JPH10338676A - Pyrazole derivative, its production, intermediate and pest controlling agent containing the same as active ingredient - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide a novel compound having an excellent pest control effect
Products, their production methods, and intermediates. [Solution] Embedded image [In the above formula, R¹Is C₁~ C_FourAlkyl group or C₁
~ C₈A haloalkyl group of R^TwoIs a hydrogen atom or
C₁~ C_FourRepresents an alkyl group. R^ThreeIs a hydrogen atom, water
Acid group, C₁~ C_FourAn alkyl group of C₁~ C_FourNo haloal
Kill group, C₁~ C _FourAn alkoxy group, even if it is substituted
Good phenoxy group, C₁~ C_FourHaloalkoxy group, C
₁~ C_FourAn alkylthio group of C₁~ C_FourAlkisulf
Inyl group, C₁~ C_FourAlkylsulfonyl group, halogen
Substituted with a substituent selected from nitro, nitro and cyano
Aryl or heteroaryl group which may be
Is shown. R^FourIs a hydrogen atom, C₁~ C_FourThe alkyl group of
Is C₁~ C_FourRepresents an acyl group. X is a nitrogen atom, and
Represents a carbon atom substituted with a halogen atom. l, n
Represents 0, 1, and 2 independently. 1 represented by
-Aryl-3-cyano-5- (het) arylalkyl
Luminopyrazole derivatives, their production, intermediates and
A pest control agent comprising the same as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative and a pesticide such as an agricultural and horticultural insecticide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art In the field of agriculture and horticulture, various insecticides for controlling various pests have been developed and put to practical use. Pyrazole compounds having insecticidal activity include 5- (substituted) compounds described in JP-A-63-316771.
An amino-3-cyano-1-phenylpyrazole derivative is disclosed, and JP-A-64-47768 discloses 1
-Aryl-5- (het) arylmethylaminopyrazole derivatives are disclosed in JP-A-5-148240.
In the publication, 1-aryl-3-cyano-5- (het) arylmethylideneiminopyrazole derivatives are disclosed.

[0003] However, none of these agricultural and horticultural insecticides are completely satisfactory in terms of insecticidal effect, insecticidal spectrum and safety. Furthermore, in recent years, the appearance of pests that have acquired resistance to commercial products has also become a problem. For example, vegetables, fruit trees, flowers, tea,
In the cultivation of wheat and rice, various types of pests that have acquired resistance to various types of pesticides (for example, organophosphorus pesticides, etc.) have appeared in various places, and control of various pests caused by these pests Are becoming more difficult year by year, and the emergence of new pesticides having different skeletons is desired.

[0004] On the other hand, there are pesticides such as dithiocarbamate and phthalimide pesticides, for which pathogenic bacteria and pests have not yet obtained resistance. However, these pesticides generally require a large amount of applied medicine and a large number of application times, and cause environmental pollution. It is not preferable from a viewpoint. As described above, development of a novel pesticidal agent that has excellent pesticidal effects, a wide pesticidal spectrum, high safety, and low adverse effects on the environment is also desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a novel pesticide which is excellent in insecticidal effect, has a wide insecticidal spectrum, is highly safe, and has little adverse effect on the environment. It is an object. Specifically, the present invention provides a 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative having the above-mentioned utility, and provides a method for efficiently synthesizing these.

[0006]

The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, have found that a novel pyrazole compound represented by the following formula is a compound having the above characteristics. Was completed. That is, the gist of the present invention is represented by the following general formula (1)

[0007]

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In the above formula, R¹Is C₁~ C_FourThe alkyl of
Group or C₁~ C₈A haloalkyl group of R^TwoIs water
Elementary atom or C₁~ C_FourRepresents an alkyl group. R^ThreeIs
Hydrogen atom, hydroxyl group, C₁~ C_FourAn alkyl group of C₁~ C
_FourHaloalkyl group of C₁~ C _FourAlkoxy group, substitution
Optionally substituted phenoxy group, C₁~ C_FourNo haloal
Coxy group, C₁~ C_FourAn alkylthio group of C₁~ C_Fourof
Alkylsulfinyl group, C₁~ C_FourAlkylsulfoni
Selected from chloro, halogen, nitro and cyano groups
An aryl group or a hetero group which may be substituted with a substituent;
Represents a aryl group. R^FourIs a hydrogen atom, C₁~ C_FourNo
Alkyl group or C₁~ C_FourRepresents an acyl group. X is nitrogen
Indicates an atom or a carbon atom substituted with a halogen atom
You. l and n each independently represent 0, 1, and 2. ] so
Represented 1-aryl-3-cyano-5- (het) ant
Alkylaminopyrazole derivatives, process for their production and
And the following general formula (3)

[0009]

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[Wherein R ² , R ³ , R ⁴ , X and l
Are as described above. ] And a use thereof as a pesticide. Hereinafter, the present invention will be described in detail.

[0011]

Substituents R ¹ represents a methyl group of the embodiment of the invention compound represented by formula (1), an ethyl group, n - propyl group, an isopropyl group, n - butyl group, isobutyl group, sec-
Butyl group, a linear or branched alkyl group of C ₁ -C ₄ in a t- butyl group and the like; or a difluoromethyl group, a trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2- Trifluoroethyl group, 2,2,
2-trichloroethyl group, 3-chloropropyl group, 3-
Bromopropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,
2,3,3,3-pentafluoropropyl group, 2,2-
Dichloro-3,3,3-trifluoropropyl group, 1,
3-difluoro-2-propyl group, 1,1,1,3,
3,3-hexafluoro-2-propyl group, 3,3,3
-Trichloropropyl group, 4-chlorobutyl group, 4,
4,4-trifluorobutyl group, 3,3,4,4,4-
C such as pentafluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, etc.
A linear or branched chain haloalkyl group having ₁ -C _8.
Of these, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkyl group is preferred.
₁ to ₄ haloalkyl groups are shown.

