JP2001072676A - Pyrazole derivative and its production, and pest control agent containing the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative which has an excellent insecticidal effect and a wide insecticidal spectrum, exhibits a high penetration transfer activity and reduced toxicity against environments, such as reduced ichthyotoxicity, and is useful as a pest control agent. SOLUTION: The compound of formula I [A is a group of formula II (R4 is H, a halogen or the like) or the like; X is N or a C-halogen; R1 is an alkyl, an alkenyl or the like; R2 is H, an acyl or the like; R3 is H or an alkyl; (n) is 0 to 2], for example, 1 (2,6-dichloro-4-trifluoromethylphenyl)-4- trifluoromethylsulfinyl-5-(pyrazin-2-ylmethylamino)pyarzole-3-carbonit rile. The compound of formula I is obtained by reacting a pyrazole derivative of formula III (R5 is H; Y is a group of formula IV or the like) with a compound of the formula: R1S(O)nX1 (X1 is chlorine or bromine) preferably in an amount of 0.8 to 5 moles at 0 to 100 deg.C in the presence of a base in a solvent (for example, toluene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative and a pesticidal composition containing the same as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, in the field of agriculture and horticulture, various pesticides such as insecticides for controlling various pests have been developed and put to practical use. For example, pyrazole compounds having insecticidal activity include those described in JP-A-62-228065, JP-A-63-316771, and JP-A-3-3127.
JP-A-118369 discloses a 3-cyano-1-phenylpyrazole derivative having an amino group which may be substituted at the 5-position, and JP-A-5-148240 discloses a substituted 1-aryl-3. -Cyano-5- (het) arylmethylideneiminopyrazole derivatives are disclosed. Further, Japanese Patent Application Laid-Open No. Sho 47-47768 discloses substituted 1-aryl-5- (het) arylmethylaminopyrazole derivatives. It has been disclosed.

[0003] However, the compounds described in the above-mentioned documents do not satisfy all of the insecticidal effects, insecticidal spectrum, safety and the like. WO9
No. 8/45274 discloses a novel 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative as a highly safe compound.

[0004] In this application, however, a compound having a pyrazine ring, a pyridazine ring or a pyrimidine ring as a hetero ring is described.
There is no description of specific compounds at all.

[0005]

[Problems to be Solved by the Invention] WO 98/45274
The compounds described in Japanese Patent Application Publication Nos. 2000-187 and 2000 have excellent insecticidal activity and reduced toxicity as compared with known compounds, but in recent years, demands for safety on living organisms and the environment other than target pests have been increasing, and in the future Means that environmental protection measures will be strengthened. Therefore, in order to develop pesticides suitable for stricter regulations, it has been an important issue to find compounds with higher safety.

In addition, permeation transfer activity is an important factor in terms of improving the efficiency of application of chemicals in controlling pests, and applying the method to soil treatment in which pests such as sucking insects are particularly effective. Therefore, it has been desired to find a novel compound having both of them.

[0007]

Means for Solving the Problems The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, have found that pyrazole-based compounds, 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivatives. A compound in which a specific nitrogen-containing hetero 6-membered ring is introduced into the amino group at the 5-position of the pyrazole ring via a methylene group selectively exhibits high osmotic transfer activity and is toxic to the environment as shown by fish toxicity. Was low.

Further, a heteroaryl group and a pyrazole ring 4
It has been found that a higher effect can be obtained by optimizing the combination with the substituent at the position, and the present invention has been completed. That is, the gist of the present invention is

[0009]

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(Where X represents N or C-halogen, R ¹ represents an alkyl group, alkenyl group, alkynyl group or haloalkyl group, R ² represents a hydrogen atom, an alkyl group or an acyl group, ³ represents a hydrogen atom or an alkyl group; A represents any one of the above A-1 to A-4; R ⁴ represents a hydrogen atom, an alkyl group, or a halogen atom, and n represents 0, 1 or 2 where A is A-
1, when n = 0, R ¹ represents a haloalkyl group (excluding a perhaloalkyl group), and A represents A-
In the case of 4, n ≠ 0 is indicated. 1) aryl represented by
A 3-cyano-5-heteroarylalkylaminopyrazole derivative and a pesticidal composition containing the same as an active ingredient.

Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION [Compound of the Present Invention]
In the compound represented by the above general formula (1)
Group R¹Represents a methyl group, an ethyl group, an n-propyl group,
Propyl group, n-butyl group, isobutyl group, sec-butyl
Or a straight-chain or branched-chain alkyl such as a t-butyl group.
Group; vinyl group, allyl group, methallyl group, 2-butenyl group
Linear or branched alkenyl groups such as; ethynyl group;
Linear or branched alkynyl such as propargyl group
Group; or fluoromethyl group, difluoromethyl group,
Trifluoromethyl group, 2-fluoroethyl group, 2-chloro
Roethyl group, 2,2,2-trifluoroethyl group, 2,
2,2-trichloroethyl group, 3-chloropropyl group,
3-bromopropyl group, 3,3,3-trifluoropro
Pill group, 2,2,3,3-tetrofluoropropyl group,
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,
Linear or branched such as 4,4-pentafluorobutyl group
A chain haloalkyl group, wherein the above alkyl group, alkenyl
Groups, alkynyl groups, or haloalkyl groups are preferably
Is C₁~ C_Fourbelongs to. Particularly preferably, C₁~
C_FourAlkyl group or C₁~ C_FourIs a haloalkyl group
And especially C₁~ C_TwoAlkyl group or C₁~ C_TwoHalo of
Alkyl groups are preferred, especially fluoromethyl groups, difur
Oromethyl group, trifluoromethyl group, 2-fluoroethyl
C such as tyl group and 2-chloroethyl group ₁~ C_TwoHalo archi
Preferred is a thiol group.

R ² is a hydrogen atom; a methyl group, an ethyl group, n
A linear or branched alkyl group such as -propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group; or methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropyl Carbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, t-
It represents a linear or branched acyl group such as butyl group, examples of the alkyl group or an acyl group, C ₁ ~
C ₄ is preferred. R ² is particularly preferably a hydrogen atom.

R ³ is a hydrogen atom; or methyl, ethyl, n-propyl, isopropyl, n-butyl,
It represents a linear or branched alkyl group such as an isobutyl group, a sec-butyl group and a t-butyl group, and the alkyl group is preferably a C ₁ -C ₄ group. R ³ is particularly preferably a hydrogen atom. A is any group represented by A-1 to A-4, and among them, A-1 is preferable.
In the present invention, the nitrogen-containing hetero 6-membered ring having the specific structure is selected, and this is linked to the 5-membered pyrazole ring via a methylene group.
It is characterized in that it is bonded to the amino group at the position.

R ⁴ is a hydrogen atom; a methyl group, an ethyl group, n
A linear or branched alkyl group such as -propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group; or chlorine atom, fluorine atom,
It represents a halogen atom such as a bromine atom. Among them, the above alkyl group is preferably C ₁ -C ₄ . R ⁴ is particularly preferably a hydrogen atom.

X is an N or C-halogen atom, preferably a C-halogen atom, and particularly preferably a C-chlorine atom. n is 0, 1, or 2
Wherein n = 0 or 1 is preferable.
It is. However, when A is A-4, n is not 0.
Also, A is an A-1, when n is 0, R ¹ is a haloalkyl group other than a perhaloalkyl group, of which preferably haloalkyl group C ₁ -C _4, particularly preferably C ₁ -C a ₂ haloalkyl group, most preferably fluoromethyl group, a fluorinated alkyl group of C _1, such as a difluoromethyl group.

As the compound of the above-mentioned general formula (1), a compound obtained by combining preferred substituents in the above description of the substituents is a more preferable compound. Among them, compounds which are preferable as a combination of substituents are R ² , R ³ and R ⁴
Is a hydrogen atom, X is a C-Cl group, and A is A-1. Here, when n is other than 0, R ¹ is preferably an alkyl group or a haloalkyl group, more preferably C _{1 to} C ₄ , and particularly preferably C _{1 to} C _2.
Is a haloalkyl group. When n = 0, R
¹ is a haloalkyl group other than a perhaloalkyl group,
Preferably of C ₁ -C _4, particularly preferably C ₁
~C a _second fluorinated alkyl group.

