Process for producing aminonitropyridines

Abstract: A process for producing an aminonitropyridine represented by the general formula [1], which comprises reacting a nitropyridine represented by the general formula [2] (wherein X 1 , X 2 and X 3 indicate a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aryl group, an aromatic heterocycle or an alkyl group, etc.; Y is an oxygen atom; and n is 0 or 1) with an O-substituted hydroxylamine represented by the general formula [3] (wherein R 4 is a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group; and R 5 is an alkyl group or an aralkyl group) or a salt thereof in the presence of a base and a metal catalyst.

Description: The present invention relates to a process for producing an aminonitropyridine by a direct amination reaction of a nitropyridine using a O-substituted hydroxylamine or a salt thereof. An aminonitropyridine can be a precursor of a diminopyridine and is an important compound as an intermediate of drugs and agricultural chemicals. As the process for synthesizing an aminonitropyridine from a nitropyridine, there has generally been known a process via a substitution reaction between a halogenated nitropyridine and an amine. However, such a process has the disadvantages of having a large number of steps and the requirement of a halogenation step causing high corrosion and a large environmental load. Some attempts to directly produce an aminonitropyridine from a nitropyridine have been made. However, for example, a process of direct amination of a nitropyridine using a hydroxylamine hydrochloride salt (J. Am. Chem. Soc., 78 , 423 (1956)) is not satisfactory because of the reaction yield. In addition, a process of directly aminating a nitropyridine using ammonia and potassium permanganate (Liebigs Ann. Chem. 875 (1991)) has the drawback that a complicated operation is required because one or more equivalents of explosive potassium permanganate is used. A process using 1-sulphenamoylthiocarbonylpyrrolidine as an amination agent (Japanese Laid-Open Patent Publication No. 7-109260) is inferior in industrial utility because the amination agent is expensive. It is an object of the present invention to provide a process which is industrially advantageous for producing an aminonitropyridine. This object could be achieved on the basis of the finding that an aminonitropyridine can be obtained in one step by directly aminating a nitropyridine with an O-substituted hydroxylamine in the presence of a base and a metal catalyst. The present invention provides a process for producing an aminonitropyridine represented by the general formula [1]: wherein X 1 , X 2 , X 3 , R 4 , Y and n are as defined below, which comprises reacting a nitropyridine represented by the general formula [2]: wherein X 1 , X 2 and X 3 are the same or different and indicate a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aryl group, a heterocycle, an alkyl group, a cycloalkyl group, an alkenyl group (the alkyl group, the cycloalkyl group and the alkenyl group may be respectively substituted with a halogen atom, an aryl group, an amino group, a hydroxyl group, a carboxyl group or an alkoxyl group), or a group OR 1 , SR 1 , NR 1 R 2 , COR 3 , COOR 3 , CONR 1 R 2 , SO 2 R 3 , SO 3 R 3 or SO 2 NR 1 R 2 , or when two of X 1 , X 2 and X 3 bond at the ortho-position, the two may bond together so that a 5- to 7-membered hydrocarbon ring or heterocycle is formed which includes 2 carbon atoms of the pyridine ring; R 1 and R 2 are the same or different and indicate a hydrogen atom, an alkyl group, an alkenyl group (the alkyl group and the alkenyl group may be respectively substituted with a halogen atom, an aryl group, an amino group, a hydroxyl group, a carboxyl group or an alkoxyl group), an aryl group or an acyl group; R 3 is a hydrogen atom, an alkyl group, an alkenyl group (the alkyl group and the alkenyl group may be respectively substituted with a halogen atom, an aryl group, an amino group, a hydroxyl group, a carboxyl group or an alkoxyl group) or an aryl group; Y is an oxygen atom; and n is 0 or 1, with an O-substituted hydroxylamine represented by the general formula [3]: R 4 NHOR 5 wherein R 4 is a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group; and R 5 is an alkyl group or an aralkyl group, or a salt thereof in the presence of a base and a metal catalyst. In the nitropyridine represented by general formula [2], the O-substituted hydroxylamine represented by general formula [3] and the aminonitropyridine represented by general formula [1], which are used in the present invention, the alkyl group indicates a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, sec-butyl group, tert-butyl group and neopentyl group. The alkoxy group indicates a straight-chain or branched alkoxyl group having 1 to 6 carbon atoms, and examples thereof include a methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, isopropoxy group, sec-butoxy group, tert-butoxy group and neopentoxy group. The aryl group indicates a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 14 carbon atoms. The heterocycle indicates a monocyclic or polycyclic, and aromatic or 3- to 6-membered non-aromatic heterocycle. Examples thereof include a phenyl group, naphthyl group, anthryl group, furyl group, pyrrolyl group, thienyl group, oxazolyl group, thiazolyl group, pyridyl group, imidazolyl group, triazolyl group, tetrazolyl group, quinolyl group, oxirane ring, aziridine ring, dihydrofuran ring, tetrahydrofuran ring, dihydropyran ring, tetrahydropyran ring, 1,3-dioxorane ring, pyrrolidine ring, piperidine ring and morpholine ring, each of which may have various substituents. The cycloalkyl group indicates a cycloalkyl having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, cyclopentyl group and cyclohexyl group. The alkenyl group indicates a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a carbon-carbon double bond, and examples thereof include a vinyl group, allyl group, propenyl group, butenyl group and pentenyl group. Examples of the aralkyl group include a benzyl group. Examples of the acyl group include an acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group and benzoyl group. Examples of the nitropyridine represented by the general formula [2] include 2-nitropyridine, 3-halogeno-2-nitropyridine, 3-cyano-2-nitropyridine, 3-aryl-2-nitropyridine, 3-alkyl-2-nitropyridine, 3-alkenyl-2-nitropyridine, 3-hydroxy-2-nitropyridine, 3-alkoxy-2-nitropyridine, 3-alkenyloxy-2-nitro-pyridine, 3-aryloxy-2-nitropyridine, 3-benzyloxy-2-nitropyridine, 3-acyloxy-2-nitropyridine, 3-amino-2-nitropyridine, 3-(N-alxylamino)-2-nitropyridine, 3-(N-alkenylamino)-2-nitropyridine, 3-(N-arylamino)-2-nitropyridine, 3-(N-acylamino)-2-nitropyridine, 3-(N,N-dialkylamino)-2-nitropyridine, 3-acetyl-2-nitropyridine, 3-alkenylcarbonyl-2-nitropyridine, 3-arylcarbonyl-2-nitropyridine, 3-benzylcarbonyl-2-nitropyridine, 3-alkoxycarbonyl-2-nitropyridine, 3-alkenyloxycarbonyl-2-nitropyridine, 2,3-dinitropyridine, 3-benzyl-2-nitropyridine, 2-nitro-3-pyridinecarboxylic acid, 3-aryloxy-carbonyl-2-nitropyridine, 3-benzyloxycarbonyl-2-nitropyridine, 3-mercapto-2-nitropyridine, 3-alkylthio-2-nitropyridine, 3-alkenylthio-2-nitropyridine, 3-arylthio-2-nitropyridine, 3-benzylthio-2-nitropyridine, 3-acylthio-2-nitropyridine, 2-nitro-3-pyridinesulfonic acid, alkyl 2-nitro-3-pyridinesulfonate, alkenyl 2-nitro-3-pyridinesulfonate, aryl 2-nitro-3-pyridinesulfonate, benzyl 2-nitro-3-pyridinesulfonate, 3-trifluoromethyl-2-nitropyridine, 3-chloromethyl-2-nitropyridine, 3-(2-methoxyethyl)-2-nitropyridine, 3-trifluoromethoxy-2-nitropyridine, 3-difluoromethoxy-2-nitropyridine, 3-(2-methoxyethoxy)-2-nitropyridine, 3-(2-chlorovinyl)-2-nitropyridine, 3-(α-styryl)-2-nitropyridine, 3-(3-methoxy-1-propenyl)-2-nitropyridine, 3-cycloalkyl-2-nitropyridine, 3-fluorocyclopropyl-2-nitropyridine, 3-(2-oxazolinyl)-2-nitropyridine, 3-(4-piperidyl)-2-nitropyridine, 3-alkylsulfonyl-2-nitropyridine, 3-alkenylsulfonyl-2-nitropyridine, 3-arylsulfonyl-2-nitropyridine, 3-benzylsulfonyl-2-nitropyridine, 