R ² is a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
C such as isobutyl group, sec-butyl group and t-butyl group
A linear or branched alkyl group having ₁ -C _4. Of these, a hydrogen atom is preferred. R ³ is an aryl group such as a phenyl group or a naphthyl group;
In and nitrogen atoms, a heteroaryl group oxygen atom and a sulfur atom include 1 to 3 heteroatoms selected arbitrarily, it may be optionally substituted with the following substituent group R ^5. In particular,

[0013]

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(Wherein R ⁵ is a hydrogen atom, a hydroxyl group, C _1-
Alkyl C _4, a haloalkyl group of C ₁ ~C _8, C ₁
-C ₄ alkoxy groups, optionally substituted phenoxy group, a haloalkoxy group _{C 1 ~C 4, C 1 ~C} 4 alkylthio group, alkylsulfinyl group C ₁ -C _4, C
Represents an alkylsulfonyl group of ₁ to ₄ carbon atoms, a halogen atom, a nitro group or a cyano group, and m is any one of 0, 1, and 2. ). Of these,

[0015]

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(Wherein R ⁵ and m are as defined above), and more preferably

[0017]

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(Wherein R ⁶ represents a hydrogen atom, a hydroxyl group, C _1-
Alkyl C _2, alkoxy groups C ₁ ~C _2, C ₁ ~
Haloalkoxy group C _2, alkylthio group of C ₁ -C _2, a halogen atom, a nitro group or a cyano group shown. )
It is. R ⁵ is a hydrogen atom; a hydroxyl group; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
C such as isobutyl group, sec-butyl group and t-butyl group
_{1 to} C ₄ linear or branched alkyl group; difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, 2,2,2- Trichloroethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3- Pentafluoropropyl group, 2,2-dichloro-3,3,3-trifluoropropyl group, 2,2-dichloro-3,3,3-trifluoropropyl group, 1,3-difluoro-2-propyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 3,3,3-trichloropropyl group, 4-chlorobutyl group, 4,4,4-trifluorobutyl group,
3,3,4,4,4-pentafluoro-butyl group, 5-chloropentyl group, 6,6,6-straight or branched chain haloalkyl group having C ₁ -C _8, such as trifluoroacetic hexyl group;
Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-
Butoxy, t - straight or branched chain alkoxy group of C ₁ -C ₄ or butoxy group; C ₁ -C ₄ alkoxy or C ₁ -C ₄ phenoxy groups that may be substituted by an alkyl group; Difluoromethoxy group, trifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2
-Trichloroethoxy group, 3-chloropropoxy group, 3
-Bromopropoxy, 3,3,3-trifluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2-dichloro- 3,3,3-trifluoropropoxy group, 2,2-dichloro-3,3,3-trifluoropropoxy group, 1,3-difluoro-2-propoxy group, 1,1,1,3,3,3 -Hexafluoro-2-propoxy group, 3,3,3-trichloropropoxy group, 4
A C ₁ -C ₄ linear or branched haloalkoxy group such as a chlorobutoxy group, a 4,4,4-trifluorobutoxy group, a 3,3,4,4,4-pentafluorobutoxy group; a methylthio group, ethylthio, n - propylthio group, isopropylthio group, n - butylthio group, isobutylthio, sec- butylthio, t - straight or branched chain alkylthio group of C ₁ -C _4, such as butylthio group; methylsulfinyl group, Ethylsulfinyl group, n-propylsulfinyl group, isopropylsulfinyl group, n
-Butylsulfinyl group, isobutylsulfinyl group,
sec- butyl sulfinyl group, t - butyl sulfinyl straight or branched chain alkylsulfinyl group of C ₁ -C _4, such as Le group; methylsulfonyl group, ethylsulfonyl group, n - propyl sulfonyl group, isopropylsulfonyl group, n - butylsulfonyl a nitro group or a cyano group; a straight-chain or branched-chain alkylsulfonyl group having C ₁ -C _4, such as a butylsulfonyl group - group, iso-butylsulfonyl group, sec- butylsulfonyl group, t; halogen atom. Among preferably a hydrogen atom; a hydroxyl group; C ₁ -C
₄ linear or branched alkyl groups; C ₁ -C ₄ linear or branched alkoxy groups; C ₁ -C ₄ linear or branched haloalkoxy groups; C ₁ -C ₄ linear or branched chains An alkylthio group; a nitro group; or a cyano group.

R ⁶ is a hydrogen atom; a hydroxyl group; a methyl group or an ethyl group; a methoxy group or an ethoxy group; a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, 2, 2, 2, A C ₁ -C ₂ haloalkoxy group such as trifluoroethoxy group, 2,2,2-trichloroethoxy group; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group , sec- butylthio, t - the C ₁ -C _4, such as butylthio group linear or branched alkylthio group; a halogen atom, a nitro group or a cyano group.

R ⁴ is a hydrogen atom; methyl group, ethyl group, n
-C ₁ -C such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc.
₄ straight-chain or branched-chain alkyl groups; or methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, t-butylcarbonyl And C ₁ -C ₄ linear or branched acyl groups. Of these, a hydrogen atom, a C ₁ -C ₄ linear alkyl group, or a C ₁ -C ₄
Is a linear acyl group. Preferred among the compounds of the present invention are compounds represented by the following general formula (2)

[0021]

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(Wherein R ¹ and n are as described above, and R ⁷ is

[0023]

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And R⁸Is C₁~ C_TwoThe alkoxy of
Group, C₁~ C_TwoHaloalkoxy group, C ₁~ C_TwoAl
A thio group, a nitro group or a cyano group;⁹Is water
Elemental atom, hydroxyl group, C₁~ C_TwoAn alkoxy group of C₁~ C
_TwoHaloalkoxy group or nitro group, R^TenIs C₁~ C
_TwoRepresents an alkyl group. ), Especially
Preferably, R⁷But,

[0025]

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[0026] As the substituent R ⁸ of the above compound, a methoxy group or an ethoxy group; a difluoromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 2, A C ₁ -C ₂ haloalkoxy group such as 2,2-trichloroethoxy group; a methylthio group or an ethylthio group; a nitro group; or a cyano group.

R ⁹ is hydrogen atom; hydroxyl group; methoxy group or ethoxy group; difluoromethoxy group, trifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 2 2,
2 haloalkoxy group C ₁ -C ₂ of trichloroethoxycarbonyl group or the like; or a nitro group. R ¹⁰ represents a methyl group or an ethyl group. Examples of the method for producing the compound of the present invention represented by the general formula (1) include the following reaction formulas 1 to 3.

[0028]

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[In the above formula, R ¹ , R ² , R ³ , X, l and n are as described above, Y is a halogen atom, a hydroxyl group or a salt thereof, or a dialkylamino group, and Z is a halogen atom. A leaving group such as an atom or a hydroxyl group. In the method of Reaction Scheme 1, the compound of the general formula (3) is converted to S (O) n
Characterized by R ¹ of. In this reaction, the compound of the general formula (3) and R ¹ S (O) n—Y (where Y and n are as defined above) are mixed with 0 in a solvent, if necessary, in the presence of a base. ° C to 150 ° C, preferably 0 ° C to 100 ° C
The reaction is carried out.

