JPH11292862A - Isoxazole compound its production and noxious organism-controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound which has an isoxazole ring having a heterocyclic group or the like as a substituent, and is useful as a noxious organism-controlling agent which has a certain effect, and allows safe use. SOLUTION: This compound is shown by formula I [A is a heterocyclic group, which can have nitro and so on as a substituent, such as triazole, or the like; B is a group such as one shown by formula II; R1 and R3 are each nitro or the like; R2 is H or the like; (m) is 0-3; R is H or the like]. 5-(2,6- Difluorophenyl)-4-(1-methyl-3-phenyl-1,2,4-triazol-5-yl)isoxazole, for example, is obtained by reacting a compound shown by formula III (R4 is H or the like; R5 is a 1-6C alkyl; R4 and R5 can form a 3-8C ring together) [e.g. 2,6-difluoro-β- dimethylamino-α-(1-methyl-3-phenyl-1,2,4-triazol-5-yl)acrylophenone] with hydroxylamine or a salt thereof (e.g. hydroxylamine hydrochloride).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel isoxazole compound, a process for producing the same, and a pesticidal agent.

[0002]

2. Description of the Related Art Conventionally, a large number of insecticides and acaricides have been used, but their efficacy is insufficient, their use is limited due to problems with drug resistance, and phytotoxicity to plants is hindered. In many cases, it is difficult to say that it is a satisfactory control agent because of its high toxicity to humans, fish, and the like. Therefore, there is a need for the development of a drug that can be used safely with few such disadvantages. Compounds having many isoxazole rings are known as compounds related to the present invention. However, there is no known compound having an insecticidal / miticidal activity among compounds in which a heterocyclic group or a phenyl group is substituted at the 4- and 5-positions of the isoxazole ring as in the present invention.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pesticidal agent which has a certain effect and can be used safely.

[0004]

According to the present invention, there is provided a compound represented by the general formula (1):

[0005]

Embedded image

Wherein A represents a heterocyclic group which may be substituted with G or a phenyl group which may be substituted with G, and G represents a nitro group, a cyano group, a halogen atom,
_1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-8 cycloalkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C
_2-6 alkenyloxy group, C _2-6 haloalkenyloxy group, C _1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylthio C _1-6 alkyl group, C _1-6 alkylsulfinyl C _1-6 Alkyl group, C _1-6 alkylsulfonyl C _1-6 alkyl group, tri C _1-6 alkylsilyl C _1-6 alkyl group, C _1-6 alkoxycarbonyl group, C _1-6 alkyl group A good phenyl C _1-6 alkyl group, a benzyloxy group optionally substituted with a halogen atom,
Naphthyl group, thienyl group, pyridyl group (optionally substituted with halogen atom, C _1-6 alkyl group or C _1-6 haloalkyl group), (nitro group, cyano group, halogen atom, C _1-6 alkyl group , C _1-6 haloalkyl group, C _1-6
Alkoxy group, methylenedioxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 alkylcarbonyl group, C _{1- 6} alkylamino group, which may be substituted with a diC _1-6 alkylamino group). G is C _3-4 bonded at adjacent substitution positions.
The alkylene group may form a 5- or 6-membered ring.

The heterocyclic group optionally substituted by W is selected from the group consisting of triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl and pyrimidinyl. It is the kind of group chosen. B
Is a phenyl group or a naphthyl group represented by the following formula

[0008]

Embedded image

[0009] (wherein, R ₁ is a nitro group, a cyano group, a halogen atom, C _1-6 alkyl groups, C _1-6 alkoxy group,
Represents a C _1-6 haloalkyl group or a C _1-6 haloalkoxy group, and R ₂ represents a hydrogen atom, a nitro group, a cyano group, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group,
_{Represents a 1-6} alkoxy group or a C _1-6 haloalkoxy group, and R ₃ represents a nitro group, a cyano group, a halogen atom,
_{Represents a 1-6} alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group or a C _1-6 haloalkoxy group, and m is
Represents 0, 1, 2 or 3. When m is 2 or more,
R ₃ may be the same or different. )

Alternatively, a heterocyclic group optionally substituted by W (W is a nitro group, a cyano group, a halogen atom, C _1-6
Alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group,
Represents C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 alkoxycarbonyl group or a phenyl group, a heterocyclic group, triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, It is a group selected from the group consisting of oxadiazolyl, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl and pyrazinyl. ). R is a hydrogen atom,
Represents a C _1-6 alkyl group or a C _1-6 alkoxycarbonyl group.

When the phenyl group or heterocyclic group of A and B has two or more substituents, the substituents G and W may be the same or different. ] The isoxazole compound represented by these.

Further, the present invention provides a compound represented by the following general formula (2):

[0013]

Embedded image

Wherein A and B have the same meanings as described above, R ₄ represents a hydrogen atom or a C _1-6 alkyl group, and R ₅ represents a C _1-6 alkyl group. R ₄ and R
₅ may form a ring together. Wherein the compound represented by the general formula (1 ′) is reacted with hydroxylamine or a salt thereof.

[0015]

Embedded image

(Wherein A and B have the same meanings as described above).

Further, the present invention is a pesticidal composition comprising one or more of the compounds represented by the general formula (1) as an active ingredient.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compound of the present invention will be described in detail. The present invention is characterized in that it contains, as an active ingredient, a compound represented by the general formula (1), a production method thereof, and one or more compounds represented by the general formula (1) as described above. It is a pesticide.

In the general formula (1), A represents a heterocyclic group which may be substituted with G or a phenyl group which may be substituted with G;

G represents a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
C _1-6 alkyl groups such as ec-butyl, t-butyl, pentyl, hexyl, etc.

Ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-
A C _2-6 alkenyl group such as pentenyl, 1-methyl-2-propenyl, 1-methyl-2-butenyl, ethynyl,
1-propynyl, 1-butynyl, 2-propynyl, 2-
A C _2-6 alkynyl group such as pentynyl,

C _3-8 cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl, fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, fluorochloromethyl, difluorochloromethyl, trichloromethyl, C _1-6 haloalkyl groups such as bromomethyl, 2,2,2-trifluoroethyl (hereinafter, simply referred to as “trifluoroethyl”), pentafluoroethyl and the like;

C _1-6 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, and C _1-6 such as trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like. _1-6 haloalkoxy group, vinyloxy, 1-propenyloxy, C _2-6 alkenyloxy groups such as 2-propenyloxy,

1-chlorovinyloxy, 2-chlorovinyloxy, 3-chloroallyloxy, 3,3-dichloroallyloxy, 1-fluorovinyloxy, 2-fluorovinyloxy, 2,2-difluorovinyloxy and the like A C _2-6 haloalkenyloxy group,

Methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl,
C _1-6 alkoxy C _1-6 alkyl group such as butoxymethyl, C _1-6 alkylthio C _1-6 of methylthiomethyl, ethylthiomethyl, methylthioethyl, propyl thio methyl, isopropylthio methyl, butyl thiomethyl
Alkyl group,

Methylsulfinylmethyl, ethylsulfinylmethyl, methylsulfinylethyl, propylsulfinylmethyl, isopropylsulfinylmethyl,
Butyl sulfinyl C _1-6 alkylsulfinyl C _1-6 alkyl group such as methyl, methylsulfonylmethyl, ethylsulfonyl methyl, methylsulfonyl ethyl, propyl sulfonyl methyl, isopropyl sulfonyl methyl, C _1-6 alkylsulfonyl C such butylsulfonyl methyl _1-6 alkyl group,

Tri-C _1-6 alkylsilyl C _1-6 alkyl groups such as trimethylsilylmethyl, trimethylsilylethyl, triethylsilylmethyl, methoxycarbonyl,
C _1-6 alkoxycarbonyl groups such as ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl,

A phenyl C _1-6 alkyl group which may be substituted with a C _1-6 alkyl group such as benzyl, phenethyl, α-methylbenzyl, α, α-dimethylbenzyl, etc .; Chlorine, bromine, benzyloxy group optionally substituted with a halogen atom such as iodine,

Naphthyl groups such as 1-naphthyl and 2-naphthyl; thienyl groups such as 2-thienyl and 3-thienyl;

Any position of the pyridine ring is a halogen atom,
Pyridyl groups such as 2-pyridyl, 3-pyridyl and 4-pyridyl which may be substituted with a C _1-6 alkyl group or a C _1-6 haloalkyl group;

[0031] Alternatively, any position nitro group on the benzene ring, cyano group, halogen atom, C _1-6 alkyl groups, C
_1-6 haloalkyl group, C _1-6 alkoxy group, a methylenedioxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl groups, C _1-6 alkylcarbonyl group, a C _1-6 alkylamino group, a phenyl group optionally substituted by di-C _1-6 alkylamino group.

Here, the C _1-6 alkylamino group includes methylamino, ethylamino, propylamino, isopropylamino, butylamino and the like, and the di-C _1-6 alkylamino group includes dimethylamino, diethylamino, ethyl Isopropylamino, dipropylamino and the like can be mentioned.

G may form a 5- or 6-membered ring by a C _3-4 alkylene group such as propylene and butylene bonded at adjacent substitution positions. Examples of the heterocycle constituting G include benzothiazole, thionaphthene, benzimidazole, benzopyrazole, benzoxazole, quinoxaline, phthalazine, cinnoline, quinazoline, quinoline, and isoquinoline.

Of these, G is a C _1-6 alkyl group, C
_3-8 cycloalkyl group, halogen atom, pyridyl group optionally substituted by C _1-6 alkyl group or C _1-6 haloalkyl group, nitro group, cyano group, halogen atom, C
_1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, methylenedioxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _{1 -6} alkylsulfonyl group, C _1-6 alkylcarbonyl group, C _1-6 alkylamino group, di C _1-6 alkylamino phenyl group which may be substituted with group is more preferable.

The heterocyclic group optionally substituted with G is
Triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl,
It is a group selected from the group consisting of tetrazolyl, oxadiazolyl, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl and pyrazinyl.

More preferred heterocyclic groups include 1,2,2
4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl,
1,3,4-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5
-Yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, oxazol-2-yl,
Oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3
-Yl, isothiazol-4-yl, isothiazol-
5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5 Yl, tetrazol-5-yl, 1,2,4-oxadiazole-3
-Yl, 1,2,4-oxadiazol-5-yl,
1,3,4-oxadiazol-2-yl, 1,2,3
-Oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,5-oxadiazole-
3-yl, 1,2,4-thiadiazol-3-yl,
1,2,4-thiadiazol-5-yl, 1,3,4-
Thiadiazol-2-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,5-thiadiazol-3-yl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl,
4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl,
5-pyrimidinyl and the like can be illustrated.

Of these, 1,2,4-triazole-
1-yl, 1,2,4-triazol-3-yl, 1,
Triazolyl groups such as 2,4-triazol-5-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-4-yl and 1,2,3-triazol-5-yl; Thiazolyl groups such as thiazol-2-yl, thiazol-4-yl and thiazol-5-yl, pyrazol-1-yl, pyrazol-3-yl and pyrazol-4
Pyrazolyl groups such as -yl and pyrazol-5-yl; and 1,2,4-thiadiazol-3-yl, 1,2,4-
Thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,2
Thiadiazolyl groups such as 5-thiadiazol-3-yl are more preferred.

B represents a phenyl group, a naphthyl group or a heterocyclic group which may be substituted by W,

R ₁ represents a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
C _1-6 alkyl groups such as ec-butyl, t-butyl, pentyl, hexyl, methoxy, ethoxy, propoxy,
C _1-6 such as isopropoxy, butoxy and t-butoxy
An alkoxy group,

Fluoromethyl, 1-fluoroethyl, 2
- fluoroethyl, difluoromethyl, trifluoromethyl, fluoro chloro, difluoromethyl chloromethyl, trichloromethyl, bromomethyl, trifluoroethyl, C _1-6 haloalkyl groups such as pentafluoroethyl,

Trifluoromethoxy, 1,1,2,2-
Represents a C _1-6 haloalkoxy group such as tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like.

R ₂ represents a hydrogen atom, a nitro group, a cyano group,
Halogen atoms such as fluorine, chlorine, bromine and iodine, C _1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, fluoromethyl, 1-fluoro Ethyl, 2-fluoroethyl, difluoromethyl,
C _1-6 such as trifluoromethyl, fluorochloromethyl, difluorochloromethyl, trichloromethyl, bromomethyl, trifluoroethyl and pentafluoroethyl
Haloalkyl group, C _1-6 alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, or trifluoromethoxy, 1,1,2,2
Represents a C _1-6 haloalkoxy group such as 2-tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like.

