TW201629018A - Novel hetero compound and use thereof - Google Patents

Abstract

An object of the present invention is to provide a heterocyclic compound or a salt thereof that controls a pest. The present invention provides a heterocyclic compound represented by Formula (1): or a salt thereof, wherein R1 and R4 are identical or different and each represents substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl group, R2 represents substituted or unsubstituted C1-4 alkyl, R3 represents substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl group, X represents C(=Y), CR5R6, NH, or NR7, Y represents oxygen or sulfur, R5 and R6 are identical or different and each represents hydrogen, or the like, R7 represents C1-4 alkyl, C1-4 alkylcarbonyl, or C1-4 alkoxycarbonyl, and the bond represented by: is a single bond or a double bond.

Description

Novel heterocyclic compounds and uses thereof Technical field

This invention relates to a novel heterocyclic compound and its use.

Background skill

Due to the long-term use of fungicides, chemical resistant fungi have emerged in recent years. It has therefore become difficult to complete the control by using known fungicides.

In such cases, there is a need to develop novel fungicides which are expected to achieve fungicidal activity not only against chemically sensitive fungi but also against chemically resistant fungi.

For example, WO 2013/164295 (Patent Document (PTL) 1) discloses a compound represented by the following chemical formula (A). PTL 1 revealed that this compound exhibited insecticidal activity. However, PTL 1 has nowhere to reveal that this compound exhibits fungicidal activity.

Listed references Patent literature

PTL 1: WO 2013/164295

Summary of invention

One of the objects of the present invention is to provide a heterocyclic compound or a salt thereof for controlling pests.

Another object of the present invention is to provide a novel fungicide which exhibits excellent fungicidal activity against not only chemically sensitive fungi but also chemical resistant fungi.

The inventors of the present invention conducted extensive research to achieve the above object and successfully synthesized a compound represented by the following chemical formula (1) or a salt thereof having fungicidal activity. The inventors of the present invention have conducted further research based on the above findings. The invention has thus been completed.

More particularly, the invention includes the following examples.

Item 1:

One of the heterocyclic compounds represented by the chemical formula (1): Or a salt thereof, wherein R ¹ and R ⁴ are the same or different, and each represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R ² represents a substituted group. Or unsubstituted C _1-4 alkyl, R ³ represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and X represents C(=Y), CR ⁵ R ⁶ , NH, or NR ⁷ , Y represents oxygen or sulfur, R ⁵ and R ⁶ are the same or different, and each represents hydrogen, hydroxyl, thiol, halogen, C _1-4 alkyl, C _1-4 halogen Alkyl, C _1-4 alkoxy C _1-4 alkyl, C _1-4 haloalkoxy C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-8 Cycloalkyl, C _3-8 cycloalkyl C _1-4 alkyl, C _1-4 alkylcarbonyl, C _1-4 alkylcarbonyloxy, C _1-4 alkoxy, C _1-4 halo Oxyl, C _1-4 alkylthio, C _1-4 haloalkylthio, C _1-4 alkanesulfonyl, C _1-4 alkylsulfinyl, arylthio, arylsulfonyl, aromatic Sulfhydryl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C _1-4 alkyl, or substituted or unsubstituted aryl group, R ⁷ table C _1-4 alkyl, C _1-4 alkylcarbonyl, or C _1-4 alkoxy carbonyl group, and with The key represented is a single key or a double key.

Item 2:

A heterocyclic compound according to item 1, or a salt thereof, wherein R ¹ represents a substituted aryl group.

Item 3:

A heterocyclic compound according to item 1 or 2, wherein R ³ represents a substituted aryl group, or a salt thereof.

Item 4:

A heterocyclic compound or a salt thereof according to any one of items 1 to 3, wherein R ⁴ represents a substituted or unsubstituted heteroaryl group.

Item 5:

The heterocyclic compound or a salt thereof according to any one of items 1 to 4, wherein R ⁴ is a substituted or unsubstituted pyridyl group.

Item 6:

A pest controlling agent comprising the heterocyclic compound according to any one of items 1 to 5 or a salt thereof.

Item 7:

A fungicide comprising the heterocyclic compound according to any one of items 1 to 5 or a salt thereof.

The heterocyclic compound or a salt thereof according to the present invention achieves excellent fungicidal efficacy against fungal plant pathogenic bacteria. Further, the heterocyclic compound or a salt thereof according to the present invention can be used as a novel fungicide which exhibits excellent fungicidal activity against chemically sensitive fungi not only against chemically sensitive fungi but also against chemical fungi.

Description of the embodiment Heterocyclic compound or salt thereof

The present invention relates to a compound represented by the chemical formula (1): Or a salt thereof (hereinafter sometimes referred to as "the compound (1) of the present invention" or "compound (1)"), wherein R ¹ and R ⁴ are the same or different, and each represents a substituted or unsubstituted a substituted aryl group, or a substituted or unsubstituted heteroaryl group, R ² represents a substituted or unsubstituted C _1-4 alkyl group, and R ³ represents a substituted or unsubstituted aryl group, or A substituted or unsubstituted heteroaryl group, X represents C(=Y), CR ⁵ R ⁶ , NH, or NR ⁷ , Y represents oxygen or sulfur, and R ⁵ and R ⁶ are the same or different and each One represents hydrogen, hydroxy, thiol, halogen, C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy C _1-4 alkyl, C _1-4 haloalkoxy C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-8 cycloalkyl, C _3-8 cycloalkyl C _1-4 alkyl, C _1-4 alkylcarbonyl, C _1-4 alkylcarbonyloxy, C _1-4 alkoxy, C _1-4 haloalkoxy, C _1-4 alkylthio, C _1-4 haloalkylthio, C _1-4 alkane Mercapto, C _1-4 alkylsulfinyl, arylthio, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, Substituted or unsubstituted aryl C _1-4 alkane a group, or a substituted or unsubstituted heteroaryl group, R ⁷ represents a C _1-4 alkyl group, a C _1-4 alkylcarbonyl group, or a C _1-4 alkoxycarbonyl group, and The key represented is a single key or a double key.

The following shows a specific example of each of the groups used in the present specification.

Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, but are not particularly limited thereto.

Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, Azolyl, different Azyl, thiazolyl, pyrazolyl, imidazolyl, Diazolyl, triazolyl, tetrazolyl, pyridyl, anthracene Base, thiadiazolyl, pyrimidinyl, tri Base, sulfhydryl, isodecyl, quinazolyl, carbazolyl, benzo Azolyl, benzopyrene Orzozolyl, benzothiazolyl, benzisothiazolyl, benzimidazolyl, oxazolyl, quinolyl, isoquinolyl, pyridohydrazino, benzofuranyl, etc., but are not particularly limited thereto . Such heteroaryl groups include those substituted with a pendant oxy or thioketone group at any substitutable position. These heteroaryl groups may be optionally substituted with from 1 to 5 (preferably from 1 to 3) substituents at any substitutable position.

Examples of the C _1-4 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, and the like C _1-4 straight chain. Or an alkyl group of a branched chain, but is not particularly limited thereto.

Examples of the halogen include fluorine, chlorine, bromine, iodine, and the like, but are not particularly limited thereto.

Examples of the C _1-4 haloalkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, and a 2- Chloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 1-fluoropropyl, 2-chloropropyl, 3-fluoropropyl, 3-chloropropyl, 3,3,3- Trifluoropropyl, 1-fluorobutyl, 1-chlorobutyl, 4-fluorobutyl, 4,4,4-trifluorobutyl, and 1 to 9 and preferably 1 to 5 halogen atoms A similar C _1-4 straight or branched alkyl group is substituted, but is not particularly limited thereto.

Examples of the C _1-4 alkoxy C _1-4 alkyl group include a methoxymethyl group, an ethoxymethyl group, a n-propoxymethyl group, an isopropoxymethyl group, a n-butoxymethyl group, and a Dibutoxymethyl, 2-methoxyethyl, and a similar alkoxyalkyl group wherein C _1-4 straight or branched alkyl is substituted by C _1-4 straight or branched alkoxy , but not particularly limited to this.

C _1-4 haloalkoxy C _1-4 alkyl examples of the group include fluoromethoxy group, chloromethoxy group, bromomethoxy group, iodomethoxy group, a difluoromethoxy group Methyl, trifluoromethoxymethyl, 2,2,2-trifluoromethoxymethyl, and a similar straight or branched alkane substituted with one 9, preferably one to five, halogen atoms An oxyalkyl group, but is not particularly limited thereto.

Examples of the C _2-4 alkenyl group include a vinyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, a 1-methylallyl group and the like, but are not particularly limited thereto.

Examples of the C _2-4 alkynyl group include an ethynyl group, a 1-propynyl group, a 1-methyl-2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, etc., but not Especially limited to this.

Examples of the C _3-8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, but are not particularly limited thereto.

Examples of the C _3-8 cycloalkyl C _1-4 alkyl group include, but are not particularly limited to, cyclopropylmethyl, cyclobutylethyl and the like.