2-nitro-3-pyridinecarboxamide, N-alkyl-2-nitro-3-pyridinecarboxamide, N-alkenyl-2-nitro-3-pyridinecarboxamide, N-aryl-2-nitro-3-pyridinecarboxamide, N-acyl-2-nitro-3-pyridinecarboxamide, N,N-dialkyl-2-nitro-3-pyridinecarboxamide, 2-nitro-3-pyridinesulfonamide, N-alkyl-2-nitro-3-pyridinesulfonamide, N-alkenyl-2-nitro-3-pyridinesulfonamide, N-aryl-2-nitro-3-pyridinesulfonamide, N-acyl-2-nitro-3-pyridinesulfonamide, N,N-dialkyl-2-nitro-3-pyridinesulifonamide, 3-(N-benzylamino)-2-nitropyridine, N-benzyl-2-nitro-3- pyridinesulfonamide, N-benzyl-2-nitro-3-pyridinecarboxamide and isomers of the above 3-substituted-2-nitropyridines, isomers having a substituent on the 4-, 5- or 6-position instead of the 3-position, 3-nitropyridine, 2-halogeno-3-nitropyridine, 2-cyano-3-nitropyridine, 2-aryl-3-nitropyridine, 2-alkyl-3-nitropyridine, 2-alkenyl-3-nitropyridine, 2-hydroxy-3-nitropyridine, 2-alkoxy-3-nitropyridine, 2-alkenyloxy-3-nitro-pyridine, 2-aryloxy-3-nitropyridine, 2-benzyloxy-3-nitropyridine, 2-acyloxy-3-nitropyridine, 2-amino-3-nitropyridine, 2-(N-alkylamino)-3-nitropyridine, 2-(N-alkenylamino)-3-nitropyridine, 2-(N-arylamino)-3-nitropyridine, 2-(N-acylamino)-3-nitropyridine, 2-(N,N-dialkylamino)-3-nitropyridine, 2-acetyl-3-nitropyridine, 2-alkenylcarbonyl-3-nitropyridine, 2-arylcarbonyl-3-nitropyridine, 2-benzylcarbonyl-3-nitropyridine, 2-alkoxycarbonyl-3-nitropyridine, 2-alkenyloxycarbonyl-3-nitropyridine, 2-benzyl-3-nitropyridine, 3-nitro-2-pyridinecarboxlic acid, 2-aryloxycarbonyl-3-nitropyridine, 2-benzyloxycarbonyl-3-nitropyridine, 2-mercapto-3-nitropyridine, 2-alkylthio-3-nitropyridine, 2-alkenylthio-3-nitropyridine, 2-arylthio-3-nitropyridine, 2-benzylthio-3-nitropyridine, 2-acylthio-3-nitropyridine, 3-nitro-2-pyridinesulfonic acid, alkyl 3-nitro-2-pyridinesulfonate, alkenyl 3-nitro-2-pyridinesulfonate, aryl 3-nitro-2-pyridinesulfonate, benzyl 3-nitro-2-pyridinesulfonate, 2-trifluoromethyl-3-nitropyridine, 2-cloromethyl-3-nitropyridine, 2-(2-methoxyethyl)-3-nitropyridine, 2-trifluoromethoxy-3-nitropyridine, 2-difluoromethoxy-3-nitropyridine, 2-(2-methoxyethoxy)-3-nitropyridine, 2-(2-chlorovinyl)-3-nitropyridine, 2-(α-styryl)-3-nitropyridine, 2-(3-methoxy-1-propenyl)-3-nitropyridine, 2-cycloalkyl-3-nitropyridine, 2-fluorocyclopropyl-3-nitropyridine, 2-(2-oxazolinyl-3-nitropyridine, 2-(4-piperidyl)-3-nitropyridine, 2-(alkylsulfonyl)-3-nitropyridine, 2-(alkenylsulfonyl)-3-nitropyridine, 2-(arylsulfonyl)-3-nitropyridine, 2-(benzylsulfonyl)-3-nitropyridine, 3-nitro2-pyridinecarboxamide, N-alkyl-3-nitro-2-pyridinecarboxamide, N-alkenyl-3-nitro-2-pyridinecarboxamide, N-aryl-3-nitro-2-pyridinecarboxamide, N-acyl-3-nitro-2-pyridinecarboxamide, N,N-dialkyl-3-nitro-2-pyridinecarboxamide, 3-nitro-2-pyridinesulfonamide, N-alkyl-3-nitro-2-pyridinesulfonamide, N-alkenyl-3-nitro-2-pyridinesulfonamide, N-aryl-3-nitro-2-pyridinesulfonamide, N-acyl-3-nitro-2-pyridinesulfonamide, N,N-dialkyl-3-nitro-2-pyridinesulfonamide, 2-(N-benzylamino)-3-nitropyridine, N-benzyl-3-nitro-2- pyridinesulfonamide, N-benzyl-3-nitro-2-pyridinecarboxamide and isomers of the above 2-substituted-3-nitropyridines, isomers having a substituent on the 4-, 5- or 6-position instead of the 2-position, 4-nitropyridine, 3-halogeno-4-nitropyridine, 3-cyano-4-nitropyridine, 3-aryl-4-nitropyridine, 3-alkyl-4-nitropyridine, 3-alkenyl-4-nitropyridine, 3-hydroxy-4-nitropyridine, 3-alkoxy-4-nitropyridine, 3-alkenyloxy-4-nitro- pyridine, 3-aryloxy-4-nitropyridine, 3-benzyloxy-4-nitropyridine, 3-acyloxy-4-nitropyridine, 3-amino-4-nitropyridine, 3-(N-alkylamino)-4-nitropyridine, 3-(N-alkenylamino)-4-nitropyridine, 3-(N-arylamino)-4-nitropyridine, 3-(N-acylamino)-4-nitropyridine, 3-(N,N-dialkylamino)-4-nitropyridine, 3-acetyl-4-nitropyridine, 3-alkenylcarbonyl-4-nitropyridine, 3-arylcarbonyl-4-nitropyridine, 3-benzylcarbonyl-4-nitropyridine, 3-alkoxycarbonyl-4-nitropyridine, 3-alkenyloxycarbonyl-4-nitropyridine, 3,4-dinitropyridine, 3-benzyl-4-nitropyridine, 4-nitro-3-pyridinecarboxylic acid, 3-aryloxycarbonyl-4-nitropyridine, 3-benzyloxycarbonyl-4-nitropyridine, 3-mercapto-4-nitropyridine, 3-alkylthio-4-nitropyridine, 3-alkenylthio-4-nitropyridine, 3-arylthio-4-nitropyridine, 3-benzylthio-4-nitropyridine, 3-acylthio-4-nitropyridine, 4-nitro-3-pyridinesulfonic acid, alkyl 4-nitro-3-pyridinesulfonate, alkenyl 4-nitro-3-pyridinesulfonate, aryl 4-nitro-3-pyridinesulfonate, benzyl 4-nitro-3-pyridinesulfonate, 3-trifluoromethyl-4-nitropyridine, 3-chloromethyl-4-nitropyridine, 3-(2-methoxyethyl)-4-nitropyridine, 3-trifluoromethoxy-4-nitropyridine, 3-difluoromethoxy-4-nitropyridine, 3-(2-methoxyethoxy)-4-nitropyridine, 3-(2-chlorovinyl)-4-nitropyridine, 3-(α-styryl)-4-nitropyridine, 3-(3-methoxy-1-propenyl)-4-nitropyridine, 3-cycloalkyl-4-nitropyridine, 3-fluorocyclopropyl-4-nitropyridine, 3-(2-oxazolinyl)-4-nitropyridine, 3-(4-piperidyl)-4-nitropyridine, 3-alkylsulfonyl-4-nitropyridine, 3-alkenylsulfonyl-4-nitropyridine, 3-arylsulfonyl-4-nitropyridine, 3-benzylsulfonyl-4-nitropyridine, 4-nitro-3-pyridinecarboxamide, N-alkyl-4-nitro-3-pyridinecarboxamide, N-alkenyl-4-nitro-3-pyridinecarboxamide, N-aryl-4-nitro-3-pyridinecarboxamide, N-acyl-4-nitro-3-pyridinecarboxamide, N,N-dialkyl-4-nitro-3-pyridinecarboxamide, 4-nitro-3-pyridinesulfonamide, N-alkyl-4-nitro-3-pyridinesulfonamide, N-alkenyl-4-nitro-3-pyridinesulfonamide, N-aryl-4-nitro-3-pyridinesulfonamide, N-acyl-4-nitro-3-pyridinesulfonamide, N,N-dialkyl-4-nitro-3-pyridinesulfonamide, 3-(N-benzylamino)-4-nitropyridine, N-benzyl-4-nitro-3- pyridinesulfonamide, N-benzyl-4-nitro-3-pyridinecarboxamide and isomers of the above 3-substituted-4-nitropyridines, isomers having a substituent on the 2-position instead of the 3-position, 2-nitroquinoline, 4-halogeno-2-nitroquinoline, 4-cyano-2-nitroquinoline, 4-aryl-2-nitroquinoline, 4-alkyl-2-nitroquinoline, 4-alkenyl-2-nitroquinoline, 4-hydroxy-2-nitroquinoline, 4-alkoxy-2-nitroquinoline, 4-alkenyloxy-2-nitroquinoline, 4-aryloxy-2-nitroquinoline, 4-benzyloxy-2-nitroquinoline, 4-acyloxy-2-nitroquinoline, 4-amino-2-nitroquinoline, 4-(N-alkylamino)-2-nitroquinoline, 4-(N-alkenylamino)-2-nitroquinoline, 4-(N-arylamino)-2-nitroquinoline, 4-(N-acylamino)-2-nitroquinoline, 4-(N,N-dialkylamino)-2-nitroquinoline, 2,4-dinitroquinoline, 4-benzyl-2-nitroquinoline, 2-nitro-4-quinolinecarboxylic acid, 4-aryloxycarbonyl-2-nitroquinoline, 4-benzyloxycarbonyl-2-nitroquinoline, 4-mercapto-2-nitroquinoline, 4-alkylthio-2-nitroquinoline, 4-alkenylthio-2-nitroquinoline, 4-arylthio-2-nitroquinoline, 4-benzylthio-2-nitroquinoline, 4-acylthio-2-nitroquinoline, 2-nitro-4-quinolinesulfonic acid, alkyl 2-nitro-4-quinolinesulfonate, alkenyl 2-nitro-4-quinolinesulfonate, aryl 2-nitro-4 quinolinesulfonate, benzyl 2-nitro-4-quinolinesulfonate, 4-trifluoromethyl-2-nitroquinoline, 4-chloromethyl-2-nitroquinoline, 4-(2-methoxyethyl)-2-nitroquinoline, 4-trifluoromethoxy-2-nitroquinoline, 4-difluoromethoxy-2-nitroquinoline, 4-(2-methoxyethoxy)-2-nitroquinoline, 4-(2-chlorovinyl)-2-nitroquinoline, 4-(α-styryl)-2-nitroquinoline, 4-(3-methoxy-1-propenyly)-2-nitroquinoline, 4-cycloalkyl-2-nitroquinoline, 4-fluorocyclopropyl-2-nitroquinoline, 4-(2-oxazolinyl)-2-nitroquinoline, 4-(4-piperidyl)-2-nitroquinoline, 4-alkylsulfonyl-2-nitroquinoline, 4-alkenylsulfonyl-2-nitroquinoline, 4-arylsulfonyl-2-nitroquinoline, 4-benzylsulfonyl-2-nitroquinoline, 2-nitro-4-quinolinecarboxamide, N-alkyl-2-nitro-4-quinolinecarboxamide, N-alkenyl-2-nitro-4-quinolinecarboxamide, N-aryl-2-nitro-4-quinolinecarboxamide, N-acyl-2-nitro-4-quinolinecarboxamide, N,N-dialkyl-2-nitro-4-quinolinecarboxamide, 2-nitro-4-quinolinesulfonamide, N-alkyl-2-nitro-4-quinolinesulfonamide, N-alkenyl-2-nitro-4-quinolinesulfonamide, N-aryl-2-nitro-4-quinolinesulfonamide, N-acyl-2-nitro-4-quinolinesulfonamide, N,N-dialkyl-2-nitro-4-quinolinesulfonamide, 4-acetyl-2-nitroquinoline, 4-alkenylcarbonyl-2-nitroquinoline, 4-arylcarbonyl-2-nitroquinoline, 4-benzylcarbonyl-2-nitroquinoline, 4-alkoxycarbonyl-2-nitroquinoline, 4-alkenyloxycarbonyl-2-nitroquinoline, 4-(N-benzylamino)-2-nitroquinoline, N-benzyl-2-nitro-4-quinolinesulfonamide, N-benzyl-2-nitro-4-quinolinecarboxamide, 3-nitroquinoline, 4-halogeno-3-nitroquinoline, 4-cyano-3-nitroquinoline, 