R ₃ represents a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
C _1-6 alkyl groups such as ec-butyl, t-butyl, pentyl, hexyl, methoxy, ethoxy, propoxy,
C _1-6 such as isopropoxy, butoxy and t-butoxy
An alkoxy group,

Fluoromethyl, 1-fluoroethyl, 2
- fluoroethyl, difluoromethyl, trifluoromethyl, fluoro chloro, difluoromethyl chloromethyl, trichloromethyl, bromomethyl, trifluoroethyl, C _1-6 haloalkyl groups such as pentafluoroethyl,

Trifluoromethoxy, 1,1,2,2-
Represents a C _1-6 haloalkoxy group such as tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like.

M represents 0, 1, 2, or 3;
In the above, R ₃ may be the same or different.

W represents a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
C _1-6 alkyl groups such as ec-butyl, t-butyl, pentyl, hexyl, methoxy, ethoxy, propoxy,
C _1-6 such as isopropoxy, butoxy and t-butoxy
An alkoxy group,

Fluoromethyl, 1-fluoroethyl, 2
- fluoroethyl, difluoromethyl, trifluoromethyl, fluoro chloro, difluoromethyl chloromethyl, trichloromethyl, bromomethyl, trifluoroethyl, C _1-6 haloalkyl groups such as pentafluoroethyl,

Trifluoromethoxy, 1,1,2,2-
Represents a C _1-6 haloalkoxy group such as tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like.

The methylthiomethyl, ethylthiomethyl, methylthioethyl, propyl thio methyl, isopropyl thiomethyl, C _1-6 alkylthio C _1-6 alkyl group such as butyl thiomethyl,

Methylsulfinylmethyl, ethylsulfinylmethyl, methylsulfinylethyl, propylsulfinylmethyl, isopropylsulfinylmethyl,
Butyl sulfinyl C _1-6 alkylsulfinyl C _1-6 alkyl group such as methyl, methylsulfonylmethyl, ethylsulfonyl methyl, methylsulfonyl ethyl, propyl sulfonyl methyl, isopropyl sulfonyl methyl, C _1-6 alkylsulfonyl C such butylsulfonyl methyl _1-6 alkyl group, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, represent a C _1-6 alkoxycarbonyl group or a phenyl group, such as t- butoxycarbonyl.

The heterocyclic group which may be substituted by W includes triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl and pyrazinyl. It is a kind of group selected from the group consisting of: ).

More preferred heterocyclic groups include 1,2,2
4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,3,4-triazol-2-yl,
1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, oxazol-2-yl, oxazole- 4-yl, oxazole-
5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-3- Yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidazol-
5-yl, tetrazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2- Yl, 1,2,3-oxadiazol-4-yl, 1,
2,3-oxadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,2
3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,5-thiadiazol-3-
Yl, 2-thienyl, 3-thienyl, 2-furyl, 3-
Furyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl,
3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-
Pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 3
-Pyrazinyl and the like.

Of these, pyrazolyl groups such as pyrazol-3-yl, pyrazol-4-yl and pyrazol-5-yl are more preferred.

In the compound of the present invention, when the phenyl group or the heterocyclic group of A and B has two or more substituents, the substituents G and W may be the same or different.

Preferred examples of the compound of the present invention include:
Examples are shown in Tables, Tables 2 and 3.

[0057]

[Table 1001]

[0058]

[Table 1002]

[0059]

[Table 1003]

[0060]

[Table 1004]

[0061]

[Table 1005]

[0062]

[Table 1006]

[0063]

[Table 1007]

[0064]

[Table 1008]

[0065]

[Table 1009]

[0066]

[Table 1010]

[0067]

[Table 1011]

[0068]

[Table 1012]

[0069]

[Table 1013]

[0070]

[Table 1014]

[0071]

[Table 1015]

[0072]

[Table 1016]

[0073]

[Table 1017]

[0074]

[Table 1018]

[0075]

[Table 1019]

[0076]

[Table 1020]

[0077]

[Table 1021]

[0078]

[Table 1022]

[0079]

[Table 2001]

[0080]

[Table 2002]

[0081]

[Table 2003]

[0082]

[Table 2004]

[0083]

[Table 2005]

[0084]

[Table 2006]

[0085]

[Table 2007]

[0086]

[Table 2008]

[0087]

[Table 2009]

[0088]

[Table 2010]

[0089]

[Table 2011]

[0090]

[Table 2012]

[0091]

[Table 2013]

[0092]

[Table 2014]

[0093]

[Table 2015]

[0094]

[Table 2016]

[0095]

[Table 2017]

[0096]

[Table 2018]

[0097]

[Table 2019]

[0098]

[Table 2020]

[0099]

[Table 2021]

[0100]

[Table 2022]

[0101]

[Table 301]

[0102]

[Table 302]

[0103]

[Table 303]

[0104]

[Table 304]

[0105]

[Table 305]

[0106]

[Table 306]

[0107]

[Table 307]

[0108]

[Table 308]

The compound of the present invention can be produced by the following method. (1) Method for producing compound in which R is a hydrogen atom

[0110]

Embedded image

(Wherein, A, B, R ₄ and R ₅ have the same meanings as described above. Further, even when R ₄ and R ₅ together form a 3- to 7-membered ring, Good.)

That is, the compound represented by the formula (2)
The compound represented by the formula (1) can be obtained by reacting hydroxylamine or a salt thereof.
The reaction includes alcohols such as methanol, ethanol, and 2-methoxyethanol; hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; N, N-dimethylformamide (DMF); Quicide (DMS
O), in a solvent such as hexamethylphosphoramide (HMPA) at a temperature from 0 ° C. to the boiling point of the solvent used,
It takes several minutes to several tens of hours. Examples of the hydroxylamine salt used in the reaction include hydrochloride, sulfate, and oxalate. Also, if desired, p
-A catalyst such as toluenesulfonic acid, sulfuric acid, Lewis acid and the like may be added.

The compound represented by the general formula (2) is
It can be produced by the following method (a) or (b).