Examples of the base for this reaction include tosylate or hydrochloride of amine compounds such as dimethylamine and pyridine.
Commonly used inorganic bases, such as alkali metal carbonates, can be used. The amount of the base used is 0.5 to 2.0 molar equivalents, preferably 0.8 to 2.0 equivalents to compound (3 ′). 1.5 molar equivalents. Examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; tetrahydrofuran and N, N-dimethylformamide and the like. Polar solvents.

The reaction for converting a nitrogen atom into R ⁴ can be carried out before or after the above reaction, if necessary. For example,
Compound (3 ′) or an alkali metal derivative thereof and R ⁴ Z
(Wherein Z represents a leaving group such as a halogen atom or a hydroxyl group) in a solvent at 0 ° C. in the presence or absence of a base.
The compound (3) can be obtained by reacting at ~ 150 ° C. Examples of the solvent in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; tetrahydrofuran and N, N-dimethylformamide. . Examples of the base in this reaction include organic bases such as pyridine and triethylamine, and alkali metal carbonates. The compound represented by the general formula (3) is
For example, it can be produced according to the following reaction formulas 4 to 7.

[0032]

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[0033]

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[0034]

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[0035]

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The method of Reaction Scheme 2 is characterized in that the compound of the following general formula (4) is reduced with a reducing agent. In this reaction, 0.2 to 5.0 molar equivalents, preferably 0.25 to 5.0 molar equivalents, relative to the compound of the following general formula (4)
2.0 molar equivalents of a reducing agent are added in the presence or absence of a solvent, and the reaction can be carried out at a temperature of -20 to 150C, preferably 0 to 120C. As the reducing agent in this reaction, sodium borohydride, sodium cyanoborohydride, lithium borohydride, lithium aluminum hydride, or the like can be used.

As the solvent used in this reaction, a polar solvent such as an ether such as diethyl ether, dioxane or tetrahydrofuran; or an alcohol such as methanol, ethanol or propanol can be used. The compound represented by the general formula (4) can be produced, for example, by the method described in JP-A-5-148240. The method of Reaction Scheme 3 is characterized in that a compound of the following general formula (5) is (het) arylalkylated. (Wherein, Z is a halogen atom,
It represents a leaving group such as a hydroxyl group. )

Compound (5) or an alkali metal derivative thereof and R ³ R ² CHZ (R ² , R ³ and Z are as defined above) in a solvent, if necessary, at 0 ° C.
It can be obtained by reacting at 150 ° C. Examples of the solvent in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; tetrahydrofuran and N, N-dimethylformamide. . Examples of the base in this reaction include organic bases such as pyridine and triethylamine, and alkali metal carbonates.

The compound of the present invention represented by the general formula (1) can be used for arthropods (especially mites, insects), nematodes, It can be used as a pest control agent for helminths or protozoa. Specifically, Hemiptera, such as planthoppers such as Betella planthoppers, brown planthoppers and brown planthoppers, leafhoppers such as black leafhoppers and leafhoppers, aphids such as peach aphids, etc .; Coleoptera such as Musca domestica, Aedes aegypti, and Culex pipiens; high insecticidal activity against eggs and larvae of insects of the order Orthoptera, useful as an active ingredient of agricultural and horticultural insecticides It is. However, insects to be controlled by the compound of the present invention are not limited to those exemplified above.

When the compound of the present invention represented by the general formula (1) is used as an agricultural and horticultural insecticide, it may be used alone or as a composition containing an agricultural chemical adjuvant commonly used in the art. It is preferably used. The dosage form of the insecticide for agricultural and horticultural use is not particularly limited, but is preferably in the form of, for example, emulsions, wettable powders, powders, flowables, fine granules, granules, tablets, oils, sprays, aerosols and the like. It is. In addition, one or more of the compounds of the present invention can be blended as an active ingredient.

The agricultural chemical auxiliaries used for producing the agricultural and horticultural insecticides are used, for example, for the purpose of improving the effect, stabilizing, and improving the dispersibility of the agricultural and horticultural insecticides. Yes, specific examples include carriers (diluents), spreading agents, emulsifiers, wetting agents, dispersants, disintegrants, and the like. Examples of the liquid carrier include aromatic hydrocarbons such as water, toluene and xylene; alcohols such as methanol, butanol, and glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; methylnaphthalene : Cyclohexane; animal and vegetable oils; and fatty acids. Solid carriers include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar,
Quartz, alumina, sawdust, nitrocellulose, starch,
Gum arabic or the like can be used. Usable emulsifiers and dispersants include ordinary surfactants, for example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine; An ionic surfactant; a nonionic surfactant; or an amphoteric ionic surfactant can be used. A spreading agent such as polyoxyethylene onyl phenyl ether and polyoxyethylene lauryl phenyl ether; a wetting agent such as dialkyl sulfosuccinate; a fixing agent such as carboxymethyl cellulose and polyvinyl alcohol; sodium lignin sulfonate and sodium lauryl sulfate And the like.

The content of the active ingredient in the agricultural and horticultural insecticide of the present invention is selected from the range of 0.1 to 99.5%.
What is necessary is just to determine suitably by various conditions, such as an application method,
For example, in the case of a powder, about 0.5 to 20% by weight, preferably
About 10 to about 10% by weight, about 1 to about 90% by weight, preferably about 10 to about 80% by weight for a wettable powder, and about 1 to about 90% by weight, preferably about 10 to 40% by weight for an emulsion. It is preferred to manufacture. For example, in the case of an emulsion, it is possible to prepare an emulsion of a stock solution by mixing a solvent, a surfactant and the like with the above-mentioned compound which is an active ingredient, and further dilute this stock solution to a predetermined concentration before use. Can be done. In the case of a wettable powder, a stock solution is prepared by mixing the above-mentioned compound of the active ingredient, a solid carrier, a surfactant and the like, and this stock solution can be diluted to a predetermined concentration before use. In the case of powder, the compound as an active ingredient and the solid carrier can be mixed and applied as it is. In the case of granules, the compound of the active ingredient, the solid carrier and a surfactant can be mixed. It can be manufactured by granulation and applied as it is. However, the production method of each of the above-mentioned preparation forms is not limited to the above-mentioned one, and can be appropriately selected by those skilled in the art according to the kind of the active ingredient and the purpose of application.

The agricultural and horticultural insecticides of the present invention include other fungicides, insecticides, acaricides, herbicides, insect growth regulators, fertilizers, soil conditioners, etc. in addition to the compound of the present invention as an active ingredient. May be added. The method for applying the agricultural and horticultural insecticide of the present invention is not particularly limited, and can be applied by any method such as foliage application, water surface application, soil treatment, seed treatment and the like. For example, in the case of foliage application, 5-
1000 ppm, preferably 10-500 ppm solution in 1
It can be used at an application rate of about 100 to 200 L per 0 ares. In the case of water application, the application rate is usually 1 to 10 kg per 10 ares for granules containing 5 to 15% of the active ingredient.
In the case of soil treatment, a solution with a concentration range of
It can be used at an application rate of about 1 to 10 L per ² .
In the case of seed treatment, about 10 to 100 ml of a solution having a concentration range of 10 to 1000 ppm per kg of seed weight can be applied.