Examples of the C _1-4 alkylcarbonyl group include methylcarbonyl (ethinyl), ethylcarbonyl (propyl), n-propylcarbonyl (butyl), isopropylcarbonyl (isobutyl), n-butylcarbonyl ( Pentamidine, isobutylcarbonyl (isoamyl), t-butylcarbonyl, tert-butylcarbonyl, and similar C _1-4 linear or branched alkylcarbonyl groups, but are not particularly limited thereto Wait.

Examples of the C _1-4 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, and a second butoxy group. A carbonyl group, a third butoxycarbonyl group, and a similar C _1-4 linear or branched alkoxycarbonyl group, but are not particularly limited thereto.

Examples of the C _1-4 alkylcarbonyloxy group include a methylcarbonyloxy group (ethoxycarbonyl), an ethylcarbonyloxy group (propenyloxy group), a n-propylcarbonyloxy group (butoxy group), and a different Propylcarbonyloxy(isobutyloxy), n-butylcarbonyloxy (pentanyloxy), isobutylcarbonyloxy (isoamyloxy), second butylcarbonyloxy, third Butylcarbonyloxy, and a similar C _1-4 linear or branched alkylcarbonyloxy group, but are not particularly limited thereto.

Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. And a C _1-4 straight chain or branched alkoxy group, but is not particularly limited thereto.

Examples of the C _1-4 haloalkoxy group include a fluoromethoxy group, a bromomethoxy group, an iodomethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, and a 2-chloroethoxy group. a group, a 1-fluoroethoxy group, a pentafluoroethoxy group, and a C _1-4 straight or branched chain alkoxy group substituted with 1 to 9, preferably 1 to 5, halogen atoms, but not Especially limited to this.

Examples of the C _1-4 alkylthio group include a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, an isobutylthio group, a second butylthio group, a third butylthio group, And a C _1-4 linear or branched alkylthio group, but is not particularly limited thereto.

Examples of the C _1-4 alkanesulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, an isopropylsulfonyl group, a n-butylsulfonyl group, an isobutylsulfonyl group, and a second butanesulfonate. a group, a tributyl sulfonyl group, and a C _1-4 linear or branched alkanesulfonyl group, but is not particularly limited thereto.

Examples of the C _1-4 alkylsulfinyl group include a sulfinyl group, an sulfinyl group, a propyl sulfinyl group, a isopropyl sulfinyl group, a n-butyl sulfinyl group, and an isobutyl sulfinium sulfonate. a base, a second sulfinyl group, a third sulfinyl group, and a C _1-4 linear or branched alkylenesulfonyl group, but is not particularly limited thereto.

Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and the like, but are not particularly limited thereto.

Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and the like, but are not particularly limited thereto.

Examples of the arylsulfonyl group include a benzenesulfonyl group, a 1-naphthalenesulfonyl group, a 2-naphthalenesulfonyl group, and the like, but are not particularly limited thereto.

Examples of the arylsulfinyl group include a sulfinyl group, a 1-naphthenesulfinyl group, a 2-naphthylsulfinyl group, and the like, but are not particularly limited thereto.

Examples of the aryl C _1-4 alkyl group include a phenylmethyl group, a phenylethyl group, a phenyl-n-propyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group and the like, but are not particularly limited thereto.

The substituted aryl or substituted heteroaryl group refers to the above-mentioned monoaryl or heteroaryl group substituted with one or more substituents. take The number of the substituents is preferably from 1 to 5, and more preferably from 1 to 3.

The substituted C _1-4 alkyl group means the above-mentioned one C _1-4 alkyl group substituted with one or more substituents. The number of substituents is preferably from 1 to 5, and more preferably from 1 to 3.

Examples of the "substituent" for a substituted C _1-4 alkyl group, a substituted aryl group, and a substituted heteroaryl group include a halogen, a nitro group, a cyano group, a hydroxyl group (hydroxy group), and sulfur. Alcohol, C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy C _1-4 alkyl, C _1-4 haloalkoxy C _1-4 alkyl, C _2-4 Alkenyl, C _2-4 alkynyl, C _3-8 cycloalkyl, C _3-8 cycloalkyl C _1-4 alkyl, C _1-4 alkylcarbonyl, C _1-4 alkoxycarbonyl, C _1-4 alkylcarbonyloxy, C _1-4 alkoxy, C _1-4 haloalkoxy, C _1-4 alkylthio, C _1-4 haloalkylthio, C _1-4 alkanesulfonate , C _1-4 alkylsulfinyl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl C _1-4 alkyl group, monosubstituted or unsubstituted heteroaryl group, etc., but is not particularly limited thereto.

Among them, preferred substituents are halogen, nitro, cyano, C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy, C _{1- a 4} -alkylthio group, and an aryloxy group, and more preferred substituents are chlorine, fluorine, bromine, nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, And phenoxy.

Preferred substituents for the substituted aryl substituted heteroaryl group, particularly represented by R ¹ , are halogen, C _1-4 haloalkyl, and C _1-4 alkoxy, and More preferred substituents are chlorine, fluorine, bromine, trifluoromethyl, methoxy, and trifluoromethoxy. The number of substituents is as described above.

A preferred substituent for the substituted alkyl group represented by R ² is a halogen, and a more preferred substituent is fluorine. The number of substituents is as described above.

Preferred substituents for substituted aryl or substituted heteroaryl groups are halogen, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy, C _{1 a 4} -alkylthio group, and an aryloxy group, and more preferred substituents are chlorine, fluorine, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, and phenoxy. The number of substituents is as described above.

Preferred substituents for the substituted aryl or substituted heteroaryl group represented by R ⁴ are halogen, nitro, cyano, C _1-4 alkyl, and C _1-4 haloalkyl, More preferred substituents are chlorine, fluorine, nitro, cyano, methyl, and trifluoromethyl. The number of substituents is as described above.

X represents C(=Y), CR ⁵ R ⁶ NH, or NR ⁷ , preferably C(=Y), CR ⁵ R ⁶ , or NH, and more preferably C(=O), CHOH, CHCl, CHOC (=O) CH ₃ , CHSCH ₃ , CHSC ₂ H ₅ , CHSO ₂ CH ₃ , or NH.

Y represents oxygen or sulfur, and is preferably oxygen.

R ⁵ and R ⁶ are the same or different and each represents hydrogen, hydroxy, thiol, halogen, C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy C _1-4 Alkyl, C _1-4 haloalkoxy C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-8 cycloalkyl, C _3-8 cycloalkyl C _{1- 4-} alkyl, C _1-4 alkylcarbonyl, C _1-4 alkylcarbonyloxy, C _1-4 alkoxy, C _1-4 haloalkoxy, C _1-4 alkylthio, C _{1- 4} -alkylsulfonyl, C _1-4 alkylsulfinyl, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl C _1-4 An alkyl group, or a substituted or unsubstituted heteroaryl group, preferably hydrogen, hydroxy, thiol, halogen, C _1-4 alkylcarbonyloxy, C _1-4 alkylthio, or C _{1 a 4} -alkylsulfonyl group, and more preferably a hydrogen, a hydroxyl group, a chlorine, a methylcarbonyloxy group, a methylthio group, an ethylthio group, or a methylsulfonyl group.

R ⁷ represents hydrogen, C _1-4 alkyl, substituted or unsubstituted C _1-4 alkoxy, substituted or unsubstituted aryl, C _1-4 alkylcarbonyl, or C _1-4 Alkoxycarbonyl, and preferably hydrogen.

The dotted line is a single button or a double button.

The substituted aryl group is preferably an aryl group having one to three halogen atoms, an aryl group having one to three nitro groups, and an aryl group having one to three cyano groups. An aryl group having one to three C _1-4 alkyl groups, an aryl group having one to three C _1-4 haloalkyl groups, having one to two halogen atoms and one to two An aryl group of one of C _1-4 haloalkyl groups, an aryl group having one to three aryloxy groups, and an aryl group having one to three C _1-4 alkoxy groups group having one to three halo C _1-4 alkoxy groups, one aryl radical, having one to three, or one of C _1-4 alkylthio groups an aryl group; more preferably having one to three lines One aryl group of one chlorine atom, one aryl group having one to three bromine atoms, one aryl group having one to three fluorine atoms, one aryl group having one to two fluorine atoms and one to two chlorine atoms a group having an aryl group of one to three trifluoromethyl groups, an aryl group having one to two trifluoromethyl groups and one to two fluorine atoms, having one to three phenoxy groups An aryl group, an aryl group having one to three methoxy groups, an aryl group having one to three trifluoromethoxy groups, or one to three methylthio groups One of the aryl groups of the group.

