TW201304681A - A nitrogen-containing hetero ring compound and an agricultural and horticultural fungicide - Google Patents

Abstract

Provided is the nitrogen-containing hetero ring compound represented by formula (I), or a salt thereof: [wherein, in formula (I), R represents OR1 group, SO2R3 group, or other group; R1 and R3 respectively and independently represent unsubstituted or substituted C1-8 alkyl group, or other group; B represents nitrogen atom or carbon atom; D represents 5-7-membered hydrocarbon ring, or other ring; E represents 5-7-membered hydrocarbon ring, or other ring; X1 and X2 respectively and independently represent halogeno group, or other group; X represents oxygen atom, or other atom; m and n represent the number of substitutions by X1 and X2, respectively], and an agricultural and horticultural fungicide including as an active ingredient at least one type selected from said compounds.

Description

Nitrogen-containing heterocyclic compounds and agricultural and horticultural fungicides

The present invention relates to a nitrogen-containing heterocyclic compound which is an agricultural and horticultural fungicide which is effective and safe to use, and an active ingredient which can be used as an agricultural and horticultural fungicide.

This application claims priority based on Japanese Patent Application No. 2011-143479, filed on June 28, 2011, and Japanese Patent Application No. 2012-006279, filed on Jan. 16, 2012. Used for this.

A variety of control agents have been used to combat the diseases of agricultural and horticultural crops. However, most of the previous control agents have inadequate control effects, limited use due to the emergence of drug-resistant pathogens, phytotoxicity or pollution in plants, or toxicity to human and animal fish or environmental impact. The reason is therefore not fully satisfactory. Therefore, there is a strong expectation of the emergence of agents with fewer shortcomings.

Patent Document 1 or 2 relating to the present invention discloses a quinoline derivative having a chemical structure similar to the compound of the present invention, and an agricultural and horticultural fungicide containing the same as an active ingredient.

Patent Document 1 WO2005/070917

Patent Document 2 WO2007/011022

An object of the present invention is to provide an agricultural and horticultural fungicide which is effective and safe to use, and an effective ingredient which can be used as a fungicide for agriculture and horticulture. a nitrogen-containing heterocyclic compound or a salt thereof.

The present inventors have conducted intensive studies to solve the above problems, and as a result, obtained a nitrogen-containing heterocyclic compound represented by the formula (I) and a salt thereof. Further, it has been found that the nitrogen-containing heterocyclic compound is effective as an active ingredient of agricultural and horticultural fungicides and can be used safely. The present invention has been completed based on these findings and further research.

That is, the present invention encompasses the following aspects.

[1] A nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof.

In the formula (I), R represents a group represented by OR ¹ , a group represented by NR ¹ R ² , a group represented by SR ¹ , a group represented by S(=O)R ³ , and a group represented by SO ₂ R ³ . a group, a group represented by S(=O)(=NR ⁴ )R ⁵ , a group represented by N=S(=O)R ⁴ R ⁵ , or a nitro group.

R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted aminomethyl group, substituted sulfonyl group, or It is an unsubstituted or substituted amino group.

R ² represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted aminomethyl group, substituted sulfonyl group, unsubstituted A hydroxyl group substituted or having a substituent, or an unsubstituted or substituted amino group.

R ³ represents an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, unsubstituted or having a C3-8 cycloalkyl group of a substituent, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heterocyclic group An unsubstituted or substituted fluorenyl group, an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted amino group.

R ⁴ and R ⁵ each independently represent an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group. , unsubstituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, or unsubstituted Or a heterocyclic group having a substituent.

In the group represented by NR ¹ R ² , R ¹ and R ² may together form an unsubstituted or substituted 3-8 member ring, =CR ^a R ^b , or =NR ^c .

R ^a and R ^b each independently represent a hydrogen atom, an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 ～ 8-alkynyl, unsubstituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted Substituted or substituted heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted anthracene group, having a substituent A sulfonyl group, an unsubstituted or substituted fluorenyl group, an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted amine group.

R ^c represents an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted C1 -8 alkyl group.

In the group represented by N=S(=O)R ⁴ R ⁵ , R ⁴ and R ⁵ may together form a 5- to 8-membered ring which is unsubstituted or has a substituent.

X ¹ each independently represents an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted (1-imino) C1~8 alkyl group, unsubstituted or substituted carboxyl group, unsubstituted Substituted or substituted amine mercapto group, unsubstituted or substituted hydroxy group, unsubstituted or substituted amino group, unsubstituted or substituted fluorenyl group, substituted sulfonyl group , halogen, cyano, or nitro.

m represents the number of X ¹ and is any integer from 0 to 5.

B represents a carbon atom or a nitrogen atom.

D X ¹ represents a substituted or unsubstituted 5 to 7 of the hydrocarbon ring, or unsubstituted or substituted with X ¹ of the 5 to 7-membered heterocyclic ring.

X ² each independently represents an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted (1-imino) C1~8 alkyl group, unsubstituted or substituted carboxyl group, unsubstituted Substituted or substituted amine mercapto group, unsubstituted or substituted hydroxy group, unsubstituted or substituted amino group, unsubstituted or substituted fluorenyl group, substituted sulfonyl group , halogen, cyano, or nitro.

n represents X ² numbers and is any integer from 0 to 3.

Any of X ² and R may together form an unsubstituted or substituted 5-8 membered ring.

E X ² represents an unsubstituted or substituted hydrocarbon of 5 to 7-membered ring, either unsubstituted or substituted with X ² of 5 to 7-membered heterocyclic ring.

X represents an oxygen atom (O), a nitrogen atom (NH), or a C1-8 alkyl group. (R") substituted nitrogen atom (NR").

[2] A nitrogen-containing heterocyclic compound or a salt thereof, wherein the formula (I) of the above [1] is represented by the formula (II).

In the above formula (II), R, X ¹ , m, X ² , n, D, B, and X have the same meanings as those in the above formula (I).

A ¹ , A ² , A ³ , and A ⁴ each independently represent a carbon atom or a nitrogen atom.

[3] A nitrogen-containing heterocyclic compound or a salt thereof, wherein the formula (II) of the above [2] is represented by the formula (III).

In the above formula (III), R, X ¹ , m, X ² , n, A ¹ , A ² , A ³ , A ⁴ , B, and X represent the same as those in the above formula (II). The same meaning.

[4] A nitrogen-containing heterocyclic compound, or a salt thereof, which is represented by the formula (IV) The formula (I) of the above [1] is shown.

In the above formula (IV), R, X ¹ , m, X ² , n, B, and X have the same meanings as those in the above formula (I).

[5] A nitrogen-containing heterocyclic compound or a salt thereof, wherein the formula (I) of the above [1] is represented by the formula (V).

In the formula (V), R, X ¹ , m, X ² , n, D, B, and X have the same meanings as those in the above formula (I).

A ⁵ , A ⁶ , and A ⁷ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the oxygen atoms are not adjacent to each other, the sulfur atoms, and the combination of the oxygen atoms and the sulfur atoms.

[6] A nitrogen-containing heterocyclic compound or a salt thereof, represented by formula (VI) Formula (V) of the above [5].

In the formula (VI), R, X ¹ , m, X ² , n, A ⁵ , A ⁶ , A ⁷ , B, and X have the same meanings as those in the above formula (V).

[7] A bactericidal agent for agricultural and horticultural, comprising at least one selected from the group consisting of the nitrogen-containing heterocyclic compound of any one of the above [1] to [6] or a salt thereof as an active ingredient.

The nitrogen-containing heterocyclic compound of the present invention is a novel compound which can be used as an active ingredient of agricultural and horticultural fungicides and the like.

The agricultural and horticultural fungicide of the present invention is a safe pharmaceutical agent which has a positive and excellent control effect, does not cause phytotoxicity to plants, has toxicity to human and animal fish, or has little influence on the environment.

Hereinafter, the present invention is divided into 1) a nitrogen-containing heterocyclic compound and 2) agricultural and horticultural fungicides, but the present invention is not limited by the examples. Additions, omissions, substitutions, and other modifications can be made without departing from the scope of the invention.

1) Nitrogen-containing heterocyclic compounds [Compound of formula (I)]

The nitrogen-containing heterocyclic compound of the present invention is a compound represented by the formula (I) (hereinafter, referred to as "compound (I)").

The nitrogen-containing heterocyclic compound of the present invention contains a hydrate, various solvates or crystal polymorphs. Further, the nitrogen-containing heterocyclic compound of the present invention contains a stereoisomer based on an asymmetric carbon atom, a double bond or the like and a mixture thereof.

First, the meaning of "unsubstituted" and "substituted" in the formula (I) will be explained.

The term "unsubstituted" means only the basis of becoming a mother. When there is no description of "substituent" and only the name of the base of the parent core is used, it means "unsubstituted" unless otherwise specified.

On the other hand, the term "having a substituent" means that any hydrogen atom which becomes a base of a mother nucleus is substituted with a group of the same or a heterogeneous structure as the mother nucleus. Therefore, the "substituent" is the other group bonded to the base which becomes the mother nucleus. The substituent may be one or two or more. Two or more substituents may be the same or different.

The term "C1~6" indicates that the number of carbon atoms to be the base of the mother nucleus is 1 to 6. The number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified into a C2 alkoxy C4 alkyl group.

The "substituent" is not particularly limited as long as it is chemically allowed and has the effects of the present invention.

Examples of the "substituent group" include a halogen group such as a fluorine group, a chlorine group, a bromine group or an iodine group; a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a secondary butyl group; C1~6 alkyl group such as isobutyl, tert-butyl, n-pentyl or n-hexyl; C3~6 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; vinyl, 1- Propylene, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentene Base, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2- C2~6 alkenyl such as hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl; C3~ such as 2-cyclopropenyl, 2-cyclopentenyl, 3-cyclohexenyl, etc. 6 cycloalkenyl; ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2 -methyl-3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl- C2~6 alkynyl group such as 3-pentynyl, 1-hexynyl, 1,1-dimethyl-2-butynyl; methoxy, ethoxy, n-propoxy, iso a C1-6 alkoxy group such as an oxy group, a n-butoxy group, a secondary butoxy group, an isobutoxy group or a tertiary butoxy group; a vinyloxy group, an allyloxy group, a propyleneoxy group, a butenyloxy group, etc. C2~6 alkenyloxy; C2~6 alkynyloxy group such as acetyleneoxy group or propargyloxy group; C6~10 aryl group such as phenyl group and naphthyl group; C6~10 aryloxy group such as phenoxy group and 1-naphthyloxy group a C7~11 aralkyl group such as a benzyl group or a phenethyl group; a C7-11 aralkoxy group such as a benzyloxy group or a phenethyloxy group; a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a benzhydryl group, C1~7醯 group such as cyclohexylcarbonyl; C1~7醯oxy group such as methyl methoxy, ethoxycarbonyl, propyl methoxy, benzyl carbonyl or cyclohexylcarbonyl; methoxycarbonyl, B C1~6 alkoxycarbonyl group such as oxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group or tert-butoxycarbonyl group; carboxyl group; hydroxyl group; pendant oxy group; chloromethyl group, chlorine C1~6 haloalkyl such as ethyl, trifluoromethyl, 1,2-dichloro-n-propyl, 1-fluoro-n-butyl, perfluoro-n-pentyl; 2-chloro-1-propenyl, C2-6 alkenyl group such as 2-fluoro-1-butenyl group; 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group, etc. C2~6 haloalkynyl; 2-chloro-n-propoxy C1~6 haloalkoxy such as 2,3-dichlorobutoxy; C2~6 haloenyloxy such as 2-chloropropenyloxy or 3-bromobutenyloxy; 4-chlorophenyl, 4- C6~10 haloaryl group such as fluorophenyl group or 2,4-dichlorophenyl group; C6~10 haloaryloxy group such as 4-fluorophenoxy group or 4-chloro-1-naphthyloxy group; a C1-7 sulfonyl group such as trifluoroethenyl, trichloroacetamido or 4-chlorobenzylidene; cyano; isocyano; nitro; isocyanate; cyanooxy; azide; Amino group; C1~6 alkylamino group such as methylamino group, dimethylamino group or diethylamino group; C6~10 arylamino group such as anilino group or naphthylamino group; benzylamino group and benzene C7~11 aralkylamino group such as ethyl ethylamine; mercaptoamino group, acetylamino group, propyl fluorenyl group, butyl decylamino group, isopropylcarbonylamino group, benzhydrylamino group C1~7-decylamino group; methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, isopropoxycarbonylamino group and the like C1~6 alkoxycarbonylamino group; amine Mercapto; dimethylamine-methyl hydrazino, phenylamine-methyl fluorenyl, N-phenyl-N-methylamine-methyl fluorenyl, etc. substituted imidomethyl; iminomethyl, (1-imine) Ethyl, (1-imino)- Isopropyl and the like imino C1~6 alkyl; hydroxyiminomethyl, (1-hydroxyimino)ethyl, (1-hydroxyimino)propyl and the like hydroxyimino C1~6 alkane C1~6 alkoxyimino C1~6 alkyl such as methoxyiminomethyl, (1-methoxyimino)ethyl; fluorenyl; isothiocyanato; cyanide Thiocyanato; methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, secondary butylthio, tertiary butyl a C1~6 alkylthio group such as a thio group; a C2-6 alkenylthio group such as a vinylthio group or an allylthio group; a C2-6 alkynylthio group such as an ethynylthio group or a propargylthio group; a C6-10 arylthio group such as a phenylthio group or a naphthylthio group; a heteroarylthio group such as a thiazolylthio group or a pyridylthio group; a C7-11 aralkyl group such as a benzylthio group or a phenethylthio group; (thiol)carbonyl, (ethylthio)carbonyl, (n-propylthio)carbonyl, (isopropylthio)carbonyl, (n-butylthio)carbonyl, (isobutyl) (thiol)carbonyl, (secondary butylthio)carbonyl, (tertiary butylthio)carbonyl, etc. (C1-6 alkylthio)carbonyl; methylsulfinyl, ethyl C1~6 alkyl sulfinyl group such as fluorenyl group, tertiary butyl sulfinyl group; C2~6 alkenyl sulfinyl group such as allylsulfinyl group; C2~ such as propargyl sulfinyl group 6 alkynylsulfinyl; C6~10 arylsulfinyl such as phenylsulfinyl; heteroazosulfinyl such as thiazolylsulfinyl, pyridylsulfinyl; benzyl C7~11 aralkyl sulfinyl group such as sulfonyl, phenethylsulfinyl, etc.; C1~6 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl or tert-butylsulfonyl C2~6 alkenylsulfonyl such as allylsulfonyl; C2-6 alkynylsulfonyl such as propargylsulfonyl; C6~10 arylsulfonyl such as phenylsulfonyl; thiazole a heteroarylsulfonyl group such as a sulfonyl group or a pyridylsulfonyl group; a C7-11 arylalkylsulfonyl group such as a benzylsulfonyl group or a phenethylsulfonyl group; a pyrrolyl group, a furyl group, a thienyl group, Imidazolyl, pyrazolyl, Azolyl, different Azyl, thiazolyl, isothiazolyl, triazolyl, 5-membered heteroaryl group such as oxazolyl, thiadiazolyl, tetrazolyl; pyridyl, pyridyl Base, pyrimidinyl, oxime Base (pyridaziny), three 6-membered heteroaryl; aziridine, epoxy, pyrrolidinyl, tetrahydrofuranyl, piperidinyl, hexahydropyridyl base, a saturated heterocyclic group such as a phenyl group; a tri-C1-6 alkyl fluorenyl group such as a trimethyl fluorenyl group, a triethyl fluorenyl group or a tert-butyl dimethyl fluorenyl group; a triphenyl fluorenyl group;

Moreover, such "substituents" may also be those in which there are other "substituents". For example, it may be one having an ethoxy group as a further substituent on the butyl group as a substituent, that is, an ethoxybutyl group.