Among them, those having a fluoromethyl group, difluoromethyl group or trifluoromethyl group in which R ¹ is C ₁ haloalkyl (excluding trifluoromethyl group when n is 0) are pesticidal agents, especially insecticides. When used as an active ingredient of the agent, the insecticidal activity is high and fish toxicity is low, which is preferable. Among the combinations of the above substituents,
The most preferred compound is 1- (2,6
-Dichloro-4-trifluoromethylphenyl) -4-
Fluoromethylthio-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile and 1-
(2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile.

[0019]

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[Production Method of the Compound of the Present Invention] The method of producing the compound of the present invention represented by the general formula (1) includes the following.
It can be produced by adding or changing a substituent as necessary after forming a pyrazole ring. Known methods are disclosed in JP-A-63-316771, JP-A-5-1482.
No. 40, JP-A-64-47768, and the production method using these methods is exemplified by the following reaction formula 1.

[0021]

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However, this method has a drawback that an expensive fluorine-containing reagent is used at an early stage of the process. Alternatively, the methods of Reaction Schemes 2 and 3 are also possible, but there are similar problems such as obtaining raw materials.

[0023]

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In WO 98/45274, pyrimyl 4-aldehyde is allowed to act on the 5-position amino group of the pyrazole derivative at the 4-position to give an imine, which is reduced to give a 4-pyridylmethylamino group at the 5-position. It is disclosed that a pyrazole derivative having the formula is obtained (Reaction formula 4).

[0025]

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The compound of the present invention can also be synthesized by the method of the above-mentioned reaction formula (4). However, the present inventors have further studied and found that the pyrazole derivative represented by the general formula (1) can be produced. As a method, it has been found that the methods shown in the following reaction formulas 5 to 10 are efficient. The following general formula (2) is a production intermediate used when producing the compound of the general formula (1) by the production method.

[0027]

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(Wherein R ² , R ³ , R ⁴ and X have the same meanings as in the general formula (1), and R ⁵ is a hydrogen atom, thiocyanato,
It represents a dithio group and a mercapto group bonded to two pyrazole rings. Z represents a halogen atom. Hereinafter, the method for producing the compound of the present invention will be described in more detail. Examples of the method for producing the compound of the present invention represented by the general formula (1) include Reaction Formulas 5 to 10. In each case, R ¹ is preferably a haloalkyl group having 1 to 2 carbon atoms.

[0029]

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Reaction formula 5 shows that a pyrazole derivative of the general formula (2) (wherein R ⁵ is a hydrogen atom and Y is Y-3) is obtained by converting R ¹ S (O) nX ¹ (where R ¹ and n are (Wherein X ¹ represents a chlorine atom or a bromine atom), and has the same meaning as in formula (1). X ¹ is preferably a chlorine atom. When n = 0, the reagent R ¹ S (O) nX ^{1 to be used}
A preferred example is trifluoromethylsulfenyl chloride (CF ₃ SCl). In this case, the obtained compound is a pyrazole derivative having a trifluoromethylsulfenyl group at the 4-position. When n = 1, a preferred example of the reagent R ¹ S (O) nX ^{1 to be} used is trifluoromethylsulfinyl chloride (CF ₃ SOCl), and the obtained compound is a pyrazole derivative having a trifluoromethylsulfinyl group at the 4-position. Become.

Hereinafter, the present reaction will be described using trifluoromethylsulfenyl chloride and trifluoromethylsulfinyl chloride as typical examples, but the same operation can be carried out when other reagents are used. When using trifluoromethylsulfinyl chloride,
Trifluoromethylsulfinyl chloride isolated in advance may be used, or may be generated in a system from a sodium or potassium salt of trifluoromethylsulfinic acid and thionyl chloride. Further, depending on the conditions, pyrazole in which the 4-position is sulfenylated may be formed in the reaction with trifluoromethylsulfinate.

[0032] In this reaction, R ₁ to the general formula (2) (wherein R ⁵ is a hydrogen atom) a compound represented by
The reaction is carried out at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., using 0.5 to 10.0 molar equivalents of S (O) nX ₁ , preferably 0.8 to 5 molar equivalents. Solvents 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; polar solvents such as tetrahydrofuran and N, N-dimethylformamide And particularly preferred are toluene and dichloromethane.

When trifluoromethylsulfenyl chloride is used, the reaction may be performed in the absence of a base, but preferably in the presence of a base, and an amine such as pyridine or triethylamine is used. When using trifluoromethylsulfinyl chloride or trifluoromethylsulfinate, an amine such as dimethylamine, pyridine or triethylamine or an inorganic base such as an alkali metal carbonate and an acid such as sulfuric acid, hydrochloric acid or toluenesulfonic acid are used. Use in combination. A preferred combination is dimethylamine and toluenesulfonic acid. These may be added separately, but are preferably added as a salt of dimethylamine and toluenesulfonic acid (dimethylamine tosylate).

Reaction formula 6 is represented by the general formula (1) (where n = 0)
Is a method for producing a pyrazole derivative of the general formula (1) (where n is 1 or 2), wherein a sulfur atom of the pyrazole derivative of the formula (1) is oxidized. Examples of the oxidation method include a chemical oxidation method using an oxidizing agent and a biochemical oxidation method using an enzyme or a bacterium.
Chemical oxidation methods are commonly used. In the chemical oxidation, 0.2 to 5.0 with respect to the compound of the general formula (2).
A molar equivalent, preferably 0.25 to 2.0 molar equivalents of the oxidizing agent is added in the presence or absence of a solvent, and
C., preferably at a temperature of 0 to 120.degree.

The oxidizing agent used in this reaction includes hydrogen peroxide, oxone, m-chloroperbenzoic acid, peracetic acid, sodium periodate, ruthenium tetroxide, ozone, t-butyl hydroperoxide, nitric acid and the like. , Preferably hydrogen peroxide. As a solvent used in this reaction, an organic solvent generally used for an oxidation reaction can be used,
Hydrocarbon solvents such as toluene and hexane, and halogenated hydrocarbon solvents such as dichloromethane and chloroform are used.

In the present invention, it is particularly preferable to carry out the reaction in the presence of an acid. Examples of the acid used include a protic acid and a Lewis acid, but a protic acid is preferred. Examples of the protic acid include dilute sulfuric acid, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, formic acid, and trifluoroacetic acid, and are preferably inorganic acids, and more preferably sulfuric acid. When sulfuric acid is used, dilute sulfuric acid having a concentration of 60 to 90% is used, and sulfuric acid having a concentration of 75 to 85% is preferably used. These acids may be used as a mixture with an organic solvent, but preferably the acid itself is used as a solvent.

A preferred combination of the oxidizing agent and the solvent is a combination of hydrogen peroxide and dilute sulfuric acid. In this reaction, a catalyst that assists oxidation may be added as necessary.
As the catalyst, a catalyst that generally assists in the oxidation of sulfide can be used, and preferably, a ruthenium compound,
Tungsten compounds, vanadium compounds, molybdenum compounds, titanium compounds and the like, and more preferably ruthenium compounds. Examples of the ruthenium compound include ruthenium trichloride and ruthenium oxide. These catalysts are used in an amount of 0.01 to sulfide as the starting material.
Mol% to 100 mol%, preferably 0.1 mol% to 20 mol%.

The reaction is carried out at a temperature of -30 ° C to 120 ° C, preferably-
Carried out in the range of 10 ° C. to room temperature, for 1 hour to 48 hours,
It is preferably carried out for 1 to 6 hours. Reaction formula 7 is represented by the general formula (2) (where R ⁵ is a thiocyanato group and Y is Y
-3) with R ¹ -X ² (R ¹ has the same meaning as in the general formula (1) and X ² represents a halogen atom or a trimethylsilyl group). 1) shows a method for producing a pyrazole derivative of (where n = 0).