The substituted heteroaryl group is preferably a heteroaryl group having one to three halogen atoms, a heteroaryl group having one to three nitro groups, and one to three cyano groups. a heteroaryl group, a heteroaryl group having one to three C _1-4 alkyl groups, a heteroaryl group having one to three C _1-4 haloalkyl groups, having one to a heteroaryl group of two halogen atoms and one to two C _1-4 haloalkyl groups, a heteroaryl group having one to three aryloxy groups, having one to three C _1-4 a heteroaryl group of one alkoxy group, a heteroaryl group having one to three C _1-4 haloalkoxy groups, or one to three C _1-4 alkylthio groups a heteroaryl group; and more preferably a heteroaryl group having one to three chlorine atoms, a heteroaryl group having one to three bromine atoms, and a heteroaryl group having one to three fluorine atoms a group, a heteroaryl group having one to two fluorine atoms and one to two chlorine atoms, a heteroaryl group having one to three trifluoromethyl groups, having one to two trifluoromethyl groups Group and one a heteroaryl group of one of two fluorine atoms, a heteroaryl group having one to three phenoxy groups, a heteroaryl group having one to three methoxy groups, and one to three a heteroaryl group of one of the trifluoromethoxy groups, or a heteroaryl group having one to three methylthio groups.

The substituted or unsubstituted heteroaryl group is particularly preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-fluoro-2-pyridyl, 5-chloro-2-pyridyl, 3 , 5-dichloro-2-pyridyl, 5-methyl-2-pyridyl, 3-methyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 4-trifluoromethyl- 2-pyridyl, 3-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-chloro-5-trifluoromethyl-2-pyridyl, 3-nitro- 5-trifluoromethyl-2-pyridyl, 3-cyano-2-pyridyl, 5-chloro-3-pyridyl, 5-trifluoromethyl-3-pyridyl, 2-fluoro-6-three Fluoromethyl-3-pyridyl, 5-pyrimidinyl, 2-pyrimidinyl, 2-thienyl, or 3-thienyl.

The salt of the heterocyclic compound represented by the chemical formula (1) may be any type of salt as long as it is agriculturally acceptable. Examples of salts include hydrochlorides, sulfates, nitrates, and similar inorganic acid salts; acetates, methanesulfonates, And similar organic acid salts; sodium salts, potassium salts, and similar alkali metal salts; magnesium salts, calcium salts, and similar alkaline earth metal salts; dimethyl ammonium salts, triethyl ammonium salts, and similar quaternary ammonium salts.

The compound (1) of the present invention includes a pyrazole compound (hereinafter referred to as "compound 1A") represented by the following chemical formula (1A) and a dihydropyrazole compound represented by the chemical formula (1B) (hereinafter referred to as "compound 1B" ").

(wherein R ¹ , R ² , R ³ , R ⁴ , and X are as defined above.)

In the compound (1) of the present invention, a preferred compound is a compound wherein R ¹ and R ^{4 are} not unsubstituted aryl groups.

Wherein a more preferred compound of the present invention is a compound or a salt thereof, wherein R ¹ and R ⁴ are the same or different, and each represents a substituted aryl group or a substituted or unsubstituted heteroaryl group. a group, R ² represents a substituted or unsubstituted C _1-4 alkyl group, R ³ represents a substituted aryl group, or a substituted or unsubstituted heteroaryl group, and X represents C(=O), CR ⁵ R ⁶ , NH, or NR ⁷ , Y represents oxygen, and R ⁵ and R ⁶ are the same or different, and each represents hydrogen, hydroxy, thiol, halogen, C _1-4 alkyl, C _1-4 Haloalkyl, C _1-4 alkoxy C _1-4 alkyl, C _1-4 haloalkoxy C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _{3- 8} -cycloalkyl, C _3-8 cycloalkyl C _1-4 alkyl, C _1-4 alkylcarbonyl, C _1-4 alkylcarbonyloxy, C _1-4 alkoxy, C _1-4 halide Alkoxy, C _1-4 alkylthio, C _1-4 alkanesulfonyl, C _1-4 alkylsulfinyl, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aromatic a substituted, unsubstituted or substituted aryl C _1-4 alkyl group, or a substituted or unsubstituted heteroaryl group, R ⁷ represents hydrogen, C _1-4 alkylcarbonyl, or C _1-4 Alkoxycarbonyl, and The key represented is a single key or a double key.

More particularly preferably, the compound of the present invention is a compound or a salt thereof, wherein R ¹ represents a 2,4-disubstituted aryl group, and R ² represents a substituted or unsubstituted C _1-4 alkyl group, R ³ represents a 2,4-disubstituted aryl or a 3-substituted aryl group, R ⁴ represents a substituted or unsubstituted 3-pyridyl group, and X represents C(=O), CR ⁵ R ⁶ , or NH, Y represents oxygen, and R ⁵ and R ⁶ are the same or different, and each represents hydrogen, hydroxy, thiol, halogen, C _1-4 alkylcarbonyloxy, C _1-4 alkylthio, or C _{1- 4} alkanesulfonyl, and Indicates that the construction is a single key or a double key.

When the compound (1) of the present invention has an isomer such as an optical isomer, a stereoisomer, a metaisomer or the like, any such a mixture of such isomers is thus contained in the compound (1). Within the scope. For example, when the compound (1) has an optical isomer, the optical isomer separated from the racemic mixture is also included in the range of the compound (1). Each of these isomers can be synthesized by known means of separation and separation (eg, concentration, solvent extraction, column chromatography) And recrystallization) are obtained as a single compound.

Method for preparing a heterocyclic compound or a salt thereof

The method for producing the compound (1) of the present invention is not particularly limited, and various methods such as Reaction Scheme 1, Reaction Scheme 2, Reaction Scheme 3, Reaction Scheme 4, Reaction Scheme 5, and Reaction Scheme 6 can be used.

Reaction process 1

As shown in the reaction scheme 1, one of the dihydropyrazole compounds or a salt thereof (hereinafter referred to as "compound (1B-1)") represented by the chemical formula (1B-1) is represented by the chemical formula (2) One of the hydrazine compounds (hereinafter referred to as "compound (2)") is prepared by reacting one of the unsaturated ketone compounds represented by the chemical formula (3) (hereinafter referred to as "the compound (3)") in the presence of a base. .

(wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above, and the wavy line indicates an optical isomer.)

In the reaction of the compound (2) with the compound (3), the ratio of the compounds used is not particularly limited, and can be appropriately selected from a wide range. The latter is typically used in an amount of from about 1 to 5 moles per mole of the former, and is preferably about the same molar amount relative to the latter.

The above reaction is carried out after a step (chlorination step) in which the compound (2) is chlorinated to produce a chloride of the compound (2). After the chlorination step, the chloride of the compound (2) is reacted with the compound (3) to give the compound (1B-1).

In the chlorination step, a chlorinating agent can be used. Examples of the monochlorinating agent include chlorine, phosphorus oxychloride (POCl ₃ ), and the like, but are not particularly limited thereto. These chlorinating agents may be used singly or in combination of two or more.

The chlorinating agent is usually used in an amount of 1 mole or more per mol of the compound (2), more preferably 1 to 10 moles, and still more preferably 1 to 8 moles. For example, when phosphorus oxychloride, which may also act as a solvent, is used as a chlorinating agent, after the chlorination step is completed, excess phosphorus oxychloride may be removed under reduced pressure to be used in the subsequent step.

Examples of the base used in the step of reacting the chlorinated product of the compound (2) or the compound (2) with the compound (3) include sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and the like alkali metal carbonate. Sodium hydroxide, potassium hydroxide, and similar alkali metal hydroxides; sodium hydride, potassium hydride, and similar alkali metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium third potassium hydride, And similar alkali metal alkoxides; and triethylamine, pyridine, and other organic bases, but are not particularly limited thereto. These bases may be used singly or in combination of two or more.

The base can be used in a stoichiometric amount or more than the stoichiometric amount relative to the compound (2). Specifically, the base is preferably used in an amount of from 1 to 5 moles per mol of the compound (2), and more preferably from 1 to 3 moles. When used, triethylamine, pyridine, or a similar organic base can be used in a large excess to serve as a reaction solvent.

The above reaction can be carried out in a suitable solvent or without a solvent. When the reaction is carried out in a solvent, the solvent which can be used in the reaction is not particularly limited insofar as it is inert to the reaction system. Examples of the solvent include n-hexane, cyclohexane, n-heptane, and similar aliphatic or aliphatic cyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and similar aromatic hydrocarbons; dichloromethane, 1, 2 - Dichloroethane, chloroform, carbon tetrachloride, and similar halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4- Alkanes, 1,2-dimethoxyethane, and similar ethers; N,N-dimethylformamide (DMF), and similar guanamines; dimethyl azine, and similar anthracenes . These solvents may be used singly or in combination of two or more as needed.

Although not limited, the reaction temperature of the above reaction is generally in the range of from -20 ° C to the boiling point of the solvent used. The reaction is preferably carried out under reflux of a solvent. The reaction time is based on, for example, a change in the reaction temperature. The reaction is usually complete from about 0.5 to about 24 hours.

Reaction process 2

As shown in Reaction Scheme 2, one of the dihydropyrazole compounds or a salt thereof (hereinafter referred to as "compound (1B-2)") represented by the chemical formula (1B-2) is obtained by allowing the compound (1B-1) Prepared by reduction in a solvent.

(wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above, and the wavy line indicates an optical isomer.)