[R]

R represents a group represented by OR ¹ , a group represented by NR ¹ R ² , a group represented by SR ¹ , a group represented by S(=O)R ³ , a group represented by SO ₂ R ³ , and S(=O). (=NR ⁴ ) a group represented by R ⁵ , a group represented by N=S(=O)R ⁴ R ⁵ or a nitro group.

[R ¹ ]

R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted aminomethyl group, substituted sulfonyl group, or It is an unsubstituted or substituted amino group.

R ¹ is of "a C1 to 8 alkyl group" by the lines 1 to 8 carbon atoms composed of saturated hydrocarbon. The C1~8 alkyl group may be a straight chain or a branched chain. Examples of the C1-8 alkyl group include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, an isopropyl group, an isobutyl group, and a secondary butyl group. , tertiary butyl, isopentyl, neopentyl, 2-methylbutyl, 2,2-dimethylpropyl, isohexyl and the like. Preferred among these are C1~6 alkyl groups.

Examples of the "C1-8 alkyl group having a substituent" include a cycloalkylalkyl group such as a cyclopropylmethyl group, a 2-cyclopropylethyl group, a cyclopentylmethyl group or a 2-cyclohexylethyl group. Is a C3-6 cycloalkyl C1-6 alkyl group; cyclopentenylmethyl, 3-cyclopentenylmethyl, 3-cyclohexenylmethyl, 2-(3-cyclohexenyl)ethyl Equivalent alkenylalkyl, preferably C4-6 cycloalkenyl C1-6 alkyl; fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, tri Fluoromethyl, trichloromethyl, tribromomethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 4-fluorobutyl, 4-chloro Butyl, 3,3,3-trifluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, perfluorohexyl, perchlorohexyl, perfluorooctyl, perchlorooctyl, a halogenated alkyl group such as 2,4,6-trichlorohexyl, perfluorodecyl, 2,2,4,4,6,6-hexachlorooctyl, preferably C1-6 haloalkyl; benzyl, benzene An arylalkyl (aralkyl) group such as ethyl, 3-phenylpropyl, 1-naphthylmethyl or 2-naphthylmethyl, preferably C6-10 aryl C1-6 alkyl; Pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl, 2-(2-pyridyl)ethyl, 2-(3-pyridyl)ethyl, 2-(4- Pyridyl)ethyl, 3-(2-pyridyl)propyl, 3-(3-pyridyl)propyl, 3-(4-pyridyl)propyl, 2-pyridyl Methyl, 3-pyridyl Methyl, 2-(2-pyridyl Ethyl, 2-(3-pyridyl) Ethyl, 3-(2-pyridyl) Propyl, 3-(3-pyridyl) , propyl, 2-pyrimidinylmethyl, 4-pyrimidinylmethyl, 2-(2-pyrimidinyl)ethyl, 2-(4-pyrimidinyl)ethyl, 3-(2-pyrimidinyl)propyl , 3-(4-pyrimidinyl)propyl, 2-furylmethyl, 3-furylmethyl, 2-(2-furyl)ethyl, 2-(3-furyl)ethyl, 3 a heteroarylalkyl group such as -(2-furyl)propyl or 3-(3-furyl)propyl, preferably a 5-6 membered heteroaryl C1-6 alkyl group; a hydroxymethyl group, a 1-hydroxy group Ethyl, 2-hydroxyethyl, 1-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 2-hydroxy- a hydroxyalkyl group such as 1,1-dimethylpropyl or 2-hydroxy-2-methylpropyl, preferably a hydroxy C1-6 alkyl group; a methoxymethyl group, an ethoxymethyl group, a 2-methyl group Oxyethyl, 2-ethoxyethyl, methoxy-n-propyl, n-propoxymethyl, isopropoxyethyl, di-butoxymethyl, tert-butoxyethyl, An alkoxyalkyl group such as 2,2-dimethoxyethyl or 2,2-dimethoxy-1,1-dimethylethyl, preferably a C1-6 alkoxy C1-6 alkyl group ; methyl methoxymethyl, ethoxymethyl, 2-ethyloxyethyl, propyl methoxymethyl, propyl methoxyethyl, etc. An alkyl group, preferably a C1-7 methoxy C1~6 alkyl group; a trialkyl decyloxyalkyl group such as a trimethyl decyloxymethyl group or a tertiary dimethyl dimethyl decyloxymethyl group; Base, preferably tri-C1~6 alkyldecyloxy C1-6 alkyl; tosyloxymethyl, 2-toluenesulfonyloxy-1,1-dimethylethyl Isoarylsulfonyloxyalkyl, preferably C6-10 arylsulfonyloxy C1~6 alkyl substituted by C1~6 alkyl; cyanomethyl, 2-cyanoethyl, 1- A cyanoalkyl group such as cyano-1-methylethyl group, preferably a cyano C1-6 alkyl group; a methyl group methyl group, a 2-mercaptoethyl group, a 3-mercaptopropyl group, and 1- Mercapto-1-methylethyl, 2-methylindolyl-1,1-dimethylethyl, ethenylmethyl, 2-ethylidylethyl, 3-ethylmercaptopropyl, 1 - mercaptoalkyl-1-methylethyl, 2-ethylindenyl-1,1-dimethylethyl and the like decylalkyl group, preferably C1-6 fluorenyl C1~6 alkyl; 2-hydroxyl 2-hydroxyiminoalkyl such as iminoethyl, 2-hydroxyimino-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 2-hydroxyiminopropyl Base, preferably 2-hydroxyimino C2-6 alkyl; ethyl hydrazinomethyl, 2-ethyl decylethyl, 3-ethyl fluorenyl a mercaptoalkyl group such as 1-ethylindenyl-1-methylethyl or 2-ethylindolyl-1,1-dimethylethyl, preferably a mercapto C1~6 alkyl group; a carboxyalkyl group such as 2-carboxyethyl, 3-carboxypropyl, 1-carboxy-1-methylethyl or 2-carboxy-1,1-dimethylethyl, preferably carboxy C1~6 Alkyl; methoxycarbonylmethyl, 2-methoxycarbonylethyl, 3-methoxycarbonylpropyl, 1-methoxycarbonyl-1-methylethyl, 2-methoxycarbonyl-1 , alkoxycarbonylalkyl such as 1-dimethylethyl, preferably C1-6 alkoxycarbonyl C1-6 alkyl; azidomethyl, 2-azidoethyl, 1-azide An azidoalkyl group such as a 1-methylethyl group, preferably an azide C1-6 alkyl group or the like.

R ¹ is of the "C2 to 8 alkenyl group" system having at least one carbon - carbon double bond carbon atoms of 2 to 8 composed of unsaturated hydrocarbon. The C2-8 alkenyl group may be a straight chain or a branched chain. Examples of the C2-8 alkenyl group include a vinyl group, a 1-propenyl group, an isopropenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 1-pentenyl group. -pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptyl Alkenyl, 6-heptenyl, 1-octenyl, 7-octenyl, 1-methyl-allyl, 2-methyl-allyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl and the like. Among these, a C2-6 alkenyl group is preferable.

Examples of the "C2-8 alkenyl group having a substituent" include 3-chloro-2. -propenyl, 4-chloro-2-butenyl, 4,4-dichloro-3-butenyl, 4,4-difluoro-3-butenyl, 3,3-dichloro-2-propene a halogenated alkenyl group such as 2,3-dichloro-2-propenyl, 3,3-difluoro-2-propenyl or 2,4,6-trichloro-2-hexenyl, preferably C2~ 6-haloalkenyl; 3-hydroxy-1-propenyl, 4-hydroxy-1-butenyl, 1-hydroxyallyl, 1-hydroxy-2-methylallyl, etc., preferably hydroxyalkenyl, preferably Hydroxy C 2 ~ 6 alkenyl and the like.

R ¹ is of the "C2 to 8 alkynyl" system having at least one carbon - carbon triple bond of carbon atoms of 2 to 8 composed of unsaturated hydrocarbon. The C2-8 alkynyl group may be a straight chain or a branched chain. Examples of the C2-8 alkynyl group include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, and a 2-pentyne group. , 3-pentynyl, 4-pentynyl, 1-hexynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-methyl-2-butyl Alkynyl, 2-methyl-3-pentynyl, 1,1-dimethyl-2-butynyl and the like. Among these, a C2-6 alkynyl group is preferable.

Examples of the "C2-8 alkynyl group having a substituent" include 3-chloro-1-propynyl group, 3-chloro-1-butynyl group, 3-bromo-1-butynyl group, and 3-bromo-2. -propynyl, 3-iodo-2-propynyl, 3-bromo-1-hexynyl, 4,4,6,6-tetrafluoro-1-decynyl, 5,5-dichloro-2 a haloalkynyl group such as a methyl-3-pentynyl group or a 4-chloro-1,1-dimethyl-2-butynyl group, preferably a C2-6 haloalkynyl group.

R ¹ is of "a C3 to 8 cycloalkyl" system having alkyl groups having 3 to 8 carbon atoms, consisting of an annular portion. Examples of the C3-8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, a C3-6 cycloalkyl group is preferred.

Examples of the "C3-8 cycloalkyl group having a substituent" include 2,3,3-trimethylcyclobutyl, 4,4,6,6-tetramethylcyclohexyl, and 1,3-dibutyl. The alkyl group-substituted cycloalkyl group such as a cyclohexyl group is preferably a C3-6 cycloalkyl group substituted by 1 to 3 C1 to 6 alkyl groups.

R ¹ is the "C4 to 8 cycloalkenyl" system having a portion of carbon atoms of the cyclic alkenyl group having 4 to 8 constituted. Examples of the C4-8 cycloalkenyl group include a 1-cyclobutenyl group, a 1-cyclopentenyl group, a 3-cyclopentenyl group, a 1-cyclohexenyl group, a 3-cyclohexenyl group, and a 3-cycloheptene group. Base, 4-cyclooctenyl and the like.

Examples of the "C4-8 cycloalkenyl group having a substituent" include alkyl substituted cycloolefins such as 2-methyl-3-cyclohexenyl and 3,4-dimethyl-3-cyclohexenyl. The group is preferably a C4-6 cycloalkenyl group substituted by 1 to 3 C1~6 alkyl groups.

R ¹ is of the "C6 ~ 10 aryl group" based rings mono- or aryl group having 6 to 10. As long as at least one ring of the polycyclic aryl group is an aromatic ring, the remaining ring may be either a saturated alicyclic ring, an unsaturated alicyclic ring or an aromatic ring. Examples of the C6-10 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a dihydroindenyl group, and a tetrahydronaphthyl group. Among these, a phenyl group is preferred.

Examples of the "C6-10 aryl group having a substituent" include 2-chlorophenyl group, 3,5-dichlorophenyl group, 4-fluorophenyl group, 3,5-difluorophenyl group, and 4-trifluoromethyl group. Alkylphenyl, 2-methoxy-1-naphthyl or the like, an alkyl-substituted aryl group, a halogen-substituted aryl group, an alkoxy-substituted aryl group, preferably substituted by a C1~6 alkyl group a C6~10 aryl group, a C6~10 aryl group substituted by a halogen, and an aryl group substituted by a C1~6 alkoxy group.

The "heterocyclic group" in R ¹ contains one to four hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as a constituent atom of the ring. The heterocyclic group may be a single ring or a polycyclic ring.

Examples of the heterocyclic group include a 5-membered heteroaryl group, a 6-membered heteroaryl group, a condensed heteroaryl group, a saturated heterocyclic group, and a partially unsaturated heterocyclic group.

Examples of the 5-membered heteroaryl group include pyrrolyl groups such as pyrrol-1-yl, pyrrol-2-yl and pyrrol-3-yl; furyl groups such as furan-2-yl and furan-3-yl; and thiophen-2-yl. , thienyl group such as thiophen-3-yl; imidazolyl group such as imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazole-5-yl; pyrazol-1-yl, pyrazol-3-yl , pyrazol-4-yl, pyrazol-5-yl and the like pyrazolyl; Zin-2-yl, Zin-4-yl, Azole-5-yl group Azolyl Zyrom-3-yl, different Azol-4-yl, different Oxazol-5-yl isomer Thiazolyl; thiazol-2-yl, thiazol-4-yl, thiazol-5-yl and the like thiazolyl; isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl and the like isothiazolyl; , 2,3-triazol-1-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, 1,2,4-triazol-1-yl , 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl and the like triazolyl; 1,2,4- Diazol-3-yl, 1,2,4- Diazol-5-yl, 1,3,4- Diazol-2-yl, etc. Diazolyl; 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl and the like thiadiazolyl a tetrazolyl group such as tetrazol-1-yl or tetrazol-2-yl.