As the reagent used in this reaction, trifluoromethyl bromide, trifluoromethyl iodide or trifluoromethyltrimethylsilane is exemplified, and trifluoromethyltrimethylsilane is preferred. Examples of the solvent used in this reaction include ether solvents such as tetrahydrofuran, diethyl ether and dimethoxyethane, hydrocarbon solvents such as toluene and hexane, and halogenated hydrocarbon solvents such as dichloromethane and chloroform. It is tetrahydrofuran.

The reaction is preferably carried out in the presence of a fluorine compound, preferably tetrabutylammonium fluoride and potassium fluoride. In this reaction, the reagent R ¹ -X ² is added to the compound represented by the general formula (2) (where R ⁵ is a hydrogen atom) in an amount of 0.5 to 10.0 molar equivalents, preferably 0.8 to 10.0. ~ 5 molar equivalents and the reaction was -2
It is carried out in the range of 0 ° C. to 120 ° C., preferably 0 ° C. to room temperature, and is carried out for 1 hour to 24 hours, preferably for 1 to 4 hours.

Reaction formula 8 shows that a pyrazole derivative of the general formula (2) (where R ⁵ is a mercapto group and Y is Y-3) is represented by R ¹ -X ³ (R ¹ is a group represented by the general formula (1) Synonymous
X ³ represents a halogen atom) and a method for producing a pyrazole derivative of the general formula (1) (where n = 0).

Examples of the reagent used include trifluoromethyl bromide and trifluoromethyl iodide. Examples of the solvent include polar solvents such as DMF and DMSO; hydrocarbon solvents such as toluene and hexane; halogenated hydrocarbon solvents such as dichloromethane and chloroform; triethylamine;
Basic solvents such as liquid ammonia can be exemplified,
Preferably, it is a polar solvent such as DMF.

The reaction is preferably carried out under trifluoromethyl radical generating conditions, and specific examples include irradiation with light, the use of a radical initiator or a redox agent, or an electron transfer agent such as methyl viologen. The reaction is between -20 ° C and 1
Carried out at 20 ° C., preferably in the range from 0 ° C. to room temperature,
It is carried out for a time of from 24 to 24 hours, preferably from 1 to 4 hours.

The method of Reaction Scheme 9 is based on the general formula (2) (where R ⁵ is a dithio group bonded to two pyrazole rings,
The pyrazole derivative of Y is Y-3) is represented by R ¹ -X ⁴ (R
¹ has the same meaning as in the general formula (1), and X ⁴ acts on a halogen atom or SO ₂ M (M is an alkali metal), wherein the general formula (1) (where n = 0 And R ³ is a hydrogen atom).

Examples of the reagent used include trifluoromethyl bromide, trifluoromethyl iodide and trifluoromethylsulfinate. DMF, DM
Examples thereof include polar solvents such as SO, hydrocarbon solvents such as toluene and hexane, and halogenated hydrocarbon solvents such as dichloromethane and chloroform, and are preferably polar solvents such as DMF.

The reaction is preferably carried out under trifluoromethyl radical generating conditions, and specific examples include irradiation with light, use of a radical initiator or a redox agent, or the use of an electron transfer agent such as methyl viologen. In the case of trifluoromethyl bromide or trifluoromethyl iodide, a radical anion generator of sulfur dioxide is preferably used in combination. As the radical anion generator of sulfur dioxide, sodium dithionate (Na ₂ S ₂ O ₄ ), Sodium hydroxymethanesulfinate (Rongalit, NaO ₂ SC
H ₂ OH), hydroxy methane sulfinic acid zinc, a mixture of sulfur dioxide and zinc, such as a mixture of sulfur dioxide and formic acid formic acid salt are exemplified. The reaction is carried out at a temperature ranging from -20 ° C to 120 ° C, preferably from 0 ° C to room temperature, for 1 hour to 24 hours.
It is carried out for an hour, preferably for 1 to 4 hours.

[0047]

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The method of Reaction Scheme 10 is a method for preparing a pyrazole derivative of the general formula (1) (where R ¹ is an alkyl group containing at least one chlorine atom or bromine atom) with hydrogen fluoride, a mixture of hydrogen fluoride and an amine, A method for producing a pyrazole derivative of the general formula (1) (where R ¹ is an alkyl group having one or more fluorine atoms) characterized by reacting with a fluorinating agent selected from the group consisting of metal fluorides. (In Reaction Scheme 10, R ⁷ is an alkyl group containing one or more chlorine atoms or bromine atoms, and R ⁸ represents an alkyl group having one or more fluorine atoms.)

Examples of the reagent used include hydrogen fluoride, a mixture of hydrogen fluoride and an organic amine, and metal fluorides such as potassium fluoride, sodium fluoride, and cobalt fluoride. Preferably, hydrogen fluoride and an organic amine are used. And mixtures with other types. As the solvent, a solvent generally used for a halogen exchange fluorination reaction can be used. Preferably, DMF is used.
And polar solvents. R ^{7 in the} raw material is preferably a trichloromethyl group, and R ⁸ is, for example, a trifluoromethyl group.

Although the method for producing the pyrazole derivative represented by the general formula (1) has been described above, the methods of Reaction Formulas 5 and 6 are preferably used. Next, a method for producing the pyrazole derivative represented by the general formula (2) will be described. Y is Y-
In the case of 3, a pyrazole derivative represented by the general formula (2) is produced from the compounds represented by the general formulas (3) and (4) as starting materials by the method represented by the reaction formulas 11 and 12. be able to.

[0051]

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Further, as shown in the above reaction scheme 13, starting from the compound of the general formula (3), AC (＝ O) —X ⁷
With an amide compound (compound of general formula (2), wherein Y is Y-1), and reducing this to a compound of general formula (2) wherein Y is Y-3. Further, an amide compound (compound of general formula (2), wherein Y is Y-1) is converted into a haloimidate compound (compound of general formula (2), wherein Y is Y-2), which is reduced to form a pyrazole derivative (In the general formula (2), Y is Y-3
Can also be exemplified.

Examples of the reducing agent used in the reduction reaction include borane THF complex, sodium borohydride, sodium cyanoborohydride, lithium borohydride and lithium aluminum hydride. As the solvent used in this reaction, ethers such as diethyl ether, dioxane or tetrahydrofuran; or methanol,
Examples include polar solvents such as alcohols such as ethanol and propanol.

The reaction is carried out at -20 ° C to 120 ° C, preferably at 0 ° C.
It is carried out in a range of from C to room temperature, and is carried out for 1 hour to 24 hours, preferably for 1 to 4 hours. Examples of the chlorinating agent used for haloimidate include phosphorus pentachloride, phosphorus oxychloride, thionyl chloride and the like. Examples of the solvent used in this reaction include non-polar solvents such as benzene, toluene, and xylene; halogen-based solvents such as carbon tetrachloride, chloroform, and dichloromethane; and ether-based solvents such as dimethoxyethane and tetrahydrofuran.

The reaction is carried out at 0 ° C. to 200 ° C., preferably at room temperature to
It is carried out in the range of 150 ° C. and is carried out for 1 to 24 hours, preferably for 1 to 4 hours. The compounds described in the general formula (1) can be produced by combining the methods described above. A typical method for producing 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile is This is shown in the following reaction formula 14.

[0056]

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[Uses of the Compound of the Present Invention] The pesticidal composition containing the compound of the present invention as an active ingredient has an effect of controlling pests, mites and other pests.
It is effective for repelling pests, extermination and control, etc. in a wide range of situations such as the fishing industry, product preservation scenes in these industries and public health. In particular, the compound of the present invention is used in agriculture, forestry, and the like, specifically, when cultivating crops, and when repelling, controlling, and controlling pests that cause damage to crops, trees, ornamental plants, and the like, and public health. It exerts an excellent effect as an insecticide or acaricide used for such purposes.