4-aryl-3-nitroquinoline, 4-alkyl-3-nitroquinoline, 4-alkenyl-3-nitroquinoline, 4-hydroxy-3-nitroquinoline, 4-alkoxy-3-nitroquinoline, 4-alkenyloxy-3-nitroquinoline, 4-aryloxy-3-nitroquinoline, 4-benzyloxy-3-nitroquinoline, 4-acyloxy-3-nitroquinoline, 4-amino-3-nitroquinoline, 4-(N-alkylamino)-3-nitroquinoline, 4-(N-alkenylamino)-3-nitroquinoline, 4-(N-arylamino)-3-nitroquinoline, 4-(N-acylamino)-3-nitroquinoline, 4-(N,N-dialkylamino)-3-nitroquinoline, 3,4-dinitroquinoline, 4-benzyl-3-nitroquinoline, 3-nitro-4-quinolinecarboxylic acid, 4-aryloxycarbonyl-3-nitroquinoline, 4-benzyloxycarbonyl-3-nitroquinoline, 4-mercapto-3-nitroquinoline, 4-alkylthio-3-nitroquinoline, 4-alkenylthio-3-nitroquinoline, 4-arylthio-3-nitroquinoline, 4-benzylthio-3-nitroquinoline, 4-acylthio-3-nitroquinoline, 3-nitro-4-quinolinesulfonic acid, alkyl 3-nitro-4-quinolinesulfonate, alkenyl-3-nitro-4-quinolinesulfonate, aryl 3-nitro-4- quinolinesulfonate, benzyl 3-nitro-4-quinolinesulfonate, 4-trifluoromethyl-3-nitroquinoline, 4-chloromethyl-3-nitroquinoline, 4-(2-methoxyethyl)-3-nitroquinoline, 4-trifluoromethoxy-3-nitroquinoline, 4-difluoromethoxy-3-nitroquinoline, 4-(2-methoxyethoxy)-3-nitroquinoline, 4-(2-chlorovinyl)-3-nitroquinoline, 4-(α-styryl)-3-nitroquinoline, 4-(3-methoxy-1-propenyl)-3-nitroquinoline, 4-cycloalkyl-3-nitroquinoline, 4-fluorocyclopropyl-3-nitroquinoline, 4-(2-oxazolinyl)-3-nitroquinoline, 4-(4-piperidyl)-3-nitroquinoline, 4-alkylsulfonyl-3-nitroquinoline, 4-alkenylsulfonyl-3-nitroquinoline, 4-arylsulfonyl-3-nitroquinoline, 4-benzylsulfonyl-3-nitroquinoline, 3-nitro-4-quinolinecarboxamide, N-alkyl-3-nitro-4-quinolinecarboxamide, N-alkenyl-3-nitro-4-quinolinecarboxamide, N-aryl-3-nitro-4-quinolinecarboxamide, N-acyl-3-nitro-4-quinolinecarboxamide, N,N-dialkyl-3-nitro-4-quinolinecarboxamide, 3-nitro-4-quinolinesulfonamide, N-alkyl-3-nitro-4-quinolinesulfonamide, N-alkenyl-3-nitro-4-quinolinesulfonamide, N-aryl-3-nitro-4-quinolinesulfonamide, N-acyl-3-nitro-4-quinolinesulfonamide, N,N-dialkyl-3-nitro-4-quinolinesulfonamide, 4-acetyl-3-nitroquinoline, 4-alkenylcarbonyl-3-nitroquinoline, 4-arylcarbonyl-3-nitroquinoline, 4-benzylcarbonyl-3-nitroquinoline, 4-alkoxycarbonyl-3-nitroquinoline, 4-alkenyloxycarbonyl-3-nitroquinoline, 4-(N-benzylamino)-3-nitroquinoline, N-benzyl-3-nitro-4-quinolinesulfonamide, N-benzyl-3-nitro-4-quinolinecarboxamide and isomers of the above 4-substituted-3-nitroquinolines, isomers having a substituent on the 2-position instead of the 4-position, 4-nitroquinoline, 2-halogeno-4-nitroquinoline, 2-cyano-4-nitroquinoline, 2-aryl-4-nitroquinoline, 2-alxyl-4-nitroquinoline, 2-alkenyl-4-nitroquinoline, 2-hydroxy-4-nitroquinoline, 2-alkoxy-4-nitroquinoline, 2-alkenyloxy-4-nitroquinoline, 2-aryloxy-4-nitroquinoline, 2-benzyloxy-4-nitroquinoline, 2-acyloxy-4-nitroquinoline, 2-amino-4-nitroquinoline, 2-(N-alkylamino)-4-nitroquinoline, 2-(N-alkenylamino)-4-nitroquinoline, 2-(N-arylamino)-4-nitroquinoline, 2-(N-acylamino)-4-nitroquinoline, 2-(N,N-dialkylamino)-4-nitroquinoline, 2,4-dinitroquinoline, 2-benzyl-4-nitroquinoline, 4-nitro-2-quinolinecarboxylic acid, 2-aryloxycarbonyl-4-nitroquinoline, 2-benzyloxycarbonyl-4-nitroquinoline, 2-mercapto-4-nitroquinoline, 2-alkylthio-4-nitroquinoline, 2-alkenylthio-4-nitroquinoline, 2-arylthio-4-nitroquinoline, 2-benzylthio-4-nitroquinoline, 2-acyilthio-4-nitroquinoline, 4-nitro-2-quinolinesulfonic acid, alkyl 4-nitro-2-quinolinesulfonate, alkenyl 4-nitro-2-quinolinesulfonate, aryl 4-nitro-2-quinolinesulfonate, benzyl 4-nitro-2-quinolinesulfonate, 2-trifluoromethyl-4-nitroquinoline, 2-chloromethyl-4-nitroquinoline, 2-(2-methoxyethyl)-4-nitroquinoline, 2-trifluoromethoxy-4-nitroquinoline, 2-difluoromethoxy-4-nitroquinoline, 2-(2-methoxyethoxy)-4-nitroquinoline, 2-(2-chlorovinyl)-4-nitroquinoline, 2-(α-styryl)-4-nitroquinoline, 2-(3-methoxy-1-propenyl)-4-nitroquinoline, 2-cycloalkyl-4-nitroquinoline, 2-fluorocyclopropyl-4-nitroquinoline, 2-(2-oxazolinyl)-4-nitroquinoline, 2-(4-piperidyl)-4-nitroquinoline, 2-alkylsulfonyl-4-nitroquinoline, 2-alkenylsulfonyl-4-nitroquinoline, 2-arylsulfonyl-4-nitroquinoline, 2-benzylsulfonyl-4-nitroquinoline, 4-nitro-2-quinolinecarboxamide, N-alkyl-4-nitro-2-quinolinecarboxamide, N-alkenyl-4-nitro-2-quinolinecarboxamide, N-aryl-4-nitro-2-quinolinecarboxamide, N-acyl-4-nitro-2-quinolinecarboxamide, N,N-dialkyl-4-nitro-2-quinolinecarboxamide, 4-nitro-2-quinolinesulfonamide, N-alkyl-4-nitro-2-quinolinesulfonamide, N-alkenyl-4-nitro-2-quinolinesulfonamide, N-aryl-4-nitro-2-quinolinesulfonamide, N-acyl-4-nitro-2-quinolinesulfonamide, N,N-dialkyl-4-nitro-2-quinolinesulfonamide, 2-acetyl-4-nitroquinoline, 2-alkenylcarbonyl-4-nitroquinoline, 2-arylcarbonyl-4-nitroquinoline, 2-benzylcarbonyl-4-nitroquinoline, 2-alkoxycarbonyl-4-nitroquinoline, 2-alkenyloxycarbonyl-4-nitroquinoline, 2-(N-benzylamino)-4-nitroquinoline, N-benzyl-4-nitro-2-quinolinesulfonamide, N-benzyl-4-nitro-2-quinolinecarboxamide, and furthermore, compounds having a 5, 6, 7, 8-tetrahydroquinoline ring, a 5, 6, 7, 8-tetrahydro[1,6]naphthyridine ring, a 7, 8-dihydro-5H-pyrano[4,3-b]pyridine ring or a 7, 8-dihydro-5H-thiopyrano[4,3-b]pyridine ring instead of a quinoline ring of the above quinoline derivatives. In addition, compounds having a N-oxide unit instead of a nitrogen atom of the 1-position in all the above pyridine derivatives and quinoline derivatives are also included. These compounds represented by general formula [2] can be prepared according to the processes described in, for example, The Chemistry of Heterocyclic Compounds, Pyridine and Its Derivatives, Part Two, Chapter VIII, p.470 (Edited by Erwin Klingsberg, 1961, Interscience Publishers Inc., New York) and Ullmann's Encyclopedia of Industrial Chemistry Vol. A22, Pyridine and Pyridine Derivatives, p.399 (Edited by Barbara Elvers et al. VCH Verlagsgesellschaft mbH D-69451, Weinheim, 1993). Examples of the aminonitropyridine represented by the general formula [1] include 5-amino-2-nitropyridine, 5-amino-3-halogeno-2-nitropyridine, 5-amino-3-cyano-2-nitropyridine, 5-amino-3-aryl-2-nitropyridine, 5-amino-3-alkyl-2-nitropyridine, 5-amino-3-alkenyl-2-nitropyridine, 5-amino-3-hydroxy-2-nitropyridine, 5-amino-3-alkoxy-2-nitropyridine, 5-amino-3-alkenyloxy-2-nitropyridine, 5-amino-3-aryloxy-2-nitropyridine, 5-amino-3-benzyloxy-2-nitropyridine, 5-amino-3-acyloxy-2-nitropyridine, 3,5-diamino-2-nitropyridine, 5-amino-3-(N-alkylamino)-2-nitropyridine, 5-amino-3-(N-alkenylamino)-2-nitropyridine, 5-amino-3-(N-arylamino)-2-nitropyridine, 5-amino-3-(N-acylamino)-2-nitropyridine, 5-amino-3-(N,N-dialkylamino)-2-nitropyridine, 5-amino-3-acetyl-2-nitropyridine, 5-amino-3-alkenylcarbonyl-2-nitropyridine, 5-amino-3-arylcarbonyl-2-nitropyridine, 5-amino-3-benzylcarbonyl-2-nitropyridine, 5-amino-3-alkorycarbonyl-2-nitropyridine, 5-amino-3-alkenyloxycarbonyl-2-nitropyridine, 5-amino-2,3-dinitropyridine, 5-amino-3-benzyl-2-nitropyridine, 5-amino-2-nitro-3-pyridinecarboxylic acid, 5-amino-3-aryloxycarbonyl-2-nitropyridine, 5-amino-3-benzyloxycarbonyl-2-nitropyridine, 5-amino-3-mercapto-2-nitropyridine, 5-amino-3-alkylthio-2-nitropyridine, 5-amino-3-alkenylthio-2-nitropyridine, 5-amino-3-arylthio-2-nitropyridine, 5-amino-3-benzylthio-2-nitropyridine, 5-amino-3-acylthio-2-nitropyridine, 5-amino-2-nitro-3-pyridinesulfonic acid, alkyl 5-amino-2-nitro-3-pyridinesulfonate, alkenyl 5-amino-2-nitro-3-pyridinesulfonate, aryl 5-amino-2-nitro-3-pyridinesulfonate, benzyl 5-amino-2-nitro-3-pyridinesulfonate, 5-amino-3-trifluoromethyl-2-nitropyridine, 5-amino-3-chloromethyl-2-nitropyridine, 5-amino-3-(2-methoxyethyl)-2-nitropyridine, 5-amino-3-trifluoromethoxy-2-nitropyridine, 5-amino-3-difluoromethoxy-2-nitropyridine, 5-amino-3-(2-methoxyethoxy)-2-nitropyridine, 5-amino-3-(2-chlorovinyl)-2-nitropyridine, 5-amino-3-(α-styryl)-2-nitropyridine, 5-amino-3-(3-methoxy-1-propenyl)-2-nitropyridine, 5-amino-3-cycloalkyl-2-nitropyridine, 5-amino-3-fluorocyclopropyl-2-nitropyridine, 5-amino-3-(2-oxazolinyl)-2-nitropyridine, 5-amino-3-(4-piperidyl)-2-nitropyridine, 5-amino-3-(alkylsulfonyl)-2-nitropyridine, 5-amino-3-alkenylsulfonyl-2-nitropyridine, 