[0114]

Embedded image

(Wherein A, B, R ₄ and R ₅ have the same meanings as described above. R ₆ is an alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy group, dimethylamino, diethylamino, A dialkylamino group such as a dipropylamino group, a halogen atom such as fluorine, chlorine, or bromine, or a leaving group such as an imidazolyl group; R ₇ represents a lower alkyl group such as a methyl, ethyl, or propyl group; , Methoxy, ethoxy, propoxy, isopropoxy, alkoxy groups such as butoxy or mono- or dimethylamino, diethylamino,
Represents a dialkylamino group such as a dipropylamino group. Hal represents a halogen atom. Also, R ₄
And R ₅ may together form a ring having 3 to 8 carbon atoms. )

[Production method (a)] First, compound (3) and compound (4) are reacted in the presence of a base to give compound (5). This reaction involves the reaction of hydrocarbons such as benzene, toluene, and xylene, diethyl ether,
Using a base such as sodium hydride, butyllithium, diisobutyllithium amide, sodium or potassium alkoxide, or a trialkylamine such as triethylamine in a solvent such as an ether such as tetrahydrofuran (THF) at -78 ° C. The reaction is carried out at a temperature up to the boiling point for several minutes to several tens of hours.

Next, compound (2) can be obtained by reacting compound (5) with compound (6). This reaction is carried out in a solvent such as hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether and THF, a solvent such as DMF, DMSO and HMPA at a temperature from 0 ° C. to the boiling point of the solvent used for a few minutes. It takes several tens of hours.

[Production method (b)] The compound (7) can be obtained by reacting the compound (3) with the compound (6). This reaction is carried out at 0 ° C. in a hydrocarbon such as benzene, toluene and xylene, an ether such as diethyl ether and THF, a halogenated hydrocarbon such as chloroform and dichloromethane, a solvent such as DMF, DMSO and HMPA. At temperatures up to the boiling point of the solvent,
It takes several minutes to several tens of hours.

Next, compound (2) can be obtained by reacting compound (7) with compound (8) in the presence of a base. This reaction is carried out using hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether and THF, halogenated hydrocarbons such as chloroform and dichloromethane, DMF, DM
In a solvent such as SO or HMPA, using a base such as sodium hydride or a trialkylamine such as triethylamine, at a temperature from -20 ° C to the boiling point of the solvent used,
It takes several minutes to several tens of hours.

The compound (5) has keto-type and enol-type tautomers, and the compound (2) and the compound (7) may have cis and trans geometric isomers. All of these isomers can be used for producing the compound of the present invention.

(2) R is a C _1-6 alkyl group or C
Preparation of compound having _1-6 alkoxycarbonyl group (A
Is a 1,2,4-triazole group)

[0122]

Embedded image

(Wherein B represents the same meaning as described above,
Represents a C _1-6 alkyl group or a C _1-6 alkoxycarbonyl group. )

The 4-cyanoisoxazole represented by the formula (c) can be obtained by reacting an acylacetonitrile represented by the formula (a) with a substituted nitrile oxide represented by the formula (b). . The reaction is carried out in a solvent such as halogenated hydrocarbons such as chloroform, dichloromethane and carbon tetrachloride, hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether and THF, and alcohols such as methanol and ethanol. ° C
To a boiling point of the solvent used.

[0125]

Embedded image

[Wherein B has the same meaning as described above;
_Represents a C _1-6 alkyl group or a C _1-6 alkoxycarbonyl group, and X and Z each independently represent a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy C
_1-6 alkyl group, C _1-6 alkylthio C _1-6 alkyl group, tri C _1-6 alkylsilyl C _1-6 alkyl group or (nitro group, cyano group, halogen atom, C _1-6 alkyl group, _1-6 haloalkyl group, C _1-6 alkoxy group, C
_1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6
Alkylsulfinyl group, a C _1-6 alkylsulfonyl group, C _1-6 alkylcarbonyl group, a di C _1-6 alkylamino group, may be substituted by C _1-6 alkylamino group) phenyl group. Ts represents a p-methylphenylsulfonyl group. ]

The compound represented by the formula (e) can be obtained by reacting the compound represented by the formula (c) with imidoyl chloride represented by the formula (d). In the reaction, 1 mol of the compound represented by the formula (c) and 0.5 to 2.0 mol of imidoyl chloride represented by the formula (d)
In the presence of 0.5 to 2.0 moles of a Lewis acid such as aluminum chloride, stannic chloride, zinc chloride, chlorobenzene, o-dichlorobenzene, dichloromethane, 1,2-
It is performed in a solvent such as dichloroethane. The reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent used.

After completion of the reaction, the desired product can be obtained by performing ordinary post-treatments. The structure of the compound of the present invention was determined from IR, NMR, MS and the like.

(Pest Control Agent) The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests and the like.
Has larvicidal and ovicidal effects. The following are typical examples.

Lepidopteran pests, for example, Spodoptera litura, armyworm, Tamanayaga, green caterpillar, Tamanaginiwaba, Konaga, chanokokakumamonhamaki, chahamaki, peach shiniga, ashihimeshingui, mikanhamoguriga, chanhohosogai, kimmonhogaogomiga, kimmonhoganogomiga, maimonhoganogomiga, maimonhoganogomiga. , Genus Pterodactyla, Hemophilus, Heliotis, Helicoverpa, Agrotis, iga, codling moth, cotton beetle and the like.

Hemiptera pests, for example, peach aphid, cotton aphid, cotton aphid, wheat aphid, pygmy beetle, blue stag beetle, lycopodium mosquito, mulberry mosquito, psyllid whitefly, tobacco whitefly, and whitefly , Brown planthopper, brown planthopper, sage brown planthopper, leafhopper, etc.

Coleoptera pests, for example, Lepidoptera, Chrysomelidae, Colorado potato beetle, rice weevil, rice weevil, adzuki beetle, beetle, beetle, beetle, diabrotica, tobacco beetle, fly beetle, pine beetle, beetle beetle , Kokunusto, cotton weevil and the like.

Diptera pests, for example, house flies, smelt flies, sentinia flies, sea flies, mandarin flies,
Botfly, rice leaf fly, Drosophila melanogaster, sand flies, Culex pipiens, Aedes aegypti, Shina anopheles etc. Thysanoptera pests, for example, Thrips palmi, Thrips palmi, and the like. Hymenopteran pests, for example, house ants, hornets, wasps and the like. Orthoptera pests, for example, German cockroaches, cockroaches, black cockroaches, tosama grasshoppers and the like.

[0134] Isoptera pests, for example, house termites and mountain termites. Lepidopterous insects, for example, human fleas, louse pests, for example, human lice, mites, for example, spider mite, Kanzawa spider mite, mandarin spider mite, apple spider mite, citrus red mite, apple rust mite, chanohomori mite, brevipalpas, eotetranicus, robinne mite, scutellidae, Dermatophagoides farinae, Oxodid tick, Haemaphysalis longicornis and the like. Plant parasitic nematodes, for example,
Sweet potato nematode, nematode nematode, soybean cyst nematode, rice singing nematode, pine wood nematode and the like.

