JPH11322716A - Production of nitrogen-containing aromatic heterocyclic carboxylic acid compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a synthetic raw material of a metallic ion masking agent, etc., by oxidizing an specific compound by using a catalytic amount of a heavy metal complex salt and an easy-to-handle oxidizing agent. SOLUTION: This objective nitrogen-containing heterocyclic carboxylic acid compound of formula II (e.g.; picolinic acid) is obtained by oxidizing a nitrogen- containing heterocyclic compound of formula I [Q is a 5 to 6-membered monocyclic or a condensed ring aromatic heterocyclic ring containing at least one N-atom; R is a primary alkyl; (n) is 1-5; X is a substituent; (m) is 0-4] with a hypohalogenic acid salt (e.g.; sodium hypochloride) in the presence of a nickel compound (suitably, a nickel (II) complex). Further the above reaction is preferably performed e.g. in an organic solvent such as acetonitrile at a temp. of 0-100 deg.C for 1-24 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid derivative useful as a metal ion masking agent or a raw material for synthesizing pharmaceuticals and agricultural chemicals.

[0002]

2. Description of the Related Art As a method for synthesizing a corresponding nitrogen-containing aromatic heterocyclic carboxylic acid derivative by oxidizing a side chain methyl group of a nitrogen-containing aromatic heterocyclic compound, oxidation of a heavy metal such as potassium permanganate or chromic acid is known. Method using an agent (for example,
Chem. Ber., 48, 1905 (1915), Synth. Meth., 22, 250), a method in which a metal oxide is used as a catalyst to react with ammonia in the gas phase (ammoxidation), followed by hydrolysis, ozone (eg, Chem. Abstr., 81, 151948), hydrogen peroxide (for example, Arch. Pharm (Weinheim Ger) 288, 426 (1955)) or high-purity oxygen (for example, Synth. Meth., 18, 219). After halogenating the side chain methyl group,
Hydrolysis method (for example, J. Chem. Soc., 123, 2883 (192
3 etc.)), electrochemically oxidatively synthesize (eg,
Chem. Heterocycl. Compd., 31, 80 (1995) and the like).

However, a method using a heavy metal oxidizing agent usually requires an oxidizing agent having a stoichiometry or more, and as a result, a waste liquid containing a large amount of heavy metal ions is generated. Improvement was needed. In addition, the synthesis by ammoxidation requires large-scale dedicated equipment and treatment of ammonia produced as a by-product after hydrolysis. In the method using ozone, hydrogen peroxide, or high-purity oxygen as the oxidizing agent, it is difficult to handle the oxidizing agent because it is gaseous or extremely unstable. However, there are inconveniences such as an increase in facility load. In the method via halogenation of a side chain methyl group, selectivity of halogenation (a distinction between a side chain methyl group and an aromatic ring) may be low, or the heterocycle itself may be oxidized under the halogenation reaction conditions. Thus, it is often difficult to obtain an intermediate halide. Further, regarding the hydrolysis of halides, the yield, reaction time, waste liquid treatment and the like were not yet satisfactory, and improvement was required. In electrochemical oxidation, there was a problem that scale-up was difficult due to the limitation of the oxidation apparatus.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to avoid the use of a large amount of heavy metal compounds and the use of an oxidizing agent which is difficult and dangerous to handle, and uses a catalytic amount of a heavy metal complex and an oxidizing agent which is easy to handle. It is to develop a method capable of producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound.

[0005]

The above object has been achieved by the following means. (1) Nitrogen-containing aromatic compound represented by general formula (II) by oxidizing nitrogen-containing aromatic heterocyclic compound represented by general formula (I) using hypohalite as an oxidizing agent in the presence of nickel compound A method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound, characterized by obtaining an aromatic heterocyclic carboxylic acid compound. General formula (I)

[0006]

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Wherein Q represents a 5- or 6-membered monocyclic or condensed-ring aromatic heterocyclic ring containing at least one nitrogen atom, R represents a primary alkyl group, and n represents 1 to 5 X represents a substituent, and m represents an integer of 0 to 4.) General formula (II)

[0008]

