals, or may be one of these platinum group metals, or may contain other elements such as selenium, tellurium, sulfur, antimony, bismuth, copper, silver, gold, zinc, tin, It may contain 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 inorganic salts such as halides, sulfates, nitrates, phosphates, and borates; organic acid salts such as acetates, oxalates, and formates; cyanides, hydroxides, oxides,
Metal salts containing sulfides, anions such as nitro groups, cyano groups, halogens, oxalate ions, etc., and metals such as salts or complexes containing ammonia, amines, phosphines, carbon oxides, chelate ligands, etc. complex compounds,
Examples include organometallic compounds having an organic ligand or an organic group.

Among these catalyst components, those containing palladium or rhodium or both are preferable, such as Pd black 1Pd-C1Pd-Alt
o3, Pd Sing, Pd-Ti0z, Pd Z
r0z, Pd-BaSO4, Pd-CaC0,, Pd-
Supported palladium catalysts such as asbestos, Pd-zeolite, Pd-molecular sheep; Pd-Pb, P
d-5eXPd-TeSPd-Hg, Pd-Tl,
Pd-P, Pd-Cu, Pd-Ag, P'd
-Fe.

Alloys or intermetallic compounds such as Pd-Co, Pd-Ni, Pd-Rh, and these alloys or intermetallic compounds supported on the above-mentioned carriers; pdct
z, PdBrz, PdIz, Pd(NOi)z, P
Inorganic salts such as d5O; Pd (OCOCII: +
) z, organic acid salts such as palladium oxalate;
Pd(CN)z i PdO; PdS; Mz
(PdX*), Mz Palladate II represented by (PdX, ) (M represents an alkali metal or ammonium ion, and X represents a nitro group, a cyano group, or a halogen);
(Pd(NH:+)*) Xt-(Pd(en)g)
Ammine complexes of palladium such as X+ [(X has the same meaning as above, en represents ethylenediamine);
PdC1z (PhCN)z, PdC1z (PR+)
z, Pd(Co)(PRi)a, Pd(PPhz)
a, PdC1(R) (PPh3) z, Pd(CJ
t) Complex compounds or organometallic compounds such as (PPb3)z, Pd(CJs)t (R represents an organic group, ph represents a phenyl group); Coordinated with a chelate ligand such as Pd(acac)2 Complex compounds (acac represents acetylacetone): Rh black; Supported rhodium catalyst similar to Pd [; Rh alloy or intermetallic compounds similar to Pd, and those supported on a carrier; R
hCl, and hydrate, RhBr+ and hydrate/Rh
Inorganic salts such as 1s and hydrates, Rhz(SO4)* and hydrates; Rhg(OCOCHz)4. Rhz
O:+, Rh0z:Ml (to Rh) and hydrate (M, x have the same meanings as above); (Rh(
Ammine complexes of rhodium such as NHs)sl, (Rh(en)3)χ3, [;Rho(Co)lt,
Rhodium carbonyl clusters such as Rhb(CO) + b; (RhCI(CO)z) 2 , Rh
C15(PR3)+, RhC1(PPh+)z, Rh
Complex compounds or organometallic compounds such as X(CO)Lx (X has the same meaning as above, and L is a ligand consisting of an organic phosphorus compound and an organic arsenic compound), RhH(Co)(PPb+)+ 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, usually the platinum group metal-containing component is 0.0001% of the aromatic aminocarboxylic acid.
A range of 50 mol% equivalent is desirable.

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, □Halogen oxoacids or their salts, complex compounds containing halogen ions, organic halides, and interhalogen compounds etc. are preferably used.

Examples of metal halides include alkali metals,
alkaline earth metals, copper, silver, zinc, cadmium, mercury,
Halides such as aluminum, gallium, thallium, germanium, tin, lead, antimony, bismuth, titanium, zirconium, vanadium, niobium, tantalum, tellurium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, and rare earth metals is 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, barium bromide, lithium iodide, and iodine. Compounds of a single metal and a single halogen, such as sodium chloride, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, and barium iodide; magnesium potassium bromide, etc. Double salts: Potassium fluoride bromide, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium iodine chloride bromide, rubidium iodine bromide, potassium iodine bromide, cesium iodine bromide, rubidium iodine bromide, etc. Examples include halides.

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 ammonia, the compound ((R・R"R'R'N") ○), the phonium compound ((R+RzHsR4p■) 'As■) Xe), sulfonium compound II ((R'R"R'R'Sb■)X
O), oxonium compound ((R'R"R"O■)
O), SuJLtH:-ium compound ((R'R"llll'
S■]xO), oxysulfonium compound ([R'R”
R3S■(0))XO), selenonium compound ((R″
R"R'Se■]X○), telluronium compound ((R
'R''R'Te■]XO), stannonium compound ((
R'R2R'Sn■)Xe'), the udonium compound IR"R"l■]X○), and the like. Here, R゛, 1, R3, and R4 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 or, depending on the case, may be a component of a ring containing an element having a lone pair of electrons.