5-amino-3-arylsulfonyl-2-nitropyridine, 5-amino-3-benzylsulfonyl-2-nitropyridine, 5-amino-2-nitro-3-pyridinecarboxamide, N-alkyl-5-amino-2-nitro-3-pyridinecarboxamide, N-alkenyl-5-amino-2-nitro-3-pyridinecarboxamide, N-aryl-5-amino-2-nitro-3-pyridinecarboxamide, N-acyl-5-amino-2-nitro-3-pyridinecarboxamide, N,N-dialkyl-5-amino-2-nitro-3-pyridlnecarboxamide, 5-amino-2-nitro-3-pyridinesulfonamide, N-alkyl-5-amino-2-nitro-3-pyridinesulfonamide, N-alkenyl-5-amino-2-nitro-3-pyridinesulfonamide, N-aryl-5-amino-2-nitro-3-pyridinesulfonamide, N-acyl-5-amino-2-nitro-3-pyridinesulfonamide, N,N-dialkyl-5-amino-2-nitro-3-pyridinesulfonamide, 5-amino-3-(N-benzylamino)-2-nitropyridine, N-benzyl-5-amino-2-nitro-3-pyridinesulfonamide, N-benzyl-5-amino-2-nitro-3-pyridinecarboxamide and isomers of the above 5-amino-3-substituted-2-nitropyridines, the isomers having a substituent on the 4-or 6-position instead of the 3-position, 3-amino-2-nitropyridine, 3-amino-4-halogeno-2-nitropyridine, 3-amino-4-cyano-2-nitropyridine, 3-amino-4-aryl-2-nitropyridine, 3-amino-4-alkyl-2-nitropyridine, 3-amino-4-alkenyl-2-nitropyridine, 3-amino-4-hydroxy-2-nitropyridine, 3-amino-4-alkoxy-2-nitropyridine, 3-amino-4-alkenyloxy-2-nitropyridine, 3-amino-4-aryloxy-2-nitropyridine, 3-amino-4-benzyloxy-2-nitropyridine, 3-amino-4-acyloxy-2-nitropyridine, 3,4-diamino-2-nitropyridine, 3-amino-4-(N-alkylamino)-2-nitropyridine, 3-amino-4-(N-alkenylamino)-2-nitropyridine, 3-amino-4-(N-arylamino)-2-nitropyridine, 3-amino-4-(N-acylamino)-2-nitropyridine, 3-amino-4-(N,N-dialkylamino)-2-nitropyridine, 3-amino-4-acetyl-2-nitropyridine, 3-amino-4-alkenylcarbonyl-2-nitropyridine, 3-amino-4-arylcarbonyl-2-nitropyridine, 3-amino-4-benzylcarbonyl-2-nitropyridine, 3-amino-4-alkoxycarbonyl-2-nitropyridine, 3-amino-4-alkenyloxycarbonyl-2-nitropyridine, 3-amino-2,4-dinitropyridine, 3-amino-4-benzyl-2-nitropyridine, 3-amino-2-nitro-4-pyridinecarboxylic acid, 3-amino-4-aryloxycarbonyl-2-nitropyridine, 3-amino-4-benzyloxycarbonyl-2-nitropyridine, 3-amino-4-mercapto-2-nitropyridine, 3-amino-4-alkylthio-2-nitropyridine, 3-amino-4-alkenylthio-2-nitropyridine, 3-amino-4-arylthio-2-nitropyridine, 3-amino-4-benzylthio-2-nitropyridine, 3-amino-4-acylthio-2-nitropyridine, 3-amino-2-nitro-4-pyridinesulfonic acid, alkyl 3-amino-2-nitro-4-pyridnesulfonate, alkenyl 3-amino-2-nitro-4-pyridinesulfonate, aryl 3-amino-2-nitro-4-pyridinesulfonate, benzyl 3-amino-2-nitro-4-pyridinesulfonate, 3-amino-4-trifluoromethyl-2-nitropyridine, 3-amino-4-chloromethyl-2-nitropyridine, 3-amino-4-(2-methoxyethyl)-2-nitropyridine, 3-amino-4-trifluoromethoxy-2-nitropyridine, 3-amino-4-difluoromethoxy-2-nitropyridine, 3-amino-4-(2-methoxyethoxy)-2-nitropyridine, 3-amino-4-(2-chlorovinyl)-2-nitropyridine, 3-amino-4-(α-styryl)-2-nitropyridine, 3-amino-4-(3-methoxy-1-propenyly-2-nitropyridine, 3-amino-4-cycloalkyl-2-nitropyridine, 3-amino-4-fluorocyclopropyl-2-nitropyridine, 3-amino-4-(2-oxazolinyl)-2-nitropyridine, 3-amino-4-(4-piperidyl)-2-nitropyridine, 3-amino-4-alkylsulfonyl-2-nitropyridine, 3-amino-4-alkenylsulfonyl-2-nitropyridine, 3-amino-4-arylsulfonyl-2-nitropyridine, 3-amino-4-benzylsulfonyl-2-nitropyridine, 3-amino-2-nitro-4-pyridinecarboxamide, N-alkyl-3-amino-2-nitro-4-pyridinecarboxamide, N-alkenyl-3-amino-2-nitro-4-pyridinecarboxamide, N-aryl-3-amino-2-nitro-4-pyridinecarboxamide, N-acyl-3-amino-2-nitro-4-pyridinecarboxamide, N,N-dialkyl-3-amino-2-nitro-4-pyridinecarboxamide, 3-amino-2-nitro-4-pyridinesulfonamide, N-alkyl-3-amino-2-nitro-4-pyridinesulfonamide, N-alkenyl-3-amino-2-nitro-4-pyridinesulfonamide, N-aryl-3-amino-2-nitro-4-pyridinesulfonamide, N-acyl-3-amino-2-nitro-4-pyridinesulfonamide, N,N-dialkyl-3-amino-2-nitro-4-pyridinesulfonamide, 3-amino-4-(N-benzylamino)-2-nitropyridine, N-benzyl-3-amino-2-nitro-4-pyridinesulfonamide, N-benzyl-3-amino-2-nitro-4-pyridinecarboxamide and isomers of the above 3-amino-4-substituted-2-nitropyridines, the isomers having a substituent on the 5- or 6-position instead of 4-position, 4-amino-3-nitropyridine, 4-amino-2-halogeno-3-nitropyridine, 4-amino-2-cyano-3-nitropyridine, 4-amino-2-aryl-3-nitropyridine, 4-amino-2-alkyl-3-nitropyridine, 4-amino-2-alkenyl-3-nitropyridine, 4-amino-2-hydroxy-3-nitropyridine, 4-amino-2-alkoxy-3-nitropyridine, 4-amino-2-alkenyloxy-3-nitropyridine, 4-amino-2-aryloxy-3-nitropyridine, 4-amino-2-benzyloxy-3-nitropyridine, 4-amino-2-acyloxy-3-nitropyridine, 2,4-diamino-3-nitropyridine, 4-amino-2-(N-alkylamino)-3-nitropyridine, 4-amino-2-(N-alkenylamino)-3-nitropyridine, 4-amino-2-(N-arylamino)-3-nitropyridine, 4-amino-2-(N-acylamino)-3-nitropyridine, 4-amino-2-(N,N-dialkylamino)-3-nitropyridine, 4-amino-2-acetyl-3-nitropyridine, 4-amino-2-alkenylcarbonyl-3-nitropyridine, 4-amino-2-arylcarbonyl-3-nitropyridine, 4-amino-2-benzylcarbonyl-3-nitropyridine, 4-amino-2-alkoxyearbonyl-3-nitropyridine, 4-amino-2-alkenyloxycarbonyl-3-nitropyridine, 4-amino-2,3-dinitropyridine, 4-amino-2-benzyl-3-nitropyridine, 4-amino-3-nitro-2-pyridinecarboxylic acid, 4-amino-2-aryloxycarbonyl-3-nitropyridine, 4-amino-2-benzyloxycarbonyl-3-nitropyridine, 4-amino-2-mercapto-3-nitropyridine, 4-amino-2-alkylthio-3-nitropyridine, 4-amino-2-alkenylthio-3-nitropyridine, 4-amino-2-arylthio-3-nitropyridine, 4-amino-2-benzylthio-3-nitropyridine, 4-amino-2-acylthio-3-nitropyridine, 4-amino-3-nitro-2-pyridinesulfonic acid, alkyl 4-amino-3-nitro-2-pyridinesulfonate, alkenyl 4-amino-3-nitro-2-pyridinesulfonate, aryl 4-amino-3-nitro-2-pyridinesulfonate, benzyl 4-amino-3-nitro-2-pyridinesulfonate, 4-amino-2-trifluoromethyl-3-nitropyridine, 4-amino-2-chloromethyl-3-nitropyridine, 4-amino-2-(2-methoxyethyl)-3-nitropyridine, 4-amino-2-trifluoromethoxy-3-nitropyridine, 4-amino-2-difluoromethoxy-3-nitropyridine, 4-amino-2-(2-methoxyethoxy)-3-nitropyridine, 4-amino-2-(2-chlorovinyl)-3-nitropyridine, 4-amino-2-(α-styryl)-3-nitropyridine, 4-amino-2-(3-methoxy-1-propenyl)-3-nitropyridine, 4-amino-2-cycloalkyl-3-nitropyridine, 4-amino-2-fluorocyclopropyl-3-nitropyridine, 4-amino-2-(2-oxazolinyl)-3-nitropyridine, 4-amino-2-(4-piperidyl)-3-nitropyridine, 4-amino-2-alkylsulfonyl-3-nitropyridine, 4-amino-2-alkenylsulfonyl-3-nitropyridine, 4-amino-2-arylsulfonyl-3-nitropyridine, 4-amino-2-benzylsulfonyl-3-nitropyridine, 4-amino-3-nitro-2-pyridinecarboxamide, N-alkyl-4-amino-3-nitro-2-pyridinecarboxamide, N-alkenyl-4-amino-3-nitro-2-pyridinecarboxamide, N-aryl-4-amino-3-nitro-2-pyridinecarboxamide, N-acyl-4-amino-3-nitro-2-pyridinecarboxamide, N,N-dialkyl-4-amino-3-nitro-2-pyridinecarboxamide, 4-amino-3-nitro-2-pyridinesulfonamide, N-alkyl-4-amino-3-nitro-2-pyridinesulfonamide, N-alkenyl-4-amino-3-nitro-2-pyridinesulfonamide, N-aryl-4-amino-3-nitro-2-pyridinesulfonamide, N-acyl-4-amino-3-nitro-2-pyridinesulfonamide, N,N-dialkyl-4-amino-3-nitro-2-pyridinesulfonamide, 4-amino-2-(N-benzylamino)-3-nitropyridine, N-benzyl-4-amino-3-nitro-2-pyridinesulfonamide, N-benzyl- 4-amino-3-nitro-2-pyridinecarboxamide and isomers of the above 4-amino-2-substituted-3-nitropyridines, the isomers having a substituent on the 5- or 6-position instead of the 2-position, 2-amino-3-nitropyridine, 2-amino-4-halogeno-3-nitropyridine, 2-amino-4-cyano-3-nitropyridine, 2-amino-4-aryl-3-nitropyridine, 2-amino-4-alkyl-3-nitropyridine, 2-amino-4-alkenyl-3-nitropyridine, 2-amino-4-hydroxy-3-nitropyridine, 2-amino-4-alkoxy-3-nitropyridine, 2-amino-4-alkenyloxy-3-nitropyridine, 2-amino-4-aryloxy-3-nitropyridine, 2-amino-4-benzyloxy-3-nitropyridine, 2-amino-4-acyloxy-3-nitropyridine, 2,4-diamino-3-nitropyridine, 2-amino-4-(N-alkylamino)-3-nitropyridine, 2-amino-4-(N-alkenylamino)-3-nitropyridine, 2-amino-4-(N-arylamino)-3-nitropyridine, 2-amino-4-(N-acylamino)-3-nitropyridine, 2-amino-4-(N,N-dialkylamino)-3-nitropyridine, 2-amino-4-acetyl-3-nitropyridine, 2-amino-4-alkenylcarbonyl-3-nitropyridine, 2-amino-4-arylcarbonyl-3-nitropyridine, 2-amino-4-benzylcarbonyl-3-nitropyridine, 2-amino-4-alkoxycarbonyl-3-nitropyridine, 2-amino-4-alkenyloxycarbonyl-3-nitropyridine, 2-amino-3,4-dinitropyridine, 2-amino-4-benzyl-3-nitropyridine, 2-amino-3-nitro-4-pyridinecarboxylic acid, 2-amino-4-aryloxycarbonyl-3-nitropyridine, 2-amino-4-benzyloxycarbonyl-3-nitropyridine, 