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(Wherein Q, X, n and m represent the general formula (I)
Is synonymous with (2) The method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound according to (1), wherein the nickel compound is a nickel (II) complex. (3) The compounds represented by the general formulas (I) and (II) are represented by the general formulas (Ia) and (II-a), respectively.
The method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound according to (1) or (2), which is a compound represented by the formula: General formula (Ia)

[0010]

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(Wherein Q ′ represents a 6-membered monocyclic or condensed-ring aromatic heterocyclic ring containing at least one nitrogen atom,
R, n, X and m have the same meanings as in formula (I). ) General formula (II-a)

[0012]

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(Wherein Q ′, X, n and m represent the general formula (I
It is synonymous with -a). In the present invention, the aromatic hetero ring means a hetero ring having aromaticity. Also, the primary alkyl group is
An alkyl group linked to an aromatic heterocycle by a primary carbon atom.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (I) or (II) will be described in detail. Q represents a 5- or 6-membered monocyclic or condensed-ring aromatic heterocyclic ring containing at least one nitrogen atom, and preferably has 1 to 4 nitrogen atoms, more preferably 1 to 3 nitrogen atoms. Examples of the 5-membered aromatic heterocycle include pyrrole, imidazole, pyrazole,
1,2,4-triazole, 1,2,3-triazole, benzimidazole, indazole, oxazole, isoxazole, oxadiazole, benzoxazole, benzo [d] isoxazole, thiazole, isothiazole, thiadiazole, benzothiazole, Benzo [d] isothiazole, tetrazole, pyrazolotriazole, pyrrolotriazole, carbazole and the like can be mentioned. As the 6-membered aromatic heterocycle, for example,
Pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, 1,3,5-triazine, 1,2,2
4-triazine, 1,8-naphthyridine, 7-azaindole, purine, tetrazaindene and the like. Q
Are preferably 6-membered aromatic heterocycles, more preferably pyridine, pyrimidine, pyridazine, pyrazine and 1,3,5-triazine, and still more preferably pyridine, pyrimidine, pyridazine and pyrazine. And particularly preferably pyridine.

R represents a primary alkyl group and preferably has 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-hexyl
-Octyl and the like, more preferably 1 to 4 carbon atoms, and particularly preferably methyl. n is 1 to 5
And preferably represents 1 to 3, more preferably 1 or 2.

X represents a substituent. Examples of the substituent represented by X include a tertiary alkyl group (an alkyl group bonded to an aromatic hetero ring through a tertiary carbon atom, preferably 4 to 30 carbon atoms, more preferably 4 to 30 carbon atoms). 20,
Particularly preferably, it has 4 to 12 carbon atoms, and examples thereof include t-butyl and t-octyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 carbon atoms)
-20, particularly preferably 6-12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An alkoxy group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy), and acyl. A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl and the like), and an alkoxycarbonyl group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, etc., and an aryloxycarbonyl group (preferably 7 carbon atoms). ~ 20,
More preferably, it has 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), and an acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms
6, particularly preferably having 2 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like. ),
Alkoxycarbonylamino group (preferably having 2 to 2 carbon atoms)
20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms,
For example, phenyloxycarbonylamino and the like can be mentioned. ), A sulfonylamino group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Dimethylsulfamoyl, phenylsulfamoyl and the like can be mentioned. ), Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl). A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, for example, mesyl,
Tosyl, and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like. ), Ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms)
12, for example, ureide, methylureide, phenylureide and the like. ), Phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, a sulfo group, a carboxyl group, and a nitro group. These substituents may be further substituted.

X is preferably a tertiary alkyl group,
Aryl group, alkoxy group, aryloxy group, acyl group, acylamino group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, halogen atom, cyano group, nitro group, carboxyl group, more preferably tertiary alkyl group, aryl group, alkoxy group A tertiary alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a halogen atom, a cyano group, an aryloxy group, an acyl group, a halogen atom, a cyano group, a nitro group, and a carboxyl group. And a nitro group, particularly preferably an aryl group, an alkoxy group, an aryloxy group, an acyl group, a halogen atom and a nitro group.

M represents an integer of 0 to 4. m is preferably from 0 to 3, more preferably from 0 to 2, and particularly preferably 0 or 1.