Reaction process 3

As shown in Reaction Scheme 3, one of the pyrazole compounds or a salt thereof (hereinafter referred to as "compound (1A-2)"), or a compound, represented by the chemical formula (1A-2) (1B-2) is produced by reducing the compound (1A-1) in a solvent.

(wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above, and the wavy line indicates an optical isomer.)

In the reduction reaction of the above Reaction Scheme 2 or Reaction Scheme 3, a reducing agent can be used. Examples of the reducing agent include boron compounds and the like, but are not particularly limited thereto. Examples of the boron compound include sodium borohydride, potassium borohydride, and a similar alkali metal borohydride compound; sodium triacetate hydride; sodium cyanoborohydride; and the like. These reducing agents may be used singly or in combination of two or more.

The reducing agent is preferably used in an amount of from 1 to 3 moles per mol of the compound (1B-1) or the compound (1A-1), and more preferably from 1.5 to 2.5 moles.

Examples of the solvent include methanol, ethanol, isopropanol, and similar lower alcohols; diethyl ether, tetrahydrofuran, 1,4-two An alkane, 1,2-dimethoxyethane, and a solvent similar to ether; benzene, toluene, and a similar aromatic hydrocarbon-based solvent, etc., but are not particularly limited thereto. Among these solvents, lower alcohols are preferred, and 2-propanol is more preferred. These solvents may be used singly or in combination of two or more.

Although not limited, the reaction temperature of the above reaction is usually in the range of from -10 ° C to the boiling point of the solvent used. The reaction is preferably carried out at room temperature. The reaction time is based on, for example, a change in the reaction temperature. The reaction is usually tied to 0.5 to about 24 hours complete.

Reaction process 4

As shown in the reaction scheme 4, one of the pyrazole compounds (hereinafter referred to as "compound (1A-1)") represented by the chemical formula (1A-1) is prepared by reacting the compound (1B-1) in a solvent. .

(wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above, and the wavy line indicates an optical isomer.)

An oxidizing agent can be used in the above oxidation reaction. Examples of such an oxidizing agent include lead compounds such as lead oxide (PbO ₂ , Pb ₃ O ₄ ), lead tetraacetate (Pb(OAc) ₄ ), lead trifluoroacetate (Pb(OCOCF ₃ ) ₄ ); copper compound Classes such as copper chloride, copper acetate, copper benzoate, copper carbonate, and copper nitrate; iron compounds such as iron chloride, iron acetate, iron sulfate, and iron nitrate; manganese compounds such as chlorination Manganese, manganese acetate, manganese oxide; zinc compounds, such as zinc chloride, and zinc acetate, etc., but are not particularly limited thereto. These oxidizing agents may be used singly or in combination of two or more.

The amount of the oxidizing agent to be used is not particularly limited. The oxidizing agent to be used is usually 1 mole or more per mole of the compound (1B-1), preferably 1 to 3 moles, and more preferably 1.5 to 2.5 moles.

Examples of the solvent include n-hexane, cyclohexane, n-heptane, and similar aliphatic or aliphatic cyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and similar aromatic hydrocarbons; dichloromethane, 1 , 2-dichloroethane, chloroform, carbon tetrachloride, and similar halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4-two Alkanes, 1,2-dimethoxyethane, and similar ethers; N,N-dimethylformamide (DMF), and similar guanamines; dimethyl azine, and similar anthracenes . These solvents may be used singly or in combination of two or more.

Although not limited, the reaction temperature of the above reaction is usually in the range of from -10 ° C to the boiling point of the solvent used. The reaction is preferably carried out at room temperature. The reaction time depends on, for example, the reaction temperature changes. The reaction is usually complete from about 0.5 to about 24 hours.

Reaction process 5

As shown in the reaction scheme 5, the pyrazole compound represented by the chemical formula (1A'-1) (hereinafter referred to as "the compound (1A'-1)") is an amine compound represented by the chemical formula (4). Hereinafter, it is prepared by reacting a compound represented by the chemical formula (5) (hereinafter referred to as "the compound (5)") in a solvent in the presence of a catalyst and a base.

(wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above, and Z represents a leaving group)

Examples of the leaving group represented by Z include chlorine, bromine, iodine, and a similar halogen atom; a substituted or unsubstituted alkylsulfonate, a substituted or unsubstituted arylsulfonate, and the like.

Specific examples of the compound (5) include a substituted or unsubstituted aryl halide, a substituted or unsubstituted heteroaryl halide, and the like; and a substituted or unsubstituted aryl halide and substituted or Unsubstituted pyridyl halides are preferred.

The compound (5) is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 5 moles per mole of the compound (4).

Examples of the base include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and similar alkali metal carbonates; sodium hydroxide, potassium hydroxide, and similar alkali metal hydroxides; sodium hydride, hydrogenation Potassium, and similar metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium butoxide, and similar alkali metal alkoxides; and triethylamine, N, N-diisopropyl Ethylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and other organic bases, but are not particularly limited thereto. These bases may be used singly or in combination of two or more.

The base can be used in a stoichiometric amount or more than the stoichiometric amount relative to the compound (4). Specifically, the base is preferably used in an amount of from 1 to 5 moles per mol of the compound (4), and more preferably from 1 to 3 moles.

The reaction can be carried out in the presence of a catalyst. Examples of the catalyst include metal catalysts (for example, metals and metal salts), copper salt complexes (for example, copper iodide and N,N'-dimethyl-ethylenediamine, a copper complex, ruthenium Amine acid, or dipyridyl), palladium complex (for example, tris(dibenzylidene-acetone)dipalladium (0), palladium acetate, and 4,5-bisdiphenylphosphine-9,9 - a complex of dimethyloxanthene) and the like.

The amount of the catalyst used is not particularly limited. Catalyst is usually The compound (4) per mole is used in an amount of 0.001 to 1 mol, preferably 0.01 to 0.5 mol, and more preferably 0.05 to 0.3.

Examples of the solvent include n-hexane, cyclohexane, n-heptane, and similar aliphatic or cycloaliphatic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and similar aromatic hydrocarbons; dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, and similar halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4-two Alkanes, 1,2-dimethoxyethane, and similar ethers; N,N-dimethylformamide (DMF), and similar guanamines; dimethylammonium and similar oximes; Acetonitrile and the like. These solvents may be used singly or in combination of two or more.

Although not limited, the reaction temperature of the above reaction is usually in the range of from -10 ° C to the boiling point of the solvent used. The reaction is preferably carried out under reflux. The reaction time depends on, for example, the reaction temperature changes. The reaction is usually complete from about 0.5 to about 24 hours.

Reaction process 6

As shown in Reaction Scheme 6, one of the pyrazole compounds (hereinafter referred to as "compound (1A'-2)") represented by the chemical formula (1A'-2) is obtained by reacting the compound (1A'-1) with the chemical formula ( 6) It is shown that one of the compounds (hereinafter referred to as "compound (6)") is prepared in a solvent in the presence or absence of a base.

(wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁷ are as defined above, and Z represents a leaving group.)

Examples of the leaving group represented by Z in the compound (6) include chlorine, bromine, iodine, and a similar halogen atom; and a substituted or unsubstituted alkylsulfonate, substituted or unsubstituted arylsulfonate. Acid esters, etc.

Specific examples of the compound (6) include a methyl halide, an ethyl halide, an ethyl hydrazine halide, a methoxycarbonyl halide, and the like.

The compound (6) is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 5 moles per mole of the compound (1A'-1).

Examples of the base include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and similar alkali metal carbonates; sodium hydroxide, potassium hydroxide, and similar alkali metal hydroxides; sodium hydride, Potassium hydride, and similar alkali metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium butoxide, and similar alkali metal alkoxides; and triethylamine, N, N-di Isopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and other organic bases, but are not particularly limited thereto. These bases may be used singly or in combination of two or more.

The base may be used in a stoichiometric amount or more than the stoichiometric amount relative to the compound (1A'-1). In particular, the base is preferably used in an amount of from 1 to 5 moles per mol of the compound (1A'-1), and more preferably from 1 to 3 moles.

Examples of the solvent include n-hexane, cyclohexane, n-heptane, and similar aliphatic or aliphatic cyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and similar aromatic hydrocarbons; dichloromethane, 1, 2 - Dichloroethane, chloroform, carbon tetrachloride, and similar halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF), 1,4- Alkanes, 1,2-dimethoxyethane, and similar ethers; N,N-dimethylformamide (DMF), and similar guanamines; dimethyl hydrazine and similar anthracenes; Acetonitrile and the like. These solvents may be used singly or in combination of two or more.

Although not limited, the reaction temperature of the above reaction is usually in the range of from -10 ° C to the boiling point of the solvent used. The reaction is preferably carried out under reflux. The reaction time depends, for example, on the reaction temperature. The reaction is usually complete from about 0.5 to about 24 hours.

The compound (2), the compound (3), the compound (4), and the compound (5) which are the starting materials in the above Reaction Scheme 1 or Reaction Scheme 5 are known compounds or compounds which are easily prepared by a known method. .

Each compound (1) obtained after the reaction shown in Reaction Scheme 1 to Reaction Scheme 6 is completely isolated and purified from the reaction mixture by known isolation and purification techniques, such as filtration, solvent extraction, recrystallization, and tube Column chromatography.