2-amino-4-mercapto-3-nitropyridine, 2-amino-4-alkylthio-3-nitropyridine, 2-amino-4-alkenylthio-3-nitropyridine, 2-amino-4-arylthio-3-nitropyridine, 2-amino-4-benzylthio-3-nitropyridine, 2-amino-4-acylthio-3-nitropyridine, 2-amino-3-nitro-4-pyridinesulfonic acid, alkyl 2-amino-3-nitro-4-pyridinesulfonate, alkenyl 2-amino-3-nitro-4-pyridinesulfonate, aryl 2-amino-3-nitro-4-pyridinesulfonate, benzyl 2-amino-3-nitro-4-pyridinesulfonate, 2-amino-4-trifluoromethyl-3-nitropyridine, 2-amino-4-chioromethyl-3-nitropyridine, 2-amino-4-(2-methoxyethyl)-3-nitropyridine, 2-amino-4-trifluoromethoxy-3-nitropyridine, 2-amino-4-difluoromethoxy-3-nitropyridine, 2-amino-4-(2-methoxyethoxy)-3-nitropyridine, 2-amino-4-(2-chlorovinyl)-3-nitropyridine, 2-amino-4-(α-styryl)-3-nitropyridine, 2-amino-4-(3-methoxy-1-propenyl)-3-nitropyridine, 2-amino-4-cycloalkyl-3-nitropyridine, 2-amino-4-fluorocyclopropyl-3-nitropyridine, 2-amino-4-(2-oxazolinyl)-3-nitropyridine, 2-amino-4-(4-piperidyl)-3-nitropyridine, 2-amino-4-alkylsulfonyl-3-nitropyridine, 2-amino-4-alkenylsulfonyl-3-nitropyridine, 2-amino-4-arylsulfonyl-3-nitropyridine, 2-amino-4-benzylsulfonyl-3-nitropyridine, 2-amino-3-nitro-4-pyridinecarboxamide, N-alkyl-2-amino-3-nitro-4-pyridinecarboxamide, N-alkenyl-2-amino-3-nitro-4-pyridinecarboxamide, N-aryl-2-amino-3-nitro-4-pyridinecarboxamide, N-acyl-2-amino-3-nitro-4-pyridinecarboxamide, N,N-dialkyl-2-amino-3-nitro-4-pyridinecarboxamide, 2-amino-3-nitro-4-pyridinesulfonamide, N-alkyl-2-amino-3-nitro-4-pyridinesulfonamide, N-alkenyl-2-amino-3-nitro-4-pyridinesulfonamide, N-aryl-2-amino-3-nitro-4-pyridinesulfonamide, N-acyl-2-amino-3-nitro-4-pyridinesulfonamide, N,N-dialkyl-2-amino-3-nitro-4-pyridinesulfonamide, 2-amino-4-(N-benzylamino-3-nitropyridine, N-benzyl-2-amino-3-nitro-4-pyridinesulfonamide, N-benzyl-2-amino-3-nitro-4-pyridinecarboxamide and isomers of the above 2-amino-4-substituted-3-nitropyridines, the isomers having a substituent on the 5- or 6-position instead of the 4-position, 6-amino-3-nitropyridine, 6-amino-4-halogeno-3-nitropyridine, 6-amino-4-cyano-3-nitropyridine, 6-amino-4-aryl-3-nitropyridine, 6-amino-4-alkyl-3-nitropyridine, 6-amino-4-alkenyl-3-nitropyridine, 6-amino-4-hydroxy-3-nitropyridine, 6-amino-4-alkoxy-3-nitropyridine, 6-amino-4-alkenyloxy-3-nitropyridine, 6-amino-4-aryloxy-3-nitropyridine; 6-amino-4-benzyloxy-3-nitropyridine, 6-amino-4-acyloxy-3-nitropyridine, 4,6-diamino-3-nitropyridine, 6-amino-4-(N-alkylamino)-3-nitropyridine, 6-amino-4-(N-alkenylamino)-3-nitropyridine, 6-amino-4-(N-arylamino)-3-nitropyridine, 6-amino-4-(N-acylamino)-3-nitropyridine, 6-amino-4-(N,N-dialkylamino)-3-nitropyridine, 6-amino-4-acetyl-3-nitropyridine, 6-amino-4-alkenylcarbonyl-3-nitropyridine, 6-amino-4-arylcarbonyl-3-nitropyridine, 6-amino-4-benzylcarbonyl-3-nitropyridine, 6-amino-4-alkoxycarbonyl-3-nitropyridine, 6-amino-4-alkenyloxycarbonyl-3-nitropyridine, 6-amino-3,4-dinitropyridine, 6-amino-4-benzyl-3-nitropyridine, 6-amino-3-nitro-4-pyridinecarboxylic acid, 6-amino-4-aryloxycarbonyl-3-nitropyridine, 6-amino-4-benzyloxycarbonyl-3-nitropyridine, 6-amino-4-mercapto-3-nitropyridine, 6-amino-4-alkylthio-3-nitropyridine, 6-amino-4-alkenylthio-3-nitropyridine, 6-amino-4-arylthio-3-nitropyridine, 6-amino-4-benzylthio-3-nitropyridine, 6-amino-4-acylthio-3-nitropyridine, 6-amino-3-nitro-4-pyridinesulfonic acid, alkyl 6-amino-3-nitro-4-pyridinesulfonate, alkenyl 6-amino-3-nitro-4-pyridinesulfonate, aryl 6-amino-3-nitro-4-pyridinesulfonate, benzyl 6-amino-3-nitro-4-pyridinesulfonate, 6-amino-4-trifluoromethyl-3-nitropyridine, 6-amino-4-chloromethyl-3-nitropyridine, 6-amino-4-(2-methoxyethyl)-3-nitropyridine, 6-amino-4-trifluoromethoxy-3-nitropyridine, 6-amino-4-difluoromethoxy-3-nitropyridine, 6-amino-4-(2-methoxyethoxy)-3-nitropyridine, 6-amino-4-(2-chlorovinyl)-3-nitropyridine, 6-amino-4-(α-styryl)-3-nitropyridine, 6-amino-4-(3-methoxy-1-propenyl)-3-nitropyridine, 6-amino-4-cycloalkyl-3-nitropyridine, 6-amino-4-fluorocyclopropyl-3-nitropyridine, 6-amino-4-(2-oxazolinyl)-3-nitropyridine, 6-amino-4-(4-piperidyl)-3-nitropyridine, 6-amino-4-alkylsulfonyl-3-nitropyridine, 6-amino-4-alkenylsulfonyl-3-nitropyridine, 6-amino-4-arylsulfonyl-3-nitropyridine, 6-amino-4-benzylsulfonyl-3-nitropyridine, 6-amino-3-nitro-4-pyridinecarboxamide, N-alkyl-6-amino-3-nitro-4-pyridinecarboxamide, N-alkenyl-6-amino-3-nitro-4-pyridinecarboxamide, N-aryl-6-amino-3-nitro-4-pyridinecarboxamide, N-acyl-6-amino-3-nitro-4-pyridinecarboxamide, N,N-dialkyl-6-amino-3-nitro-4-pyridinecarboxamide, 6-amino-3-nitro-4-pyridinesulfonamide, N-alkyl-6-amino-3-nitro-4-pyridmesulfonamide, N-alkenyl-6-amino-3-nitro-4-pyridmesulfonamide, N-aryl-6-amino-3-nitro-4-pyridinesulfonamide, N-acyl-6-amino-3-nitro-4-pyridinesulfonamide, N,N-dialkyl-6-amino-3-nitro-4-pyridinesulfonamide, 6-amino-4-(N-benzylamino)-3-nitropyridine, N-benzyl-6-amino-3-nitro-4-pyridinesulfonamide, N-benzyl- 6-amino-3-nitro-4-pyridinecarboxamide and isomers of the 6-amino-4-substituted-3-nitropyridines, the isomers having a substituent on the 2- or 5-postion instead of the 4-position, 3-amino-4-nitropyridine, 3-amino-5-halogeno-4-nitropyridine, 3-amino-5-cyano-4-nitropyridine, 3-amino-5-aryl-4-nitropyridine, 3-amino-5-alkyl-4-nitropyridine, 3-amino-5-alkenyl-4-nitropyridine, 3-amino-5-hydroxy-4-nitropyridine, 3-amino-5-alkoxy-4-nitropyridme, 3-amino-5-alkenyloxy-4-nitropyridine, 3-amino-5-aryloxy-5-nitropyridine, 3-amino-5-benzyloxy-4-nitropyridine, 3-amino-5-acyloxy-4-nitropyridine, 3,5-diamino-4-nitropyridine, 3-amino-5-(N-alkylamino)-4-nitropyridine, 3-amino-5-(N-alkenylamino)-4-nitropyridine, 3-amino-5-(N-arylamino)-4-nitropyridine, 3-amino-5-(N-acylamino)-4-nitropyridine, 3-amino-5-(N,N-dialkylamino)-4-nitropyridine, 3-amino-5-acetyl-4-nitropyridine, 3-amino-5-alkenylcarbonyl-4-nitropyridine, 3-amino-5-arylcarhonyl-4-nitropyridine, 3-amino-5-benzylcarbonyl-4-nitropyridine, 3-amino-5-alkoxycarbonyl-4-nitropyridine, 3-amino-5-alkenyloxycarbonyl-4-nitropyridine, 3-amino-4,5-dinitropyridine, 3-amino-5-benzyl-4-nitropyridine, 3-amino-4-nitro-5-pyridinecarboxylic acid, 3-amino-5-aryloxycarbonyl-4-nitropyridine, 3-amino-5-benzyloxycarbonyl-4-nitropyridine, 3-amino-5-mercapto-4-nitropyridine, 3-amino-5-alkylthio-4-nitropyridine, 3-amino-5-alkenylthio-4-nitropyridine, 3-amino-5-arylthio-4-nitropyridine, 3-amino-5-benzylthio-4-nitropyridine, 3-amino-5-acylthio-4-nitropyridine, 3-amino-4-nitro-5-pyridinesulfonic acid, alkyl 3-amino-4-nitro-5-pyridinesulfonate, alkenyl 3-amino-4-nitro-5-pyridinesulfonate, aryl 3-amino-4-nitro-5-pyridinesulfonate, benzyl 3-amino-4-nitro-5-pyridinesulfonate, 3-amino-5-trifluoromethyl-4-nitropyridine, 3-amino-5-chloromethyl-4-nitropyridine, 3-ainino-5-(2-methoxyethyl)-4-nitropyridine, 3-amino-5-trifluoromethoxy-4-nitropyridine, 3-amino-5-difluoromethoxy-4-nitropyridine, 3-amino-5-(2-methoxyethoxy)-4-nitropyridine, 3-amino-5-(2-chlorovinyl)-4-nitropyridine, 3-amino-5-(α-styryl)-4-nitropyridine, 3-amino-5-(3-methoxy-1-propenyl)-4-nitropyridine, 3-amino-5-cycloalkyl-4-nitropyridine, 3-amino-5-fluorocyclopropyl-4-nitropyridine, 3-amino-5-(2-oxazolinyl)-4-nitropyridine, 3-amino-5-(4-piperidyl)-4-nitropyridine, 3-amino-5-alkylsulfonyl-4-nitropyridine, 3-amino-5-alkenylsulfonyl-4-nitropyridine, 3-amino-5-arylsulfonyl-4-nitropyridine, 3-amino-5-benzylsulfonyl-4-nitropyridine, 3-amino-4-nitro-5-pyridinecarboxamide, N-alkyl-3-amino-4-nitro-5-pyridinecarboxamide, N-alkenyl-3-amino-4-nitro-5-pyridinecarboxamide, N-aryl-3-amino-4-nitro-5-pyridinecarboxamide, N-acyl-3-amino-4-nitro-5-pyridinecarboxamide, N,N-dialkyl-3-amino-4-nitro-5-pyridinecarboxamide, 3-amino-4-nitro-5-pyridinesulfonamide, N-alkyl-3-amino-4-nitro-5-pyridinesulfonamide, N-alkenyl-3-amino-4-nitro-5-pyridinesulfonamide, N-aryl-3-amino-4-nitro-5-pyridinesulfonamide, N-acyl-3-amino-4-nitro-5-pyridinesulfonamide, N,N-dialxyl-3-amino-4-nitro-5-pyridinesulfonamide, 3-amino-5-(N-benzylamino)-4-nitropyridine, N-benzyl-3-amino-4-nitro-5-pyridinesulfonamide, N-benzyl- 3-amino-4-nitro-5-pyridinecarboxamide and isomers of the above 3-amino-5-substituted-4-nitropyridines, the isomers having a substituent on the 2- or 