Examples of the 6-membered heteroaryl group include a pyridyl group such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl; -2-yl, pyridyl -3-ylpyrrolidine Pyrimidine group; pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl and the like pyrimidine; -3-yl, 嗒 -4-yl isomer Base Base.

Examples of the condensed heteroaryl group include an indol-1-yl group, an indol-2-yl group, an indol-3-yl group, an indol-4-yl group, an indol-5-yl group, an indol-6-yl group, and吲哚-7-yl; benzofuran-2-yl, benzofuran-3-yl, benzofuran-4-yl, benzofuran-5-yl, benzofuran-6-yl, benzofuran -7-yl; benzothiophen-2-yl, benzothiophen-3-yl, benzothiophen-4-yl, benzothiophen-5-yl, benzothiophen-6-yl, benzothiophen-7 -yl;benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, benzo Zin-2-yl, benzo Zin-4-yl, benzo Zyrid-5-yl, benzothiazol-2-yl, benzothiazol-4-yl, benzothiazol-5-yl; quinolin-2-yl, quinolin-3-yl, quinolin-4-yl , quinoline-5-yl, quinoline-6-yl, quinoline-7-yl, quinoline-8-yl and the like.

Examples of the other heterocyclic group include a 3-membered saturated heterocyclic ring such as aziridine-1-yl, aziridine-2-yl or oxiranyl; pyrrolidin-1-yl and pyrrolidine-2. 5-membered saturated heterocyclic ring such as a pyridyl-3-yl group, a pyrrolidin-3-yl group, a tetrahydrofuran-2-yl group, a tetrahydrofuran-3-yl group, a [1,3]dioxiran-2-yl group, a piperidin-1-yl group, Piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, piperid -1-yl, piperazine -2-base, Porphyrin-2-yl, Porphyrin-3-yl, 6-membered saturated heterocyclic ring such as phenyl-4-yl; 1,3-benzodioxole-4-yl, 1,3-benzodioxol-5-yl 1,4-benzoic acid Alkan-5-yl, 1,4-benzoic Alkan-6-yl, 3,4-dihydro-2H-1,5-benzodioxan (benzodioxepin)-6-yl, 3,4-dihydro-2H-1,5-benzodioxan -7-yl, 2,3-dihydrobenzofuran-4-yl, 2,3-dihydrobenzofuran-5-yl, 2,3-dihydrobenzofuran-6-yl, 2,3 - Dihydrobenzofuran-7-yl and the like.

Examples of the "heterocyclic group having a substituent" include 4-chloro-2-pyridyl and 3-chloro-2-pyridyl. Base, 4-methyl-2-pyridyl, 5-trifluoromethyl-2-pyrimidinyl, 3-methyl-2-quinolyl and the like.

The "C1~8 fluorenyl group" in R ¹ is a hydrogen atom, a C1-7 alkyl group, a C2-7 alkenyl group, a C2-7 alkynyl group, a C6-7 aryl group or a 5-7 membered heterocyclic group bonded to a carbonyl group. The basis of the formation.

Examples of the C1-8 fluorenyl group include a mercapto group; an ethyl group, a propyl group, a n-propylcarbonyl group, a n-butylcarbonyl group, a pentanoyl group, a valeryl group, a octyl group, and an isopropyl group. An alkylcarbonyl group such as a carbonyl group, an isobutylcarbonyl group, a trimethylethenyl group or an isovalinyl group, preferably a C1-6 alkylcarbonyl group; an alkenylcarbonyl group such as an acryloyl group or a methacryloyl group; And it is a C2-6 alkenylcarbonyl group; an alkynylcarbonyl group such as a propargyl group; preferably a C2-6 alkynylcarbonyl group; an arylcarbonyl group such as a benzhydryl group; a heterocyclic carbonyl group such as a 2-pyridylcarbonyl group or a thienylcarbonyl group; .

Examples of the "C1-8 thiol group having a substituent" include a monofluoroethyl group, a monochloroethyl group, a monobromoethane group, a difluoroacetic acid group, a dichloroethylene group, and a dibromoethenyl group. , trifluoroethane, trichloroethane, tribromoethenyl, 3,3,3-trifluoropropenyl, 3,3,3-trichloropropenyl, 2,2,3,3 And a halogen-fluorenyl group such as 3-pentafluoropropenyl group, preferably a C1-7-halogen group.

The "carboxy group having a substituent" in R ¹ is a C1~6 alkyl group, a C2-6 alkenyl group, a C2~6 alkynyl group, a C6~10 aryl group, a C6~10 aryl C1~6 alkyl group or a 5-6 group. The heterocyclic group is bonded to a carbonyl group.

Examples of the "carboxy group having a substituent" include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, and a n-butoxycarbonyl group. Alkoxycarbonyl group such as isobutoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl or n-hexyloxycarbonyl, preferably C1-6 alkoxycarbonyl; ethyleneoxycarbonyl, allyloxycarbonyl Isooxycarbonyl group, preferably C2-6 alkenyloxycarbonyl; acetyleneoxycarbonyl, alkynyloxycarbonyl, etc. alkynyloxycarbonyl, preferably C2-6 alkynyloxycarbonyl; phenoxycarbonyl, naphthalene The aryloxycarbonyl group such as an oxycarbonyl group is preferably a C6-10 aryloxycarbonyl group; an aralkoxycarbonyl group such as a benzyloxycarbonyl group; preferably a C6-10 aryl C1-6 alkyloxycarbonyl group.

The "amine-containing mercapto group having a substituent" in R ¹ is a C1-6 alkyl group, a C2-6 alkenyl group, a C2~6 alkynyl group, a C6-10 aryl group, a C6-10 aryl C1-6 alkyl group, Or a 5- to 6-membered heterocyclic group bonded to an amine methyl sulfhydryl group.

Examples of the "amine-containing mercapto group having a substituent" include a monoalkylamine formazan such as a methylamine-methyl group, an ethylamine-methyl group, a dimethylamine-methyl group or a diethylamine-methyl group. Or a dialkylamine methyl sulfhydryl group, preferably a mono C1~6 alkylamine carbenyl group or a di C1~6 alkylamine carbenyl group; a phenylamine carbenyl group, a 4-methylphenylamine group The monoarylaminecarbamyl group such as a mercapto group is preferably a mono C6 to 10 arylaminecarbamyl group or the like.

Examples of the "sulfonyl group having a substituent" in R ¹ include a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, and Isobutylsulfonyl, secondary butylsulfonyl, tert-butylsulfonyl, n-pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, 1-ethylpropyl An alkylsulfonyl group such as a sulfonyl group, a n-hexylsulfonyl group or an isohexylsulfonyl group, preferably a C1-6 alkylsulfonyl group; a haloalkylsulfonyl group such as a trifluoromethylsulfonyl group; Preferably, it is a C1~6 haloalkylsulfonyl group; an arylsulfonyl group such as a phenylsulfonyl group or a 4-methylphenylsulfonyl group; preferably a C6-10 sulfonyl group; a sulfonic acid group; An alkoxysulfonyl group such as a methoxysulfonyl group or an ethoxysulfonyl group, preferably a C1-6 alkoxysulfonyl group; an aminesulfonyl group; an N-methylaminesulfonyl group, N- An aminesulfonyl group such as ethylaminesulfonyl, N,N-dimethylaminesulfonyl, N,N-diethylaminesulfonyl, preferably a mono C1-6 alkylsulfonyl group or a mono-arylamine sulfonyl group such as a phenylamine sulfonyl group; a phenylamine sulfonyl group; a 4-methylphenylamine sulfonyl group; preferably a mono C6-10 aryl sulfonyl sulfhydryl group. Wait .

Examples of the "amino group having a substituent" include an alkylamino group such as a methylamino group, an ethylamino group, a n-propylamino group, an n-butylamino group, a dimethylamino group or a diethylamino group. Preferably, it is a mono C1~6 alkylamino group or a di C1~6 alkylamino group; a mono C1~6 alkylene amine group such as a methylene amino group or an ethylene amino group; a phenylamine group, 4 a monoarylamine group such as a methylphenylamino group, preferably a mono C6-10 arylamino group; a diarylamine group such as a di-1-naphthylamino group, preferably a di C6-10 arylamine An arylalkylamine group such as a benzylamino group, preferably a C6-10 aryl C1-6 alkyl group; an acetamidoamine group, a trifluoroethenylamino group, a benzhydrylamino group, etc. a mercaptoamine group, preferably a C1-6-fluorenylamino group; an alkoxycarbonylamino group such as a methoxycarbonylamino group or a tertiary butoxycarbonylamino group, preferably a C1-6 alkoxycarbonylamine Base.

[R ² ]

R ² represents a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted aminomethyl group, substituted sulfonyl group, unsubstituted A hydroxyl group substituted or having a substituent, or an unsubstituted or substituted amino group.

In the ² R 'C1 ~ 8 alkyl, "" C2 ~ 8 alkenyl, "" C2 ~ 8 alkynyl, "" C3 ~ 8 cycloalkyl group "," C4 ~ 8 cycloalkenyl group "," C6 ~ 10 "aryl", "heterocyclic group", "C1~8 fluorenyl group", "carboxyl group having a substituent", "amine-containing mercapto group having a substituent", "sulfonyl group having a substituent", "having a substitution" The amino group of the group may be the same as those exemplified for R ¹ .

Examples of the "hydroxy group having a substituent" in R ² include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a n-pentyloxy group, a n-hexyloxy group, a decyloxy group, and a dodecyloxy group. Base, lauryloxy, isopropoxy, isobutoxy, secondary butoxy, tert-butoxy, 1-ethylpropoxy, isohexyloxy, 4-methylpentyloxy, 3- Methylpentyloxy, 2-methylpentyloxy, 1-methylpentyloxy, 3,3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethyl Butyoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethyl Alkoxy group such as butoxy group, preferably C1-6 alkoxy group; cycloalkylalkoxy group such as cyclopropylmethoxy group or 2-cyclopentylethoxy group, preferably C3-8 cycloalkyl group C1~6 alkoxy; aralkyloxy group such as benzyloxy group, preferably C6-10 aryl C1-6 alkyloxy; chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoro a haloalkoxy group such as a methoxy group, a 1-fluoroethoxy group, a 1,1-difluoroethoxy group, a 2,2,2-trifluoroethoxy group or a pentafluoroethoxy group, preferably a C1~6 group. Haloalkoxy; vinyloxy, 1-propenyloxy, allyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1 -hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 1-methyl-2-propenyloxy, 2-methyl- Alkenyloxy group such as 2-propenyloxy, 1-methyl-2-butenyloxy or 2-methyl-2-butenyloxy, preferably C2-6 alkenyloxy; acetyleneoxy, propyne Oxy, propargyloxy, 1-butynyloxy, 2-butynyloxy, 3-butynyloxy, 1-pentynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-hexynyloxy, 1-methyl-2-propynyloxy, 2-methyl-3-butynyloxy, 1-methyl-2-butynyloxy, Alkynyloxy group such as 2-methyl-3-pentynyloxy, 1,1-dimethyl-2-butynyloxy, preferably C2-6 alkynyloxy; cyclopropoxy, cyclobutoxy , cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, 2-methylcyclopropoxy, 2-ethylcyclopropoxy, 2,3,3-trimethylcyclobutane Oxyl, 2-methylcyclopentyloxy, 2-ethylcyclohexyloxy, 2-ethylcyclooctyloxy, 4,4,6,6-tetramethylcyclohexyloxy, 1,3- Cycloalkane such as dibutylcyclohexyloxy The group is preferably a C3-6 cycloalkoxy group; an aryloxy group such as a phenoxy group, a naphthyloxy group, a decyloxy group, a decyloxy group, a dihydromethoxy group or a tetrahydronaphthyloxy group, preferably a C6~ group. 10 aryloxy; aryloxy (aralkyloxy) such as benzyloxy, phenethyloxy or 2-naphthylmethoxy, preferably C6-10 aryl C1-6 alkyl; Alkoxy, propenyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, pentyloxy, trimethylacetoxy, etc. An alkoxy group, preferably a C1-7 methoxy group; an alkoxycarbonylalkyloxy group such as a methoxycarbonylmethyloxy group or a 1-methoxycarbonyl-1-methylethyloxy group; It is a C1~6 alkoxycarbonyl C1-6 alkyloxy group; a trialkyldecyloxy group such as a trimethyldecyloxy group or a tert-butyl dimethyl decyloxy group; preferably a C1~ 6 alkyl decyloxy and the like.

[R ³ ]

R ³ represents an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, unsubstituted or having a C3-8 cycloalkyl group of a substituent, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heterocyclic group An unsubstituted or substituted fluorenyl group, an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted amino group.

R ³ in the "C1 ~ 8 alkyl,""C2 ~ 8 alkenyl,""C2 ~ 8 alkynyl,""C3 ~ 8 cycloalkyl group", "C4 ~ 8 cycloalkenyl group", "C6 ~ 10 Examples of the aryl group, the "heterocyclic group" and the "amino group having a substituent" are the same as those exemplified for R ¹ . R ³ in the "group having a substituent of a hydroxyl group" include the same as those exemplified by R ^2.

Examples of the "thiol group having a substituent" in R ³ include an alkylthio group such as a methylthio group or an ethylthio group, preferably a C1-6 alkylthio group; a phenylthio group and a 4-methyl group. An arylthio group such as a phenylthio group, preferably a C6-10 arylthio group; a mercaptothio group such as an ethylsulfonylthio group or a benzhydrylthio group; preferably a C1~6 mercaptothio group; .