[0135] In recent years, Conaga, Planthopper, Leafhopper,
Many insect pests and spider mites, such as aphids, have developed resistance to organophosphates, carbamates and acaricides, causing a problem of insufficient efficacy of these drugs. Is desired. The compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against not only susceptible strains but also pests of organophosphorus, carbamate or pyrethroid-resistant strains and mites of acaricide-resistant strains.

The compound of the present invention is a highly safe drug having little phytotoxicity, low toxicity to fish poisons and warm-blooded animals. Also,
The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contact substances such as ship bottoms and fish nets.

When the thus-obtained compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be used in the form of a general pesticide for use as a pesticide. That is, they can be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like.

When a solid agent is intended as an additive or carrier, a vegetable powder such as soybean grains and flour; a mineral fine powder such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc. Organic and inorganic compounds such as sodium benzoate, urea, sodium sulfate are used.

For liquid dosage forms, petroleum fractions such as kerosene, xylene and solvent naphtha,
Cyclohexane, cyclohexanone, DMF, DMS
O, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water and the like are used as solvents.

In order to obtain a uniform and stable form in these preparations, a surfactant may be added, if necessary. Although there is no particular limitation on the surfactant, for example, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, sorbitan to which polyoxyethylene is added Nonionic surfactants such as higher fatty acid esters, tristyryl phenyl ether to which polyoxyethylene is added, sulfate salts of alkyl phenyl ether to which polyoxyethylene is added, alkyl benzene sulfonates, sulfate salts of higher alcohols, and alkyl Naphthalene sulfonate, polycarboxylate, lignin sulfonate,
Examples thereof include a formaldehyde condensate of an alkylnaphthalene sulfonate and a copolymer of isobutylene-maleic anhydride.

The amount of the active ingredient is preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight. The wettable powders, emulsions, suspensions, and flowables thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the powders and granules are sprayed on the plant as it is. used.

Needless to say, the compound of the present invention is sufficiently effective alone, but it can also be used as a mixture with one or more of various fungicides, pesticides or synergists. .

Representative examples of fungicides, insecticides, acaricides, and plant growth regulators which can be used by mixing with the compound of the present invention are shown below.

Fungicides: captan, folpet, thiuram, ziram, zineb, maneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintosen, captaphor, iprodione, prosimidon, vinclozolin, fluoroimide, thymoxanil, mepronil, flutranil, pencyclon, oxyn Carboxin, fosetyl aluminum, propamocarb, triadimefon, triadimenol, propiconazole, diclobutrazole, bitertanol, hexaconazole,
Microbutanil, flusilazole, etaconazole,
Fluotrimazole, flutriafene, benconazole, diconazole, cyproconazoles, fenarimol, triflumizole, prochloraz, imazalil,
Perfurazoate, tridemorph, fenpropimorph,
Triforine, butiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl,
Furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, himexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyl hydroxide Tin, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepanipyrim, fermzone, triclamide, metasulfocarb, fluazinam, ethinolac, etoquinomorph Pyroquilon, Teclophthalam, Fusalide, Phenazine oxide, Thiabendazole, Tricycla Lumpur, vinclozolin, cymoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid.

Pest control agents: organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiomethon,
Hosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, flatiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb and the like.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propmethrin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, ethtoline Fenprox, cycloprothrin, trolametrin, silafluofen, profenprox, acrinatrine and the like.

Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiu Ron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap, thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic virus.

Nematicides: fenamiphos, phosthiazate and the like.

Acaricides: chlorbenzylate, phenisobromolate, dicophor, amitraz, BPPS, benzomate, hexithiax, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate , Tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like.

Plant growth regulators: gibberellins (eg, gibberellin A ₃ , gibberellin A ₄ , gibberellin A ₇ ), I
AA, NAA, etc.

[0151]

EXAMPLES Next, the compounds of the present invention will be described more specifically with reference to Reference Examples and Examples.

Reference Example 1 Production of 2,6-difluoro-α- (1-methyl-3-phenyl-1,2,4-triazol-5-yl) acetophenone

[0153]

Embedded image

7.95 ml of a 1.6 M n-butyllithium-hexane solution and 1.78 m of diisopropylamine
of lithium diisopropylamide (LDA) prepared from a 20 ml solution of TMF in 1 ml of 1,5-dimethyl-3-phenyl-1,2,4-triazole in 2 g of THF10.
The resulting solution was added dropwise to the resulting solution at -78 ° C and stirred at the same temperature for 30 minutes. There, methyl 2,6-difluorobenzoate 2.1
9 g of a THF (10 ml) solution was added dropwise at −78 ° C., and after the completion of the addition, the temperature was gradually returned to room temperature and left overnight. After pouring the reaction solution into 100 ml of ice water, the crystals obtained by neutralizing with concentrated hydrochloric acid were filtered to obtain 1.9 g of the target compound. Yield 60
%

Reference Example 2 2,6-difluoro-β-dimethylamino-α- (1-
Methyl-3-phenyl-1,2,4-triazole-5
-Il) Production of acrylophenone

[0156]

Embedded image

2,6-difluoro-α- (1-methyl-
3-phenyl-1,2,4-triazol-5-yl)
To a solution of 1 g of acetophenone in 10 ml of toluene,
-Dimethylformamide dimethyl acetal 1.22 m
and heated to reflux for 2 hours. After the reaction solution was concentrated under reduced pressure, it was crystallized from ethanol to obtain 1.16 g of the desired compound. 87% yield

Example 1 5- (2,6-difluorophenyl) -4- (1-methyl-3-phenyl-1,2,4-triazol-5-yl) isoxazole (compound No. 4-1) Manufacture

[0159]

Embedded image

To a solution of 1.15 g of 2,6-difluoro-β-dimethylamino-α- (1-methyl-3-phenyl-1,2,4-triazol-5-yl) acrylophenone in 17 ml of ethanol was added hydrochloric acid. Hydroxylamine
26 g and a small amount of p-toluenesulfonic acid were added, and the mixture was heated under reflux for 4 hours. The residue obtained by concentrating the reaction solution under reduced pressure was partitioned between chloroform and water, and the organic layer was concentrated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (ethyl acetate / n-hexane = 5/95) to obtain 0.91 g of the desired compound. Yield 88% mp.
138-140 ° C

Reference Example 3 Production of 2- (2-dimethylaminovinyl) -4-phenylthiazole

[0162]

Embedded image

3 g of 2-methyl-4-phenylthiazole
And t-butoxybis (dimethylamino) methane 8.82
The solution was heated to reflux at 130 ° C. for 6 hours in 6 ml of DMF. The reaction solution was concentrated under reduced pressure to obtain 4.62 g of a residue containing the target compound. Used for the next reaction without purification.