When the compound (1) has a meta isomer, each of the isomers can be separated by a usual separation step such as cerium oxide gel chromatography.

Pest control agent

The compound (1) of the present invention can be used as an active ingredient of a pest controlling agent. Examples of pest control agents include agents (fungicides or virucides) for controlling plant diseases causing problems in farms and horticultural fields; and pests, mites, and nematodes for controlling problems in farms and horticultural fields. Or pesticides for soil pests (insecticides, acaricides, nematicides, or soil insecticides for agriculture and horticulture); animal ectoparasite control agents (eg, acaricides, acaricides, and acaricides) Agent).

In order to be an active ingredient of a pest control agent, it can be indefinite The compound (1) of the present invention is used in the non-component. However, it is generally preferred to form a mixture with a solid carrier, a liquid carrier, or a gaseous carrier (propellant), and optionally with a surfactant and for pharmaceutical preparation and according to known methods of preparation. This compound is used in combination with other adjuvants of various types such as oil solutions, emulsions, wettable powders, flowable articles, granules, dust powders, sprays, fumigants, and the like.

The compound (1) of the present invention is usually contained in such a formulation in a ratio of 0.01 to 95% by weight, and preferably 0.1 to 50% by weight.

Examples of solid carriers which can be used in the formulation include solid carriers in the form of fine powders or granules, such as clay (for example, kaolin, diatomaceous earth, synthetic hydrated cerium oxide, bentonite, clay, and acid) Clay), talc, ceramics, other inorganic minerals (eg, calcite, quartz, sulfur, activated carbon, calcium carbonate, and hydrated cerium oxide), and chemical fertilizers (eg, ammonium sulfate, ammonium phosphate, calcium nitrate, urea) , and ammonium chloride).

Examples of liquid carriers include water, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene). , aliphatic hydrocarbons (eg, hexane, cyclohexane, kerosene, and light oil), esters (eg, ethyl acetate and butyl acetate), nitriles (eg, acetonitrile and isobutyronitrile), ethers (for example, diisopropyl ether and two Alkanes, acid amides (eg, N,N-dimethylformamide and N,N-dimethylacetamide), halogenated hydrocarbons (eg, dichloromethane, trichloroethane, and tetra Carbon chloride), dimethyl hydrazine, soybean oil, cottonseed oil, and similar vegetable oils.

Examples of the gaseous carrier include butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyoxyethylene adducts thereof, and polyglycol ethers. Classes, polyhydric alcohol esters, sugar alcohol derivatives, and the like.

Examples of the adjuvant for pharmaceutical preparation include a fixing agent, a dispersing agent, a stabilizer, and the like.

Examples of fixing agents and dispersing agents include casein, gelatin, polysaccharides (for example, tannin powder, gum arabic, cellulose derivatives, and alginic acid), lignin derivatives, bentonite, sugars, and water-soluble synthetic polymerization. (for example, polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid).

Examples of stabilizers include PAP (acidic isopropyl phosphate), BHT (2,6-di-t-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol, and 3 - a mixture of t-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids, fatty acid esters, and the like.

The pest controlling agent used in the present invention is preferably used by itself or by diluting it with water or the like to use the compound (1). The pest control agent of the present invention can be used by mixing with, for example, other pest control agents, such as known insecticides, nematicides, fungicides, herbicides, plant growth control agents, synergists, Soil conditioners, animal feeds, etc., or they may be used simultaneously without mixing with such agents.

The amount of the pest controlling agent of the present invention is not limited, and can be appropriately selected from a wide range according to various conditions, such as the concentration of the active ingredient, the type of the preparation, the type of the disease or pest to be treated, the plant type, and the disease. Severity, application time, method of application, chemicals to be used in combination (insecticides, nematicides, acaricides, fungicides, herbicides, plants) Growth control agents, synergists, soil conditioners, etc., and the amount and type of fertilizer.

When used as a fungicide, the compound (1) of the present invention is usually used in an amount of from 0.01 to 500 g / 100 m ² , and preferably from 1 to 200 g / 100 m ² .

When used as an acaricide, the compound (1) of the present invention is usually used in an amount of from 0.1 to 500 g / 100 m ² , and preferably from 1 to 200 g / 100 m ² .

When the emulsion, the water-soluble powder, the water-soluble preparation, and the like are used by being diluted with water, the concentration is 0.1 to 1,000 ppm, and preferably 1 to 500 ppm. Granules, dust, and the like can be used without dilution.

The amount and concentration of the compound to be administered may be appropriately increased or decreased depending on the formulation type, application time, application site, application method, insect form, severity of damage, and the like.

The compound (1) of the present invention is characterized by having a particularly excellent fungicidal activity and a wide range of activities. This compound can be used to control plant diseases attributed to various fungal pathogens or antifungal pathogens. Examples of such fungal pathogens include causing cucumber gray mold, rice blast, rice sheath blight, apple powdery mildew, apple spotted leaf disease, persimmon powdery mildew, grape powdery mildew, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew , Xiaohuang No. gray mold, tomato late blight, strawberry powdery mildew, tobacco powdery mildew and so on.

The compound (1) of the present invention is effective as an agricultural or horticultural insecticide, acaricide, nematicide, or soil insecticide. In particular, the compound (1) of the present invention is effective for controlling pests such as peach aphid, cotton aphid, and similar aphids; Plutella xylostella, cabbage moth, Turnip, and apple aphid Moth, cockroach, tobacco nocturnal moth, gypsy moth, rice vertical nightingale, tea worm, potato beetle, yellow squash, cotton weevil, rice brown pheasant, spider mites, scale insect, bug, Whitefly, thrips, cockroaches, flower flies, scarab beetles, cod leaf moths, sugar moths, ants, and agricultural pests; slugs, snails, and similar gastropods; cockroaches, cockroaches, house flies, and house mosquitoes, And insects similar to harmful hygiene; wheat moth, mung bean elephant, red worm, yellow mealworm, and similar storage grain insects; clothing moth, felt black mites, underground termites, and similar injuries to insects and injuries to families and families Insects, etc., mites, such as, two-spotted spider mites, cinnabar leaf mites, citrus leaf mites, sage leaf mites, European red dragonfly, tea scorpion, citrus scorpion scorpion, thorn foot root mites, and similar plant parasitic mites Rotten casein, dust mites, papayas, and similar household dust mites, and soil pests such as root knot nematodes, cyst nematodes, root rot nematodes, white tip nematodes, strawberry nematodes, pine nematodes, and Similar plant parasitic nematodes; ball worms, moths, and similar isopods.

The pest controlling agent of the present invention is also effective for controlling pests of various chemical resistant agents such as an organic phosphorus agent, a carbamate agent, a synthetic pyrethroid agent, and a neonicotin agent.

example

The invention is described in more detail with reference to the following examples; however, the invention is not limited to such examples.

Production Example 1: Production of N'-(2-chlorophenyl)acetamidine

For the cooled solution of 1-(chlorophenyl)indole (3.0 g, 21.12 mmol, 1 eq.) in dichloromethane (40 mL), triethylamine (6.41 g, 63.36 millimolar, 3 equivalents), followed by the addition of acetic anhydride (2.59 grams, 25.35 millimoles, 1.2 equivalents). Then, the resulting mixture was stirred at room temperature for 3 hours. Then, the reaction mixture was poured into cold water and extracted with dichloromethane. The combined organic layers were washed with distilled water, dried over sodium sulfate and evaporated The crude product thus obtained was used in the subsequent reaction without any purification.

¹ H NMR (DMSO-d ⁶ ): δ 9.79 (bs, 1H), 7.37 (bs, 1H), 7.28-7.26 (m, 1H), 7.17-7.13 (m, 1H), 6.76-6.72 (m, 2H) ), 1.92 (s, 3H).

Production Example 2: Production of (E)-3-(4-chloro-fluorophenyl)-1-(pyridin-3-yl)prop-2-en-1-one

1-(pyridin-3-yl)ethanone (4.00 g, 33.05 mmol, 1 eq.) in THF/water (40/20 mL) and 2- fluoro, 4-chlorobenzaldehyde (7.8 g, 49.58) A solution of millimolar, 1.5 eq.), slowly added aqueous NaOH (1.3 g, 33.05 mmol, 1.0 eq. in 10 mL of distilled water). Then, the resulting mixture was stirred at room temperature for 12 hours. Then, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a silica gel gel eluting with ethyl acetate and n-hexane as eluent to give 1.90 g of the title compound.

¹ H NMR (DMSO-d ⁶ ): δ 9.32 (d, J = 1.6 Hz, 1H), 8.85-8.83 (m, 1H), 8.48-8.45 (m, 1H), 8.22 (t, J = 8.4 Hz, 1H), 8.05 (d, J = 15.6 Hz, 1H), 7.80 (d, J = 15.6 Hz, 1H), 7.63-7.58 (m, 2H), 7.45-7.43 (m, 1H).