[R ⁴ ]

R ⁴ represents an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkynyl group, unsubstituted or having a C3-8 cycloalkyl group of a substituent, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted hetero Ring base.

In the ⁴ R 'C1 ~ 8 alkyl, "" C2 ~ 8 alkenyl, "" C2 ~ 8 alkynyl, "" C3 ~ 8 cycloalkyl group "," C4 ~ 8 cycloalkenyl group "," C6 ~ 10 aryl group "," heterocyclic group "for R ¹ include those the same as those exemplified.

[R ⁵ ]

R ⁵ represents an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, unsubstituted or having a C3-8 cycloalkyl group of a substituent, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted hetero Ring base.

R ⁵ is of "C1 ~ 8 alkyl,""C2 ~ 8 alkenyl,""C2 ~ 8 alkynyl,""C3 ~ 8 cycloalkyl group", "C4 ~ 8 cycloalkenyl group", "C6 ~ 10 aryl group "," heterocyclic group "for R ¹ include those the same as those exemplified.

In the group represented by NR ¹ R ² , R ¹ and R ² may together form an unsubstituted or substituted 3-8 member ring, or may form =CR ^a R ^b or =NR ^c . Examples of the above 3- to 8-membered ring include an aziridine ring, a pyrrolidine ring, a piperidine ring, and a piperidine. ring, A saturated heterocyclic ring such as a phenyl ring.

R ^a and R ^b each independently represent a hydrogen atom, an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 ～ 8-alkynyl, unsubstituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted Substituted or substituted heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted anthracene group, having a substituent A sulfonyl group, an unsubstituted or substituted fluorenyl group, an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted amine group.

"C1~8 alkyl", "C2~8 alkenyl", "C2~8 alkynyl", "C3~8 cycloalkyl", "C4~8 cycloalkenyl", "C4~8 cycloalkenyl" in "R ^a and R ^b " C6~10 aryl", "heterocyclic group", "C1~8 fluorenyl group", "carboxyl group having a substituent", "amine-containing mercapto group having a substituent", "sulfonyl group having a substituent", The "amino group having a substituent" may be the same as those exemplified as R ¹ . The "hydroxy group having a substituent" in R ^a and R ^b may be the same as those exemplified as R ² . The "thiol group having a substituent" in R ^a and R ^b may be the same as those exemplified as R ³ .

R ^c represents an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted C1 -8 alkyl group.

R ^c is the "C1 ~ 8 alkyl group" for R ¹ include those the same as those exemplified. The "hydroxy group having a substituent" in R ^c may be the same as those exemplified as R ² .

In the group represented by N=S(=O)R ⁴ R ⁵ , R ⁴ and R ⁵ may together form a 5- to 8-membered ring which is unsubstituted or has a substituent. Examples of the above 5- to 8-membered ring include a tetrahydrothiophene ring, a tetrahydrothiopyran ring, and [1.4] oxygen sulfur. A sulfur-saturated heterocyclic ring such as a ring.

[X ¹ , m]

X ¹ each independently represents an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted (1-imino) C1~8 alkyl group, unsubstituted or substituted carboxyl group, unsubstituted Substituted or substituted amine mercapto group, unsubstituted or substituted hydroxy group, unsubstituted or substituted amino group, unsubstituted or substituted fluorenyl group, substituted sulfonyl group , halogen, cyano, or nitro.

m represents the number of X ¹ and is any integer from 0 to 5.

"C1~8 alkyl", "C2~8 alkenyl", "C2~8 alkynyl", "C3~8 cycloalkyl", "C4~8 cycloalkenyl", "C6~10" in X ¹ "aryl", "heterocyclic group", "C1~8 fluorenyl group", "carboxyl group having a substituent", "amine-containing mercapto group having a substituent", "sulfonyl group having a substituent", "having a substitution" The amino group of the group may be the same as those exemplified for R ¹ . The "hydroxy group having a substituent" in X ¹ may be the same as those exemplified as R ² . The "thiol group having a substituent" in X ¹ may be the same as those exemplified as R ³ .

The "(1-imino) C1~8 alkyl group" in X ¹ is a group in which an alkyl group of C1 to 7 is bonded to an iminomethyl group or an iminomethyl group. Examples of the (1-imino) C1-8 alkyl group include an iminomethyl group, a (1-imino)ethyl group, a (1-imino)propyl group, and a (1-imino) butyl group. A group, a (1-imino)pentyl group, a (1-imino)hexyl group, a (1-imino)heptyl group, or the like. Among these, (1-imino) C1-6 alkyl group is preferable.

As a "substituent (1-imino) C1~8 alkyl group", it can be listed a hydroxyiminomethyl group, a (1-hydroxyimino)ethyl group, a (1-hydroxyimino)propyl group, a (1-hydroxyimino)butyl group or the like (1-hydroxyimino) alkane Base, preferably (1-hydroxyimino) C1-6 alkyl; methoxyiminomethyl, (1-ethoxyimino)methyl, (1-methoxyimino) Ethyl, (1-tertiary butoxyimino)ethyl, (1-ethoxyimino)ethyl, etc. (1-alkoxyimino)alkyl, preferably (1) -(C1~6 alkoxy)imino)C1~6 alkyl group and the like.

Examples of the "halogen group" in X ¹ include a fluorine group, a chlorine group, a bromine group, and an iodine group.

[B, D]

B represents a carbon atom or a nitrogen atom. That is, a pyridine ring having a condensation "D" or a pyridine having a "D" condensation ring.

D represents an unsubstituted or substituted with X ¹ of the 5 to 7-membered hydrocarbon ring or an unsubstituted or substituted with X ¹ of the 5 to 7-membered heterocyclic ring.

Examples of the hydrocarbon ring of 5 to 7 members include an aromatic hydrocarbon ring such as a benzene ring; a C5-7 cycloolefin ring such as a cyclopentene ring, a cyclohexene ring or a cycloheptene ring; a furan ring, a thiophene ring, a pyrrole ring, and an imidazole. Ring, pyrazole ring, thiazole ring, Oxazole ring, different Oxazole ring, pyridine ring, pyridyl Ring, pyrimidine ring, anthracene An aromatic 5~7 member heterocyclic ring such as a ring, a nitrogen ring or a diazonium ring; an unsaturated 5~7 member such as a dihydro-2H-pyran ring, a dihydro-2H-thiopyran ring or a tetrahydropyridine ring. Ring and so on.

Among these, an aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. Specifically, the compound of the present invention preferably has a quinoline ring or a quinolin A compound of a porphyrin ring.

[X ² , n]

X ² each independently represents an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, Substituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted Heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted (1-imino) C1~8 alkyl group, unsubstituted or substituted carboxyl group, unsubstituted Substituted or substituted amine mercapto group, unsubstituted or substituted hydroxy group, unsubstituted or substituted amino group, unsubstituted or substituted fluorenyl group, substituted sulfonyl group , halogen, cyano, or nitro.

n represents the number of X ² and is any integer from 0 to 3.

"C1~8 alkyl", "C2~8 alkenyl", "C2~8 alkynyl", "C3~8 cycloalkyl", "C4~8 cycloalkenyl", "C6~10" in X ² "aryl", "heterocyclic group", "C1~8 fluorenyl group", "carboxyl group having a substituent", "amine-containing mercapto group having a substituent", "sulfonyl group having a substituent", "having a substitution" The amino group of the group may be the same as those exemplified for R ¹ . The "hydroxy group having a substituent" in X ² may be the same as those exemplified as R ² . The "thiol group having a substituent" in X ² may be the same as those exemplified as R ³ . X ² in the "(1-amino) C1 ~ 8 alkyl group", "halogen", and include X ¹ are the same as those illustrated.

Any of X ² and R may together form an unsubstituted or substituted 5-8 membered ring.

[E]

E represents an unsubstituted or substituted with X ² of 5 to 7-membered hydrocarbon ring or an unsubstituted or substituted with X ² of 5 to 7-membered heterocyclic ring.

Examples of the hydrocarbon ring of 5 to 7 members include an aromatic hydrocarbon ring such as a benzene ring; a C5-7 cycloolefin ring such as a cyclopentene ring, a cyclohexene ring or a cycloheptene ring; a furan ring, a thiophene ring, a pyrrole ring, and an imidazole. Ring, pyrazole ring, thiazole ring, Oxazole ring, different Oxazole ring, isothiazole ring, pyridine ring, pyridyl Ring, pyrimidine ring, anthracene An aromatic 5~7 member heterocyclic ring such as a ring, a nitrogen azide ring or a diazepine ring.

Among these, an aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred.

[X]

X represents an oxygen atom (O), a nitrogen atom (NH), or a nitrogen atom (NR" substituted by a C1-8 alkyl group (R"). Here, "C1 ~ 8 alkyl group" for R ¹ include the same as those exemplified by.

The salt of the compound of the present invention is not particularly limited as long as it is an agriculturally acceptable salt. Examples of the salt include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid; salts of alkali metals such as lithium, sodium and potassium; salts of alkaline earth metals such as calcium and magnesium; and transitions such as iron and copper. a salt of a metal; a salt of an organic base such as ammonia, triethylamine, tributylamine, pyridine or hydrazine.

[Compound represented by formula (II)]

The compound of the present invention is preferably a compound represented by the formula (II) (hereinafter sometimes referred to as "compound (II)").

Here, in the above formula (II), R, X ¹ , m, X ² , n, D, B, and X have the same meanings as those in the above formula (I).

[A ¹ , A ² , A ³ , A ⁴ ]

A ¹ , A ² , A ³ , and A ⁴ each independently represent a carbon atom or a nitrogen atom. That is, it constitutes a benzene ring, a pyridine ring, and a hydrazine ring. Ring, pyrimidine ring, pyridyl Ring, or three ring.

[Compound represented by formula (III)]

The compound of the present invention is preferably a compound represented by the formula (III) (hereinafter sometimes referred to as "compound (III)").

The compound represented by the formula (III) is a compound of "benzene" which is a benzene ring. That is, the compound of the present invention preferably has a quinoline ring or a quinolin A compound of a porphyrin ring.

Here, in the above formula (III), R, X ¹ , m, X ² , n, A ¹ , A ² , A ³ , A ⁴ , B, and X have the same meanings as described above.

[Compound represented by formula (IV)]

The compound of the present invention is preferably a compound represented by the formula (IV) (hereinafter sometimes referred to as "compound (IV)").

The compound represented by the formula (IV) is a compound in which "D" is a benzene ring and "A ¹ to A ⁴ " is a carbon atom. That is, the compound of the present invention preferably has a quinoline ring or a quinolin Any of the porphyrin rings and a compound with a benzene ring.

Here, in the above formula (IV), R, X ¹ , m, X ² , n, B, and X have the same meanings as described above.

[Compound represented by formula (V)]

Further, the compound of the present invention is preferably a compound represented by the formula (V) (hereinafter sometimes referred to as "compound (V)").

Here, in the formula (V), R, X ¹ , m, X ² , n, D, B, and X have the same meanings as those in the above formula (I).

[A ⁵ , A ⁶ , A ⁷ ]

A ⁵ , A ⁶ , and A ⁷ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. However, the oxygen atoms are not adjacent to each other, the sulfur atoms, and the combination of the oxygen atoms and the sulfur atoms.

That is, the ring containing A ⁵ , A ⁶ , and A ⁷ constitutes a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a thiazole ring, Oxazole ring, different Oxazole ring, isothiazole ring.

[Compound represented by formula (VI)]

The compound of the present invention is preferably a compound represented by the formula (VI) (hereinafter sometimes referred to as "compound (VI)").

The compound represented by the formula (VI) is a compound of "benzene" which is a benzene ring.

Here, in the formula (VI), R, X ¹ , m, X ² , n, A ⁵ , A ⁶ , A ⁷ , B, and X have the same meanings as those in the above formula (V).

[Method for Producing Compound of the Present Invention]

The compound of the present invention can be produced, for example, by the synthesis method shown below.

(Synthesis method 1)

The compound (II) can be produced by reacting a compound represented by the formula (1) with a compound represented by the formula (2) by a known method.

In the formula, R, X ¹ , m, X ² , n, D, A ¹ to A ⁴ , B, and X have the same meanings as described above. Q represents a halogen group.

In the present invention, a useful intermediate for the production of 7,8-difluoro-3-iodo-quinoline.

(Synthesis method 2)

The compound (II) can be produced by reacting a compound represented by the formula (3) with a compound represented by the formula (4) by a known method.

In the formula, R, X ¹ , m, X ² , n, D, A ¹ to A ⁴ , B, X, and Q have the same meanings as described above.

In the present invention, 8-fluoro-3-hydroxyquinoline, 7,8-difluoro-3-hydroxyquinoline, 8-fluoro-3-hydroxy-2-methylquinoline, or 7,8-difluoro- A useful intermediate for the manufacture of 3-hydroxy-2-methylquinoline.

(Synthesis method 3)

The compound (V) can be produced by reacting a compound represented by the formula (1) with a compound represented by the formula (5) by a known method.

In the formula, R, X ¹ , m, X ² , n, D, A ⁵ to A ⁷ , B, X, and Q have the same meanings as described above.

(Synthesis method 4)

The compound (V) can be produced by reacting a compound represented by the formula (3) with a compound represented by the formula (6) by a known method.

In the formula, R, X ¹ , m, X ² , n, D, A ⁵ to A ⁷ , B, X, and Q have the same meanings as described above.

The salt of the compound of the present invention can be produced by bringing an inorganic acid compound, an organic acid compound, an alkali metal compound, an alkaline earth metal compound, a transition metal compound, an ammonium compound or the like into contact with the compound (I).

In any of the reactions, after the completion of the reaction, the target can be efficiently separated by a usual subsequent treatment operation in organic synthetic chemistry and, if necessary, a conventionally known separation and purification means.

The structure of the target can be identified and confirmed by ¹ H-NMR spectroscopy, IR spectroscopy, mass spectrometry or elemental analysis.