Among the compounds represented by the general formula (I) used in the present invention, more preferred are the compounds represented by the general formula (Ia).
The compound represented by I) is represented by the general formula (II-a).

Among the compounds represented by the general formula (I) used in the present invention, more preferred are the compounds represented by the general formula (Ib).
The compound represented by I) is represented by the general formula (II-b). General formula (Ib)

[0021]

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(Wherein Q ″ represents a 6-membered monocyclic aromatic heterocycle containing at least one nitrogen atom, n represents an integer of 1 to 5. X represents a substituent, and m represents 0 to Represents an integer of 4.) General formula (II-b)

[0023]

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(Wherein Q ″, X, n, and m are the general formulas (I-
Synonymous with b). )

Examples of the compound represented by the formula (I) used in the reaction of the present invention are shown below, but the present invention is not limited by these.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The general formula (II) obtained by the method of the present invention
The compound represented by is exemplified below.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The nickel compound used in the present invention is:
Preferably, it means a compound having Ni (II), and in addition to oxides, hydroxides, halides, sulfates, nitrates,
A single salt such as a carbonate or a complex salt (complex) is used. The nickel complex in the present invention is formed from a monodentate or polydentate ligand having Ni (II) as a central metal and having a nitrogen, sulfur or oxygen atom as a coordinating element. Examples of the monodentate ligand include nitrogen-containing aromatic heterocycles such as 1-methylimidazole and 4-t-butylpyridine, and ammonia. Examples of the polydentate ligand include bidentate to hexadentate ligands. Examples of the bidentate ligand include bipyridine, 1,10-phenanthroline, 8-hydroxyquinolyl, dimethylglyoxyl, glycine, and salicylaldoxime. , Ethylenediamine, etc., as the tridentate ligand, diethylenetriamine, etc., and as the tetradentate ligand, for example, tris (3-aminopropyl) amine, 1,4,8,11-
And tetraazacyclotetradecane. As the hexadentate ligand, ethylenediaminetetraacetic acid (ED
TA) and trimethylenediaminetetraacetic acid.

The ligand of the nickel complex is a multidentate ligand having a large complex stability constant in order to avoid ligand exchange with a nitrogen-containing heteroaromatic compound as a reaction substrate and extend the life of a catalyst cycle. Children are more preferred. In some cases, a compound represented by the general formula (II), which is a product of this reaction, may be used as a ligand. Among the polydentate ligands, a bidentate or tetradentate ligand is preferred. This is due to the fact that nickel (II) easily adopts a planar four conformation and forms a stable complex in this state.

The preferred range of the stability constant of the nickel (II) complex used in this reaction varies depending on the relationship with the nitrogen-containing heterocycle of the general formula (I) used in the reaction.
It is preferably 4 or more and 30 or less, more preferably 6 or more and 25 or less, and still more preferably 8 or more and 20 or less. Specific complexes include, for example, nickel tetra (1-methylimidazolyl), nickel bisbipyridyl, nickel monobipyridyl, nickel bis (1,10
-Phenanthryl), nickel bis (8-hydroxyquinolyl), nickel bis (salicylaldoxime), nickel-EDTA (ethylenediaminetetraacetic acid) and the like. The hypohalite used in the present invention is:
Alkali metal (sodium, potassium, etc.) or alkaline earth metal (calcium, barium, etc.) salts such as hypochlorous acid and hypobromite, typical examples are sodium hypochlorite, hypobromite Acid sodium. Sodium hypohalite can be prepared by adding a halogen to a high concentration aqueous sodium hydroxide solution. Since sodium hypochlorite is commercially available as an aqueous solution of about 5% concentration, the solution can be used as it is, which is preferable in terms of availability.

The ratio of the reaction substrate represented by the general formula (I), the hypohalite as an oxidizing agent, and the nickel complex as a catalyst varies depending on the number of primary alkyl groups involved in oxidation. The molar ratio of hypohalite to one primary alkyl group is 3 times or more and 30 times or less, more preferably 5 times or more and 15 times or less, and the nickel complex is preferably 0.005 times or more. It is 0.5 times or less, more preferably 0.01 times or more and 0.2 times or less, and further preferably 0.05 times or more and 0.15 times or less.