6-position instead of the 5-position, 3-amino-2-nitroquinoline, 3-amino-4-halogeno-2-nitroquinoline, 3-amino-4-cyano-2-nitroquinoline, 3-amino-4-aryl-2-nitroquinoline, 3-amino-4-alkyl-2-nitroquinoline, 3-amino-4-alkenyl-2-nitroquinoline, 3-amino-4-hydroxy-2-nitroquinoline, 3-amino-4-alkoxy-2-nitroquinoline, 3-amino-4-alkenyloxy-2-nitroquinoline, 3-amino-4-aryloxy-2-nitroquinoline, 3-amino-4-benzyloxy-2-nitroquinoline, 3-amino-4-acyloxy-2-nitroquinoline, 3,4-diamino-2-nitroquinoline, 3-amino-4-(N-alkylamino)-2-nitroquinoline, 3-amino-4-(N-alkenylamino)-2-nitroquinoline, 3-amino-4-(N-arylamino)-2-nitroquinoline, 3-amino-4-(N-acylamino)-2-nitroquinoline, 3-amino-4-(N,N-dialkylamino)-2-nitroquinoline, 3-amino-2,4-dinitroquinoline, 3-amino-4-benzyl-2-nitroquinoline, 3-amino-2-nitro-4-quinolinecarboxylic acid, 3-amino-4-aryloxycarbonyl-2-nitroquinoline, 3-amino-4-benzyloxycarbonyl-2-nitroquinoline, 3-amino-4-mercapto-2-nitroquinoline, 3-amino-4-alkylthio-2-nitroquinoline, 3-amino-4-alkenylthio-2-nitroquinoline, 3-amino-4-arylthio-2-nitroquinoline, 3-amino-4-benzylthio-2-nitroquinoline, 3-amino-4-acylthio-2-nitroquinoline, 3-amino-2-nitro-4-quinolinesulfonic acid, alkyl 3-amino-2-nitro-4-quinolinesulfonate, alkenyl 3-amino-2-nitro-4-quinolinesulfonate, aryl 3-amino-2-nitro-4-quinolinesulfonate,benzyl 3-amino-2-nitro-4-quinolinesulfonate, 3-amino-4-trifluoromethyl-2-nitroquinoline, 3-amino-4-chloromethyl-2-nitroquinoline, 3-amino-4-(2-methoxyethyl)-2-nitroquinoline, 3-amino-4-trifluoromethoxy-2-nitroquinoline, 3-amino-4-difluoromethoxy-2-nitroquinoline, 3-amino-4-(2-methoxyethoxy)-2-nitroquinoline, 3-amino-4-(2-chlorovinyl)-2-nitroquinoline, 3-amino-4-(α-styryl)-2-nitroquinoline, 3-amino-4-(3-methoxy-1-propenyl)-2-nitroquinoline, 3-amino-4-cycloalkyl-2-nitroquinoline, 3-amino-4-fluorocyclopropyl-2-nitroquinoline, 3-amino-4-(2-oxazolinyl)-2-nitroquinoline, 3-amino-4-(4-piperidyl)-2-nitroquinoline, 3-amino-4-alkylsulfonyl-2-nitroquinoline, 3-amino-4-alkenylsulfonyl-2-nitroquinoline, 3-amino-4-arylsulfonyl-2-nitroquinoline, 3-amino-4-benzylsulfonyl-2-nitroquinoline, 3-amino-2-nitro-4-quinolinecarboxamide, N-alkyl-3-amino-2-nitro-4-quinolinecarboxamide, N-alkenyl-3-amino-2-nitro-4-quinolinecarboxamide, N-aryl-3-amino-2-nitro-4-quinolinecarboxamide, N-acyl-3-amino-2-nitro-4-quinolinecarboxamide, N,N-dialkyl-3-amino-2-nitro-4-quinolinecarboxamide, 3-amino-2-nitro-4-quinolinesulfonamide, N-alkyl-3-amino-2-nitro-4-quinolinesulfonamide, N-alkenyl-3-amino-2-nitro-4-quinolinesulfonamide, N-aryl-3-amino-2-nitro-4-quinolinesulfonamide, N-acyl-3-amino-2-nitro-4-quinolinesulfonamide, N,N-dialkyl-3-amino-2-nitro-4-quinolinesulfonamide, 3-amino-4-acetyl-2-nitroquinoline, 3-amino-4-alkenylcarbonyl-2-nitroquinoline, 3-amino-4-arylcarbonyl-2-nitroquinoline, 3-amino-4-benzylcarbonyl-2-nitroquinoline, 3-amino-4-alkoxycarbonyl-2-nitroquinoline, 3-amino-4-alkenyloxycarbonyl-2-nitroquinoline, 3-amino-4-(N-benzylamino)-2-nitroquinoline, N-benzyl-3-amino-2-nitro-4-quinolinesulfonamide, N-benzyl- 3-amino-2-nitro-4-quinolinecarboxamide, 2-amino-3-nitroquinoline, 4-amino-3-nitroquinoline, 2-amino-4-halogeno-3-nitroquinoline, 2-amino-4-cyano-3-nitroquinoline, 2-amino-4-aryl-3-nitroquinoline, 2-amino-4-alkyl-3-nitroquinoline, 2-amino-4-alkenyl-3-nitroquinoline, 2-amino-4-hydroxy-3-nitroquinoline, 2-amino-4-alkoxy-3-nitroquinoline, 2-amino-4-alkenyloxy-3-nitroquinoline, 2-amino-4-aryloxy-3-nitroquinoline, 2-amino-4-benzyloxy-3-nitroquinoline, 2-amino-4-acyloxy-3-nitroquinoline, 2,4-diamino-3-nitroquinoline, 2-amino-4-(N-alkylamino)-3-nitroquinoline, 2-amino-4-(N-alkenylamino)-3-nitroquinoline, 2-amino-4-(N-arylamino-3-nitroquinoline, 2-amino-4-(N-benzylamino)-3-nitroquinoline, 2-amino-4-(N-acylamino)-3-nitroquinoline, 2-amino-4-(N,N-dialkylamino)-3-nitroquinoline, 2-amino-3,4-dinitroquinoline, 2-amino-4-benzyl-3-nitroquinoline, 2-amino-3-nitro-4-quinolinecarboxylic acid, 2-amino-4-aryloxycarbonyl-3-nitroquinoline, 2-amino-4-benzyloxycarbonyl-3-nitroquinoline, 2-amino-4-mercapto-3-nitroquinoline, 2-amino-4-alkylthio-3-nitroquinoline, 2-amino-alkenylthio-3-nitroquinoline, 2-amino-4-arylthio-3-nitroquinoline, 2-amino-4-benzylthio-3-nitroquinoline, 2-amino-4-acylthio-3-nitroquinoline, 2-amino-3-nitro-4-quinolinesulfonic acid, alkyl-2-amino-3-nitro-4-qumolinesulfonate, alkenyl 2-amino-3-nitro-4-quinolinesulfonate, aryl 2-amino-3-nitro-4-qumolinesulfonate, benzyl 2-amino-3-nitro-4-quinolinesulfonate, 2-amino-4-trifluoromethyl-3-nitroquinoline, 2-amino-4-chloromethyl-3-nitroquinoline, 2-amino-4-(2-methoxyethyl)-3-nitroquinoline, 2-amino-4-trifluoromethoxy-3-nitroquinoline, 2-amino-4-difluoromethoxy-3-nitroquinoline, 2-amino-4-(2-methoxyethoxy)-3-nitroquinoline, 2-amino-4-(2-chlorovinyl)-3-nitroquinoline, 2-amino-4-(α-styryl)-3-nitroquinoline, 2-amino-4-(3-methoxy-1-propenyl)-3-nitroquinoline, 2-amino-4-cycloalkyl-3-nitroquinoline, 2-amino-4-fluorocyclopropyl-3-nitroquinoline, 2-amino-4-(2-oxazolinyl)-3-nitroquinoline, 2-amino-4-(4-piperidyly)-3-nitroquinoline, 2-amino-4-alkylsulfonyl-3-nitroquinoline, 2-amino-4-alkenylsulfonyl-3-nitroquinoline, 2-amino-4-arylsulfonyl-3-nitroquinoline, 2-amino-4-benzylsulfonyl-3-nitroquinoline, 2-amino-3-nitro-4-quinolinecarboxamide, N-alkyl-2-amino-3-nitro-4-quinolinecarboxamide, N-alkenyl-2-amino-3-nitro-4-quinolinecarboxamide, N-aryl-2-amino-3-nitro-4-quinolinecarboxamide, N-acyl-2-amino-3-nitro-4-quinolinecarboxamide, N,N-dialkyl-2-amino-3-nitro-4-quinolinecarboxamide, 2-amino-3-nitro-4-quinolinesulfonamide, N-alkyl-2-amino-3-nitro-4-quinolinesulfonamide, N-alkenyl-2-amino-3-nitro-4-quinolinesulfonamide, N-aryl-2-amino-3-nitro-4-quinolinesulfonamide, N-acyl-2-amino-3-nitro-4-quinolinesulfonamide, N,N-dialkyl-2-amino-3-nitro-4-quinolinesulfonamide, 2-amino-4-acetyl-3-nitroquinoline, 2-amino-4-alkenylcarbonyl-3-nitroquinoline, 2-amino-4-arylcarbonyl-3-nitroquinoline, 2-amino-4-benzylcarbonyl-3-nitroquinoline, 2-amino-4-alkoxycarbonyl-3-nitroquinoline, 2-amino-4-alkenyloxycarbonyl-3-nitroquinoline, 2-amino-4-(N-benzylamino)-3-nitroquinoline, N-benzyl-2-amino-3-nitro-4-quinolinesulfonamide, N-benzyl-2-amino-3-nitro-4-quinolinecarboxamide and isomers of the above 2-amino-4-substituted-3-nitroquinolines, the isomers having a substituent on the 2-position and an amino group on the 4-position, 3-amino-4-nitroquinoline, 3-amino-2-halogeno-4-nitroquinoline, 3-amino-2-cyano-4-nitroquinoline, 3-amino-2-aryl-4-nitroquinoline, 3-amino-2-alkyl-4-nitroquinoline, 3-amino-2-alkenyl-4-nitroquinoline, 3-amino-2-hydroxy-4-nitroquinoline, 3-amino-2-alkoxy-4-nitroquinoline, 3-amino-2-alkenyloxy-4-nitroquinoline, 3-amino-2-aryloxy-4-nitroquinoline, 3-amino-2-benzyloxy-4-nitroquinoline, 3-amino-2-acyloxy-4-nitroquinoline, 2,3-diamino-4-nitroquinoline, 3-amino-2-(N-alkylamino)-4-nitroquinoline, 3-amino-2-(N-alkenylamino)-4-nitroquinoline, 3-amino-2-(N-arylamino)-4-nitroquinoline, 3-amino-2-(N-benzylamino)-4-nitroquinoline, 3-amino-2-(N-acylamino)-4-nitroquinoline, 3-amino-2-(N,N-dialkylamino)-4-nitroquinoline, 3-amino-2,4-dinitroquinoline, 3-amino-2-benzyl-4-nitroquinoline, 3-amino-4- nitro-2-quinolinecarboxylic acid, 3-amino-2-aryloxycarbonyl-4-nitroquinoline, 3-amino-2-benzyloxycarbonyl-4-nitroquinoline, 3-amino-2-mercapto-4-nitroquinoline, 3-amino-2-alkylthio-4-nitroquinoline, 3-amino-2-alkenylthio-4-nitroquinoline, 3-amino-2-arylthio-4-nitroquinoline, 3-amino-2-benzylthio-4-nitroquinoline, 3-amino-2-acylthio-4-nitroquinoline, 3-amino-4-nitro-2-quinolinesulfonic acid, alkyl 3-amino-4-nitro-2-quinolinesulfonate, alkenyl 3-amino-4-nitro-2-quinolinesulfonate, aryl 3-amino-4-nitro-2-quinolinesulfonate, benzyl 3-amino-4-nitro-2-quinolinesulfonate, 3-amino-2-trifluoromethyl-4-nitroquinoline, 3-amino-2-chloromethyl-4-nitroquinoline, 3-amino-2-(2-methoxyethyl)-4-nitroquinoline, 3-amino-2-trifluoromethoxy-4-nitroquinoline, 3-amino-2-difluoromethoxy-4-nitroquinoline, 3-amino-2-(2-methoxyethoxy)-4-nitroquinoline, 3-amino-2-(2-chlorovinyl)-4-nitroquinoline, 3-amino-2-(α-styryl)-4-nitroquinoline, 3-amino-2-(3-methoxy-1-propenyl)-4-nitroquinoline, 3-amino-2-cycloalkyl-4-nitroquinoline, 3-amino-2-fluorocyclopropyl-4-nitroquinoline, 3-amino-2-(2-oxazolinyl)-4-nitroquinoline, 