The method of applying the insecticide for livestock and pets of the present invention is not particularly limited, and it can be applied by any method such as a method of applying to pet collars and a method of spraying livestock. Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to the following Examples.

[0045]

【Example】

<Example 1> Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-5- (4-pyridylmethylamino) pyrazole 1- (2,6-dichloro-4-tri) 2.0 g of (fluoromethylphenyl) -3-cyano-5-aminopyrazole,
0.7 g of pyridine-4-aldehyde and 50 ml of toluene
Was added to the mixture, and the mixture was heated under reflux for 5 hours. After removing insolubles, the solvent was distilled off under reduced pressure, and the residue was washed with hexane and a small amount of chloroform.
2.0 g of (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-5- (4-pyridylmethylideneimino) pyrazole were obtained. ^{Mp: 194 ~195 ℃ 1 HNMR (CDCl} 3): 6.87 (1H, s), 7.57 (2H, d), 7.79 (2H, s), 8.
69 (1H, s), 8.76 (2H, d)

1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-5- (4-pyridylmethylideneimino) pyrazole 1.7 g of methanol 20
To the ml solution was slowly added 0.3 g of sodium borohydride. After stirring at room temperature for 1 hour, ice was added and concentrated hydrochloric acid was gradually added to neutralize. Ethyl acetate was added and extracted. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography to obtain 1.5 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-5- (4-pyridylmethylamino) pyrazole. Melting point:> 300 ° C ¹ H NMR (CDCl ₃ ): 3.98 (1 H, t), 4.37 (2 H, d), 5.80 (1 H, s),
7.22 (2H, d), 7.80 (2H, s), 8.59 (2H, d)

Example 2 1- (2,6-dichloro-)
4-trifluoromethylphenyl) -3-cyano-4-
Production of trifluoromethylsulfenyl-5- (4-pyridylmethylamino) pyrazole (Compound No. 1) 1- (2,6-dichloro-4) obtained in Example 1 above
-Trifluoromethylphenyl) -3-cyano-5-
0.5 g of (4-pyridylmethylamino) pyrazole was suspended in 10 ml of dichloromethane, and 0.2 ml of trifluoromethylsulfenyl chloride in 10 ml of dichloromethane was added dropwise at -20 ° C. Remove the cold bath and stir for 3 hours.
Ice water was added and extracted. After washing the organic layer with saturated saline,
Dry over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography to obtain 0.4 g of the compound (No. 1) shown in Table 1 below. The NMR of the above compound was as follows. ¹ H NMR (CDCl ₃ ): 4.51 (2H, d), 4.65 (1 H, b), 7.05 (2H, d),
7.70 (2H, s), 8.53 (2H, d)

Example 3 1- (2,6-dichloro-)
4-trifluoromethylphenyl) -3-cyano-4-
Production of trifluoromethylsulfenyl-5- (4-pyridylmethylamino) pyrazole (Compound No. 1) 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4-trifluoromethyl To a solution of 2.6 g of sulfenyl-5- (4-pyridylmethylideneimino) pyrazole in 15 ml of methanol was slowly added 0.37 g of sodium borohydride, stirred at room temperature for 3 hours, added ice, and added concentrated hydrochloric acid. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and the residue was purified by silica gel column chromatography to give the compounds shown in Table 1 below. (No. 1) 1.2 g was obtained.

Example 4 1- (2,6-dichloro-)
4-trifluoromethylphenyl) -3-cyano-4-
Preparation of trifluoromethylsulfenyl-5-[(3-methoxy-4-hydroxyphenyl) methylamino] pyrazole (Compound No. 2) 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- To a solution of 2.8 g of cyano-4-trifluoromethylsulfenyl-5-[(3-methoxy-4-hydroxyphenyl) methylideneimino] pyrazole in 15 ml of methanol was slowly added 0.37 g of sodium borohydride. After stirring at room temperature for 3 hours, ice was added and concentrated hydrochloric acid was gradually added to neutralize. Ethyl acetate was added and extracted. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography to obtain 1.4 g of the compound (No. 2) shown in Table 1 below. The NMR of the above compound was as follows. _{^{1 HNMR (CDCl 3): 3.87}} (3H, s), 4.32 (2H, m), 4.43 (1H, b),
5.60 (1H, bs), 6.62 (2H, m), 6.83 (1H, m), 7.73 (2H, s)

Example 5 The compounds shown in Table 1 were obtained according to the methods of Examples 2 to 4. ^{No. 3 1 H-NMR (CDCl} 3): 4.42 (2H, d), 4.54 (1H, bt), 7.12 (2H, m),
7.29 (3H, m), 7.68 (2H, s) No. 4 1 H-NMR (CDCl 3): 2.32 (3H, s), 4.36 (2H, d), 4.47 (1H, t),
7.01 (2H, d), 7.10 (2H, d), 7.67 (2H, s) No. 5 1 H-NMR (CDCl 3): 1.30 (9H, s), 4.38 (2H, d), 4.50 (1H, m),
7.05 (2H, d), 7.32 (2H, d), 7.69 (2H, s) No. 6 1 H-NMR (CDCl): 4.31 (2H, d), 4.38 (1H, m), 4.83 (1H, s ),
6.75 (2H, d), 7.01 (2H, d), 7.71 (2H, s) No. 7 1 H-NMR (CDCl 3): 3.79 (3H, s), 4.34 (2H, d), 4.43 (1H, m),
6.82 (2H, d), 7.05 (2H, d), 7.70 (2H, s) No. 8 ¹ H-NMR (CDCl ₃ ): 1.32 (6H, d), 4.32 (2H, d), 4.40 (1H, m),
4.51 (1H, m), 6.80 (2H, d), 7.02 (2H, d), 7.71 (1H, s) No. 9 1 H-NMR (CDCl 3): 4.39 (2H, d), 4.45 (1H, b), 6.9−7.4 (9
H, m), 7.73 (2H, s) No.10 ¹ H-NMR (CDCl ₃ ): 4.42 (2H, d), 4.48 (1H, m), 7.01 (4H, q),
7.15 (2H, d), 7.60 (2H, d), 7.73 (2H, s)