As the organic solvent used in the reaction, those which are not oxidized by hypohalite and are capable of dissolving the reaction substrate represented by the general formula (I) are preferable. For example, acetonitrile, benzene, acetone, dichloromethane, dioxane And the like. Of these, acetonitrile is preferred as the solvent. The amount of the organic solvent used varies depending on the solubility of the reaction substrate, but is 1 to 100 times, more preferably 5 to 50 times the weight ratio of the reaction substrate. When a solvent such as benzene or dichloromethane that is immiscible with the aqueous solution of hypohalous acid is used, a phase transfer catalyst such as a quaternary alkylammonium salt should be used in combination with the purpose of improving a decrease in reactivity due to a heterogeneous state. Is preferred.

The reaction temperature is preferably from 0 ° C. to 10 ° C.
The temperature is 0 ° C or lower, more preferably 10 ° C or higher and 80 ° C or lower, further preferably 15 ° C or higher and 50 ° C or lower.
The reaction time is preferably from 1 hour to 24 hours, more preferably from 3 hours to 18 hours,
More preferably, it is 4 hours or more and 12 hours or less.

In the reaction, the order of adding the compound of the formula (I), the hypohalite and the nickel compound is not particularly limited, and the reaction can be carried out in any order. If it is assumed, it is desirable to take a form in which hypohalite, which is an oxidizing agent, is added dropwise at the end from the viewpoint of reaction control.

The method of isolating the desired product after the completion of the reaction varies depending on the nature of the carboxylic acid of the general formula (II) formed. First, the excess hypohalite is removed from sodium sulfite or hydrosulfite. After reduction and removal with sodium sulfite or the like, the pH is adjusted in consideration of the pKa of the target substance. If the desired product has low water solubility and can be extracted with an organic solvent, extraction is performed at this stage to separate the water-soluble product from the nickel compound, and the product can be purified by conventional means such as recrystallization or column chromatography. When the target substance has high water solubility and the extraction operation is difficult and the target substance is a solid, the reaction solution is concentrated and the target substance is salted out. When salting out is difficult, the reaction solution is concentrated, and a water-soluble organic solvent is added to remove as much of the by-produced inorganic salt as possible, followed by recrystallization with a water-containing solvent. If the target product cannot be isolated by the above operation, it is considered that the coexistence of the nickel compound may cause the isolation hindrance. Therefore, the nickel compound is removed by a cation exchange column and then recrystallized. When the coexistence of a small amount of inorganic salt hinders the isolation, the inorganic salt is removed by a desalting apparatus having an electrophoretic filtration membrane, and the desired product is isolated. When the target substance is a liquid, the nickel compound is removed by an ion exchange column, and the inorganic salt is removed by a desalter to isolate the target substance.

[0051]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Embodiment 1 Synthesis of picolinic acid by oxidation of α-picoline 0.93 g (10 mmol) of α-picoline was added to acetonitrile 5
The solution was dissolved in 0 ml, and 20 ml (corresponding to 1 mmol) of a 0.05 M nickel bisbipyridyl complex aqueous solution was added thereto. Then, 100 ml (corresponding to 0.1 mol) of a 5% aqueous sodium hypochlorite solution was added dropwise while the solution was vigorously stirred. . After the stirring was continued for 6 hours at room temperature, the reaction solution was analyzed by HPLC. As a result, it was confirmed that picolinic acid was generated at a conversion rate of 26% with respect to the starting material in the content calculation based on the calibration curve. Was.

Embodiment 2 FIG. Synthesis of Isonicotinic Acid by Oxidation of γ-Picoline Oxidation reaction was performed in the same manner as in Example 1 except that γ-picoline was used instead of α-picoline, and the reaction solution was analyzed by HPLC. It was confirmed that isonicotinic acid was produced at a conversion of 15% with respect to the starting material.