3-amino-2-(4-piperidyl)-4-nitroquinoline, 3-amino-2-alkylsulfonyl-4-nitroquinoline, 3-amino-2-alkenylsulfonyl-4-nitroquinoline, 3-amino-2-arylsulfonyl-4-nitroquinoline, 3-amino-2-benzylsulfonyl-4-nitroquinoline, 3-amino-4-nitro-2-quinolinecarboxamide, N-akyl-3-amino-4-nitro-2-quinolinecarboxamide, N-alkenyl-3-amino-4-nitro-2-quinolinecarboxamide, N-aryl-3-amino-4-nitro-2-qumolinecarboxamide, N-acyl-3-amino-4-nitro-2-quinolinecarboxamide, N,N-dialkyl-3-amino-4-nitro-2-quinolinecarboxamide, 3-amino-4-nitro-2-quinolinesulfonamide, N-alkyl-3-amino-4-nitro-2-quinolinesulfonamide, N-alkenyl-3-amino-4-nitro-2-quinolinesulfonamide, N-aryl-3-amino-4-nitro-2-quinolinesulfonamide, N-acyl-3-amino-4-nitro-2-quinolinesulfonamide, N,N-dialkyl-3-amino-4-nitro-2-quinolinesulfonamide, 3-amino-2-acetyl-4-nitroquinoline, 3-amino-2-alkenylcarbonyl-4-nitroquinoline, 3-amino-2-arylcarbonyl-4-nitroquinoline, 3-amino-2-benzylcarbonyl-4-nitroquinoline, 3-amino-2-alkoxycarbonyl-4-nitroquinoline, 3-amino-2-alkenyloxycarbonyl-4-nitroquinoline, 3-amino-2-(N-benzylamino)-4-nitroquinoline, N-benzyl-3-amino-4-nitro-2-quinolinesulfonamide and N-benzyl-3-amino-4-nitro-2-quinolinecarboxamide. Furthermore, compounds having a 5,6,7,8-tetrahydroquinoline ring, a 5,6,7,8-tetrahydro[1,6]naphthyridine ring, a 7,8-dihydro-5H-pyrano[4,3-b]pyridine ring or a 7,8-dihydro-5H-thiopyrano[4,3-b]pyridine ring instead of a quinoline ring of the above aminated quinoline derivatives are included. In addition, compounds having a N-oxide unit instead of a nitrogen atom of 1-position in all the above aminated pyridine derivatives and aminated quinoline derivatives are also included. Examples of the O-substituted hydroxylamine represented by general formula [3] used in the present invention include O-methylhydroxylamine, O-ethylhydroxylamine, O-tert-butylhydroxylamine, N,O-dimethylhydroxylamine, O-benzylhydroxylamine, N-cyclohexyl-O-methylhydroxylamine, and N-benzyl-O-methylhydroxylamine. The O-substituted hydroxylamine may be used in the uncombined form or in the form of an inorganic salt such as a hydrochloride or a sulfate. As the metal catalyst in the present invention, for example, various transition metals such as copper, manganese, iron, nickel, cobalt, silver, chrome and zinc or compounds thereof can be used. Examples of such metal compounds include halides, oxides, sulfides, hydroxides, carboxylates, nitrates, sulfates, carbonates, phosphates, thiocyanates, chromates, perchlorates, alkoxides, cyanides, acetylacetonates, thiolates, amine complexes, pyridine complexes and pyridine N-oxide complexes of the above-listed various metals. As the metal catalyst, for example, copper, copper (I) chloride, copper (II) chloride, copper (I) bromide, copper (II) bromide, copper (I) iodide, copper (II) iodide, copper (I) oxide, copper (II) oxide, copper sulfide, copper acetate, copper nitrate, copper sulfate, copper carbonate, copper hydroxide, copper cyanide, copper acetylacetonate, copper phosphate, copper thiocyanate, copper chromate, copper perchlorate, copper methoxide, thiophenol copper, copper-pyridine complex, copper-pyridine N-oxide complex, zinc chloride, zinc fluoride, zinc iodide, zinc acetate, zinc naphthenate, zinc nitrate, zinc sulfate, zinc oxide, zinc sulfide, zinc thiocyanate, zinc pyrithione, zinc-pyridine complex, zinc-pyridine N-oxide complex, manganese chloride, cobalt chloride, nickel chloride, iron (II) chloride, iron (III) chloride, various iron oxides and silver oxide can be used. Among them, copper compounds and zinc compounds are preferred. The zinc compounds are particularly preferred. A halide, a carboxylate, a nitrate and a sulfate of zinc are especially preferred. In addition, these metal compounds containing crystal water can also be used The reaction is conducted in the presence of a base, but the base is not specifically limited. For example, there can be suitably used a alkali metal compound such as an alkali metal hydroxide, an ally metal hydride, an alkali metal amide or an alkali metal alkoxide Examples of the base include sodium hydroxide, potassium hydroxide, sodium hydride, sodium amide, lithium amide, lithium diisopropylamide, sodium methoxide, sodium ethoxide and potassium tert-butoxide. The O-substituted hydroxylamine or a salt thereof is generally used in the range of about 0.5 mol to about 5 mol, preferably in the range of about 0.8 mol to about 2 mol, per mol of the nitropyridines [2]. The metal catalyst is generally used in the range of about 0.1 mol to about 5 mol, preferably in the range of about 0.8 mol to about 1.2 mol, per mol of the nitropyridines [2]. The base is, in general, used in the range of about 1 mol to about 15 mol, preferably in the range of about 2 mol to about 5 mol, per mol of the nitropyridines [2]. In general, the reaction is conducted in the presence of a solvent. Examples of the solvent include an aprotic polar solvent such as N,N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, sulfolane, N-methyl-2-pyrrolidone, etc.; an ether solvent such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran and diethoxymethane; an aromatic solvent such as benzene, toluene and chlorobenzene; an aromatic heterocyclic solvent such as pyridine; an aliphatic hydrocarbon solvent such as hexane and heptane; an alcohol solvent such as tert-butylalcohol; or liquid ammonia. These may be used alone or in combination. The amount of the solvent to be used is in the range of about 1 to about 200 times by weight to the nitropyridines [2]. The reaction temperature is generally within the range of about -40°C to about 100°C, preferably about 0°C to about 50°C. An aminonitropyridine of general formula [1] can be prepared by mixing and reacting a nitropyridine of general formula [2] with an O-substituted hydroxylamine of general formula [3] or salt thereof in the presence of a base and a metal catalyst. Exemplary embodiments of a process of the present invention include that a mixture of a nitropyridine of general formula [2] and an O-substituted hydroxylamine of general formula [3] or salt thereof is added to a mixture of a base and a metal catalyst. The objective compound produced by the process of the present invention can be easily isolated and purified from a reaction mixture, using conventional means such as distillation, extraction, recrystallization and various chromatographies. According to the present invention, an aminonitropyridine which is useful as an intermediate in the production of drugs or agricultural chemicals can be produced quickly, cheaply and safely. Thus, the present invention provides an extremely useful industrial process. Processes for producing aminonitropyridines are also described in Japanese Application Nos. 07-069203 and 07-315234. Examples The following Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. The following abbreviations are used in the Examples. DMF: N,N-dimethylformamide, DMSO: dimethyl sulfoxide, THF: tetrahydrofuran, DEM: diethoxymethane, DME: ethylene glycol dimethyl ether, Me: methyl group Example 1 6-Methoxy-3-nitropyridine (154 mg, 1 mmol) and O-methylhydroxylamine (71 mg, 1.5 mmol) were dissolved in DMSO (2 ml), and the resulting solution was added dropwise to a DMSO solution (3 ml) containing potassium tert-butoxide (336 mg, 3 mmol) and zinc (II) chloride (136 mg, 1 mmol) at 25°C. After completion of the addition, the resulting mixture was stirred at 25°C for 9 hours and an aqueous saturated ammonium chloride solution (50 ml) was added, followed by extraction with ethyl acetate (80ml). A resulting organic layer was dried over anhydrous magnesium sulfate, and then isolated and purified by subjecting to silica gel thin layer chromatography [eluent: ethyl acetate/hexane = 1/1] to obtain 147 mg of 2-amino-6-methoxy-3-nitropyridine (yield: 87%). Examples 2 to 13 Aminonitropyridines were prepared according to the same manner as that described in Example 1 except for changing 6-methoxy-3-nitropyridine ad DMSO as shown in Table 1. Results are shown in Table 1. Example No X 1 X 2 X 3 Solvent Position to be aminated Conversion rate (%) Yield (%) 2 6-MeO H H DEM 2 88 62 3 