Reference Example 4 Production of 2-chloro-β-dimethylamino-α- (4-phenylthiazol-2-yl) acrylophenone

[0165]

Embedded image

4.62 g of the residue containing 2- (2-dimethylaminovinyl) -4-phenylthiazole obtained in Reference Example 3 was dissolved in 30 ml of diethyl ether, and 2.64 g of triethylamine and 2- After 3 g of chlorobenzoyl chloride was sequentially added, the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to obtain 6.91 g of a residue containing the target compound. Used for the next reaction without purification.

Example 2 5- (2-chlorophenyl) -4- (4-phenylthiazol-2-yl) isoxazole (compound No. 4-
9) Manufacturing

[0168]

Embedded image

To a solution of 6.91 g of the residue containing 2-chloro-β-dimethylamino-α- (4-phenylthiazol-2-yl) acrylophenone obtained in Reference Example 4 in 60 ml of ethanol, hydroxylamine hydrochloride was added. 1.80g
And a small amount of p-toluenesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The residue obtained by concentrating the reaction solution under reduced pressure was partitioned between chloroform and water, and the organic layer was concentrated under reduced pressure. The resulting mixture was subjected to silica gel column chromatography (ethyl acetate / n-hexane = 20/80 and n-hexane /
(Benzene = 20/80) to give the target compound 1.82.
g was obtained. T of three steps of Reference Example 3, Reference Example 4, and Example 2
otal yield 20% n _D ^23.5 1.6613

Example 3 1) 5- [2- (5-Chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -2-oxoethyl] -1-methyl-3-phenyl-1,2 Of 4,4-triazole (iii)

[0171]

Embedded image

An n-butyllithium-hexane solution (1.
6M) 4.21 ml and diisopropylamine 0.94
Lithium diisopropylamide (LDA) prepared from a 13 ml solution of THF was added dropwise at −78 ° C. to 7 ml of a THF solution of 1.06 g of 1,5-dimethyl-3-phenyl-1,2,4-triazole (i). Then, the mixture was stirred as it was for 30 minutes. To this reaction mixture, a THF solution (7 ml) of 1.64 g of 5-chloro-4-methoxycarbonyl-1-methyl-3-trifluoromethylpyrazole (ii) was added dropwise at -78 ° C, and the temperature was gradually raised to room temperature. And stirred overnight at room temperature. The reaction solution was poured into 100 ml of ice water, the whole was neutralized with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration to obtain 1.49 g (yield: 63%) of the title compound (iii).

2) 5- [2- (5-Chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -1
-Dimethylaminomethylene-2-oxoethyl] -1-
Methyl-3-phenyl-1,2,4-triazole (i
v) Manufacturing

[0174]

Embedded image

Compound (iii) 1.49 obtained above
1.3 ml of N, N-dimethylformamide dimethyl acetal was added to a solution of g of toluene in 15 ml, and the mixture was refluxed for 5 hours. After the reaction solution was concentrated under reduced pressure, ethanol was added to the residue, and the precipitated crystals were collected by filtration to give the title compound (i
v) 1.49 g (88% yield) were obtained.

3) 5- (5-Chloro-1-methyl-3-)
Trifluoromethylpyrazol-4-yl) -4- (1
-Methyl-3-phenyl-1,2,4-triazole-
5-yl) isoxazole (v, compound number 5-1)
Manufacturing of

[0177]

Embedded image

To a solution of 1.39 g of the compound (iv) obtained above in 14 ml of ethanol was added 0.3% of hydroxylamine hydrochloride.
26 g and a catalytic amount of p-toluenesulfonic acid were added, and the whole was heated under reflux for 3 hours. After completion of the reaction, chloroform and water were added to the residue obtained by concentrating the reaction solution under reduced pressure, liquid separation was performed, the organic layer was separated, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate / n-hexane = 40/60) to obtain 0.78 g (yield: 60%) of the title compound (v). mp. 118-119 ° C

Reference Example 5 2-fluoro-α- (4-tert-butylphenyl)
Synthesis of acetophenone

[0180]

Embedded image

Under a nitrogen stream, 0.04 g of tris (dibenzylideneacetone) dipalladium chloroform adduct,
(R)-(+)-2,2'-bis (di-p-tolylphosphino) -1,1'-binaphthyl [(R) -Tol-B
INAP] 0.07 g, and sodium tert-
0.34 g of butoxide was placed in a 100 ml flask, 20 ml of THF was poured into the flask, and 1-bromo-4-t was further added.
0.58 g of tert-butylbenzene and 0.44 g of o-fluoroacetophenone were added, and the mixture was stirred at 70 ° C. for 8 hours. After completion of the reaction, diethyl ether was added to the reaction solution, and the mixture was washed with water. The organic layer was separated, and the solvent was distilled off under reduced pressure. The obtained residue was subjected to silica gel column chromatography (ethyl acetate / n-hexane = 2/98). And eluted by continuously changing the mixture ratio of ethyl acetate and n-hexane so that ethyl acetate / n-hexane = 10/90.) To obtain 0.36 g of the desired compound. (Yield 49%)

Example 4 4- (4-tert-butylphenyl) -5- (2-fluorophenyl) isoxazole (Compound No. 4-1)
5) Manufacturing

[0183]

Embedded image

In Reference Example 2, 0.36 g of 2-fluoro-α- (4-tert-butylphenyl) acetophenone was added.
After the same treatment as in Example 1, the resulting mixture was subjected to silica gel column chromatography (ethyl acetate / n
-Hexane = 5/95) to give the desired compound 0.3
5 g were obtained. (89% yield)

Reference Example 6 2- [2- (5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -2-oxoethyl]
Synthesis of -4- (2,6-difluorophenyl) thiazole

[0186]