Example 1: Production of (4-(4-chloro-2-fluorophenyl)-1-(2-chlorophenyl)-4,5-dihydro-3-methyl-1H-pyrazole-5-yl) (pyridin-3-yl)methanone (1B-71)

In phosphorus oxychloride (POCl _3, 2.64 g, 17.20 mmol, 5 eq) of N '- (2- chlorophenyl) acetyl hydrazide (0.88 g, 4.82 mmol, 1.4 eq.) In a mixture of The mixture was refluxed for 3 hours under a nitrogen atmosphere, and then the volatiles were removed under reduced pressure.

The crude material thus obtained was diluted with chloroform (10 ml), and triethylamine (0.696 g, 6.88 mmol, 2.0 eq.) was slowly added, after which (E)-3-(4-chloro-fluorophenyl) was added. )-1-(pyridin-3-yl)prop-2-en-1-one (0.90 g, 3.44 mmol, 1 eq.). Then, the reaction mixture was refluxed for 10 hours.

Then, the reaction mixture was poured into cold water and extracted with dichloromethane. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a silica gel gel eluting with ethyl acetate and n-hexane as eluent to give 0.50 g of the title compound.

Table 1 shows the ¹ H-NMR data of the title compound 1B-71 thus obtained.

Example 2: Production of (4-(4-chloro-2-fluorophenyl)-1-(2-chlorophenyl)-4,5-dihydro-3-methyl-1H-pyrazole-5-yl) (pyridin-3-yl)methanol (1B-75)

(4-(4-Chloro-2-fluorophenyl)-1-(2-chlorophenyl)-4,5-dihydro-methyl-1H-pyrazole-5- in methanol (5 mL) a cooling solution of (pyridin-3-yl)methanone (1B-71, 0.12 g, 0.28 mmol, 1 eq.) in a nitrogen atmosphere Sodium borohydride (0.01 g, 0.28 mmol, 1 eq.) was added portionwise. Then, the resulting mixture was stirred at room temperature for 30 minutes. After distilling the solvent under reduced pressure, the mixture was extracted with ethyl acetate. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a silica gel gel eluting with ethyl acetate and n-hexane as eluent to afford 0.10 g of the title compound.

Table 1 shows the ¹ H-NMR data of the title compound 1B-75 thus obtained.

Example 3: Production of (4-(4-chloro-2-fluorophenyl)-1-(2-chlorophenyl)-3-methyl-1H-pyrazol-5-yl)(pyridin-3-yl) Methyl ketone (1A-77)

(4-(4-Chloro-2-fluorophenyl)-1-(2-chlorophenyl)-4,5-dihydro-3-methyl-1H-pyridyl in dichloromethane (10 ml) a solution of oxazol-5-yl)(pyridin-3-yl)methanone (1B-71, 0.30 g, 0.70 mmol, 1 eq.) in part at room temperature under nitrogen Lead tetraacetate (0.37 g, 0.84 mmol, 1.2 equivalents) was added. Then, the reaction mixture was stirred at room temperature for 18 hours, after which it was filtered through a celite bed. Then, the filtrate was diluted with methylene chloride. The organic layer was washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a cerium oxide gel using a mixture of ethyl acetate and n-hexane as eluent to afford 0.22 g of the title compound 1A-77.

Table 1 shows the ¹ H-NMR data of the title compound 1A-77 thus obtained.

Example 4: Production of (4-(2,4-dichlorophenyl)-1-(2,4-difluorophenyl)-3-methyl-1H-pyrazol-5-yl)(pyridine-3- Methyl)methanol (1A-80)

(4-(2,4-Dichlorophenyl)-1-(2,4-difluorophenyl)-3-methyl-1H-pyrazol-5-yl) in methanol (5 ml) A solution of pyridin-3-yl)methanone (1A-77, 0.10 g, 0.22 mmol, 1 eq.) was added portionwise with sodium borohydride (0.008 g, 0.22 m. , 1 equivalent). Then, the reaction mixture was stirred at room temperature for 30 minutes. After distilling the solvent under reduced pressure, the mixture was extracted with ethyl acetate. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a cerium oxide gel using a mixture of ethyl acetate and n-hexane as an eluent to give 0.07 g of the title compound 1A-80.

Table 1 shows the ¹ H-NMR data of the title compound 1A-80 thus obtained.

Example 5: Production of (4-(4-chloro-2-fluorophenyl)-1-(4-chlorophenyl)-4,5-dihydro-3-methyl-1H-pyrazole-5-yl) (pyridin-3-yl)methanone (1B-72)

In POCl ₃ (2.94 g, 19.15 mmol, 5 eq) of N '- (4- chlorophenyl) acetyl hydrazide (0.98 g, 5.36 mmol, 1.4 eq.) The mixture was refluxed under a nitrogen atmosphere at 3 After an hour, the volatiles were removed under reduced pressure.

The crude material thus obtained was diluted with chloroform (10 ml), and triethylamine (0.78 g, 7.66 mmol, 2.0 eq.) was slowly added thereto, followed by (E)-3-(4-chloro-2-) Fluorophenyl)-1-(pyridin-3-yl)prop-2-en-1-one (1.0 g, 3.83 mmol, 1 eq.). The resulting mixture was then refluxed for 10 hours. Then, the reaction mixture was poured into cold water and extracted with dichloromethane. Combination The organic layer was washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a cerium oxide gel using a mixture of ethyl acetate and n-hexane as an eluent to give 0.70 g of the title compound IB-72.

Table 3 shows the ¹ H-NMR data of the title compound 1B-72 thus obtained.

Example 6: Production of (4-(4-chloro-2-fluorophenyl)-1-(4-chlorophenyl)-4,5-dihydro-3-methyl-1H-pyrazole-5-yl) (pyridin-3-yl)methanol (1B-76)

(4-(4-Chloro-2-fluorophenyl)-1-(4-chlorophenyl)-4,5-dihydro-methyl-1H-pyrazole-5- in methanol (5 ml) A cooling solution of (pyridin-3-yl)methanone (1B-72, 0.1 g, 0.23 mmol, 1 eq.) was added portionwise sodium borohydride (0.086 g, 0.234 millimolar, 1 equivalent). Then, the reaction mixture was stirred at room temperature for 30 minutes. After distilling the solvent under reduced pressure, the mixture was extracted with ethyl acetate. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained was purified by column chromatography on a cerium oxide gel using a mixture of ethyl acetate and n-hexane as eluent to give 0.70 g of the title compound 1B-76.

Table 1 shows the ¹ H-NMR data of the title compound 1B-76 thus obtained.

Example 7: Production of (4-(4-chloro-2-fluorophenyl)-1-(4-chlorophenyl)-3-methyl-1H-pyrazol-5-yl)(pyridin-3-yl) Ketone (1A-78)

(4-(4-Chloro-2-fluorophenyl)-1-(4-chlorophenyl)-4,5-dihydro-3-methyl-1H-pyridyl in dichloromethane (10 mL) Zyrid-5-yl)(pyridin-3-yl) A solution of ketone (1B-72, 0.30 g, 0.70 mmol, 1 eq.) was partially partially added with lead tetraacetate (0.43 g, 0.983 mmol, 1.4) at room temperature under a nitrogen atmosphere. equivalent). The reaction mixture was then stirred at room temperature for 18 hours and then filtered through a pad of plastic. Then, the filtrate was diluted with methylene chloride. The organic layer was washed with distilled water, dried over sodium sulfate, filtered, and evaporated. The crude product thus obtained was purified by column chromatography on cerium oxide gel eluting with ethyl acetate and n-hexane as an eluent to give 0.20 g of the title compound 1A-78.

Table 1 shows the ¹ H-NMR data of the title compound 1A-78 thus obtained.

Example 8: Production of (4-(4-chloro-2-fluorophenyl)-1-(4-chlorophenyl)-3-methyl-1H-pyrazol-5-yl)(pyridin-3-yl) Methanol (1A-79)

(4-(4-Chloro-2-fluorophenyl)-1-(4-chlorophenyl)-3-methyl-1H-pyrazol-5-yl) (pyridine) in methanol (5 mL) A solution of 3-yl)methanone (1-78, 0.10 g, 0.23 mmol, 1 eq.) was added portionwise with sodium borohydride (0.008 g, 0.22 m. equivalent). Then, the reaction mixture was stirred at room temperature for 30 minutes. After distilling the solvent under reduced pressure, the mixture was extracted with ethyl acetate. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered and evaporated The crude product thus obtained was purified by column chromatography on ruthenium dioxide eluting with ethyl acetate and n-hexane as eluent to give 0.07 g of the title compound 1A-79.

Table 1 shows the ¹ H-NMR data of the title compound 1A-79 thus obtained.