No. 11 ¹ H-NMR (CDCl ₃ ): 4.43 (2H, d), 4.50 (1 H, bt), 6.25 6.48
6.76 (1H, t), 7.05 (2H, d), 7.12 (2H, d), 7.70 (2H, s) No.12 1 H-NMR (CDCl 3): 4.44 (2H, d), 4.57 (1H, t), 7.15 (4H, s),
^{7.69 (2H, s) No.13 1} H-NMR (CDCl 3): 4.35 (4H, m), 4.46 (1H, m), 6.87 (2H, d),
7.09 (2H, d), 7.61 (2H, s) No.14 1 H-NMR (CDCl 3): 4.39 (2H, d), 4.49 (1H, t), 6.98 (2H, t),
7.10 (2H, m), 7.70 (2H, s) No.15 1 H-NMR (CDCl 3): 4.41 (2H, d), 4.52 (1H, b), 7.06 (2H, d),
7.27 (2H, d), 7.69 (2H, s)

No. 16 ¹ H-NMR (CDCl ₃ ): (4.40,2H, d), (4.54,1H, m), (7.00,2H,
d), (7.42,2H, d) , (7.69,2H, s), No.17 1 H-NMR (CDCl 3): 4.47 (2H, d), 4.54 (1H, m), 6.98 (1H, t ),
7.09 (1H, t), 7.19 (1H, d), 7.27 (1H, m), 7.69 (2H, s) No.18 1 H-NMR (CDCl 3): 4.49 (2H, d), 7.72 (1H, t), 7.23 (4H, m),
^{7.65 (2H, s) No.19 1} H-NMR (CDCl 3): 4.52 (2H, d), 4.68 (1H, t), 7.24 (2H, d),
7.55 (2H, d), 7.66 (2H, s) No.20 1 H-NMR (CDCl 3): 2.46 (3H, s), 4.37 (2H, d), 4.46 (1H, t),
7.04 (2H, d), 7.17 (2H, d), 7.70 (2H, s)

No. 21 ¹ H-NMR (CDCl ₃ ): 3.05 (3H, s), 4.71 (2H, d), 6.19 (1H, t),
7.41 (2H, d), 7.74 (2H, s), 7.88 (2H, d) No.22 1 H-NMR (CDCl 3): 1.32 (6H, d), 4.32 (2H, d), 4.40 (1H, m),
4.51 (1H, m), 6.80 (2H, d), 7.02 (2H, d), 7.71 (1H, s) No.23 1 H-NMR (CDCl 3): 4.64 (3H, m), 7.33 (2H, d), 7.70 (2H, s),
8.16 (2H, d) No.24 ¹ H-NMR (CDCl ₃ ): 4.77 (2H <d), 5.01 (1H, m), 7.46 (2H, m),
7.61 (1H, m), 7.66 (2H, s), 8.01 (1H, d) No.25 1 H-NMR (CDCl 3): 4.64 (2H, d), 6.35 (1H, t), 7.43 (2H, d),
7.54 (2H, m), 7.73 (2H, s)

No. 26 ¹ H-NMR (CDCl ₃ ): 1.44 (3H, t), 4.04 (2H, q), 4.30 (2H, d),
4.42 (1H, b), 5.65 (1H, s), 6.60 (2H, d), 6.82 (1H, d),
^{7.71 (2H, s) No.27 1} H-NMR (CDCl 3): 4.47 (2H, d), 4.67 (1H, t), 7.21 (2H, s),
7.31 (1H, s), 7.68 (2H, s) No.28 1 H-NMR (CDCl 3): 4.43 (2H, d), 4.63 (1H, b), 6.98 (2H, d),
7.25 (1H, d), 7.70 (2H, s) No.29 1 H-NMR (CDCl 3): 4.49 (2H, d), 4.60 (1H, m), 6.95 (3H, m),
^{7.72 (2H, s) No.30 1} H-NMR (CDCl 3): 4.66 (2H, d), 6.48 (1H, m), 7.37 (1H, d
d), 7.49 (1H, d), 7.74 (2H, s), 7.76 (1H, d)

No. 31 ¹ H-NMR (CDCl ₃ ): 4.31 (2H, d), 4.42 (1 H, t), 5.95 (2 H, s),
6.59 (2H, m), 6.71 (1H, d), 7.72 (2H, s) .No. 32 ¹ H-NMR (CDCl ₃ ): 4.59 (2H, d), 4.63 (1H, m), 7.19 (1H , d),
7.49 (2H, m), 7.60 (3H, d), 7.77 (3H, m) No.33 1 H-NMR (CDCl 3): 4.05 (3H, s + b), 7.22 (1H, m), 7.48 ( 1
H, d), 7.72 (2H , s), 8.42 (1H, s), 8.53 (1H, d), No.34 1 H-NMR (CDCl 3): 4.60 (2H, d), 6.11 (1H, b ), 7.20 (2H,
m), 7.67 (1H, t), 7.79 (2H, s), 8.40 (1H, d),

No. 35 ¹ H-NMR (CDCl ₃ ): 4.65 (2H, d), 5.74 (1 H, t), 7.03 (2H, d),
7.74 (2H, d), 7.77 (2H, s) No.36 1 H-NMR (CDCl 3): 4.54 (2H, d), 4.71 (1H, m), 6.98 (1H, d),
7.11 (1H, s), 7.73 (2H, s), 8.29 (2H, d) No.37 1 H-NMR (CDCl 3): 4.45 (1H, b), 4.53 (2H, d), 7.28 (1H, d),
7.47 (1H, dd), 7.74 (2H, s), 8.20 (1H, d) No.38 1 H-NMR (CDCl 3): 3.87 (3H, s), 4.4-4.6 (3H, m), 7.11 ( 1
H, s), 7.25 (1H , d), 7.40 (2H, m), 8.17 (1H, d) No.39 1 H-NMR (CDCl 3): 2.33 (3H, s), 4.58 (2H, d) , 6.45 (1H, m),
6.99 (1H, d), 7.05 (1H, d), 7.56 (1H, t), 7.81 (2H, s) No.40 1 H-NMR (CDCl 3): 4.623 (2H, d), 6.50 (1H, m), 7.12 (2H,
s), 7.77 (2H, s)

No. 41 ¹ H-NMR (CDCl ₃ ): 4.74 (2H, d), 6.09 (1 H, m), 7.84 (2H, s),
7.96 (1H, s), 8.65 (1H, s) No.42 1 H-NMR (CDCl 3): 4.44 (3H, s), 6.17 (1H, d), 6.29 (1H, d),
7.31 (1H, d), 7.78 (2H, s) No.43 1 H-NMR (CDCl 3): 4.28 (1H, bm), 4.29 (2H, d), 6.22 (1H,
d), 7.30 (1H, s ), 7.37 (1H, d), 7.77 (2H, s) No.44 1 H-NMR (CDCl 3): 2.21 (3H, s), 4.36 (3H, bs), 5.87 (1H,
s), 6.04 (1H, d ), 7.78 (2H, s) No.45 1 H-NMR (CDCl 3): 4.36 (1H, m), 4.44 (2H, d), 6.17 (1H, d),
6.22 (1H, d), 7.80 (2H, s)