[0058] The specific use scene, target pest,
The method of use and the like will be described, but the present invention is not limited to the following description. The pests specifically exemplified are not limited to target pests, and the exemplified pests also include adults, larvae, eggs, and the like. (A) Agriculture, forestry scenes, etc .; Pest control agents containing the compound of the present invention as an active ingredient include agricultural crops such as food crops (rice, wheat, corn, potato, sweet potato, beans, etc.), vegetables (brassaceae crops, Spinach, eggplant, tomato, leek, etc.), fruit trees (citrus, apple, grape, thigh, etc.), special crops (tobacco, tea, sugar beet, sugar cane, cotton, olives, etc.), pasture and feed crops (sorghum) , Grasses, legumes, etc.)
And repelling and controlling pests such as arthropods, molluscs, nematodes, and various fungi that damage them when cultivating plants and ornamental plants (herbs, flowers, garden trees, etc.) It is valid. Further, the compound of the present invention can be used to repel pests when storing harvested products from the above-mentioned crops, such as cereals, fruits, nuts, spices, tobacco, and the like, and products that have been subjected to drying, powdering, and the like. It is also effective for extermination. It is also effective in protecting standing trees, fallen trees, processed wood, stored wood, and the like from damage by pests such as termites and beetles.

Specific pests include, for example, those belonging to the phylum Arthropoda, Mollusca and Nematoda:
The following can be mentioned. Examples of the arthropod phylum Insecta include the following. As Lepidoptera, for example, Noctuidae such as Spodoptera litura, Helicoverpa armigera, Artemisia moth, and Tamanagininuwaba;
Anthophoridae, such as Anopheles japonicus and Papilio persica; Aminidae, such as Mina moga; Pterodaceae such as peach sink moth; Singing moth such as peach sink moth; Iragidae such as iraga; Lycaenidae of the family; Paeoniaceae such as Artemisia japonica; It can gel.

As the order Coleoptera, for example, Scarabaeidae, such as Scutellaria squid, Scarabaeidae, and Beetle;
Beetles, such as Citrus beetles; Beetles, such as Marc beetles; Weevil family; beetle weevil family such as arid beetle; weevil family such as weevil and rice weevil.

As the Hemiptera, for example, stink bugs such as chafered stink bugs and sting bugs; crested stink bugs such as pear stink bugs; crested stink bugs such as crested stink bugs; Gastropodidae such as Nashigumbai; Scarabaeidae such as Pseudomonidae; Cicadaidae such as Nichiniizemi; Coleoptera such as Grape Awafuki;
Lepidoptera, such as the leafhopper leafhopper and the leafhopper leafhopper; Lepidoptera, such as the leafhopper leafhopper; Phylloceraceae, such as Krya aphid; Berberidae, such as apple beetle; Aphid, such as cotton aphid, peach aphid, and okabonoa aphid; And the like; and Pterodactylidae, such as pear and round insects.

As the Thripidae, there may be mentioned the Thripidae family, such as Citrus thrips, Thrips palmi, Thrips palmi, etc .; Hymenoptera include, for example, honeybees such as wasps, honeybees such as apple honeybees, honeybees such as apple honeybees, and honeybees such as chestnut wasps.

Examples of the dipterans include the order of the genus Dermatophyta, such as soybean flies; the genus Mesinidae, such as the fruit flies; Department. As the Orthoptera, for example, grasshoppers such as crickets; crickets such as green worms;
And the like; and the like;

As the order of the order Collembola, there may be mentioned, for example, a family of bugs, such as the beetles; a family of bugs, such as the beetles. Examples of the termites include termites such as Taiwan termites, and examples of the earwigs include earwigs such as earwigs.

Examples of arthropod phylum crustaceans and arachnids include the following. As the isopod of the crustacean, there may be mentioned, for example, the family Acaratidae, such as the cadaver bug. As the spider mite of the order of the spiders, for example, Dermatophagoids such as Dermatophagoids and Cyclamenidae;
Red mite, such as wheat mite; Red mite, such as grape spider mite; Spider mite, such as spider mite, Kanzawa mite, red mite, apple spider mite; it can.

The mollusc phylum Gastropods include, for example, the midgastropods of the gastropods; be able to. The following can be exemplified as the nematode phylum and the tail line. Examples of the genus Pteridophyta include, for example, Anguinaceae, such as Imogusa nematode; Tilenkorinkusu, such as Namiikusu nematode; Platylenex, such as Kitanegusaresuenchi, Minaminekurosesenchu; Heterodela family such as nematodes; meloidogyne family such as sweet potato nematodes; cliconiaceae such as nematodes; nototilencaceae such as strawberry bark nematodes;

Examples of the order Caudata of the order Crustacea include Longiduraceae, such as O. nematode; and Trichodulaceae, such as Yumihari nematode. Further, the compound of the present invention is also effective for repelling, controlling, and controlling pests that damage trees or affect tree vigor such as natural forests, artificial forests, and urban green spaces. In such a situation, specific pests include the following. Examples of the arthropod phylum Insecta and Arachnida include the following.

Examples of the Lepidoptera include, but are not limited to, the family Scutellariae such as sugidoguga and the gypsy moth; Hirrigidae, such as A. americana; Moglitiviga, such as Shiimoglitiviga;

As the Coleoptera, for example, Scarabaeidae such as Scarabae beetle and Nagachakogane; Taeopteridae such as Pseudocarabidae; Cerambycidae such as pine beetle; Chrysomelidae such as cedar beetle; A beetle family, such as a weevil, etc .; a bark beetle family, such as a pine bark beetle and a bark beetle;

The Hemiptera includes, for example, aphid family such as Aphid aphid; mosquito aphid family such as P. sylvestris; Examples of the Hymenoptera include honeybees such as Larch red wasp, etc .; honeybees such as pine wood wasp, etc .;

Examples of the order Diptera include, for example, the parasitoids, such as the scutellidae; the flies, such as L. japonicus; Examples of the spiders of the order Arachnida include spider mites and spider mites.

Examples of the nematodes of the order Nematoda, Nematoda, include Parasitaferrenaceae, such as pine wood nematodes. The pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in addition to other active compounds such as insecticides, pesticides, and the like in the above-mentioned preparations effective in agriculture and forestry, and in any use form prepared by the preparations. It can be used in combination or as a mixture with mites, nematicides, fungicides, synergists, plant regulators, herbicides, poison baits and the like. Specific examples of the above-mentioned other active compounds include:
The following can be exemplified, but not limited to these.

Active compounds such as insecticides and acaricides: Examples of organic phosphorus agents include dichlorvos, fenitrothion, malathion, naled, chlorpyrifos, diazinon, tetrachlorvinphos, fenthion, isoxathion, and the like.
Methidathion, salicion, acephate, dimeton-S
Methyl, disulfotone, monocrotophos, azinephosmesyl, parathion, hosalon, pirimiphosmethyl, prothiophos and the like can be mentioned. Examples of the carbamate include metorcarb, fenobcarb, propoxur, carbaryl, ethiophenecarb, pirimicarb, bendiocarb, carbosulfan, carbofuran, mesomil, thiodicarb and the like.
Examples of the organic chlorine agent include lindane, DDT, endosulfan, aldrin, chlordane and the like. Examples of pyrethroids include permethrin,
Cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, acrinatrine, fenvalerate, etofenprox, silafluofen, fulvalinate,
Flucitrinate, bifenthrin, allethrin, phenothrin, fenpropatrin, cyphenothrin, framethrin, resmethrin, transfluthrin, praletrin, flufenprox, halofanprox, imiprothrin and the like can be mentioned. Neonicotinoid agents include, for example, imidacloprid, nitenpyram, acetamiprid, tefuranitodine, thiamethoxam, thiacloprid and the like.