Production Example 3: Production of 2-(2,4-difluorophenyl)-3-oxobutyronitrile

A stirred solution of p-xylene (60 ml) and ethanol (30 ml), sodium sulphate (17.7 g, 0.261 mol, 2.0 eq.) was added at 0 ° C over 10 min. After 10 minutes, the solution was heated to 55 °C. After 30 minutes, a solution of 2-(2,4-difluorophenyl)acetonitrile (20.0 g, 0.13 mol, and 1.0 eq.) in acetic acid (80 mL) was slowly added to the reaction mixture. The reaction mass was stirred at 55 ° C for 6 hours. After the reaction, the solution was cooled, and the solvent was evaporated under reduced pressure through an evaporator. Cold water (100 ml) was poured into the reaction mixture, and the resulting mixture was treated with 1N aqueous HCl and maintained at a pH of 2-3 in an ice-cooled bath. The reaction mixture was extracted with EtOAc (EtOAc)EtOAc. The crude product thus obtained was treated with n-pentane and ether to give 2-(2,4-difluorophenyl)-3-oxobutyronitrile (20.5 g) as a solid product.

¹ H NMR (CDCl ₃ ) δ : 7.42 - 7.38 (m, 1H), 7.01-6.91 (m, 2H), 4.93 (s, 1H), 2.36 (s, 3H).

Production Example 4: Production of 1,4-bis(2,4-difluorophenyl)-3-methyl-1H-pyrazole-5-amine

Partially partial addition of acetic acid to a solution of 2-(2,4-difluorophenyl)-3-oxobutyronitrile (1.0 g, 0.005 mol, 1.0 eq.) in ethanol (15 mL) Sodium (0.49 g, 0.006 mol, 1.2 eq.), then 1-(2,4-difluorophenyl)indole hydrochloride (1.25 g, 0.007 m, 1.5 eq.). The reaction solution was stirred at 90 ° C for 10 hours. After the reaction, the solution was cooled, and the solvent was evaporated under reduced pressure through an evaporator. Cold water (20 ml) was poured into the reaction mixture and the resulting mixture was treated with 1N aqueous HCl and maintained in an ice-cold bath. Hold at a pH of 2-3. The reaction mixture was extracted with EtOAc EtOAc EtOAc. The crude product thus obtained was treated with n-pentane and ether to give 1,4-bis(2,4-difluorophenyl)-3-methyl-1H-pyrazole-5-amine (1.4 g) as brown Solid product.

^{1 H NMR (DMSO-d6)} δ: 7.56-7.46 (m, 2H), 7.42-7.36 (m, 1H), 7.30-7.21 (m, 1H), 6.98 (m, 1H), 5.17 (br.s, 2H), 1.99 (s, 3H).),

Production Example 5: 1-(2,4-Dichlorophenyl)-4-(2,4-difluorophenyl)-3-methyl-1H-pyrazole-5-amine

Partially partial addition of acetic acid to a solution of 2-(2,4-difluorophenyl)-3-oxobutyronitrile (1.0 g, 0.005 mol, 1.0 eq.) in ethanol (15 mL) Sodium (0.49 g, 0.006 mol, 1.2 eq.), followed by 1-(2,4-dichlorophenyl)phosphonium hydrochloride (1.5 g, 0.007 mol, 1.5 eq.). The reaction solution was stirred at 90 ° C for 10 hours. After the reaction, the solution was cooled, and the solvent was evaporated under reduced pressure through an evaporator. Cold water (20 ml) was poured into the reaction mixture, and the solution was extracted ethyl acetate (4×50 ml). The organic layer was washed with brine, dried over sodium sulfate, filtered and evaporated. The crude product thus obtained is treated with n-pentane and ether to give 1-(2,4-dichlorophenyl)-4-(2,4-difluorophenyl)-3-methyl-1H-pyrazole- 5-amine (1.5 g), as a brown solid product.

^{1 H NMR (DMSO-d6)} δ: 7.83 (s, 1H), 7.58-7.50 (m, 2H), 7.39 (dd, J = 8.4Hz, 15.2Hz, 1H), 7.29-7.24 (m, 1H), 7.13-7.08 (m, 1H), 5.16 (bs, 2H), 2.00 (s, 3H).

Example 9: Production of N-(1,4-bis(2,4-difluorophenyl)-3-methyl-1H-pyrazol-5-yl)pyridin-3-amine (1A'-89)

a solution of 1,4-bis(2,4-difluorophenyl)-3-methyl-1H-pyrazole-5-amine (0.3 g, 0.0009 mol, 1.0 eq.) in toluene (10 mL) A part of a portion was added with cesium carbonate (1.21 g, 0.0037 mol, 4.0 eq.), and thereafter, 3-bromopyridine (0.148 g, 0.0009 mol, 1.0 eq.) was added dropwise. The reaction solution was flushed with nitrogen for 20 minutes. After 20 minutes, palladium(II) acetate (0.063 g, 0.00009 mol, 0.1 equivalent) followed by 4,5-bisdiphenylphosphino-9,9-dimethyloxaxan (0.108 g, 0.0001 Mo) Ears, 0.2 equivalents) were added under a nitrogen atmosphere and rinsed again for 5 minutes. The reaction mixture was stirred at 100 ° C for about 8 hours.

After the reaction, the reaction solution was cooled and filtered through a plug of plastic bed. The filtrate was evaporated under reduced pressure through an evaporator. The resulting concentrate was diluted with EtOAc (3 mL). A crude product is produced. The crude product was purified by column chromatography on a cerium oxide gel and a mixture of ethyl acetate and n-hexane (40:60) as eluent to give 0.23 g of the title compound 1A'-89. White solid product.

Table 1 shows the ¹ H-NMR data of the title compound 1A'-89 thus obtained.

Example 10: Production of N-(1-(2,4-dichlorophenyl)-4-(2,4-difluorophenyl)-3-methyl-1H-pyrazol-5-yl)pyridine-3 -amine (1A'-91)

For 1-(2,4-dichlorophenyl)-4-(2,4- in toluene (10 ml) A solution of difluorophenyl)-3-methyl-1H-pyrazole-5-amine (0.3 g, 0.0008 mol, 1.0 eq.), partially portionwise added with cesium carbonate (1.1 g, 0.0033 mol) 4.0 equivalents, after which 3-bromopyridine (0.134 g, 0.0008 mol, 1.0 eq.) was added dropwise. The reaction solution was flushed with nitrogen for 20 minutes. After 20 minutes, palladium (II) acetate (0.057 g, 0.00008 mol, 0.1 equivalent) followed by 4,5-bisdiphenylphosphino-9,9-dimethyloxaxan (0.098 g, 0.0001 Mo) Ears, 0.2 equivalents) were added under a nitrogen atmosphere and rinsed again for 5 minutes. The reaction mixture was stirred at 100 ° C for about 8 hours.

After the reaction, the reaction solution was cooled and filtered through a plug of plastic bed. The filtrate was evaporated under reduced pressure through an evaporator. The resulting concentrate was diluted with water (10 mL), EtOAc (EtOAc (EtOAc) A crude product. The crude product was purified by column chromatography on a cerium oxide gel and a mixture of ethyl acetate and n-hexane (40:60) as eluent to obtain 0.155 g of the title compound 1A'-91. A white solid product.

Table 2 shows the ¹ H-NMR data of the title compound 1A'-91 thus obtained.

Example 11:

The compounds shown in Tables 1, 2, and 3 except for the compounds obtained in Examples 1 to 10 were produced by a method similar to that described in Examples 1 to 10.

Tables 1, 2 and 3 show the MS and ¹ H-NMR data of the thus obtained compounds of the present invention.

The abbreviations in Tables 1, 2 and 3 are indicated below.

F: Fluorine

Cl: chlorine

Br: Bromine

Me: methyl

Et: ethyl

Ph: phenyl

CF ₃ : trifluoromethyl

OCF ₃ : trifluoromethoxy

OH: hydroxyl

Ome: methoxy

Oac: Ethyl

CN: Cyano

NO ₂ : Nitro

S: sulfur atom

O: oxygen atom

Py: pyridyl

M.Pt.: melting point

MS: Mass Spectrometry

No.: Compound number

Preparation Example 1: Emulsion

Ten parts of each of the inventive compounds were dissolved in 45 parts of Solvesso 150 and 35 parts of N-methylpyrrolidone. 10 parts of an emulsifier (trade name: Sorpol 3005X, manufactured by Toho Chemical Industry Co., Ltd.) was added. The mixture was mixed by stirring to produce a 10% emulsion.

Preparation Example 2: Wettable powder

20 parts of each of the inventive compounds were added to 2 parts of sodium lauryl sulfate, 4 parts of sodium lignosulfonate, 20 parts of a synthetic hydrated ceria fine powder, and a mixture of 54 parts of clay. The mixture was mixed by stirring with a juicer to produce a 20% wettable powder.

Preparation Example 3: Granules

Two parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite, and 83 of clay were added to 5 parts of each of the inventive compounds, and each mixture was thoroughly mixed by stirring. Add an appropriate amount of water. The resulting mixture was further stirred and pelletized by a pelletizer. The granules were air dried to yield 5% granules.

Preparation Example 4: Dust Powder

One part of each of the inventive compounds is dissolved in an appropriate amount of acetone. Five parts of a synthetic hydrated ceria fine powder, 0.3 parts of acidic isopropyl phosphate (PAP), and 93.7 parts of clay were added. The mixture was mixed by stirring with a juicer, and acetone was removed by evaporation to produce 1% dust powder.