2) Agricultural and horticultural fungicides

The agricultural and horticultural fungicide of the present invention contains at least one selected from the group consisting of the nitrogen-containing heterocyclic compound of the present invention or a salt thereof as an active ingredient.

The agricultural and horticultural fungicide of the present invention has excellent sterilization against a wide range of filamentous fungi, for example, bacteria belonging to the genus Oomycetes, Ascomycetes, Deuteromycetes, and Basidiomycetes. force.

In order to prevent various diseases occurring when cultivating agricultural and horticultural crops including flowers, turf, and pasture, the agricultural and horticultural fungicides of the present invention can be used in methods such as seed treatment, stem and leaf spreading, soil application, or surface application.

For example, beet: Cercospora beticola, Aphanomyces cochlloides; Thanatephorus cucumeris; Thanatephorus cucumeris; Peanut: Mycosphaerella arachidis, Black smut (Mycosphaerella berkeleyi); Cucumber: Sphaerotheca fuliginea, Pseudoperonospora cubensis, Mycosphaerella melonis, Fusarium oxysporum, Sclerotinia sclerotiorum, Botrytis ( Botrytis cinerea), Colletotrichum orbiculare, Cladosporium cucumerinum, Corynespora cassicola, Pythium debaryanam, Rhizoctonia solani Kuhn, Pseudomonas syringae pv.Lecrymans ); tomato: Botrytis cinerea, leaf mold (Cladosporium) Fulvum), Phytophthora infestans; eggplant: Botrytis cinerea, Corynespora melongenae, Erysiphe cichoracearum, Mycovellosiella nattrassii; Strawberry: Botrytis cinerea ), powdery mildew (Sohaerotheca humuli), anthracnose (Colletotrichum acutatum, Colletotrichum fragariae), Phytophthora cactorum; onion: gray decay disease (Botrytis allii), gray mold (Botrytis cinerea), white spot blight (Botrytis squamosa) ), Perunopora destructor; Cabbage: Plasmodiophora brassicae, Erwinia carotovora, Peronospora parasitica; Green beans: Sclerotinia sclerotiorum, Botrytis Cinerea); apple: powdery mildew (Podosphaera leucotricha), black star disease (Venturia inaequa1is), candidiasis (Monilinia mali), black spot disease (Mycosphaerella pomi), rot disease (Valsa mali), spotted leaf disease (Alternaria mali) , brown disease (Gymnosporangium yamadae), ring disease (Botryosphaeria berengeriana), anthracnose (Glomere Lla cingulata, Colletotrichum acutatum, Diplocarpon mali, Zygophiala jamaicensis, Gloeodes pomigena; persimmon: Phyllactinia kakicola, anthracnose (Gloeosporium kaki), keratosis Disease (Cercospora kaki); Peach: Monilinia fructicola, Cladosporium carpophilum, Phomopsis sp.; Cherry: Monilinia fructicola; Grape: Botrytis cinerea, Powdery mildew (Uncinula necator), late rot (Glomerella cingulata, Colletotrichum acutatum), Plasmopara viticola, Elsinoe ampelina, Pseudocercospora vitis, Black rot (Guignardia bidwellii); Pear: Ventura nashicola, Gymnosporangium asiaticum, Alternaria kikuchiana, Botryosphaeria berengeriana, Phyllactinia mali; Tea: Pestalotia theae, Anthracnose (Colletotrichum theae-sinensis); Citrus: Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum, Botrytis cinerea, Diaporthe citri, Ulcer Disease (Xanthomonas campestris pv. Citri); wheat: powdery mildew (Erysiphe graminis f.sp.tritici), scab (Gibberella zeae), red rust (Puccinia re Condita), brown snow rot (Pythium iwayamai), red snow rot (Monographella nivalis), eye disease (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), leaf blight (Leptosphaeria nodorum), Typhula incarnata, Myriosclerotinia borealis, Gaeumanomyces graminis; Barley: Pyrenophora graminea, Rhynchosporium secalis, naked black spikes Disease (Ustilago tritici, U.nuda); Rice: Pyricularia oryzae, Rhizoctonia solani, Gibberella fujikuroi, Cochliobolus niyabeanus, Seedling blight Pythium graminicolum), Xanthomonas oryzae, Burkholderia plantarii, Acidovorax avenae, Burkholderia glumae; Tobacco: Sclerotinia sclerotiorum, powdery mildew (Erysiphe cichoracearum); Tulip: Botrytis cinerea; Kobresia: Sclerotinia borealis, Pythium aphanidermatum; Orchard grass: Erysiphe graminis; Soy: Purple spot disease (Cercospora kikuchii), Perunopora Manshurica, Phytophthora sojae; Potato, tomato: Phytophth Ora infestans).

Moreover, the agricultural and horticultural fungicide of the present invention has an excellent bactericidal effect against resistant bacteria. As the resistant bacteria, thiophanate methyl, benomyl, and befenfen are mentioned. Benzimidazole-based fungicides such as (carbendazim) exhibit resistance to Botrytis cinerea or Cercospora beticola, Venturia inaequalis, and Venturia nashicola; Carboxylimine-based bactericides (for example, vinclozolin, procymidone, and iprodione) exhibit resistance to Botrytis cinerea.

Examples of diseases suitable for the agricultural and horticultural fungicides of the present invention include: black spot disease of apple, gray mold of cucumber, powdery mildew of wheat, tomato blight, red rust of wheat, rice blast of rice, cucumber Blight and so on.

Further, the agricultural and horticultural fungicide of the present invention has less phytotoxicity and is less toxic to fish or warm-blooded animals, and is a highly safe agent.

The agricultural and horticultural fungicide of the present invention can be used in the form of a pesticide, that is, in the form of a pesticide preparation such as a hydrating agent, a granule, a powder, an emulsion, an aqueous solvent, a suspension, or a granule hydrating agent.

Examples of the additives and carriers used in the solid preparation include vegetable powders such as soybean powder and wheat flour, mineral micro-powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, and clay, and sodium benzoate. Organic and inorganic compounds such as urea and mirabilite.

Examples of the solvent used in the liquid preparation include kerosene, xylene, and petroleum-based aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl hydrazine, alcohol, acetone, and trichloroethylene. , methyl isobutyl ketone, mineral oil, vegetable oil, water, and the like.

Further, in order to make the preparations into a uniform and stable form, it may be as needed To add a surfactant.

The surfactant which can be added is not specifically limited. For example, an alkylphenyl ether to which polyoxyethylene is added, an alkyl ether to which polyoxyethylene is added, a higher fatty acid ester to which polyoxyethylene is added, and a sorbitan to which polyoxyethylene is added may be mentioned. a non-ionic surfactant such as a higher fatty acid ester or a tristyrylphenyl ether to which polyoxyethylene is added, a sulfate ester of an alkylphenyl ether to which polyoxyethylene is added, an alkylbenzenesulfonate, and an advanced A sulfate salt of an alcohol, an alkylnaphthalenesulfonate, a polycarboxylate, a lignosulfonate, a formaldehyde condensate of an alkylnaphthalenesulfonate, an isobutylene-maleic anhydride copolymer, or the like.

The hydrating agent, emulsion, suspending agent, aqueous solvent or granule hydrating agent obtained in such a manner can be diluted with water to a specific concentration to prepare a dissolving solution, a suspension or an emulsion, and dispersed to a plant or the like. Further, the powder or granules can be directly used for spreading to plants and the like.

The amount of the active ingredient in the agricultural and horticultural fungicide of the present invention is preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight based on the total amount of the preparation.

The application amount of the agricultural and horticultural fungicide of the present invention varies depending on weather conditions, preparation form, application period, application method, application site, disease prevention target, target crop, etc., but usually the amount of the active ingredient per 1 hectare is 1~ 1000 g, preferably 10 to 100 g.

When the hydrating agent, the emulsion, the suspending agent, the aqueous solvent, the granule hydrating agent or the like is diluted with water, the application concentration is 1 to 1000 ppm, preferably 10 to 250 ppm.

In the agricultural and horticultural fungicide of the present invention, other bactericides or insecticides, acaricides, and synergists may be mixed. Moreover, the invention can be used simultaneously or sequentially Agricultural and horticultural fungicides and other fungicides or insecticides, acaricides, synergists.

Representative examples of other fungicides, insecticides, acaricides, and plant growth regulators which can be used in combination are listed below.