No. 46 ¹ H-NMR (CDCl ₃ ): 4.38 (1 H, b), 4.45 (2 H, d), 6.23 (1 H, s),
7.31 (1H, s), 7.79 (2H, s) No.47 1 H-NMR (CDCl 3): 4.58 (1H, m), 4.66 (2H, d), 6.47 (1H, d),
7.22 (1H, d), 7.82 (2H, s) No.48 1 H-NMR (CDCl 3): 4.42 (1H, m), 4.63 (2H, d), 6.88 (1H, d),
6.93 (1H, t), 7.24 (1H, m), 7.75 (2H, s) No.49 ¹ H-NMR (CDCl ₃ ): 4.44 (3H, b), 6.83 (1H, d), 7.07 (1H, m),
7.28 (1H, dd), 7.73 (2H, s) No.50 1 H-NMR (CDCl 3): 2.43 (3H, s), 4..35 (1H, m), 4.52 (2H,
d), 6.55 (1H, d), 6.65 (1H, d), 7.76 (2H, s),

No. 51 ¹ H-NMR (CDCl ₃ ): 3.84 (3H, s), 4.29 (1H, m), 4.45 (2H, d),
5.17 (1H, d), 6.50 (1H, d), 7.77 (2H, s) No.52 1 H-NMR (CDCl 3): 4.38 (1H, t), 4.57 (2H, d), 6.64 (1H, d),
6.87 (1H, d), 7.77 (2H, s) No.53 1 H-NMR (CDCl 3): 4.54 (1H, t), 4.73 (2H, d), 6.85 (1H, d),
7.76 (1H, d), 7.79 (2H, s) No.54 1 H-NMR (CDCl 3): 4.83 (2H, d), 5.17 (1H, t), 7.30 (1H, d),
7.66 (1H, d), 7.76 (2H, s) No.55 1 H-NMR (CDCl 3): 2.27 (3H, s), 2.61 (3H, s), 4.59 (2H, d),
4.97 (1H, b), 7.78 (2H, s)

No. 56 ¹ H-NMR (CDCl ₃ ): 1.53 (3 H, m), 4.28 (1 H, t), 4.54 (2 H, d),
5.52 (1H, m), 6.91 (1H, s), 7.79 (2H, s) No.57 1 H-NMR (CDCl 3): 3.51 (3H, s), 4.01 (1H, t), 4.47 (2H, d),
6.05 (2H, m), 6.63 (1H, t), 7.78 (2H, s) No.58 1 H-NMR (CDCl 3): 1.19 (3H, t), 2.57 (2H, q), 3.68 (3H, s),
4.09 (1H, m), 4.50 (2H, d), 5.94 (1H, s), 7.80 (2H, s) No.59 1 H-NMR (CDCl 3): 4.34 (1H, t), 4.58 (2H, d), 7.12 (2H, m),
7.22 (1H, d), 7.38 (2H, m), 7.66 (2H, s) .8.14 (1H, b) No.60 ¹ H-NMR (CDCl ₃ ): 3.75 (3H, s), 4.33 (1H, s) m), 4.56 (2H, d),
6.96 (1H, s), 7.12 (1H, t), 7.26 (2H, m), 7.37 (1H, d),
7.65 (2H, s)

No. 61 ¹ H-NMR (CDCl ₃ ): 3.81 (3H, s), 4.30 (1 H, t), 4.56 (2H, d),
6.84 (1H, s), 6.89 (1H, dd), 7.09 (1H, d), 7.27 (1H, d),
7.69 (2H, s), 8.03 (1H, b) No.62 1 H-NMR (CDCl 3): 4.11 (2H, m), 6.45 (1H, b), 6.48 (1H, t),
6.98 (4H, q), 7.58 (1H, s), 7.63 (1H, s) No.63 1 H-NMR (CDCl 3): 4.61 (2H, m), 6.58 (1H, t), 7.4-7.65 ( Five
H, m), 7.94 (1H , d) No.64 1 H-NMR (CDCl 3): 3.83 (3H, s), 4.01 (2H, d), 5.58 (1H, s),
6.30 (1H, m), 6.40 (1H, d), 6.55 (1H, s), 6.75 (1H, d),
7.63 (1H, s), 7.68 (1H, s) No.65 1 H-NMR (CDCl 3): 4.17 (2H, d), 6.62 (1H, m), 6.89 (2H, d),
7.54 (1H, s), 7.61 (1H, s), 8.47 (2H, d)

No. 66 ¹ H-NMR (CDCl ₃ ): 4.16 (2H, d), 6.41 (1 H, m), 7.19 (1 H, m),
7.38 (1H, d), 7.61 (1H, s), 7.67 (1H, s), 8.23 (1H, s),
8.52 (1H, d) No.67 ¹ H-NMR (CDCl ₃ ): 4.34 (2H, d), 7.00 (1H, b), 7.17 (2H, m),
7.65 (1H, m), 7.71 (1H, s), 7.74 (1H, s), 8.38 (1H, d) No.68 1 H-NMR (CDCl 3): 4.30 (2H, d), 6.21 (1H, t), 6.74 (1H, d),
6.88 (1H, t), 7.21 (1H, d), 7.70 (2H, d) No.69 1 H-NMR (CDCl 3): 4.49 (2H, d), 4.73 (1H, t), 7.04 (2H, d),
7.69 (2H, s), 8.51 (2H, m) No.70 1 H-NMR (CDCl 3): 4.50 (2H, d), 4..73 (1H, m), 7.04 (2H,
d), 7.69 (2H, s), 8.52 (2H, d)