Examples of insect growth regulators such as phenylbenzoylurea agents include diflubenzuron, chlorofluazuron, triflumuron, flufenoxuron, hexaflumuron, lufenuron, teflubenzuron, buprofezin, tebufenozide, chromafenozide, methoxyfenozide, cyromazine and the like. be able to.

Examples of juvenile hormone agents include pyriproxyfen, phenoxycarb, mesoprene, hydroprene and the like. Examples of insecticidal substances produced by microorganisms include abamectin, milbemectin, nikkomycin, emamectin benzoate,
Ivermectin, spinosadado and the like can be mentioned.

Other insecticides include, for example, cartap, bensultap, chlorfenapyr, diafenthiuron, nicotine sulfate, methaldehyde, fipronil, pymetrozine, indoxacarb, tolfenpyrad and the like. Active compounds for acaricides include, for example, dicophor, phenisobromolate, benzomate, tetradiphone, polynactin complex, amitraz, propargyl, fenbutatin oxide, tricyclohexyltin hydroxide, tebufenpyrad, pyridaben, fenpyroximate, pyrimidifen, fenazaquin,
Clofentezine, Hexythiazox, Acequinosyl,
Examples thereof include quinomethionate, phenothiocarb, ethoxazole, bifenazate and the like.

Examples of the active compounds of the nematicide include methyl isocyanate, phosthiazate, oxamyl, mesulfenphos and the like. As a bait,
For example, monofluoroacetic acid, warfarin, beartetralyl, difacine and the like can be mentioned. Active compounds for fungicides include, for example, inorganic copper, organocopper, sulfur, maneb, thiuram, thiadiazine, captan, chlorothalonil, iprovenphos, thiophanatemethyl, benomyl, thiabendazole, iprodione, procymidone, pencyclon, metalaxyl, sandphane, biletone, triflumi Examples thereof include sol, fenarimol, triforine, dithianone, triazine, fluazinam, probenazole, dietofencarb, isoprothiolane, pyroquilon, iminoctadine acetate, echromezole, dazomet, and clesoxime methyl.

As the active compound of the synergist, for example, bis
-(2,3,3,3-tetrachloropropyl) ether, N- (2-
Ethylhexyl) bisclo [2,1,1] hept-5-ene-2,3-
Examples thereof include dicarboximide and α- [2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene. Examples of active compounds such as herbicides include bialaphos, sethoxydim, trifluralin, mefenacet and the like. Examples of active compounds for plant regulators include indolebutyric acid, ethephon, 4-CPA and the like. Active compounds of the repellent include, for example, carane-3,4-diol, N, N-diethyl-m-triamide (Deet), limonene, linalool,
Citronellal, menthol, hinokitiol, menthol, graniol, eucalyptol and the like can be mentioned.

The mode of use of the pesticidal composition of the present invention is arbitrary, and the pesticidal compound is added to the compound of the general formula (1).
For example, it is formulated into a wettable powder, a wettable powder, a water solvent, an emulsion, a liquid, a flowable such as a suspension in water or an emulsion in water, a capsule, a powder, a granule, an aerosol and the like. The content of the active ingredient compound such as the compound of the present invention in these preparations is optional, but is usually 0.001 in total amount of the active ingredient.
It is selected from the range of 1 to 99.5% by weight, and may be appropriately determined depending on various conditions such as the form of the formulation and the method of application, for example, wettable powder, wettable powder, aqueous solvent, emulsion, liquid, flowable, About 0.01 to 90% by weight, preferably 1 to 50% by weight for capsules and the like, about 0.1 to 50% by weight for powders and granules,
Preferably 1 to 10% by weight, about 0.001 to about aerosols etc.
It is preferable to manufacture the composition so as to contain about 20% by weight, preferably 0.01 to 2% by weight of the active ingredient.

The pesticide adjuvants used include, for example, a carrier (diluent), a spreading agent, and an emulsifier for the purpose of improving pest repellent effect, controlling effect, controlling effect, and improving stabilization and dispersibility. , A wetting agent, a dispersant, a disintegrant and the like can be used. As the liquid carrier, water, toluene, aromatic hydrocarbons such as xylene, methanol, butanol, alcohols such as glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethylsulfoxide, methylnaphthalene, Cyclohexane,
Animal and vegetable oils, fatty acids and the like can be mentioned. As solid carriers, clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose,
Starch, gum arabic and the like can be used. Usable surfactants can be used as emulsifiers and dispersants, for example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cations. A nonionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used. A spreading agent such as polyoxyethylene nonyl 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; Can be used.

For example, in the case of a wettable powder, the active ingredient is mixed with the compound of the general formula (I), a solid carrier, a surfactant and the like to produce a raw powder, and the raw powder is used at a predetermined concentration. Can be diluted with water and applied. In the case of an emulsion, a stock solution emulsion can be prepared by mixing a solvent, a surfactant and the like with the above-mentioned compound of the active ingredient, and this stock solution can be further diluted with water to a predetermined concentration before use. it can. In the case of powder, the compound of the active ingredient and the solid carrier can be mixed and applied as it is, and in the case of granules, the compound of the active ingredient, the solid carrier and a surfactant can be mixed and used. 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 method, and can be appropriately selected by those skilled in the art according to the kind of the active ingredient, the purpose of application, and the like.

The method of use depends on the type and amount of pests,
Depending on the type of crops and trees to be targeted, cultivation form and growth state, for example, arthropods, gastropods, nematodes, etc. are usually affected by these pests, Or for places where damage is expected to occur, generally 0.1 to 1000 g of active ingredient per 10 ares,
Preferably, 1 to 100 g may be applied.

Specific application methods include, for example, the above-mentioned wettable powders, wettable powders, aqueous solvents, emulsions, solutions, suspensions in water and emulsions in water, and capsules. It may be diluted with water and sprayed on crops, trees, etc. in the range of 10 to 1000 liters per 10 ares depending on the type of target crops, trees, etc., cultivation form and growth state. In the case of powders, granules, and aerosols, the preparations may be applied to crops, trees, and the like in the range of the above-mentioned methods of use.

When the target pest infects crops, trees and the like mainly in soil, for example, wettable powder, wettable powder, aqueous solvent, emulsion, liquid, suspension in water, emulsion in water Tablets, capsules, etc., diluted with water.
It may be applied in the range of 5 to 500 liters per 10 ares. At this time, the medicine may be sprayed on the soil surface so as to be even over the entire application area, or may be irrigated into the soil. When the form of the preparation is a powder or granule, the preparation may be sprayed on the soil surface as it is so as to be uniform over the entire area to be applied. In addition, when spraying or irrigation, it may be applied only around seeds, crops, trees, etc. which are desired to be protected from damage by pests. Good.

Further, a pesticidal composition containing the compound of the present invention as an active ingredient may be adhered around plant seeds by a known method. By such a treatment, not only the seeds are sown, but also the damage caused by pests in the soil can be prevented.
Fruits and the like can be protected from damage by pests.

When protecting the above-mentioned trees, fallen trees, processed wood, stored wood, etc. from damage by termites, beetles, etc., for example, an oil agent is applied to the surrounding soil of trees, wood, etc.
Examples of the method include spraying, injecting, irrigation, and coating an emulsion, a wettable powder, and a sol, and spraying a drug in a use form such as a powder or a granule. In such a situation, the pesticidal composition containing the compound of the present invention as an active ingredient is used alone or with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents, synergists and the like. Can be used in combination or as a mixture.

The content of the active ingredient compound such as the compound of the present invention in these preparations is optional, but is usually 0.0001 to 95% by weight in total of the active ingredient, and 0.005 to 95% by weight for oils, powders, granules and the like. -10% by weight, and preferably 0.01-50% by weight in emulsions, wettable powders and sols. Specifically, for example, when controlling and controlling termites and beetles, 0.01 to 100 g of the active ingredient compound per 1 m ² may be sprayed on the soil or wood surface. (B) Livestock industry, fisheries scene, etc. The pesticidal agent containing the compound of the present invention as an active ingredient is internally or externally parasitic on animals such as pets bred in the livestock industry, fisheries industry and at home. Damage of arthropods, nematodes, flukes, tapeworms, protozoa, etc., which cause direct harm, such as feeding, blood feeding, etc. It is effective in repelling, controlling and controlling, and can be used for prevention and treatment of diseases related to these pests.