Preparation Example 5: Flowable preparation

20 parts of each of the inventive compounds were mixed with 20 parts of water containing 3 parts of polyoxyethylene tristyrylphenyl ether phosphate triethanolamine and 0.2 parts of Rhodorsil 426R. The mixture was subjected to wet pulverization with a DYNO-Mill and mixed with 60 parts of water containing 8 parts of propylene glycol and 0.32 parts of xanthan gum to produce a 20% suspension in water.

Test Examples The following demonstrates that the compounds of the present invention are useful as one of the fungicides.

Test Example 1: Fungicidal test for cucumber gray mold

A small amount of Botrytis mycelia was collected from a culture tube and aseptically transferred to a potato dextrose agar (PDA) plate. The plate on which the gray mold was inoculated was kept in the dark for five days, then, under blue-black light (BLB) for four days, and finally in the dark at 20 °C for four days.

At the same time, 100 ml of YG (0.2% yeast extract + 1% glucose) solution was prepared using distilled water. 20 ml of the YG solution was poured into the plate and the surface was scraped with a brush. The obtained suspension was filtered through toilet paper. The filtrate thus obtained was diluted with a YG solution to a spore of 1 × 10 ⁶ cfu per ml.

A solution of each of the inventive compounds (200 ppm) was sprayed onto cucumbers freshly cut into the three-leaf stage or later. One of the treated plants has been cut off and placed on a wet toilet paper on a plastic tray. 50 μl of the spore suspension (YG solution) was dropped on the middle of the cotyledons by using a micropipette. Then, a small piece of cotton wool was placed on the spore suspension, and 50 μl of the YG solution was again dropped on the cotton wool. The plastic disc containing the cotyledons is placed in a box containing water in the lower portion and maintained at room temperature (20 ° C).

Five days after inoculation, the radiation growth of the fungus was measured, and the activity of each compound was calculated as a preventive value according to the following equation.

equation

Prevention value = {1 - (average radius of lesions in treated plants / average radius of lesions in untreated plants)} × 100

Compounds exhibiting 50% or more disease control values at 500 ppm are as follows: Compound Nos: 1A-29, 1A-30, 1A-53, 1A-62, 1A-67, 1A-93, 1A-112, 1A- 113, 1A-121; 1A'-13, 1A'-24, 1A'-28, 1A'-29, 1A'-30, 1A'-31, 1A'-32, 1A'-33, 1A'-37 , 1A'-38, 1A'-60, 1A'-61, 1A'-64, 1A'-65, 1A'-66, 1A'-67, 1A'-75; 1B-42, 1B-56, 1B -57, 1B-66, 1B-70, 1B-103, 1B-105, 1B-107, 1B-108, 1B-112, 1B-115.

Test Example 2: Fungicidal test for cucumber powdery mildew

An aqueous solution (100 ppm) of Sorpol 355 (manufactured by Toho Chemical Industry Co., Ltd.) was added to a methanol solution of each test compound to give a sample solution (500 ppm). Each sample solution was sprayed on a pot (7.5 cm in diameter) of cucumber (14 days after inoculation) and dried with air. A suspension containing one of the cucumber powdery mildew spores (1.0 x 10 ⁵ cells/ml) was sprayed onto each plant using a spray gun. After air drying, the plants were left in an acrylic resin greenhouse, and after 10 days, the severity of the disease was examined. The preventive value is calculated by comparison with the disease severity of the untreated plant: The preventive value is calculated by comparing the disease severity of the untreated plant using the following equation.

equation

Prevention value = {1 - (average radius of lesions in treated plants / average radius of lesions in untreated plants)} × 100

Compounds exhibiting disease control values of 80% or more at 500 ppm are as follows: Compound Nos: 1A-18, 1A-20, 1A-22, 1A-25, 1A-28, 1A-29, 1A-30, 1A- 31, 1A-32, 1A-33, 1A-34, 1A-35, 1A-36, 1A-37, 1A-38, 1A-44, 1A-45, 1A-50, 1A-51, 1A-52, 1A-53, 1A-56, 1A-57, 1A-58, 1A-59, 1A-60, 1A-61, 1A-62, 1A-63, 1A-64, 1A-65, 1A-66, 1A- 67, 1A-68, 1A-70, 1A-71, 1A-73, 1A-76, 1A-79, 1A-80, 1A-83, 1A-84, 1A-85, 1A-86, 1A-87, 1A-88, 1A-89, 1A-90, 1A-91, 1A-92, 1A-93, 1A-95, 1A-96, 1A-97, 1A-98, 1A-99, 1A-100, 1A- 105, 1A-106, 1A-107, 1A-108, 1A-109, 1A-110, 1A-111, 1A-112, 1A-113, 1A-114, 1A-115, 1A-116, 1A-117, 1A-118, 1A-119, 1A-120, 1A-121, 1A-122, 1A-123, 1A-124; 1A'-1, 1A'-9, 1A'-10, 1A'-11, 1A' -13, 1A'-14, 1A'-16, 1A'-17, 1A'-21, 1A'-23, 1A'-34, 1A'-35, 1A'-36, 1A'-37, 1A' -54, 1A'-56, 1A'-59, 1A'-64, 1A'-65, 1A'-74, 1A'-76, 1A'-78, 1A'-79, 1A'-85, 1A' -86, 1A -87, 1A'-88, 1A'-89, 1A'-90, 1A'-91, 1A'-92, 1A'-94, 1A'-95, 1A'-96, 1A'-97, 1A' -98, 1A'-101, 1A'-104, 1A'-106, 1A'-107, 1A'-108, 1A'-109, 1A'-110, 1A'-111, 1A'-112, 1A'-113, 1A'-114, 1A'-115, 1A'-116, 1A'-117, 1A'-118, 1A'-119, 1A'-120, 1A'-121, 1A'-122, 1A'-123, 1A'-124; 1B-7, 1B-22, 1B-28, 1B-30, 1B-31, 1B-32, 1B-33, 1B-34, 1B-35, 1B-36, 1B-38, 1B-41, 1B-43, 1B-45, 1B-46, 1B-47, 1B-50, 1B- 51, 1B-52, 1B-53, 1B-54, 1B-55, 1B-56, 1B-57, 1B-59, 1B-60, 1B-61, 1B-63, 1B-64, 1B-65, 1B-66, 1B-67, 1B-69, 1B-70, 1B-72, 1B-73, 1B-75, 1B-76, 1B-78, 1B-79, 1B-80, 1B-81, 1B- 82, 1B-83, 1B-84, 1B-85, 1B-86, 1B-87, 1B-88, 1B-89, 1B-90, 1B-91, 1B-92, 1B-93, 1B-94, 1B-95, 1B-96, 1B-97, 1B-98, 1B-99, 1B-100, 1B-101, 1B-102, 1B-103, 1B-104, 1B-105, 1B-106, 1B- 107, 1B-108, 1B-109, 1B-110, 1B-111, 1B-112, 1B-115, 1B-116, 1B-117, 1B-118.

Claims (7)

a heterocyclic compound represented by the chemical formula (1), Or a salt thereof, wherein R ¹ and R ⁴ are the same or different and each represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R ² represents a substituted group; Or unsubstituted C _1-4 alkyl, R ³ represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and X represents C(=Y), CR ⁵ R ⁶ , NH, or NR ⁷ , Y represents oxygen or sulfur, R ⁵ and R ⁶ are the same or different, and each represents hydrogen, hydroxyl, thiol, halogen, C _1-4 alkyl, C _1-4 halogen Alkyl, C _1-4 alkoxy C _1-4 alkyl, C _1-4 haloalkoxy C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-8 Cycloalkyl, C _3-8 cycloalkyl C _1-4 alkyl, C _1-4 alkylcarbonyl, C _1-4 alkylcarbonyloxy, C _1-4 alkoxy, C _1-4 halo Oxyl, C _1-4 alkylthio, C _1-4 haloalkylthio, C _1-4 alkanesulfonyl, C _1-4 alkylsulfinyl, arylthio, arylsulfonyl, aromatic Sulfhydryl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C _1-4 alkyl, or substituted or unsubstituted aryl group, R ⁷ It shows C _1-4 alkyl, C _1-4 alkylcarbonyl, or C _1-4 alkoxy carbonyl group, and with The key represented is a single key or a double key. The heterocyclic compound of Claim 1 or a salt thereof, wherein R ¹ represents a substituted aryl group. A heterocyclic compound or a salt thereof according to claim 1 or 2, wherein R ³ represents a substituted aryl group. The heterocyclic compound or a salt thereof according to any one of claims 1 to 3, wherein R ⁴ represents a substituted or unsubstituted heteroaryl group. The heterocyclic compound or a salt thereof according to any one of claims 1 to 4, wherein R ⁴ is a substituted or unsubstituted pyridyl group. A pest controlling agent comprising the heterocyclic compound according to any one of claims 1 to 5 or a salt thereof. A fungicide comprising the heterocyclic compound or a salt thereof according to any one of claims 1 to 5.