Embedded image

To a solution of 0.5 g of 2-methyl-4- (2,6-difluorophenyl) thiazole in 5 ml of THF was added:
1.6 M n-butyllithium-n hexane solution 1.8
ml was added dropwise at -78 ° C. After stirring at the same temperature for 1 hour, 0.68 g of 5-chloro-4-methoxycarbonyl-1-methyl-3-trifluoromethylpyrazole was added.
A 7 ml solution of HF was added dropwise, and the reaction solution was returned to room temperature and further stirred for 1 hour. Pour the reaction solution into water, separate the organic layer,
The residue obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (ethyl acetate / n-hexane = 5/9).
Purification was performed in 5) to obtain 0.4 g of the desired compound. (Yield 9
1%)

Example 5 5- (5-Chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -4- [4- (2,6-difluorophenyl) thiazol-2-yl] isoxazole Production of (Compound No. 5-21)

[0189]

Embedded image

2- [2- (5-chloro-1-methyl-3)
-Trifluoromethylpyrazol-4-yl) -2-oxoethyl] -4- (2,6-difluorophenyl) thiazole was obtained after treating 0.4 g in the same manner as in Reference Example 2 and Example 1. The mixture was subjected to silica gel column chromatography (ethyl acetate / n-hexane = 5/9).
Purification was performed in 5) to obtain 0.2 g (yield 47%) of the target compound.

Reference Example 7 4- [2- (5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -2-oxoethyl]
Synthesis of -tert-butylbenzene

[0192]

Embedded image

4-tert-butylbenzylbromide prepared from 4.34 g and magnesium 0.46 g
To a solution of tert-butylbenzylmagnesium bromide in 10 ml of diethyl ether was added 5-chloro-4-cyano-1-methyl-3-trifluoromethylpyrazole.
A solution of 0 g in 3 ml of diethyl ether was added dropwise at -78 ° C, and after completion of the addition, the mixture was allowed to stand at room temperature overnight. After pouring the reaction solution into water, concentrated hydrochloric acid was added to dissolve insolubles. The organic layer was separated, and the residue obtained by evaporating the solvent under reduced pressure was subjected to silica gel column chromatography (ethyl acetate / n-hexane =
精製) to obtain 1.48 g of the target compound.
(86% yield)

Example 6 4- (4-tert-butylphenyl) -5- (5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) isoxazole (Compound No. 5-23)
Manufacturing of

[0195]

Embedded image

4- [2- (5-chloro-1-methyl-3)
-Trifluoromethylpyrazol-4-yl) -2-oxoethyl] -tert-butylbenzene (1.34 g) was treated in the same manner as in Reference Example 2 and Example 1, and the resulting mixture was subjected to silica gel column chromatography (acetic acid). The residue was purified by ethyl / n-hexane = 1/4) to obtain 1.20 g (yield: 82%) of the target compound.

Reference Example 8 1- [2- (5-Chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -2-oxoethyl]
Synthesis of -3- (2,6-difluorophenyl) pyrazole

[0198]

Embedded image

0.5 g of 3- (2,6-difluorophenyl) pyrazole and 4-bromoacetyl-5-chloro-1
1.0 g of methyl-3-trifluoromethylpyrazole
With acetonitrile 10m together with potassium carbonate 0.3g
Heated to reflux for 1 hour. After concentrating the reaction solution, the mixture was diluted with ethyl acetate, and the mixture obtained by concentrating the organic layer was subjected to silica gel column chromatography (ethyl acetate / n-ethyl acetate).
Hexane = 1/1) and 0.36 g of the desired compound
I got (Yield 32%)

Example 7 5- (5-Chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -4- [3- (2,6-difluorophenyl) pyrazol-1-yl] isoxazole Production of (Compound No. 5-24)

[0201]

Embedded image

1- [2- (5-chloro-1-methyl-3)
-Trifluoromethylpyrazol-4-yl) -2-oxoethyl] -3- (2,6-difluorophenyl) pyrazole 0.32 g was treated in the same manner as in Reference Example 2 and Example 1, and the resulting mixture was treated with The residue was purified by silica gel column chromatography (ethyl acetate / n-hexane = 1/1) to obtain 0.15 g of the desired compound. (Yield 40
%)

The compounds of the present invention produced, including the above Examples, are shown in Tables 4 and 5.

[0204]

[Table 401]

[0205]

[Table 402]

[0206]

[Table 501]

[0207]

[Table 502]

[0208]

[Table 503]

In the above table, compound numbers 4-8, 4-13,
4-14, 5-17, 5-19, 5-23 and 5-2
The ¹ H-NMR data of ^No. 4 is shown in Table 6 below.

[0210]

[Table 6]

(Pest control agent) Next, some examples of the composition of the present invention will be described. However, the additives and the ratio of addition are not limited to these examples, and can be varied over a wide range. It is possible. Parts in Formulation Examples represent parts by weight.

Example 8 Water-dispersible powder 40 parts of the compound of the present invention 53 parts of diatomaceous earth 4 parts of higher alcohol sulfate ester 3 parts of alkylnaphthalene sulfonate If the above are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

Example 9 Emulsion 30 parts of the compound of the present invention 33 parts of xylene 30 parts of dimethylformamide 7 parts of polyoxyethylene alkylaryl ether By mixing and dissolving the above, an emulsion having an active ingredient of 30% is obtained.

Example 10 Dust 10 parts of the compound of the present invention 89 parts of talc 1 part of polyoxyethylene alkylaryl ether 1 part If the above components are uniformly mixed and finely pulverized, the active ingredient 10
% Powder.

Example 11 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Sodium phosphate 1 part The above components were thoroughly pulverized and mixed, and water was added and kneaded well.
The granules are dried by granulation to obtain granules having an active ingredient of 5%.

Example 12 Suspension The compound of the present invention 10 parts Sodium ligninsulfonate 4 parts Sodium dodecylbenzenesulfonate 1 part Xanthan gum 0.2 part Water 84.8 parts The above mixture was mixed until the particle size became 1 micron or less. If wet milled, a 10% active ingredient suspension is obtained.

[0219]

EFFECT OF THE INVENTION Test Example 1 Efficacy against armyworm According to the formula of wettable powder shown in Example 4 of the above-mentioned drug,
Diluted with water to give a compound concentration of 125 ppm.
Corn leaves were immersed in the chemical solution for 30 seconds, air-dried, and then put into a petri dish containing five third-generation larvae of the armyworm. Glass cover, temperature 25 ℃, humidity 65%
And the insecticidal rate was examined after 5 days. Two repetitions. As a result, 4-1, 4-9, 4-13, 4-1
Compounds of 4, 5-20, 5-21, and 5-22 exhibited an insecticidal rate of 100%. On the other hand, the insecticidal rate of the control compound chlordimeform was 40%. The compound numbers correspond to the compound numbers in Table 4.