Examples of the target animal include vertebrates (for example, livestock such as cows, sheep, goats, horses, and pigs; farmed fish; birds such as poultry; dogs, cats, mice, rats, hamsters, squirrels, and ferrets) And pets and experimental animals selected from mammals, fish and the like. Among the pests, the following can be exemplified as Arthropod Insecta and Arachnida. As the diptera, for example, the family Afidae such as Yamatobu, Tsumetogebuyu, and the red flies; Houseflies such as blowfly, housefly and sandflies; Dermatidae; Dermatidae, such as Aedes aeruginosa; Drosophilidae, such as Drosophila melanogaster and Drosophila; Mosquitoes, such as Aedes albopictus, Culex pipiens, Aedes albopictus;
Examples of blackflies such as Oubuyu;

Examples of the order Laminoptera include human fleas such as cat flea and dog flea. Examples of the lice include Liceflies, such as pig lice and bovine lice; Liceflies, such as horse lice; Liceflies, such as bovine lice; Liceflies, such as chicken lice.

Examples of the mites of the arthropod spiders include the ticks of the spider ticks, such as the ticks mite, the ticks, the ox tick, the swelling tick, the sick mite; Dermatophagoids such as Dermatophagoids and Acarina; and Dermatophagoides such as Dermatophagoids and Bovine Dermatophagoides.

Examples of the nematodes of the nematode phylum include the following. Examples of the order Coleoptera include hookworms, pig nematodes, pig lungworms, hairy nematodes, and bovine intestinal nodules. As the roundworm, for example, roundworm, roundworm of chicken, etc. can be mentioned. As the flatworm phylum,
For example, Schistosoma japonicum, Liver Tetsu, Desertia japonica, Westermani lung fluke, Japanese chicken egg fluke etc. can be mentioned.

Examples of tapeworms include foliate tapeworms, tapeworms, Beneden tapeworms, square tapeworms, striated tapeworms, and tapeworms. In the protozoan phylum flagellates, as the root flagellates, for example, Histomonas, etc., as the protoflagellate, for example, Leishmania, Trypanosoma, etc., as the polyflagellate, for example, Giardia, etc. For example, Trichomonas and the like can be mentioned.

[0093] Furthermore, as the amoeba of the fleshytes, for example, Entamoeba and the like, for the sporeworm Piroplasma, for example, Theilaria, Babesia, and the like, and for the late-sporozoa, for example, Eimeria, Plasmodium, and Toxoplasma And the like. The pesticidal composition containing the compound of the present invention as an active ingredient is a formulation effective in the livestock industry or the fishing industry described above, and in any use form prepared by the formulation, alone or in the form of another active compound, such as an insecticide , Acaricide, nematicide, fungicide, synergist, plant regulator, herbicide, poison bait, and the like. Specific examples of the other active compounds include “(A)
Agriculture, forestry scene, etc. ", but are not limited thereto.

Specific methods of application include, for example, pharmaceutical compositions that can be mixed with feeds of livestock and pets, or that can be orally ingested, such as tablets and pills containing pharmaceutically acceptable carriers and coating substances. Orally or as a capsule, paste, gel, beverage, medicated feed, medicinal drinking water, medicated bait, sustained-release large pill, other sustained-release device kept in the gastrointestinal tract, or spray , Powder, grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo and the like.

As a method of transdermal administration or topical administration, a device (for example, a collar, a medallion, an ear tag, or the like) attached to an animal to control an arthropod locally or systemically can also be used. Specific oral administration methods and transdermal administration methods when used as an anthelmintic for livestock and pets are shown below, but in the present invention, these administration methods are not necessarily limited to the following description.

When administered orally as a medicinal beverage preparation, the suspension is usually dissolved in a suitable non-toxic solvent or water together with a suspending agent such as bentonite or a wetting agent or other excipients. Alternatively, a dispersion may be used, and an antifoaming agent may be contained as necessary. In beverage preparations, generally the amount of the active ingredient compound is 0.01 to 1.0% by weight, preferably 0.01 to 1.0%.
0.1% by weight.

For oral administration in a dry solid unit dosage form, capsules, pills or tablets containing a predetermined amount of the active ingredient are usually employed. These forms of use are prepared by homogeneously admixing the active ingredient with suitably comminuted diluents, fillers, disintegrants and / or binders such as starch, lactose, talc, magnesium stearate, vegetable gums and the like. Is done. In such a unit-use prescription, the weight and content of the anthelmintic may be appropriately set according to the type of host animal to be treated, the degree of infection, the type of parasite, and the weight of the host.

In the case of administration by feed, there can be mentioned, for example, a method in which the active ingredient compound is uniformly dispersed in the feed, a method in which the drug is used as a top dressing or a form in the form of pellets. In order to achieve an antiparasitic effect, the final feed usually contains 0.0001 to 0.05% by weight of the active ingredient compound, preferably 0.0005 to 0.01% by weight.
It contains.

When dissolved or dispersed in a liquid carrier excipient, it may be parenterally administered to the animal by injection into the forestomach, intramuscularly, intratracheally or subcutaneously. Because of parenteral administration, the active ingredient compounds are preferably mixed with vegetable oils such as peanut oil, cottonseed oil and the like. In such a formulation,
Generally 0.05 to 50% by weight of the active ingredient compound, preferably 0.1
0.20.2% by weight. In addition, a preparation mixed with a carrier such as dimethyl sulfoxide or a hydrocarbon solvent can be directly and topically applied to the external surface of livestock or pets by spraying or direct pouring. (C) Public health scene, etc. The pest control agent comprising the compound of the present invention as an active ingredient
Avoidance of pests in public health situations, such as adversely affecting the food and living environment, further harming the human body, and carrying and transmitting pathogens, for maintaining public health, etc. It is also effective for extermination and control. Specifically, the pesticidal agent of the present invention is, for example, wood products such as dwelling itself, indoor and outdoor wood, wooden furniture, stored food, clothing, books, animal products (skin, wool, wool, feathers, etc.). Effective for repelling, extermination and control of lepidoptera, beetles, spots, cockroaches, flies, mites, etc., which cause damage to plant and plant products (clothing, paper, etc.) and adversely affect sanitary life It is. Specific examples of such pests in public health situations include the following.

Examples of arthropod phylum insects include the following. As the Lepidoptera, for example, the stag beetles such as Moncladidae; And the genus Iridaceae;

As the Coleoptera, for example, the family Ceratopogonidae, such as Blue horned beetle; The beetle family, such as beetle anemone; Beetles, such as weevil; weevil, such as weevil; beetles; Lepidoptera of the family Lepidoptera, such as Nisesemaru lepidopteran; It can gel.

The Hymenoptera include, for example, wasp family such as wasp, ant family such as giant ant, and bee family such as giant beetle.
As the diptera, for example, mosquitoes such as yamato falcon; smeltaceae such as brassicae; chironaceae such as sessile chironomid; Etc .; Drosophilidae such as Sentinia fly; Drosophilidae such as Drosophila melanogaster;
Cheese fly such as cheese fly can be mentioned.

Examples of the order Laminoptera include human fleas such as human fleas. As the order of the viscera, there may be mentioned, for example, the family Papilionidae such as the purple beetle. The cockroaches include, for example, German cockroaches such as German cockroaches and Chinese cockroaches; and cockroaches such as Brown cockroaches, Black cockroaches, and Japanese cockroaches.