Bactericides: (1) Benzimidazole: Benomyl, Carbendazim, Fuberidazole, Thiabendazole, Thiophanate-methyl, etc. (2) Dicarboxy quinone imine system: Chlozolinate, Iprodione, Procymidone, Vinclozolin, etc.; (3) DMI-bactericide system: Column (Imazalil), Oxpoconazole, Pefurazoate, Prochloraz, Triflumizole, Triforine, Pyrifenox, Fenarimol, Nerimo ( Nuarimol), Azaconazole, Bitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Epoxiconazole , Fenbuconazole, fluquinconazole, Flusilazole, Flutriafol, Hexaconazole, Imibenconazole, Ipconazole, chlorpyrifos Metconazole, Myclobutanil, Penconazole, Propiconon, Prothioconazole, Simeconazole, Tebuconazole, Tetraconazole , Triadimefon, Triadimenol, Triticonazole, Etaconazole, Furconazole-cis, etc.; (4) Phenylguanamine: Bendula ( Benalaxyl), Furalaxyl, Metalaxyl, right Metalaxyl-M, Oxadixyl, Ofurace, etc.; (5) Amines: Aldimorph, Dodemorph, Fenpropimorph ), Tridemorph, Fenpropidin, Piperalin, Spiroxamine, etc.; (6) Phosphorothiolate: EDDP, propyl chelsone (Iprobenfos), white pine (Pyrazophos), etc.; (7) dithiazide (dithiolane): Isoprothiolane, etc.; (8) Carboxamide: Benodanil, Boscalid, Carboxin, and Fenfuram ), Flutolanil, Furametpyr, Mepronil, Oxycarboxin, Penthiopyrad, Thifluzamide, etc.; (9) Hydroxy-( 2-Amino)pyrimidines: Bupirimate, dimethirimol, ethirimol, etc.; (10) AP bactericide (Anilino Pyrimidine, anilinopyrimidine): Cypro (Cyprodinil), Mepanipyrim, Pyrimethanil, etc.; (11) N-phenyl carbazate: Diethofencarb, etc.; (12) QoI-bactericide (Qo inhibitor) ): Azoxystrobin, Picoxystrobin, Pyraclostrobin, Kresoxim-methyl, Trifloxystrobin, Dimoxystrobin, Phenoxybacter Metominostrobin, Orysastrobin, Famoxadone, Fluoxastrobin, Fenamidone, Metomin (en), phenyl pyrrole, phenylpyrrole, Fenpiconyl, Fludioxonil, etc.; (14) quinoline: Quinoxyfen, etc.; 15) AH fungicides (aromatic hydrocarbons): biphenyl, Chloroneb, Dicloran, Quintozene, Tecnazene, Tolclofos-methyl, etc.; (16) MBI-R series: Phthalide, Pyroquilon, Tricyclazole, etc.; (17) MBI-D series: Gap Carpropamid, Diclocymet, Fenoxanil, etc.; (18) SBI agents: Fenhexamid, Pyributicarb, Terbinafine (19) Phenylurea: Pencycuron, etc.; (20) QiI-bactericide (Qi inhibitor): Cyazofamid, etc.; (21) Benzylamine: acetochlor ( Zoxamide); (22) Enorpyranuron; Blasticidin, Mildiomycin, etc.; (23) Hepopyranosyl: Jia Kasugamycin, etc.; (24) glucoside Pyranosyl): Streptomycin, Validamycin, etc.; (25) Cyanoacetamide: Cymoxanil, etc.; (26) Carbamate: Iodine Iodocarb, Propamocarb, Prothiocarb, Polycarbamate, etc.; (27) Uncoupling agent: Binapacryl, Dinocap, Ferimzone, Fluazinam, etc.; (28) organotin compounds: triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, etc.; 29) Phosphate: phosphorous acid, Tolclofos-methyl, Fosetyl, etc.; (30) phthalic acid system: Tecloftalam, etc.; (31) Benzo three (benzotriazine) series: imidazole (Triazoxide), etc.; (32) benzenesulfonamide: Flusulfamide, etc.; (33) 嗒 Ketone (pyridazinone): Diclomezine, etc.; (34) CAA bactericide (Carboxylic Acid Amides): Dimethomorph, Flumorph, Thiafen ( Benthiavalicarb), Iprovalicarb, Mandipropamid, etc.; (35) tetracycline: oxytetracycline, etc.; (36) thioamine formate: Methasulfocarb, etc.; (37) Others Compounds: Etridiazole, Polyoxin, Oxolinic acid, Hydroxyisoxazole, Octhilinone, Silthiopham, Difluoro Diflumetorim, Acibenzolar-S-methyl, Probenazole, Tiadinil, Ethaboxam, Cyflufenamid , Proquinazid, Metrafenone, Fluopicolide, Copper Hydroxide, Organocopper, Sulfur, Ferbam, Manzeb, Manganese Maneb, Metiram, Propineb, Thiuram, Zineb, Ziram, Captan Ptan), Captafol, Folpet, Chlorothalonil, Dichlofluanid, Tolylfluanid, Dodine, Kekejing Guazatine), Iminoctadine acetate, Iminoctadine dodecylbenzenesulfonate, Anilazine, Dithianon, Chloropicrin, Mellon Dazomet), Chinomethionat, Cyprofuram, Silthiopham, Agrobacterium, Fluoroquinone, etc.; insecticides, acaricides, nematicides, soil-killing pesticides , insect repellent: (1) organic (thio) phosphate system: Acephate, Azamethiphos, Azinphos-methyl, Azinphos-ethyl , Bromophos-ethyl, Bromfenvinphos, BRP, Chlorpyrifos, Methyl Tossson, Ethoxysone, Chlorfenvinphos, Cadusafos, Plus Carbophenothion, Chlorethoxyfos, Chlormephos, Coumaphos, Cyanofenphos Cyanophos, CYAP, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Demeton-S -methyl), Dimethylvinphos, Demeton-S-methyl-sulfone, Dialifos, Diazion, Dchlofenthion, Fruit and Vegetable Phosphorus Dioxabenzofos), Disulfoton, Ethion, Ethoprophos, Etrimfos, EPN, Fenamiphos, Fenitrothion, Fenicide Fenthion), Fensulfothion, Flupyrazofos, Fonofos, Formothion, Phosmethylan, Heptenophos, Etopox ( Isazofos), Iodofenphos, Isofenphos, Isoxathion, Iprobenfos, Malathion, Mevinphos, Methamidophos, Methidathion, Monocrotophos, Mecarbam, Methacrifos, Naled, Omethoate, Oxydemeton-methyl, Paraoxon, Parathion, methyl parathion, Phenthoate, Phosalone, benefit Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Pirimiphos-ethyl, Propenofos , Prothiofos, Fosthiazate, Phosphocarb, Propaphos, Propetamphos, Prothoate, Pyridaphenthion, Pyraclofos, Quinalphos, Salithion, Sulprofos, Sulfotepp, Tetrachlorvinphos, Terbufos, Triassic (Triazophos), Trichlorfon, Tebupirimfos, Temephos, Thiometon, Vamidothion; (2) Carbamate: Cotton Bell (Alanycarb), Aldicarb, Bendiocarb, Benfuracarb, Carbaryl, Carbofu Ran), butyl plus carbosulfan, Fenoxycarb, Fenothiocarb, Methiocarb, Methomyl, Oxamyl, Bigap (Pirimicarb), Propoxur, Thiodicarb, Triazamate, Ethiofencarb, Fenobucarb, MIPC, MPMC, MTMC, Bifson ( Pyridaphenthion), Furathiocarb, XMC, Aldoxycarb, Allyxycarb, Aminocarb, Bendiocarb, Bufencarb, Carnivores (Butacarb), Butocarboxime, Butoxycarboxim, Cloethocarb, Dimetilaan, Formetanate, Isoprocarb, Smet ( Metam-sodium), Metolcarb, Promecarb, Thiofanox, Trimethacarb, Xylylcarb; (3) Pyrethroid (pyrethroid) ) Department: Allethrin, Bifenthrin, Cyfluthrin, β-赛芙宁, Cyhalothrin, λ-赛洛宁, 赛素宁 (Cyp Henothrin), Cypermethrin, α-赛灭宁, β-赛灭宁, ζ-赛灭宁, 地灭宁 (Deltamethrin), Esfenvalerate, Ethofenprox, fen Fenpropathrin, Fenvalerate, Imiprothrin, Permethrin, Prallethrin, Pyrethrin, Pyrethrin I, Pyrethrin II, Resmethrin, Silafluofen, Fluvalinate, Tefluthrin, Tetramethrin, Tralomethrin, and Byfunning Transfluthrin), Profluthrin, Dimefluthrin, Acrinathrin, Cycroprothrin, Halfenprox, Flucythrinate, Biology Bioallethrin, Bioethanomethrin, Biopermethrin, Bioresmethrin, Transpermethrin, Empenthrin, V Fenfluthrin, Fenpirithrin, Flubrocythrinate, III Flufenprox, Flumethrin, Metofluthrin, Phenothrin, Protrifenbute, Pytesmethrin, and telfluethrin; (4) Growth Regulatory substances: (a) Chitin synthesis inhibitors: Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufinon (Lufenuron), Novaluron, Teflubenzuron, Triflumuron, Bistrifluron, Noviflumuron, Buprofezin, Co-match Hexathiazox, Etoxazole, Clofentezine, Fluazuron, Penfluron; (b) Ecdysone antagonist: Halofenozide, fenfen Methoxyfenozide, Tebufenozide, Chromafenozide, azadirachtin; (c) juvenile hormone-like substances: Pyriproxyfen, Methhoprene, Diofenolan, Epofenonane, Hydroprene, Iridinide (Ki) Noprene), rimene (Triprene); (d) lipid biosynthesis inhibitors: Spirodiclofen, Spiromesifen, Spirotetramat, Flonicamid; (5) Nicotinic receptor agonist/antagonist compounds: Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, race Thiaccloprid, Thiamethoxam, Nithiazine, Nicotine, Bensultap, Cartap, Flupyradifurone; (6) GABA antagonist compounds: (a) B Acetoprole, Ethiprole, Fipronil, Vaniliprole, Pyraproprole, Pyriprazole; (b) Organochlorines: Camphechlor, Chlordane, Endosulfan, HCH, γ-HCH, Heptachlor, Methoxychlor; (7) Large ring Ester insecticides: Abamectin, Emamectin benzoate, Milbemectin, Lepimectin, Spinosad , Ivermectin, Selamectin, Doramectin, Eprinomectin, Moxidectin; (8) METI I compound: Fenicide ( Fenazaquin), Pyridaben, Tebufenpyrad, Tolfenpyrad, Flufenerim, Hydramethylnon, Fenpyroximate, Pyrimidifen , Dicofol; (9) METI II and III compounds: Acequinocyl, Fluacrypyrim, Rotenone; (10) Uncoupler Compound: Chlorfenapyr ), Binapacryl, Dinobuton, Dinocap, DNOC; (11) Oxidative phosphorylation inhibitor compounds: Cyhexatin, Diafenthiuron, Fenbu Fenbutatin oxide, Propargite, Azocyclotin; (12) suede disturbing compound: Cyromazine; (13) mixed functional oxidase inhibitor compound: piperonyl butoxide ( Piperonyl butoxide); (14) sodium channel blocker compounds: Indoxacarb, Metaflumizone (15) Microbial pesticides: BT agents, entomopathogenic virus agents, entomopathogenic filamentous fungi, nematode pathogenic filamentous fungi; Bacillus species, Beauveria bassiana, Metarhizium anisopliae, pseudo-cyan Paecilomyces genus, Thuringiensin, Verticillium genus; (16) Latrophilin receptor acting drug: Depsipeptide, Cyclodepsipeptide ), 24-membered cyclodepsipeptide, Emodepside; (18) Octopamine-acting drug: Amitraz; (19) Liano Ryanodine derivative drugs: Flubendiamide, Chlorantraniliprole, Cyantraniliprole; (20) Magnesium-stimulating ATPase inhibitor: Thiocyclam, Thiosultap, Nereist toxin; (21) Ingestion inhibitor: Pyrmetrozine; (22) Growth inhibitor: Clofentezine, Etoxazole; (23) Other: Benclothiaz, Bifenazate, acetamiprid (Pyridalyl), sulfur, Cyenopyrafen, Cyflumetofen, Amidoflumet, Tetradifon, Chlordimeform, 1,3-Dichloropropene, DCIP, Phenisobromolate, Benzomate, Polyacetaldehyde, Spinetoram, 1-Ethyl-3,4-dihydro-3-[(3-pyridylmethyl) Amino]-6-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-2(1H)-quinazolinone (Pyrifluquinazon), Benzoximate, Newly killed (Bromopropylate), Quinomethionate, Chlorobenzilate, Chloropicrin, Clothiazoben, Dicyclanil, Fenoxacrim, Aromatic Fluoramine Fentrifanil), Flubenzimine, Flufenzine, Gossyplure, (R,Z)-5-(1-decene)dihydrofuran-2(3H) - Japonilure, Metoxadiazone, petroleum, potassium oleate, Sulfluramid, Tetrasul, Triarathene; (24) insect repellent (a Benzoimidazole: Fenbendazole, Albendazole, Trichlorobenzene Tricribendazole, Oxibendazole; (b) Lycium Benzene: Closantel, Oxyclozanide; (c) Substituted Phenol: Nitroiodide Nitroxynil; (d) pyrimidine: Pyrinel; (e) imidazothiazole: Levamisole; (f) tetrahydropyrimidine: Praziquantel; (g) other drives Insecticides: cyclodiene, Ryania, Clorsulon, Metronidazole; plant growth regulators: separation acid, indolebutyric acid, Uniconazole, Ethychlozate, Ethephon, Cloxyfonac, Chlormequat, Chlorella Extract, Calcium Peroxide, Cyanamide, Dichlorprop , gemcitabine, Daminozide, sterol, Trinexapac ethyl, Mepiquat chloride, Paclobutrazol, paraffin, piperonyl butoxide, pyriprene ( Pyraflufen-ethyl), fururprimidol, propyl jasmonate, prohexadione calcium, Benzylaminop Urine), Pendimethalin, Forchlorfenuron, Butanyl Potassium, 1-Naphthylacetamide, 4-CPA, MCPB, Choline, 8-Hydroxyquinoline Sulfate (oxyquinoline sulfate) ), Ethychlozate, Butralin, 1-methylcyclopropene, and aviglycine hydrochloride.

[Examples]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1

8-fluoro-3-(3-fluoro-2-(propane-2-sulfinyl)-phenoxy)-quinoline [8-fluoro-3-[3-fluoro-2-(propane-2-) Synthesis of sulfinyl)-phenoxy]-quinoline] (Compound No. 1-13)

In a 50 mL flask, charged with 8-fluoro-3-quinolinol 0.37 g (2.27 mmol) and 10 mL of N,N-dimethylformamide. Thereto were added 0.50 g (2.27 mmol) of 1,3-difluoro-2-(propane-2-sulfonyl)benzene and 0.50 g (2.27 mmol) of potassium carbonate. Thereafter, it was heated at 100 ° C for 3 hours. It is then cooled to room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over magnesium sulfate. Filter and concentrate. The resulting reaction mixture was purified using a Shanshan column. Obtained 8-fluoro-3-(3-fluoro-2-(propan-2-sulfonyl)-phenoxy)-quinoline 0.42 g (51%).

Example 2

Synthesis of 8-fluoro-3-(3-fluoro-2-nitro-phenoxy)-quinoline [Compound of 8-fluoro-3-(3-fluoro-2-nitro-phenoxy)-quinoline] No. 2-2)

In a 200 mL flask, 5.13 g (31.42 mmol) of 8-fluoro-3-quinolinol and 100 mL of acetonitrile were charged. Commercially available 5.00 g (31.42 mmol) of 1,3-difluoro-2-nitrobenzene and 8.68 g (62.84 mmol) of potassium carbonate were added thereto. Thereafter, the mixture was heated under reflux for 20 hours. Cool to room temperature. Filter and concentrate. The resulting reaction mixture was purified using a cerium oxide gel column. 6.03 g (63%) of 8-fluoro-3-(3-fluoro-2-nitro-phenoxy)-quinoline was obtained.

Example 3

Synthesis of 2-fluoro-6-(8-fluoro-quinolin-3-yloxy)-phenylamine (Compound No.) 2-5)

In a 500 mL flask was charged 8-fluoro-3-(3-fluoro-2-nitro- Phenoxy)-quinoline 6.03 g (19.94 mmol) and ethyl acetate 100 mL. 1.06 g of 10% Pd/C was added thereto, and the mixture was stirred under a hydrogen atmosphere at room temperature for 24 hours. Filter and concentrate. The resulting reaction mixture was purified using a cerium oxide gel column. 2-Fluoro-6-(8-fluoro-quinolin-3-yloxy)-phenylamine 4.39 g (81%) was obtained.

Example 4

Trifluoro-N-(2-fluoro-6-(8-fluoro-quinolin-3-yloxy)phenyl)-methanesulfonamide [trifluoro-N-[2-fluoro-6-(8-fluoro) Synthesis of -quinolin-3-yloxy)-phenyl]-methanesulfonamide] (Compound No. 2-20)

A 50 mL flask was charged with 0.31 g (1.13 mmol) of 2-fluoro-6-(8-fluoro-quinolin-3-yloxy)-phenylamine and 10 mL of dichloromethane. It was cooled to 0 °C. Then, 0.48 g (1.70 mmol) of trifluoromethanesulfonic anhydride was added, and the mixture was stirred at room temperature for 20 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over magnesium sulfate. Filter and concentrate. The resulting reaction mixture was purified using a Shanshan column. 0.30 g (65%) of trifluoro-N-(2-fluoro-6-(8-fluoro-quinolin-3-yloxy)phenyl)-methanesulfonamide was obtained.

Example 5

Trifluoro-N-(2-fluoro-6-(8-fluoro-quinolin-3-yloxy)-phenyl)-N-methyl-methanesulfonamide [trifluoro-N-[2-fluoro- Synthesis of 6-(8-fluoro-quinolin-3-yloxy)-phenyl]-N-rmethyl-methanesulfonamide] (Compound No. 2-21)

Add a trifluoro-N-(2-fluoro-6-(8-fluorine) to a 50 mL flask -Quinolin-3-yloxy)phenyl)-methanesulfonamide 0.15 g (0.37 mmol) and acetone 10 mL. 0.15 g (0.74 mmol) of methyl iodide and 0.10 g (0.74 mmol) of potassium carbonate were added thereto, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was filtered and concentrated. The concentrate was purified on a cerium oxide gel column. 0.11 g (73%) of trifluoro-N-(2-fluoro-6-(8-fluoro-quinolin-3-yloxy)-phenyl)-N-methyl-methanesulfonamide was obtained.

Example 6

5-fluoro-2-[3-fluoro-2-(propan-2-sulfonyl)phenoxy]quin Synthesis of 5-fluoro-2-[3-fluoro-2-(propane-2-sulfonyl)phenoxy]quinoxaline) (Compound No. a1-10)

(Step 1) 5-Fluoro-2-(3-fluoro-2-isopropylsulfonylphenoxy)quine Synthesis of 5-fluoro-2-(3-fluoro-2-isopropylsulfanylphenoxy-quinoxaline)

2-chloro-5-fluoroquine 2-chloro-5-fluoroquinoxaline 0.14 g (0.75 mmol) and 3-fluoro-2-isopropylsulfanylphenol 0.14 g (0.75 mmol) of dimethyl group To 10 mL of the guanamine solution, 0.12 g (0.90 mmol) of potassium carbonate was added at room temperature. Then, the temperature was raised to 100 ° C and stirred for 4 hours. After cooling to room temperature, the solution was poured into a separatory funnel containing 100 mL of ethyl acetate and 100 mL of water, and separated into an aqueous layer and an organic layer. The aqueous layer was extracted with 100 mL of ethyl acetate to separate an organic layer. The obtained organic layer was combined, washed with brine (50 mL) and dried over magnesium sulfate. Then, the mixture was filtered and the solvent was evaporated under reduced pressure. The residue obtained was purified by EtOAc (EtOAc) (hexane:EtOAc) toield of 5-fluoro-2-(3-fluoro-2-isopropylsulfanylphenoxy)-quinoxaline 0.23 g (92%).