Moreover, X represents a halogen selected from BrsI.

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 in which the anion is a halogen, include amines or nitrogen-containing compounds, phosphine compounds, arsine compounds, stibine compounds, oxy compounds, sulfide compounds, It is easily obtained by reaction with sulfoxide compounds, selenide compounds, telluride compounds, etc., and these may be produced outside the reaction system or may be produced within the reaction system. Of course, it may be produced by another method, or it may be produced within the reaction system by another method.

Preferred among these are halogenated ammonium compounds, halogenated phosphonium compounds, halogenated anthonium compounds, and halogenated sulfonium compounds, and 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; amines such as primary amines, secondary amines, and tertiary amines; hydroxylamines; hydrazine; hydrazones; amino acids; oximes; imidoesters; amides and various nitrogen-containing heterocyclics. There are compounds etc.

Halogen oxoacids and their salts have an oxidation number of positive 1.
3.5.7 halogen oxygen acids and their salts, specifically hypobromous acid, bromate acid, perbromate acid, hypoiodic acid, iodic acid, iodic acid, and orthoperiodine. 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.

A complex compound containing a halogen may contain either a cationic or anionic halogen, and includes, for example, 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 triiodite, iodopentaammine chromium triiodite, and bis(2,2'-bipyridine) copper diiodite are used.

In addition, organic halides are those represented by the general formula % (in the formula, R6 is an m-valent organic group, X is Br or ■, and m is an integer of 1 or more), When m is 2 or more, X may be a different halogen species. Further, the halogen X may be bonded to a heteroatom other than carbon, such as nitrogen, phosphorus, oxygen, sulfur, selenium, etc.

Examples of such organic halides include methyl halide, ethyl halide, methylene halide,
Aliphatic mono- and polyhalides such as haloform and tetrahalogenmethane; aromatic mono- and polyhalides such as halogenbenzene, dihalogenbenzene (each isomer), iodosobenzene, iodoxybenzene; halogenated cyclohexane, halogen Alicyclic halides such as cyclobutane; aromatic aliphatic halides such as halogenated benzyl and halogenated phenethyl; heterocycles such as halogenated furan, halogenated tetrahydrofuran, halogenated thiophene, halogenated imidazole, and halogenated piperidine Formula halides; acid halides such as acetyl halides and benzoyl halides; N-
N-halides such as 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. Furthermore, hydrogen bromide, as a compound containing bromine or iodine,
Hydrogen halides such as hydrogen iodide or hydrohalic acids 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 are 1
It is possible to use only the seeds or a mixture of two or more kinds.

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 0.001% relative to the amount of metal element in the platinum group element-containing component used.
It is preferable to use it in a range of 10.000 to 10.000 times the mole.

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 (1) % formula % (1) (in the formula, Ar represents a divalent aromatic group). Any type of substance may be used as long as it 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), and aminopyridinecarboxylic acid (each isomer). ), aminoquinolinecarboxylic acid (each isomer), aminofurancarboxylic acid (each isomer), and the following general formula (rV) (wherein A is a mere chemical bond, or -〇-1-8-1 -SO, -1-CO
-1-CONH-1-C00-1-C(R')(R")
A divalent group selected from - and -NCR')-, and R1 and R2 are H1 aliphatic groups and alicyclic groups. ) Examples include compounds (isomers) in which an amino group and a carboxyl group are bonded to the diphenyl compound represented by the formula.

In addition, in these aromatic aminocarboxylic acids, at least one hydrogen on the aromatic ring has another substituent, such as a halogen atom, a nitro group, a sia/i, an alkyl group, an alicyclic group, an aromatic group, It may be substituted with an aralkyl group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, or the like.

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, and 2-amino-naphthalene-5-carboxylic acid. naphthalene-6-carboxylic acid, p-<4-7 minophenyl)benzoic acid, p-
(4-amino-phenoxy)benzoic acid, p-(4-amino-phenylcarbamoyl)benzoic acid, and N-(4-amino-phenyl)terephthalic monoamide.