As the Orthoptera, for example, the family Corrugidae such as Madara camphoridae and Camamadia can be mentioned. Examples of the louse include Liceae such as head lice; Liceaceae such as Lice lice. As the Hemiptera, for example, bed bugs such as bed bugs;

Examples of the termites include the termites of the termites such as the termites and termites; the termites of the termites such as the termites; Can be mentioned. Examples of the order Staphylococcus include the family Staphylidae, such as yamatos spots and sea skewers.

Examples of the arthropod spiders include the following. As the mites, for example, ticks such as Schurze ticks; Dermatophagoides such as house dust mites; Cyperidae such as southern mites; Lice mites such as lice mites; Acne mites such as Dermatophagoides;
Examples of the mites may include, but are not limited to, the mites of the tsutsugamushi beetle, etc .;

Examples of the true spiders include the spiders of the order Aphididae, such as the Japanese spider; the spiders such as the red spider; the spiders of the spider, such as the red spider;
Jumping spiders such as Miss jumping flies can be mentioned. As the scorpiones, there may be mentioned, for example, the scorpion family, such as the scorpion.

As other arthropod phylums, examples of the order Lepidoptera of the Labialoda class include those of the family Ceratopogonidae, such as Tobismae and Aosumukadashi, and examples of the order Coleoptera include those of the family Coleoptera, such as the geese. Examples of the arthropod phylum, Ophiaceae include, for example, the family Papilionidae, such as Toyake-yasuda. Furthermore, examples of the annelid fasciata include, for example, Yamaviridae such as Yamavir.

The pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in combination with other active compounds such as insecticides in the above-mentioned preparations effective in public health and in any use form prepared by the preparations. Miticides, nematicides,
It can be used in combination or as a mixture with fungicides, synergists, plant regulators, herbicides, poison baits and the like. Specific examples of the other active compounds include “(A) Agriculture, forestry, etc.”
Can be listed, but the present invention is not necessarily limited to these.

The form of use of the pesticidal composition of the present invention is arbitrary. For example, when protecting the above-mentioned animal products and plant products, spraying oils, emulsions, wettable powders, powders, etc., and resin evaporants Can be controlled by methods such as installation of smokers and aerosols, installation of granules, tablets and poison baits, and spraying of aerosols. The amount of the active ingredient compound in these preparations is preferably 0.0001 to 95% by weight.

As an application method, for pests, for example, arthropods that directly harm or arthropods that are disease carriers, for example, oils, emulsions, Spraying / injection / irrigation / application of wettable powders, spraying powders, etc.
Examples of the method include a method of treating with a preparation such as a ULV agent. They can be applied in other forms such as granules, tablets or poison bait, or by dripping floating powder, granules, etc. into waterways, wells, reservoirs, water tanks and other running or stationary water. Just fine.

Furthermore, for "dokuga" which is also a pest in agriculture and forestry, "(A) Agriculture, forestry scene, etc."
Can be controlled by the same method as described in the section, and for flies and the like, a method in which the active ingredient is mixed in feces by mixing in livestock feed, and mosquitoes It is also effective to volatilize the air with an electric mosquito trap.

The formulations in these use forms are present as a mixture with other active compounds, as mentioned above, for example insecticides, acaricides, nematicides, fungicides, repellents or synergists. It is also preferable that these preparations contain the active ingredient compound in a total amount of 0.0001 to 95% by weight. In addition, it is also possible to use together with other active compounds at the time of use.

When protecting a house or wooden furniture from damage by termites or beetles, for example, spraying / injecting / irrigating / applying oils, emulsions, wettable powders and sols to and around them. , Powders, granules and the like, and a method of spraying a medicine in a use form. In such a situation, the compound of the present invention alone or other active compounds,
For example, it can be used in combination or as a mixture with an insecticide, acaricide, nematicide, fungicide, repellent, synergist and the like.

The content of the active ingredient compound such as the compound of the present invention in these preparations is arbitrary, but is usually 0.0001 to 95% by weight in total of the active ingredient, and 0.005 to 95% by weight for oils, powders, granules and the like. -10% by weight, and preferably 0.01-50% by weight in emulsions, wettable powders and sols. Specifically, for example, in the case of controlling and controlling termites and beetles, 0.01 to 100 g of the active ingredient compound per 1 m ² may be sprayed on the periphery or directly on the surface.

When repelling, exterminating, or controlling pests, such as causing harm to the human body or carrying or transmitting pathogens,
In addition to the above, suitable ingestible pharmaceutical compositions such as tablets, pills, capsules, pastes, gels, beverages, medicated feeds, medicaments, and the like, containing pharmaceutically acceptable carriers and coating materials. Oral administration, such as drinking water, medicated bait, sustained-release large pills, and other sustained-release devices kept in the gastrointestinal tract, or spray, powder,
It can be administered transdermally as grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo and the like. Specific pharmaceutical formulations are described in “(B) Livestock Industry,
The formulation can be carried out in the same manner as in the method described in the section of “Fishing industry scene”.

[0117]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to the following Examples without departing from the scope of the invention. (Example 1) 1- (2,6-Dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile (Compound No. 5) Production of 10.0 g of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinylpyrazole-3-carbonitrile, 2.5 g of formylpyrazine and 80 ml of toluene P in the mixture
0.1 g of toluenesulfonic acid monohydrate was added, and the mixture was heated and refluxed for 10 hours while removing generated water. After cooling to room temperature, 30 ml of ice water was added for extraction. The organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give crude 1-
(2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylideneimino) pyrazole-3-
Carbonitrile was obtained.

1- (2,6-dichloro-4- obtained above)
To a solution of (trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylideneimino) pyrazole-3-carbonitrile in 100 ml of methanol was slowly added 0.9 g of sodium borohydride. After stirring at room temperature for 1 hour, ice and ethyl acetate were 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, and the compounds (N
o. 5) 7.0 g was obtained. Melting point 169 ° C. ¹ H NMR (CDCl ₃ ): 4.37 (2H, m), 6.81 (1H, m), 7.74 (2H, d),
8.39 (1H, d), 8.50 (2H, m) (Example 2) 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinyl-5-
(Pyrazin-2-ylmethylamino) pyrazole-3-
Preparation of Carbonitrile (Compound No. 1) 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl-4-methylsulfinylpyrazole-3-carbonitrile 5.6 g, formylpyrazine 2.
20 mg of p-toluenesulfonic acid monohydrate was added to a mixture of 0 g and 60 ml of toluene, and the mixture was refluxed for 3 hours while removing generated water. After cooling to room temperature, 0.1 ml of triethylamine and 30 ml of ice water were added for extraction. The organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give crude 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinyl-5- (pyrazine-
There was obtained 2-ylmethylideneimino) pyrazole-3-carbonitrile.

The 1- (2,6-dichloro-4- obtained above)
To a solution of trifluoromethylphenyl) -4-methylsulfinyl-5- (pyrazin-2-ylmethylideneimino) pyrazole-3-carbonitrile in 50 ml of methanol was slowly added 0.7 g of sodium borohydride. After stirring at room temperature for 1 hour, ice and ethyl acetate were 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, and the compound (No. 1) 5.1 shown in Table 1 below was used.
g was obtained. Mp _{^{198 ℃, 1 HNMR (CDCl 3}} ): 3.33 (3H, s), 4.18 (2H, d), 7.15 (1H, t),
7.71 (2H, s), 8.41 (2H, d), 8.51 (1H, d) (Example 3) 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfenyl-5-
Production of (1-oxy-pyridin-3-ylmethylamino) pyrazole-3-carbonitrile (Compound No. 14) 0.1 g of 60% sodium hydride was suspended in 10 ml of N, N-dimethylformamide at 10 ml to give 5-amino-1- 1 g of (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-perazole-3-carbonitrile was gradually added.
After stirring at room temperature for 20 minutes, 15 drops of 15-crown-5-ether and then 0.3 g of 3-chloromethylhydroxy-1-oxytate were added, and the mixture was stirred at room temperature. After standing overnight, water and ethyl acetate were added and neutralized with 1N hydrochloric acid. After liquid separation, 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 a compound (No. 14) described in Table 1 below.
9 g were obtained.