6-MeO H H THF 2 93 59 4 6-MeO H H DME 2 86 43 5 6-MeO H H toluene 2 78 19 6 2-Cl H H DMSO 4,6 97 36 (28/8) 7 2-Cl H H DME 4 89 34 8 2-Cl H H DEM 4 54 24 9 6-Cl H H DME 2,4 82 22 (9/13) 10 2-NH 2 H H DMSO 6 68 58 11 2-NH 2 H H DMF 6 100 53 12 6-NH 2 H H DEM 2 65 17 13 6-OH H H DEM 2 53 9 Example 14 23 mg of 2,6-diamino-3-nitropyridine was obtained according to the same manner as that described in Example 1 except for using 2-amino-3-nitropyridine (139 mg, 1 mmol) in place of 6-methoxy-3-nitropyridine and using potassium hydroxide (4 mmol) in place of potassium tert-butoxide (yield: 15%). Example 15 4-Nitropyridine (124 mg, 1 mmol) and O-methylhydroxylamine (71 mg, 1.5 mmol) were dissolved in DMF (2 ml), and the resulting solution was added dropwise to a DMF solution (3 ml) containing potassium tert-butoxide (336 mg, 3 mmol) and zinc (II) chloride (136 mg, 1 mmol) at 25°C. After completion of the addtion, the resulting mixture was stirred at 25°C for one hour and an aqueous saturated ammonium chloride solution (50 ml) was added, followed by extraction with ethyl acetate (80 ml). A resulting organic layer was dried over anhydrous magnesium sulfate, and then isolated and purified by subjecting to silica gel thin layer chromatography [eluent: ethyl acetate/hexane = 1/1] to obtain 35 mg of 3-amino-4-nitropyridine (yield: 25%). Example 16 43 mg of 3-amino-4-nitropyridine was obtained according to the same manner as that described in Example 15 except for using zinc pyrithione (317 mg, 1 mmol) in place of zinc (II) chloride (yield: 31%). Example 17 39 mg of 3-amino-4-nitropyridine was obtained according to the same manner as that described in Example 15 except for using zinc naphthenate (817 mg) in place of zinc (II) chloride (yield: 28 %). Example 18 43 mg of 3-amino-4-nitropyridine was obtained according to the same manner as that described in Example 15 except for using lithium amide (69 mg, 3 mmol) in place of potassium tert-butoxide (yield: 31%). Example 19 4-Nitropyridine N-oxide (140 mg, 1 mmol) and O-methylhydroxylamine (71 mg, 1.5 mmol) were dissolved in DMF (2 ml), and the resulting solution was added dropwise to a DMF solution (3 ml) containing potassium tert-butoxide (336 mg, 3 mmol) and zinc (II) chloride (136 mg, 1 mmol) at 25°C. After completion of the addtion, the resulting mixture was stirred at 25°C for one hour and an aqueous saturated ammonium chloride solution (50 ml) was added, followed by extraction with ethyl acetate (80 ml). A resulting organic layer was dried over anhydrous magnesium sulfate, and then isolated and purified by subjecting to silica gel thin layer chromatography [eluent: ethyl acetate] to obtain 58 mg of 3-amino-4-nitropyridine N-oxide (yield: 38%). Example 20 54 mg of 3-amino-4-nitropyridine N-oxide was obtained according to the same manner as that described in Example 19 except for using copper (I) chloride (99 mg, 1 mmol) in place of zinc (II) chloride (yield: 35%). Example 21 26 mg of 3-amino-4-nitropyridine N-oxide was obtained according to the same manner as that described in Example 19 except for using cobalt (II) chloride (130 mg, 1 mmol) in place of zinc (II) chloride (yield: 17 %). Example 22 43 mg of 3-amino-4-nitroquinoline N-oxide was obtained according to the same manner as that described in Example 19 except for using 4-nitroquinoline N-oxide (190 mg, 1 mmol) in place of 4-nitropyridine N-oxide (yield: 21%). Examples 23 to 53 Aminonitropyridines (compounds [1] shown in Tabel 2) are prepared according to the same manner as that described in Example 1 except for changing 6-methoxy-3-nitropyridine to compounds [2] shown in Table 2.

Claims: A process for producing an aminonitropyridine represented by the general formula [1]: wherein X 1 , X 2 , X 3 , R 4 ,Y and n are as defined below, which comprises reacting a nitropyridine represented by the general formula [2]: wherein X 1 , X 2 and X 3 are the same or different and indicate a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aryl group, a heterocycle, an alkyl group, a cycloalkyl group, an alkenyl group (the alkyl group, the cycloalkyl group and the alkenyl group may be respectively substituted with a halogen atom, an aryl group, an amino group, a hydroxyl group, a carboxyl group or an alkoxyl group) or a group OR 1 , SR 1 , NR 1 R 2 , COR 3 , COOR 3 , CONR 1 R 2 , SO 2 R 3 , SO 3 R 3 or SO 2 NR 1 R 2 , or when two of X 1 , X 2 and X 3 bond at the ortho-position, the two may bond together so that a 5- to 7-membered hydrocarbon ring or heterocycle is formed which includes 2 carbon atoms of the pyridine ring; R 1 and R 2 are the same or different and indicate a hydrogen atom, an alkyl group, an alkenyl group (the alkyl group and the alkenyl group may be respectively substituted with a halogen atom, an aryl group, an amino group, a hydroxyl group, a carboxyl group or an alkoxyl group), an aryl group or an acyl group; R 3 is a hydrogen atom, an alkyl group, an alkenyl group (the alkyl group and the alkenyl group may be respectively substituted with a halogen atom, an aryl group, an amino group, a hydroxyl group, a carboxyl group or an alkoxyl group) or an aryl group; Y is an oxygen atom; and n is 0 or 1, with an O-substituted hydroxylamine represented by the general formula [3]: R 4 NHOR 5 wherein R 4 is a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group; and R 5 is an alkyl group or an aralkyl group, or a salt thereof in the presence of a base and a metal catalyst. The process according to claim 1, wherein the O-substituted hydroxylamine represented by general formula [3] or salt thereof is selected from an O-methylhydroxylamine, an O-ethylhydroxylamine, an O-tert-butylhydroxylamine, an O-benzylhydroxylamine, a N,O-dimethylhydroxylamine and salts thereof. The process according to claim 1 or 2, wherein the salt of the O-substituted hydroxylamine represented by general formula [3] is an inorganic acid salt. The process according to claim 3, wherein the salt of the O-substituted hydroxylamine represented by general formula [3] is a hydrochloride salt. The process according to any one of claims 1 to 4, wherein the base is an alkali metal compound. The process according to claim 5, wherein the alkali metal compound is selected from an alkali metal alkoxide, an alkali metal hydroxide and an alkali metal amide. The process according to any one of claims 1 to 6, wherein the metal catalyst is selected from copper and copper compounds. The process according to claim 7, wherein the copper compound is a halide, a sulfide, a carboxylate, a nitrate, a sulfate, an acetylacetonate, an alkoxide, a hydroxide or a thiolate of copper. The process according to any one of claims 1 to 6, wherein the metal catalyst is selected from zinc and zinc compounds. The process according to claim 9, wherein the zinc compound is halide, a sulfide, a carboxylate, a nitrate, a sulfate, an acetylacetonate, an alkoxide, a hydroxide or a thiolate of zinc. The process according to any one of claims 1 to 10, wherein the O-substituted hydroxylamine is used in the range of about 0.5 mol to about 5 mol per mol of the nitropyridine represented by general formula [2]. The process according to any one of claims 1 to 11, wherein the base is used in the range of about 1 mol to about 15 mol per mol of the nitropyridine represented by general formula [2]. The process according to any one of claims 1 to 12, wherein the metal catalyst is used in the range of about 0.1 mol to about 5 mol per mol of the nitropyridine represented by general formula [2]. The process according to any one of claims 1 to 13, wherein a reaction temperature is about -40°C to about 100°C. The process according to any one of claims 1 to 14, wherein a mixture of the nitropyridine represented by general formula [2] and the O-substituted hydroxylamine represented by general formula [3] or salt thereof is added to a mixture of the base and the metal catalyst.

Inventors: MIYAKE KUNIHITO, SEKO SHINZO, MIYAKE, KUNIHITO, SEKO, SHINZO
Applicants: SUMITOMO CHEMICAL CO, SUMITOMO CHEMICAL COMPANY LIMITED
Application year: 1996
Main classification: C07D213
IPC codes: C07D213, C07D491, C07D471, C07D215