The alcohols used in the present invention include monohydric and polyhydric alcohols. Examples of such alcohols include linear or branched monovalent or polyvalent alkanols and alkanols having 1 to 2 carbon atoms, monovalent or polyvalent cycloalkanols, cycloalkanols, and aralkyl alcohols. It will be done. Furthermore, these alcohols may contain other substituents, such as a halogen atom, 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, propatool (each isomer), butanol (
each isomer), pentanol (each isomer), hexanol (each isomer), heptatool (each isomer), octatool (each isomer), nonylfluco-/L/ (each 1 isomer)
, decyl alcohol (each isomer), undecyl alcohol (each isomer), lauryl alcohol (each isomer),
Aliphatic alcohols such as tridecyl alcohol (each isomer), tetradecyl alcohol (each isomer), and pentadecyl alcohol (each isomer); cyclohexanol,
Cycloalkanols such as cycloalkanol 7 Ethylene glycol monomethyl ether, 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 Alkylene glycol monoethers such as monoethyl ether; aralkyl alcohols such as benzyl alcohol, etc. 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 gas containing oxygen, or may be air or other gases that do not inhibit the reaction of pure oxygen, such as nitrogen, argon, helium,
It may be diluted by adding an inert gas such as carbon dioxide. In some cases, it may also contain gases such as hydrogen, carbon oxide, 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, and particularly preferred are aromatic nitrocarboxylic acids having the same skeleton structure as the raw material aromatic aminocarboxylic acid. In this case, the raw material aromatic aminocarboxylic acid and 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 less than or more than the equivalent amount, but
Oxygen/carbon oxide or oxygen/alcohol mixtures should be used outside 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, but 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; Ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; Acetone, methyl ethyl ketone, etc. Examples include ketones; esters such as ethyl acetate and ethyl benzoate; amides such as N,N-dimethylformamide pyrrolidone and hexamethylphosphoramide.

Furthermore, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene; 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, triple-kyl orthoborates, and the like.

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. In addition, the reaction pressure is 1 to 500 kg/cnl, preferably 20 to 3
00 kg/J, and the reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from 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 mmo 1 ) of para-aminobenzoic acid was placed in a stirred autoclave with an internal volume of 200 n+1.
Ethanol 60mA, palladium black 42.4mg<0
．． 4tag atom), sodium iodide 120mg
(0.8 mmoβ) and replaced the system with -carbon oxide, then 70 kg/c+d of -carbon oxide, and then air was injected to bring the total pressure to 100 kg/cT1. 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 conversion rate of para-aminobenzoic acid was 98%. It was found that para-ethoxycarbamoylbenzoic acid was produced with a yield of 95% and a selectivity of 97%.After ethanol was distilled off from this reaction solution and the obtained yellow solid was washed with dilute hydrochloric acid and water, By recrystallizing from a mixed solvent of ethanol and water, 6.8 g of barethoxycarbamoylbenzoic acid was obtained as white needle crystals (melting point 198-200°C).If sodium iodide was not used, urethane The reaction hardly progressed.

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 the yield of meta-ethoxycarbamoylbenzoic acid was 92%. %, selection rate 96
It was generated in %.

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%, and the selectivity was It was generated in 97% of cases.

Example 4 The reaction was carried out in the same manner as in Example 1 except that 1-aminonaphthalenecarboxylic acid-5 was used instead of para-aminobenzoic acid. As a result, the reaction rate of 1-aminonaphthalenecarboxylic acid-5 was 93%. , 1-ethoxycarbamoylnaphthalenecarboxylic acid-5 yield 88%, selectivity 95%
It was generated with .

Examples 5 to 13 Table 1 shows the results of producing paraethoxycarbamoylbenzoic acid from para-aminobenzoic acid in the same manner as in Example 1 except for changing the catalyst system. In these examples, para-aminobenzoic acid is 40 mmol,
Ethanol is 60ml, platinum group metal or compound containing platinum group element is platinum group metal Q, 5mg ato
n+, bromine, iodine, or compounds containing these are 0.
8 mmo6 was 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, and then reducing the co-supported carbon with hydrogen at 350°C.

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.
Mo! ! , methanol 60ml, palladium chloride 0.5mmo 1% potassium iodide 1.5mmoff
After replacing the inside of the system with carbon monoxide, 130 kg/cni of -carbon oxide was injected under pressure. 170 while stirring
The reaction was carried out at ~180°C for 3 hours. As a result of analyzing the reaction solution, the reaction rates of para-aminobenzoic acid and para-nitrobenzoic acid were 30% and 38%, respectively, and 1 lmmo 1 of para-methoxycarbamoylbenzoic acid was produced.

(Effect of the invention)

Claims (6)

[Claims] (1) In the presence of an oxidizing agent and a catalyst consisting of 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, (I)H_2N-Ar-
COOH (I) (wherein, Ar represents a divalent aromatic group) is an aromatic aminocarboxylic acid represented by carbon monoxide and formula (II) ROH (II) (wherein, R represents an aliphatic group) or represents an aromatic aliphatic group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) R represents an aliphatic group or an aromatic aliphatic 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) Compounds containing bromine or iodine are alkali metal or alkaline earth metal halides, halogenated onium compounds, compounds that can produce these compounds in a reaction system, halogen oxoacids or salts thereof, halogens. The method according to any one of claims 1 to 3, wherein the compound is at least one selected from complex compounds having ions and organic halides. (5) The method according to claim 1, in which 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.