Test Example 2 Efficacy against Cotton Aphid A cotton aphid adult was inoculated to a cucumber, which had been germinated 10 days after sowing in a three-dimensional bowl. One day later, the adults were removed and the cucumber parasitized with the nymphs born was added to the cucumber having a compound concentration of 125 p in accordance with the formulation of the emulsion described in Example 5 of the drug.
The drug diluted with water to pm was sprayed. Temperature 2
They were placed in a thermostatic chamber at 5 ° C. and a humidity of 65%, and the insecticidal rate was examined 6 days later. The test is in duplicate. As a result, Compound Nos. 4-1, 4-2, 4-3, 4-7, 4-8, 4-10, 4
-11, 4-13, 4-14, 5-1, 5-5, 5-7, 5-
9, 5-10, 5-11, 5-12, 5-13, 5-14, 5-1
Compounds 5, 5, 20 and 5-21 showed an insecticidal rate of 100%. On the other hand, the insecticidal rate of the control compound pirimicarb was 9%. The compound numbers correspond to the compound numbers in Tables 4 and 5.

Test Example 3 Efficacy Against Dermatophagoid Spider Mites Seventeen adult females of organic phosphoric acid-resistant spider mites were inoculated on the first true leaf 7 to 10 days after germination of kidney beans sown in 2-inch pots. According to the formulation of the wettable powder described in Example 4 of the drug, a drug solution diluted with water was sprayed so that the compound concentration became 125 ppm. After being placed in a constant temperature room at a temperature of 25 ° C. and a humidity of 65%, and after 3 days of spraying, the adults were removed, and on the 11th day, it was investigated whether or not the eggs laid during these three days could develop to the adults. The acaricidal effectiveness was determined by the following equation. As a result, Compound Nos. 5-1 and 5-2,
5-3, 5-4, 5-5, 5-6, 5-7, 5-8, 5
-9, 5-10, 5-11, 5-12, 5-13, 5-14, 5-
The compounds 15, 15-16, 5-18 and 5-21 showed 100% acaricidal efficacy. On the other hand, the control compound, chlordimeform, had an acaricidal efficacy of 55%. The compound numbers correspond to the compound numbers in Table 5. The acaricidal effectiveness was determined by the following equation.

[0220]

(Equation 1)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takao Iwasa 345 Takada, Odawara-shi, Kanagawa Japan Nippon Soda Co., Ltd.Odawara Research Laboratories (72) Inventor Masahiro Kawaguchi 345 Odawara-shi, Kanagawa Pref. Inventor Koichiro Aoyagi 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd.Odawara Research Laboratories (72) Inventor Takehiko Nakamura 345 Takada, Odawara-shi, Kanagawa Japan Nippon Soda Co., Ltd.Odawara Research Laboratories

Claims (3)

[Claims] 1. A compound of the general formula (1) [In the formula, A represents a heterocyclic group optionally substituted with G or a phenyl group optionally substituted with G;
Nitro group, cyano group, halogen atom, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-8
Cycloalkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _2-6 alkenyloxy group, C _2-6 haloalkenyloxy group, C _1-6 alkoxy C _{1 -6} alkyl group, C _1-6 alkylthio C _1-6 alkyl group, C _1-6 alkylsulfinyl C _1-6 alkyl, C _1-6 alkylsulfonyl C _1-6 alkyl group, tri C _1-6 alkylsilyl C _1-6 alkyl group, C _1-6 alkoxycarbonyl group, phenyl C _1-6 alkyl group optionally substituted with C _1-6 alkyl group, benzyloxy group optionally substituted with halogen atom, naphthyl Group, thienyl group, (halogen atom, C _1-6 alkyl group or C
_1-6 haloalkyl optionally substituted with a group) pyridyl group, (nitro group, a cyano group, a halogen atom, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 alkoxy group,
Methylenedioxy group, C _1-6 haloalkoxy group, C _{1-6
Alkylthio} group, C _1-6 alkylsulfinyl group, C
_1-6 alkylsulfonyl group, a C _1-6 alkylcarbonyl group, C _1-6 alkylamino group, may be substituted with di-C _1-6 alkylamino group) phenyl group. Also,
G may form a 5- or 6-membered ring by a C _3-4 alkylene group bonded at an adjacent substitution position. G
Heterocyclic group optionally substituted with, triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thienyl, furyl,
A group selected from the group consisting of pyrrolyl, pyridyl and pyrimidinyl groups. B represents a phenyl group or a naphthyl group represented by the following chemical formula 2: (Wherein R ₁ is a nitro group, a cyano group, a halogen atom,
C _1-6 alkyl groups, C _1-6 alkoxy group, a C _1-6 haloalkyl group or a C _1-6 haloalkoxy group, R ₂ represents a hydrogen atom, a nitro group, a cyano group, a halogen atom, C _{1- 6} alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group or C
_{Represents a 1-6} haloalkoxy group, R ₃ is a nitro group, a cyano group, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group or a C _1-6 haloalkoxy group And m represents 0, 1, 2, or 3. When m is 2 or more, R ₃ may be the same or different. Or a heterocyclic group optionally substituted by W (W is a nitro group, a cyano group, a halogen atom, a C _1-6 alkyl group,
C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C
_1-6 represents an alkoxycarbonyl group or a phenyl group,
The heterocyclic group optionally substituted with W is selected from the group consisting of triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl and pyrazinyl. Is a kind of group. ). R represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxycarbonyl group. When the phenyl group or heterocyclic group of A and B has two or more substituents, the substituents G and W may be the same or different. ]
An isoxazole compound represented by the formula: 2. A compound of the general formula (2) (Wherein, A and B represent the same meaning as described above;
₄ represents a hydrogen atom or a C _1-6 alkyl group;
₅ represents a C _1-6 alkyl group. Further, R ₄ and R ₅ may together form a ring having 3 to 8 carbon atoms. )
Wherein the compound represented by the general formula (1 ′) is reacted with hydroxylamine or a salt thereof. (Wherein, A and B have the same meanings as described above). 3. A compound of the general formula (1) (Wherein A, B and R have the same meanings as described above), which comprises one or more of the isoxazole compounds represented by the formula (1) as an active ingredient.