2-chloro-5-fluoroquine The porphyrin system is synthesized by referring to the production method described in J. Med. Chem. 1981, 24, 93-101.

Further, 3-fluoro-2-isopropylsulfonylphenol was synthesized by the production method described in WO2003/091239.

(Step 2) 5-Fluoro-2-[3-fluoro-2-(propan-2-sulfonyl)phenoxy]quina Synthesis of porphyrin (Compound No. a1-10)

5-fluoro-2-(3-fluoro-2-isopropylsulfanylphenoxy)-quinoxaline 0.23 g (0.69 mmol) was dissolved in a mixed solvent of 2-propanol 4 mL: 2 mL of water. 0.98 g (1.58 mmol) of Oxone (manufactured by DuPont Co., Ltd.) was added thereto, and the mixture was stirred at room temperature for 20 hours. The solution was poured into a separatory funnel containing 100 mL of ethyl acetate and 100 mL of water, and separated into an aqueous layer and an organic layer. The aqueous layer was extracted with 100 mL of ethyl acetate to separate an organic layer. The resulting organic layer was mixed. It was washed with 50 mL of brine and dried over magnesium sulfate. Then, the mixture was filtered and the solvent was evaporated under reduced pressure. The residue obtained was purified by the column chromatography (L) (hexane: ethyl acetate) to give the desired compound 5-fluoro-2-[3-fluoro-2-(propane-2-sulfonyl)phenoxy]quinoxaline0. 19g (76%).

Example 7

6-fluoro-2-[3-chloro-2-(propan-2-sulfonyl)phenoxy]quin Synthesis of 6-Fluoro-2-[3-chloro-2-(propane-2-sulfonyl)phenoxy]quinoxaline) (Compound No. a1-16)

(Step 1) 6-Fluoro-3,4-dihydro-1H-quin Synthesis of oxa-2-one

40.0 g of 2,4-difluoronitrobenzene was dissolved in 400 mL of acetonitrile, and 35.1 g of ethyl glycinate hydrochloride and 32.3 g of diisopropylethylamine were added, and the mixture was heated under reflux for 15 hours. After cooling the reaction liquid to room temperature, it was concentrated under reduced pressure to a volume of about 1/3, and then added to water and extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. The solvent was evaporated under reduced pressure. 40 g of this crystal was dissolved in 400 mL of methanol, and 1.8 g of 10% palladium carbon was added thereto, and the mixture was stirred under a hydrogen atmosphere for 18 hours. The Celite was filtered, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 6-fluoro-3,4-dihydro-1H-quine. Oxa-2-one 23.9 g. The NMR (300 MHz, CDCl ₃ ) δ system is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) d 3.87 (d, 2H), 4.37 (bs, 1H), 6.30-6.35 (m, 2H), 6.62 (d, 1H), 9.37 (bs, 1H).

(Step 2) 2-Chloro-6-fluoroquine Synthesis of porphyrin

6-fluoro-3,4-dihydro-1H-quine 23.9 g of oxa-2-one and 37.6 g of manganese dioxide were added to 300 ml of benzene, and the mixture was heated under reflux for 6 hours while being dehydrated by a Dean-Stark apparatus. After cooling the reaction liquid to room temperature, it was filtered, and the mixture was filtered with Celite, and the insoluble matter was washed with 1 L of acetone and 1 L of ethyl acetate. The filtrate was mixed, and the solvent was evaporated under reduced pressure, and the residue was washed with ethyl acetate and acetone to afford 1.7 g of crystals. The total amount of the obtained crystals was added to 30 mL of phosphorus trichloride, and the mixture was heated under reflux for 6 hours. After cooling the reaction mixture to room temperature, excess phosphorus trichloride was distilled off under reduced pressure. Ice water was added to the obtained residue, which was neutralized with a saturated sodium hydrogen carbonate solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and evaporated. The resulting residue was purified by silica gel column chromatography to obtain 2-chloro-6-fluoroquine. The porphyrin was 1.67 g. The NMR (300 MHz, CDCl ₃ ) δ system is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) d 7.58 (m, 1H), 7.75 (m, 1H), 8.03 (m, 1H), 8.78 (s, 1H).

(Step 3) Synthesis of 3-Chloro-2-(propane-2-sulfonyl)phenol

150.7 g of 2,6-dichlorothiophenol and 171.7 g of 2-iodopropane were dissolved in 2.5 L of acetonitrile, and 174.5 g of potassium carbonate was added thereto, followed by heating under reflux for 3 hours. After the reaction liquid was cooled to room temperature, the solvent was evaporated under reduced pressure, and water was added to the residue and ethyl acetate. The extract was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give 204.3 g of crude crystals of isopropyl 2,6-dichlorophenyl sulfide. 180.8 g of this crude crystal was dissolved in 2.5 L of dichloromethane, and 421.4 g of m-chloroperbenzoic acid (max 77% by Aldrich) was added thereto, and the mixture was stirred at room temperature for 5 hours. Saturated sodium hydrogencarbonate water was added to the reaction solution, and after stirring for 1 hour, chloroform and water were added to carry out liquid separation. The organic layer was washed with saturated aqueous sodium hydrogencarbonate, and dried over magnesium sulfate. The solvent was evaporated to dryness to give the crude crystals of isopropyl 2,6-dichlorophenylhydrazine 222.9 g. 207.0 g of this crude crystal was dissolved in 2 L of dimethylformamide, and 101.5 g of 2-(methanesulfonyl)ethanol was added, and then sodium hydride (60% oil dispersion) was added little by little at 0 ° C with stirring. ) 98.1g. After the reaction solution was stirred at room temperature for 2 hours, it was neutralized with a 1N hydrochloric acid solution and extracted with ethyl acetate. The extract was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography, whereby 120.7 g of 3-chloro-2-(propane-2-sulfonyl)phenol was obtained. The NMR (300 MHz, CDCl ₃ ) δ system is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) d 1.37 (d, 6H), 3.85 (sep, 1H), 6.93 (d, 1H), 7.01 (d, 1H), 7.37 (t, 1H), 10.44 (s) , 1H).

(Step 4) 6-Fluoro-2-[3-chloro-2-(propan-2-sulfonyl)phenoxy]quina Synthesis of porphyrin

2-chloro-6-fluoroquine 35.82 g of bromine and 45.82 g of 3-chloro-2-(propane-2-sulfonyl)phenol were dissolved in 586 mL of dimethylformamide, and 32.38 g of potassium carbonate was added thereto, and the mixture was stirred at 100 ° C for 24 hours. After cooling the reaction solution to room temperature, it was added to water and extracted with ethyl acetate. After the extract was washed with water, it was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue obtained was purified by silica gel column chromatography to obtain 6-fluoro-2-[3-chloro -2-(propane-2-sulfonyl)phenoxy]quin Porphyrin 61.7 g (83%).

Melting point: 144-145 ° C

The nitrogen-containing heterocyclic compound obtained in the above examples and the nitrogen-containing heterocyclic compound which can be synthesized by the same method as in any of the above examples are shown in Tables 1 to 8.

R, (X ¹ ) m, (X ² ) n , and X in the first and second tables represent those in the formula (1-A).

R, (X ¹ ) m, (X ² ) n , and X in the third table represent those in the formula (1-B).

R, (X ¹ ) m, B, (X ² ) n, A ² ~ A ⁴ , and X in the fourth table represent those in the formula (1-C).

R, (X ¹ ) m, B, (X ² ) n, A ⁶ , A ⁷ , and X in the fifth table represent those in the formula (1-D).

R, (X ¹ ) m, B, (X ² ) n, A ³ , and X in the sixth table represent those in the formula (1-E).

R, B, (X ² ) n, A ³ , and X in the seventh table represent those in the formula (1-F).

R, B, (X ² ) n, A ³ , and X in the eighth table represent those in the formula (1-G).

In the physical property column, the melting point (°C) or the refractive index (n _D ) is presented. Here, the number attached above (n _D ) indicates the measured temperature (°C).

Among the compounds shown in the above table, ¹ H-NMR (300 MHz, CDCl ₃ ) δ was measured for the compound in which * is described in the physical property column. One of the results of the measurement is presented below.

Compound 1-1: 6.89-7.00 (m, 2H), 7.14-7.17 (m, 2H), 7.43 (d, 1H), 7.51 (t, 1H), 7.59-7.66 (m, 2H), 8.09 (d, 1H), 8.56 (d, 1H).

Compound 1-4: 7.08 (m, 1H), 7.31-7.34 (m, 2H), 7.41 (m, 1H), 7.48-7.77 (m, 4H), 8.11 (m, 1H), 8.83 (d, 1H) .

Compound 1-5: 5.07 (s, 2H), 7.02 (m, 1H), 7.05-7.23 (m, 8H), 7.32 (d, 1H), 7.47 (m, 1H), 7.57-7.63 (m, 2H) , 8.10 (d, 1H), 8.85 (d, 1H).

Compounds 1-8: 1.37 (d, 6H), 2.76 (m, 1H), 7.03 (t, 1H), 7.36-7.63 (m, 5H), 7.71-7.87 (m, 3H), 8.28 (s, 1H) , 8.81 (d, 1H).

Compound 1-12: 1.23 (d, 6H, J = 6.8 Hz), 3.54 (m, 1H), 6.89 (m, 1H), 7.05 (m, 1H), 7.29-7.37 (m, 3H), 7.43-7.46 (m, 2H), 8.86 (d, 1H, J = 2.8 Hz)

Compounds 1-14: 3.31 (s, 3H), 7.06 (m, 1H), 7.34-7.42 (m, 2H), 7.48-7.53 (m, 2H), 7.64-7.71 (m, 2H), 8.14 (m, 1H), 8.90 (d, 1H).

Compound 1-17: 3.40 (s, 3H), 7.01 (m, 1H), 7.3-7.7 (m, 6H), 8.87 (d, 1H).

Compound 1-18: 2.89 (d, 6H, J = 7.2 Hz), 3.67 (m, 1H), 6.87 (m, 1H), 7.11 (m, 1H), 7.36 (m, 1H), 7.49-7.51 (m, 2H), 7.56-7.64 (m 2H), 8.85 (d, 1H, J = 2.8 Hz)

Compound 1-32: 1.22 (t, 3H, J = 7.2 Hz), 1.78 (s, 6H), 4.25 (q, 2H, J = 7.2 Hz), 7.03 (m, 1H), 7.33 (m, 1H), 7.42-7.57 (m, 5H), 8.82 (m, 1H)

1-3. , 3H), 7.65 (m, 1H), 8.84 (d, 1H, J = 2.8 Hz)

Compound 1-90: 1.43 (d, 6H), 2.73 (s, 3H), 3.79 (sep, 1H), 6.87 (dd, 1H), 7.3-7.5 (m, 4H), 7.61 (m, 2H), 8.01 (d, 1H)

Compound 2-1: 7.13 (dd, 1H), 7.31 (m, 1H), 7.5-7.8 (m, 5H), 8.04 (dd, 1H), 7.12 (d, 1H), 8.82 (s, 1H).

Compound 2-7: 3.31 (s, 3H), 3.73 (s, 3H), 6.92 (m, 1H), 7.04-7.15 (m, 3H), 7.23-7.42 (m, 3H), 8.22 (d, 1H) .

Compound 2-11: 4.28 (s, 4H), 6.71 (dd, 1H), 7.00 (m, 1H), 7.15-7.45 (m, 15H), 8.60 (d, 1H).

Compounds 2-15: 1.96 (s, 3H), 3.18 (s, 3H), 6.84 (m, 1H), 7.06 (m, 1H), 7.30-7.40 (m, 2H), 7.49-7.52 (m, 2H) , 7.64 (m, 1H), 8.77 (d, 1H, J = 2.7 Hz)

Compounds 2-16: 1.92 (s, 3H), 3.29 (s, 3H), 6.97 (m, 1H), 7.28-7.41 (m, 3H), 7.50-7.53 (m, 2H), 7.65 (m, 1H) , 8.78 (d, 1H).

Compound 2-18: 1.99 (s, 3H), 4.26 (d, 1H), 5.62 (d, 1H), 6.67 (m, 1H), 6.95-7.06 (m, 4H), 7.18-7.23 (m, 3H) , 7.28-7.52 (m, 4H), 8.28 (d, 1H).

Compounds 2-19: 3.39 (s, 3H), 6.68 (m, 1H), 7.01 (m, 1H), 7.31-7.44 (m, 2H), 7.48-7.58 (m, 2H), 7.77 (m, 1H) , 8.79 (d, 1H, J = 2.8 Hz)

Compounds 2-21: 3.47 (s, 3H), 6.70 (m, 1H), 7.01 (m, 1H), 7.30-7.43 (m, 2H), 7.49-7.58 (m, 2H), 7.83 (m, 1H) , 8.86 (d, 1H, J = 2.4Hz)

Compound a1-81:1.35(d,6H),3.77(sep,1H),7.32(m,1H),7.52(m,1H),7.62-7.69(m,3H),8.08(m,1H),8.74 (s, 1H)

Compounds a1-87: 0.91 (d, 6H), 2.19 (sep, 1H), 3.29 (d, 2H), 7.28 (dd, 1H), 7.54 (dd, 1H), 7.58-7.68 (m, 4H), 8.08 (dd, 1H), 8.75 (s, 1H)

Compound a1-94: 0.94 (d, 6H), 2.21 (sep, 1H), 3.29 (d, 2H), 7.28 (dd, 1H), 7.44 (m, 1H), 7.54 (dd, 1H), 7.61 (t) , 1H), 7.67 (dd, 1H), 7.73 (dd, 1H), 8.75 (s, 1H)

Compound b2-53: 7.17 (s, 1H), 7.4-7.7 (m, 8H), 7.92 (d, 1H), 8.73 (d, 1H)

(preparation)

Next, some examples of the agricultural and horticultural fungicides of the present invention are shown, but the additives and the addition ratios are not limited by the examples, and can be varied within a wide range. Further, the parts in the formulation examples represent parts by weight.