No. 71 ¹ H-NMR (CDCl ₃ ): 4.50 (2H, d), 4..75 (1 H, t), 7.04 (2H,
d), 7.69 (2H, s ), 8.52 (2H, d) No.72 1 H-NMR (CDCl 3): 2.25 (3H, s), 4.31 (1H, b), 4.37 (2H, d),
7.14 (2H, m), 7.29 (3H, m), 7.67 (2H, s) No.73 1 H-NMR (CDCl 3): 2.24 (3H, s), 4.40 (1H, m), 4.51 (2H, d),
7.10 (2H, d), 7.70 (2H, s), 8.52 (2H, d) No.74 ¹ H-NMR (CDCl ₃ ): 1.24 (3H, t), 2.66 (2H, q), 4.45 (2H, d),
4.54 (1H, t), 7.06 (2H, d), 7.66 (2H, s), 8.49 (2H, d) No.75 ¹ H-NMR (CDCl ₃ ): 1.28 (6H, d), 3.13 (1H, m), 4.39 (2H, d),
4.64 (1H, t), 7.04 (2H, d), 7.64 (2H, s), 8.47 (2H, d) No.76 1 H-NMR (CDCl 3): 3.87 (3H, s), 4.24 (2H, s), 6.87 (2H, d),
7.73 (2H, s), 8.48 (2H, d) No.77 1 H-NMR (CDCl 3): 2.25 (3H, s), 4.17 (1H, d), 5.16 (1H, d),
6.72 (2H, d), 7.26 (1H, s), 7.71 (1H, s), 8.33 (2H, d) No.78 1 H-NMR (CDCl 3): 4.61 (2H, d), 4.67 (1H, m), 7.49 (2H, m),
7.70 (2H, s), 8.00 (1H, s), 8.13 (1H, m)

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

Formulation examples and test examples of agricultural and horticultural insecticides containing the compound of the present invention as an active ingredient will be shown below, but the form of use of the compound of the present invention is not limited to the following.

<Formulation Example 1> Water-dispersible powder 20 parts by weight of the compound of the present invention, 20 parts by weight of carplex # 80 (white carbon, Shionogi & Co., Ltd., trade name), ST kaolin clay (Kaolinite, Tsuchiya Kaolin Co., Ltd.) 52 parts by weight), 5 parts by weight of Solpol 9047K (anionic surfactant, Toho Chemical Co., trade name), 3 parts by weight of Lunox P65L (anionic surfactant, Toho Chemical Co., Ltd.) The mixture was mixed and uniformly mixed and pulverized to obtain a wettable powder containing 20% by weight of the active ingredient.

<Formulation Example 2> Powder 2 parts by weight of the compound of the present invention, clay (manufactured by Nippon Talc) 9
3 parts by weight, carplex # 80 (white carbon,
5 parts by weight of Shionogi & Co., Ltd. (trade name) were uniformly mixed and pulverized to produce a powder containing 2% by weight of the active ingredient.

<Formulation Example 3> Emulsion 20 parts by weight of the compound of the present invention was dissolved in a mixed solvent consisting of 35 parts by weight of xylene and 30 parts by weight of dimethylformamide, and dissolved in Solpol 3005X (a nonionic surfactant and an anionic surfactant). Addition of a mixture of activators, Toho Chemical Co., Ltd., 15 parts by weight, and 20% by weight of active ingredient
Emulsion was obtained.

<Formulation Example 4> Flowable agent 30 parts by weight of the compound of the present invention, Solpol 9047K5
Parts by weight, 3 parts by weight of Sorbone T-20 (nonionic surfactant, Toho Chemical Co., Ltd., trade name), 8 parts by weight of ethylene glycol and 44 parts by weight of water are mixed and pulverized with Dynomill (manufactured by Shinmaru Enterprises). Then, 10 parts by weight of a 1% by weight aqueous solution of xanthan gum (natural polymer) was added to the slurry-like mixture, and the mixture was thoroughly mixed and pulverized.
By weight, a flowable agent was obtained.

Test Example 1: Insecticidal effect on larvae of brown planthoppers Rice shoots and seedlings were set on a glass cylinder (inner diameter 3 cm × length 17 cm), and five fourth-stage larvae of brown planthoppers were released. 0.5 ml of a water dilution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Formulation Example 3 was sprayed on the above-mentioned glass cylinder using a spray tower (manufactured by Mizuho Rika) (1 concentration, 2 repetitions). The larvae were kept in a constant temperature room at 25 ° C., and after 5 days from the treatment, the larvae were examined for viability and writhing. The results are shown in Table 2 (the compound numbers in the table correspond to Table 1).

[0074]

[Table 5]

[0075]

[Table 6]

[0076]

[Table 7]

Test Example 2: Insecticidal effect on moth larvae A cut cabbage leaf (6 cm in diameter) was immersed in a water dilution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Preparation Example 1 for 1 minute. Air-dry after immersion in a plastic cup (7 c inside diameter)
In m), five third instar larvae of the Japanese moth were released into the cup (one concentration, two repetitions). Keep in a 25 ° C constant temperature room,
Four days after the release, the larvae were examined for life and death and agony.
Insect kill rate (%) was determined as the death of 2 heads. The results are shown in Table 3 (in the following table, the compound numbers correspond to Table 1).

[0078]

[Table 8]

[0079]

[Table 9]

[0080]

[Table 10]

Test Example 3: Insecticidal effect on the larvae of Spodoptera litura The cut leaf of cabbage (6 cm in diameter) was immersed for 1 minute in a water dilution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Preparation Example 1. Air-dry after immersion in plastic cup
m), five third-instar larvae of Spodoptera litura were released into the cup (one concentration, two repetitions). The larvae were kept in a constant temperature room at 25 ° C., and after 5 days from the release, the larvae were examined for life and death and writhing, and the killing rate (%) was determined assuming that the writhing larva was 死 dead. The results are shown in Table 4 (in the table below, the compound numbers correspond to Table 1).

[0082]

[Table 11]

[0083]

[Table 12]

Test Example 4: Insecticidal effect of adzuki beetle on adult insects Two azuki beans were placed in a glass cylinder (inner diameter 3 cm × length 15 cm), and 10 adzuki beetles were released. 0.3 ml of a water dilution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Formulation Example 3 was sprayed onto the above-mentioned glass cylinder using a spray tower (manufactured by Mizuho Rika) (1 concentration, 2 repetitions). The larvae were kept in a constant temperature room at 25 ° C., and after 4 days from the treatment, the larvae were examined for viability and writhing, and the writhing larvae were killed by 死 to determine the insecticidal rate (%).
The results are shown in Table 5 (the compound numbers in the table correspond to Table 1).

[0085]

[Table 13]

[0086]

[Table 14]

[0087]

[Table 15]

Test Example 5: Pesticidal effect on larvae of peach peach aphid The petiole of a radish leaf was inserted into a screw bottle (capacity: 10 ml) filled with water, and peach peach aphid was added to each of 5 to 5 liters per leaf.
Six animals were inoculated. After inoculation, they were placed in a glass cylinder (diameter: 3.5 cm, height: 15 cm, with a mesh lid), and aphids were grown in a thermostatic chamber at 25 ° C. for 3 days. After removing the aphid adults from the radish leaves, the leaves were immersed (about 5 seconds) in a water dilution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Preparation Example 3, and returned into the glass cylinder ( 1 concentration, 2 replicates). It was kept in a constant temperature room at 25 ° C, and on the fourth day after the treatment, the number of aphids on the radish leaves was investigated, and the insecticidal rate (%) was determined based on the results. The results are shown in Table 6 (the compound numbers in the table correspond to Table 1).