Example 3. Synthesis of 2,6-pyridinedicarboxylic acid by oxidation of 2,6-lutidine 1.1 g (10 mmol) of 2,6-lutidine was dissolved in 50 ml of acetonitrile, and 0.05 M nickel bis After adding 20 ml (corresponding to 1 mmol) of the bipyridyl complex aqueous solution, 100 ml (corresponding to 0.1 mol) of a 5% aqueous sodium hypochlorite solution was added dropwise while the solution was vigorously stirred.
After stirring was continued for 6 hours at room temperature, the reaction solution was analyzed by HPLC.
It was confirmed that pyridinedicarboxylic acid was produced at a conversion of 46% based on the starting material.

After completion of the reaction, 12 g (0.069 mol) of sodium hydrosulfite was added to the reaction solution and dissolved to decompose excess sodium hypochlorite. The reaction solution was concentrated to about 1/2 volume using an evaporator, and then left overnight. The precipitate was collected by suction filtration and washed with methanol. The obtained crude product was recrystallized from water to give 2,6-
0.5 g of pyridinedicarboxylic acid was obtained. Structure of isolation yield: 30% isolated desired product compares preparation and ¹ H-NMR spectrum was confirmed.

HPLC analysis conditions: Column: TSK-gel ODS-80 manufactured by Tosoh Corporation
TM Eluent A: 0.1% H ₃ PO ₄ , Et ₃ N in water Ｂ B: 0.1% H ₃ PO ₄ , Et ₃ N in methanol / water = 90/10 Detection wavelength: 254 nm Flow rate: 1 ml / Component B ratio: Examples 1 and 2; 5% Example 3; 15%

Comparative Example 1 21 g of sodium hydroxide (95
% Of 0.5 mol) in 180 ml of water, ice-cooled to 10 ° C. or lower, and then 13 ml of bromine.
(0.25 mol) was added dropwise to prepare an aqueous solution of sodium hypobromite. The aqueous solution of sodium hypobromite contains α
-3 g (32.2 mmol) of picoline was added to the reaction system at 10 ° C.
When the reaction was carried out dropwise while keeping below, an orange reaction product was deposited. The precipitate is collected by suction filtration (crude yield 3).
g), as a result of ¹ H-NMR analysis, the product was not picolinic acid. The product showed the same combination of spectra with the same signal number and the same integration ratio as α-picoline, and it was confirmed that oxidation of the methyl group did not proceed. However, the chemical was different from α-picoline and α-picoline-N-oxide. The shift values are shown.

[0058]

According to the present invention, a nitrogen-containing aromatic heterocyclic carboxylic acid compound can be produced under mild conditions without using a large amount of heavy metal compounds or an oxidizing agent which is difficult to handle.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 231/14 C07D 231/14 237/08 237/08 237/24 237/24 239/26 239/26 239/28 239/28 241/12 241/12 241/24 241/24 261/10 261/10 263/34 263/34 263/58 263/58 277/24 277/24 277/56 277/56 277/64 277/64 277 / 68 277/68 471/04 114 471/04 114N 473/00 473/00 487/04 142 487/04 142 146 146 521/00 521/00

Claims (3)

[Claims] 1. A method comprising oxidizing a nitrogen-containing aromatic heterocyclic compound represented by the general formula (I) using a hypohalite as an oxidizing agent in the presence of a nickel compound to obtain a compound represented by the general formula (II): A method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound, which comprises obtaining a nitrogen-containing aromatic heterocyclic carboxylic acid compound. General formula (I) (Wherein Q represents a 5- or 6-membered monocyclic or condensed-ring aromatic heterocycle containing at least one nitrogen atom, R represents a primary alkyl group, and n represents an integer of 1 to 5) Represent.
X represents a substituent, and m represents an integer of 0 to 4. ) General formula (II) (In the formula, Q, X, n and m have the same meanings as in the general formula (I).) 2. The method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound according to claim 1, wherein the nickel compound is a nickel (II) complex. 3. The compound represented by the general formula (I) or (II) is a compound represented by the general formula (Ia) or (II-a), respectively. Or the method for producing a nitrogen-containing aromatic heterocyclic carboxylic acid compound according to 2. General formula (Ia) (In the formula, Q ′ represents a 6-membered monocyclic or condensed-ring aromatic heterocyclic ring containing at least one nitrogen atom, and R, n, X, and m have the same meanings as in formula (I).) Formula (II-a) (In the formula, Q ′, X, n and m have the same meaning as in the general formula (Ia).)