The above was uniformly mixed and pulverized to fineness to obtain a hydrating agent having an active ingredient of 40%.

The above mixture was dissolved to obtain an emulsion having an active ingredient of 10%.

The above was uniformly mixed and pulverized to fineness to obtain a powder having an active ingredient of 10%.

Formulation Example 4 Granules

The mixture was thoroughly pulverized and mixed, and water was sufficiently kneaded, and then granulated and dried to obtain a granule having an active ingredient of 5%.

The above was mixed and wet-pulverized until the particle size reached 3 μm or less to obtain a suspending agent having 10% of the active ingredient.

After uniformly mixing and pulverizing the above to a fine amount, an appropriate amount of water is added, which After kneading, it is made into a clay shape. The clay was granulated and dried to obtain a granule hydrating agent having an active ingredient of 40%.

(Biological test example 1) Apple scab prevention test

The emulsion obtained in Formulation Example 2 was diluted to a concentration of 125 ppm of the active ingredient, and spread to an apple seedling cultivated in a vegetarian pot (variety "Guoguang", 3 to 4 leaf stage), and naturally dried at room temperature. Thereafter, the conidia of Venturia inaequalis were inoculated, and the indoors were kept at 20 ° C and high humidity for 2 weeks every 12 hours. A comparison was made between the appearance of lesions on the leaves and those without treatment, and the control effect was obtained.

For compound numbers 1-2, 1-5, 1-8, 1-10, 1-1-1, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18 , 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1 -32, 1-33, 1-34, 1-35, 1-36, 1-37, 1-39, 1-41, 1-60, 1-61, 1-89, 1-90, 1-91 , 2-1, 2-2, 2-3, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-13, 2-15, 2-16, 2 The compounds of -18, 2-19, 2-20, and 2-21 were tested for the prevention of apple scab, and as a result, any of the compounds showed a control value of 75% or more.

For compound numbers a1-1, a1-2, a1-3, a1-4, a1-5, a1-10, a1-11, a1-12, a1-13, a1-14, a1-15, a1-16 , a1-18, a1-32, a1-62, a1-74, a1-75, a1-76, a1-77, a1-78, a1-79, a1-80, a1-81, a1-82, a1 -83, a1-84, a1-85, a1-86, a1-87, a1-88, a1-89, a1-90, a1-91, a1-92, a1-93, a1-94, a1-95 , b3 The compounds of -2 and b4-2 were tested for apple scab resistance, and as a result, any of the compounds showed a control value of 75% or more.

(Biological test example 2) Cucumber gray mold control test

The emulsion obtained in Formulation Example 2 was diluted to a concentration of 100 ppm of the active ingredient, and dispersed in a cucumber seedling cultivated in a vegetarian pot (variety "phase mold half white", cotyledon stage), and naturally dried at room temperature. Thereafter, a conidia suspension inoculated with Botrytis cinerea was added dropwise, and kept in a dark room at 20 ° C for 4 days. A comparison was made between the appearance of lesions on the leaves and those without treatment, and the control effect was obtained.

For compound numbers 1-3, 1-8, 1-9, 1-10, 1-12, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20 , 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, 1 -33, 1-34, 1-35, 1-41, 1-60, 1-61, 1-62, 1-63, 1-64, 1-65, 1-66, 1-67, 1-68 , 1-69, 1-70, 1-71, 1-72, 1-89, 1-90, 1-91, 2-2, 2-3, 2-6, 2-8, 2-9, 2 Compounds of -16, 2-18, 2-19, and 2-21 were subjected to a cucumber gray mold control test, and as a result, any of the compounds showed a control value of 75% or more.

For compound numbers a1-2, a1-3, a1-4, a1-5, a1-6, a1-7, a1-10, a1-11, a1-12, a1-13, a1-14, a1-15 , a1-16, a1-17, a1-18, a1-19, a1-20, a11-2, a1-32, a1-62, a1-74, a1-75, a1-76, a1-77, a1 -78, a1-79, a1-80, a1-81, a1-82, a1-83, a1-84, a1-85, a1-86, a1-87, a1-88, a1-89, a1-90 , a1- 91, a1-92, a1-93, a1-94, a1-95, b3-2, b3-12, and b4-2 compounds were tested for cucumber gray mold, and as a result, any compound showed more than 75% Defence value.

(Biological test example 3) Rice blast disease water surface application test (inoculation after 14 days)

The rice seedlings (variety "Koshihikari", 1 leaf stage) cultivated in pots filled with commercially available soil and filled with water were used to drip the water obtained in Formulation Example 2 at a concentration of 400 ppm of the active ingredient. deal with. After 14 days from the spotting treatment, the conidia suspension of Magnaporthe grisea was spray-inoculated. It is kept in a dark room at 25 ° C and high humidity for 2 days. Thereafter, the room was kept at 25 ° C for 8 days in which the brightness and darkness were repeated every 12 hours. A comparison was made between the appearance of lesions on the leaves and the untreated seedlings, and the control effect was obtained.

The rice blast water surface application test was carried out for the compounds of the compound numbers a1-4, a1-5, a1-10, a1-11, a1-12, and a1-13. As a result, any of the compounds showed a control value of 60% or more.

(Biological test example 4) Rice blast disease water surface application test (inoculation after 2 days)

The rice seedlings (variety "Koshihikari", 1 leaf stage) cultivated in pots filled with commercially available soil and filled with water were used to drip the water obtained in Formulation Example 2 at a concentration of 400 ppm of the active ingredient. deal with. After 2 days from the spotting treatment, the conidia suspension of Magnaporthe grisea was spray-inoculated. It is kept in a dark room at 25 ° C and high humidity for 2 days. Thereafter, the light and dark changes are repeated every 12 hours. The indoor temperature of 25 ° C is maintained for 8 days. A comparison was made between the appearance of lesions on the leaves and those without treatment, and the control effect was obtained.

Compound numbers showing more than 60% of the control values: a1-88, a1-91

(Biological test example 5) Seed treatment test of cucumber stalk rot

For the cucumber seed contaminated with Fusarium oxysporum (variety "phase mold half white"), the emulsion of the compound of the present invention was used for seed treatment in such a manner that the active ingredient was 1 g/kg of seed. The seeds were sown, and after 3 weeks, the degree of disease was compared with that of the untreated person to determine the control effect.

Compound numbers showing more than 75% of the control values: a1-88, a1-91, a1-93

[Industrial Availability]

The present invention can provide a nitrogen-containing heterocyclic compound or a salt thereof which is useful as an active ingredient for agricultural and horticultural fungicides, which is effective and safe to use.

Claims (7)

a nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof; [In the formula (I), R represents a group represented by OR ¹ , a group represented by NR ¹ R ² , a group represented by SR ¹ , a group represented by S(=O)R ³ , and a group represented by SO ₂ R ³ . a group, a group represented by S(=O)(=NR ⁴ )R ⁵ , a group represented by N=S(=O)R ⁴ R ⁵ , or a nitro group; R ¹ represents a hydrogen atom, unsubstituted or C1-8-alkyl group having a substituent, a C2-8 alkenyl group having an unsubstituted or substituted group, a C2-8 alkynyl group having an unsubstituted or substituted group, an unsubstituted or substituted C3-8 ring group Alkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted heterocyclic group, unsubstituted or substituted a C1-8 fluorenyl group, an unsubstituted or substituted carboxy group, an unsubstituted or substituted amine carbenyl group, a substituted sulfonyl group, or an unsubstituted or substituted amine R ² represents a hydrogen atom, an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, Unsubstituted or substituted C3-8 cycloalkyl, unsubstituted or substituted a C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted C1-8 fluorenyl group, a substituted or substituted carboxy group, an unsubstituted or substituted amine carbenyl group, a substituted sulfonyl group, an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted amine R ³ represents an unsubstituted or substituted C 1-8 alkyl group, an unsubstituted or substituted C 2-8 alkenyl group, an unsubstituted or substituted C 2 -8 alkynyl group, unsubstituted Or a C3-8 cycloalkyl group having a substituent, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted group a cyclic group, an unsubstituted or substituted fluorenyl group, an unsubstituted or substituted hydroxy group, or an unsubstituted or substituted amino group; R ⁴ and R ⁵ each independently represent unsubstituted or have a C1-8 alkyl group of a substituent, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2-8 alkyne a C3-8 cycloalkyl group having an unsubstituted or substituted group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-10 aryl group, or not or a substituted heterocyclic group having a substituent of the group; the group represented by NR ¹ R ^2, R ¹ is and R ² may together form an unsubstituted or having from 3 to 8-membered ring of the substituent group, = CR ^a R ^b, or =NR ^c ; R ^a and R ^b each independently represent a hydrogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, unsubstituted or substituted a C2-8 alkynyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6~10 aromatic group Heterocyclic, unsubstituted or substituted heterocyclic group, unsubstituted or substituted C1-8 fluorenyl group, unsubstituted or substituted carboxy group, unsubstituted or substituted anthracene group having a sulfo substituent group of acyl, unsubstituted or substituted group of the mercapto group, unsubstituted or having a substituent of a hydroxyl, amino or an unsubstituted or substituted group of; R ^c table Unsubstituted or substituted with a hydroxyl group of, or unsubstituted or substituted alkyl group having C1 ~ 8 group of; yl N = S (= O) R 4 R 5 in the illustrated, R ⁴ and R ⁵ may Forming a 5- to 8-membered ring which is unsubstituted or substituted; X ¹ each independently represents an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, Unsubstituted or substituted C2-8 alkynyl, unsubstituted or substituted C3-8 cycloalkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted a C6-10 aryl group, an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted C1-8 fluorenyl group, an unsubstituted or substituted (1-imino) C1 group ~8 alkyl, unsubstituted or substituted carboxy group, unsubstituted or substituted amine mercapto group, unsubstituted or substituted hydroxy group, unsubstituted or substituted amino group, not a substituted or unsubstituted group having the mercapto group, a sulfo group of the acyl substituent, a halogen group, a cyano group, or nitro group; m represents the number ¹ and X is any one integer of 0 ~ 5; B represents a carbon atom Or a nitrogen atom; D represents an unsubstituted or substituted with X ¹ of the 5 to 7-membered hydrocarbon ring or an unsubstituted or substituted with X ¹ of the 5 to 7 membered heterocyclic ring; X ² each independently represent an unsubstituted or C1-8-alkyl group having a substituent, a C2-8 alkenyl group having an unsubstituted or substituted group, a C2-8 alkynyl group having an unsubstituted or substituted group, an unsubstituted or substituted C3-8 ring group Alkyl, unsubstituted or substituted C4-8 cycloalkenyl, unsubstituted or substituted C6-10 aryl, unsubstituted or substituted heterocyclic group, unsubstituted or substituted a C1-8 fluorenyl group, an unsubstituted or substituted (1-imino) C1-8 alkyl group, an unsubstituted or substituted carboxyl group, an unsubstituted or substituted amine formamidine Alkyl, unsubstituted or substituted hydroxy group, unsubstituted or substituted amine group, unsubstituted or substituted fluorenyl group, substituted sulfonyl group, halogen group, cyano group, or nitrate n; n represents the number of X ² and is any integer from 0 to 3; any of X ² and R may together form an unsubstituted or substituted 5-8 member ring; E indicates no Unsubstituted or substituted with X ² of 5 to 7-membered hydrocarbon ring or an unsubstituted or substituted with X ² of 5 to 7-membered heterocyclic ring; X-represents an oxygen atom, a nitrogen atom, or substituted alkyl group of C1 ~ 8 N atom〕. A nitrogen-containing heterocyclic compound or a salt thereof, wherein formula (II) represents formula (I) of claim 1; (In the formula (II), R, X ¹ , m, X ² , n, D, B, and X represent the same meanings as in the formula (I) of claim 1; A ¹ , A ² , A ³ and A ⁴ each independently represent a carbon atom or a nitrogen atom). A nitrogen-containing heterocyclic compound or a salt thereof, wherein the formula (II) represents the formula (II) of the second item of the patent application; (In the formula (III), R, X ¹ , m, X ² , n, A ¹ , A ² , A ³ , A ⁴ , B, and X represent the formula (II) in the second item of the patent application scope. The same meaning). A nitrogen-containing heterocyclic compound or a salt thereof, wherein formula (IV) represents formula (I) of claim 1; (In the formula (IV), R, X ¹ , m, X ² , n, B, and X represent the same meanings as in the formula (I) of the first aspect of the patent application). A nitrogen-containing heterocyclic compound or a salt thereof, wherein the formula (V) represents the formula (I) of the first aspect of the patent application; (In the formula (V), R, X ¹ , m, X ² , n, D, B, and X represent the same meanings as those in the formula (I) of the first aspect of the patent application; A ⁵ , A ⁶ and A ⁷ each independently represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom; however, the oxygen atoms are not adjacent to each other, the sulfur atom, and the combination of the oxygen atom and the sulfur atom. A nitrogen-containing heterocyclic compound or a salt thereof, which is represented by the formula (VI), wherein the formula (V) of claim 5; (In the formula (VI), R, X ¹ , m, X ² , n, A ⁵ , A ⁶ , A ⁷ , B, and X represent the same as those in the formula (V) of claim 5 Meaning). A bactericidal agent for agricultural and horticultural use, which comprises at least one of a nitrogen-containing heterocyclic compound or a salt thereof according to any one of claims 1 to 6 as an active ingredient.