[0089]

[Table 16]

Test Example 6: Low concentration test Compounds Nos. 2 and 57 were used as control compounds, Compound I described in JP-A-63-316771, and JP-A-5-15-1.
Using compounds II and III described in 48240, the effect on the moth larvae was examined at different concentrations. The results are shown in Table 7 (the compound numbers in the table correspond to Table 1).

[0091]

[Table 17]

[0092]

[Table 18]

Test Example 7: Test Example of Single Dose Administration by Gavage Oral Administration in Mice 1 was used to examine the acute toxicity (oral) in mice. JP-A-63 as a control compound
Compound IV described in Japanese Patent No. 316761 was similarly subjected to the test. 300 mg of each compound was suspended in 10 ml of a 0.5% CMC-Na aqueous solution, and the suspension was added to a CD-1 mouse male (6 weeks old, manufactured by Charles River) at 10 mg / kg mouse.
ml of the adjusted solution was orally administered by gavage (5 animals /
Group), the number of mice that died 7 days after administration was examined, and the mortality was determined. Table 8 shows the results.

[0094]

[Table 19]

[0095]

The 1-aryl-3-cyano-5 of the present invention
The-(het) arylalkylaminopyrazole derivative is useful as a novel pesticidal agent having excellent pesticidal effects, a wide pesticidal spectrum, high safety, and little adverse effect on the environment.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 405/12 231 C07D 405/12 231 409/12 231 409/12 231 417/12 231 417/12 231 (72) Inventor Tanaka Ken 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory

Claims (13)

[Claims] [Claim 1] The following general formula (1)[In the above formula, R¹Is C₁~ C_FourAlkyl group or C₁
~ C₈A haloalkyl group of R^TwoIs a hydrogen atom or
C₁~ C_FourRepresents an alkyl group. R^ThreeIs a hydrogen atom, water
Acid group, C₁~ C_FourAn alkyl group of C₁~ C_FourNo haloal
Kill group, C₁~ C _FourAn alkoxy group, even if it is substituted
Good phenoxy group, C₁~ C_FourHaloalkoxy group, C
₁~ C_FourAn alkylthio group of C₁~ C_FourAlkisulf
Inyl group, C₁~ C_FourAlkylsulfonyl group, halogen
Substituted with a substituent selected from nitro, nitro and cyano
Aryl or heteroaryl group which may be
Is shown. R^FourIs a hydrogen atom, C₁~ C_FourThe alkyl group of
Is C₁~ C_FourRepresents an acyl group. X is a nitrogen atom, and
Represents a carbon atom substituted with a halogen atom. l, n
Represents 0, 1, and 2 independently. 1 represented by
-Aryl-3-cyano-5- (het) arylalkyl
Luminopyrazole derivatives. 2. The 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1, wherein R ² is a hydrogen atom. (3) R ³ is (In the above formula, R ⁵ represents a hydrogen atom, a hydroxyl group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₈ haloalkyl group, a C ₁ -C ₄ alkoxy group, an optionally substituted phenoxy group,
Haloalkoxy group _{1 ~C 4,} C _{1 ~C 4} alkylthio group, alkylsulfinyl group _{C 1 ~C 4, C 1 ~C} 4
Represents an alkylsulfonyl group, a halogen atom, a nitro group or a cyano group. m represents any one of 0, 1, and 2. 2. The 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1, wherein (4) R ³ is (In the above formula, R ⁵ represents a hydrogen atom, a hydroxyl group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₈ haloalkyl group, a C ₁ -C ₄ alkoxy group, an optionally substituted phenoxy group,
Haloalkoxy group _{1 ~C 4,} C _{1 ~C 4} alkylthio group, alkylsulfinyl group _{C 1 ~C 4, C 1 ~C} 4
Represents an alkylsulfonyl group, a halogen atom, a nitro group or a cyano group. m represents any one of 0, 1, and 2. 2. The 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1, wherein (5) R ³ is (In the above formula, R ⁶ is a hydrogen atom, a hydroxyl group, a C ₁ -C ₂ alkyl group, a C ₁ -C ₂ alkoxy group, a C ₁ -C ₂ haloalkoxy group, a C ₁ -C ₂ alkylthio group, A 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1, wherein the derivative is a halogen atom, a nitro group or a cyano group. 6. The following general formula (2):(R in the above formula⁷IsAnd R⁸Is C₁~ C_TwoAn alkoxy group of C₁~ C_Two
Haloalkoxy group, C ₁~ C_TwoAlkylthio group, d
Toro or cyano, R⁹Is a hydrogen atom, a hydroxyl group, C₁
~ C_TwoAn alkoxy group of C₁~ C_TwoHaloalkoxy group
Or a nitro group, R^TenIs C₁~ C_TwoRepresents an alkyl group of
You. 1) -aryl-3-cyano-5- (f)
G) Arylalkylaminopyrazole derivatives. 7. R ⁷ is embedded image The 1-aryl- according to claim 5, wherein
3-cyano-5- (het) arylalkylaminopyrazole derivatives. 8. The following general formula (3): [In the above formula, R ² , R ³ , R ⁴ , X and l are each as defined in claim 1. 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivatives represented by the formula: 9. The following general formula (3): [In the above formula, R ² , R ³ , R ⁴ , X and l are each as defined in claim 1. ] Is represented by R ¹
S (O) n-Y (wherein, R ¹ and n are as indicated in claim 1, Y is a halogen atom, a hydroxyl group or a salt thereof,
Or a dialkylamino group). 1-Aryl-3 according to claim 1,
-Cyano-5- (het) arylalkylaminopyrazole derivatives. 10. The following general formula (3): [In the above formula, R ² , R ³ , R ⁴ , X and l are each as defined in claim 1. ] Is represented by R ¹
S (O) n-Y (wherein, R ¹ and n are as indicated in claim 1, Y is a halogen atom, a hydroxyl group or a salt thereof,
Or a dialkylamino group). 11. A pest control agent comprising the 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1 as an active ingredient. 12. An insecticide comprising the 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1 as an active ingredient. 13. An agricultural and horticultural insecticide comprising the 1-aryl-3-cyano-5- (het) arylalkylaminopyrazole derivative according to claim 1 as an active ingredient.