Melting point 189-191 ° C. ¹ H NMR (CDCl ₃ ): 4.2-4.5 (2H, m), 7.03 (1H, d), 7.12 (1H,
t), 7.18 (1H, t), 7.74 (2H, s), 8.03 (2H, m) (Example 4) N- [3-cyano-1- (2,6-dichloror-4-trifluoromethylphenyl) ) Preparation of pyrazol-5-yl] pyrazin-2-carboxamide 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole-3-carbonitrile
0.5% (1.6 mmol), 0.24 g (1.7 mmol) of methyl pyrazinecarboxylate and 0.5 ml of acetonitrile in a mixture of 28% CH ₃ ONa /
0.3 g (1.6 mmol) of CH ₃ OH was slowly added. After stirring at room temperature for 2 hours, 5 ml of water and then concentrated hydrochloric acid were added to adjust the pH to 2, and crystals precipitated. The mixture was extracted with 10 ml of ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. After filtering off the sodium sulfate, it was concentrated, and the resulting crystals were filtered. The crystals were washed with a small amount of hexane and ethyl acetate, dried,
0.5 g of [3-cyano-1- (2,6-dichlororolo-4-trifluoromethylphenyl) pyrazol-5-yl] pyrazine-2-carboxamide was obtained (77% yield). Example 5 Production of 1- (2,6-dichloror-4-trifluoromethylphenyl) -5- (pyrazin-2-ylchloromethylimino) pyrazole-3-carbonitrile N- [3-cyano-1 139 g (0.33 mol) of-(2,6-dichlororolo-4-trifluoromethylphenyl) pyrazol-5-yl] pyrazine-2-carboxamide;
A mixture of 72.6 g (0.35 mol) of phosphorus pentachloride and 300 ml of toluene was heated under reflux for 2 hours. An additional 5 g of phosphorus pentachloride was added, and the mixture was heated under reflux for 1 hour. Cooled to room temperature and left overnight. After stirring for 30 minutes, the crystals were filtered and washed with toluene. The crystals were dissolved in 1 liter of chloroform and extracted by adding water. The organic layer was washed twice with water, washed with saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off, the obtained crystals were washed with hexane, and 112.3 g of 1- (2,6-dichloror-4-trifluoromethylphenyl) -5- (pyrazin-2-ylchloromethylimino) pyrazole- 3
-Carbonitrile (79% yield) was obtained. Example 6 Production of 1- (2,6-dichloror-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile 85 mg (2.2 mmol) of sodium borohydride ) Was added to a suspension of 2 ml of ethanol in 1- (2,6-dichloro-
4-trifluoromethylphenyl) -5- (pyrazine-
0.5 g (1.1 mmol) of 2-ylchloromethylimino) pyrazole-3-carbonitrile was gradually added at 20 ° C or lower. After stirring for 1 hour at room temperature, the mixture was
When gradually poured into 0 ml, crystals precipitated. After stirring for 30 minutes, the mixture was filtered, and the crystals were washed with water until the pH of the filtrate reached 6. The obtained crystals were dissolved in ethyl acetate, and the mixture was extracted with saturated saline. After anhydrous magnesium sulfate was added to the organic layer and dried, the mixture was filtered and the organic layer was concentrated, and the resulting crystals were filtered. The crystals were washed with a small amount of hexane and ethyl acetate, dried and dried. 42 g (92% yield) were obtained. Example 7 Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole 1- (2,6 -Dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole (3.0 g) was treated with dehydrated methylene chloride 30 under nitrogen atmosphere.
Then, 14 ml of a dehydrated methylene chloride solution of trifluoromethylsulfenyl chloride was added dropwise at room temperature over about 1 hour, and the mixture was stirred overnight. A saturated aqueous solution of sodium bicarbonate was added thereto, and the organic layer was washed several times with a saturated aqueous solution of sodium bicarbonate and water, and then purified by silica gel column chromatography. After removing the solvent, vacuum drying,
3.59 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulphenyl-5- (pyrazin-2-ylmethylamino) pyrazole were obtained. Example 8 Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile Trifluoromethane 234 mg of potassium sulfinate
(1.3 mmol), 358 mg (1.6 mmol) of p-toluenesulfonic acid dimethylamine salt, 1- (2,6
-Dichloro-4-trifluoromethylphenyl) -5-
(Pyrazin-2-ylmethylamino) pyrazole-3-
413 mg (1.0 mmol) of carbonitrile
The suspension was suspended in 1.0 ml of 2-dichloroethane, and under cooling with water, 301 mg (2.5 mmol) of thionyl chloride was added. 6
After the temperature was raised to 0 ° C. and stirred for 30 minutes, the reaction mixture was analyzed by high performance liquid chromatography to find 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (Pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile yield 1
It was formed at 1%. The conversion of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile was 95%. Example 9 Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile Trifluoro 1.725 g of potassium methanesulfinate
(10.0 mmol), p-toluenesulfonic acid dimethylamine salt 895 mg (4.1 mmol), p-toluenesulfonic acid monohydrate 951 mg (5.0 mmol)
Is suspended in 5.0 ml of 1,2-dichloroethane, and 1.506 g (12.6 mmol) of thionyl chloride is cooled under ice-cooling.
Was added. After stirring at room temperature for 3 hours, 1.03 g (2.5 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile was added. The temperature was raised to 40 ° C., and the mixture was stirred for 5 hours. The reaction mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, extracted with dichloromethane, and the organic phase was dried over anhydrous magnesium sulfate. The oil obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography, and 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazine 487 mg of 2--2-ylmethylamino) pyrazole-3-carbonitrile (yield 38
%) Was isolated. Example 10 Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile (1- (2,6-dichloro-4-trifluoromethylphenyl) -3-carbonitrile-5- (pyrazine-
7.89 g (8.88 mmol) of 2-ylmethylamino) pyrazol-4-yl) -disulfide, 5.44 g (31.6 m) of potassium trifluoromethylsulfinate
mol) and 0.40 g (1.24 mmol) of dioxobis (acetylacetonato) molybdenum were dissolved in 350 ml and 110 ml of acetonitrile, and 3.4 ml (27.2 mmol) of an 80% t-butyl hydroperoxide solution was dissolved.
l) was added dropwise at room temperature. Further, every 4 hours, 5.44 g of potassium trifluoromethylsulfinate (31.6 m
mol) and 3.4 ml (27.2 mmol) of an 80% t-butyl hydroperoxide solution were repeated twice, followed by stirring at room temperature for 15 hours. Thereafter, 5.44 g (31.6 g) of potassium trifluoromethylsulfenate was again obtained.
mmol) and 3.4 ml (27.2 mmol) of an 80% t-butyl hydroperoxide solution, and the mixture was stirred for 6 hours. After the precipitated light brown crystals were separated by filtration, acetonitrile was distilled off from the filtrate under reduced pressure, and ethyl acetate was added thereto for extraction. After washing the organic layer with water, the solvent is removed under reduced pressure,
After column chromatography purification (Hex / AcOEt = 5/2), 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5 was obtained.
-(Pyrazin-2-ylmethylamino) pyrazole-3
0.88 g (1.7 mm) of pale yellow crystals of carbonitrile
ol) in a yield of 9.6%. Example 11 Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile Nitrogen Under an atmosphere, 50 mg (0.11 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-thiocyanato-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile in methanol 1 0.1 ml of sodium borohydride in 0.5 ml solution
(0.24 ml), and the mixture was stirred at room temperature for 2 hours. After distilling off the solvent from the reaction solution under reduced pressure, under nitrogen,
After adding 2 ml of DMF and cooling in a dry ice-acetone bath, a trifluoromethylating agent M manufactured by Daicel Chemical Industries, Ltd.
EC-12 54.5 mg (0.11 mmol) DM
0.5 ml of F solution was added. After stirring at room temperature for 1 hour, ethyl acetate and water were added for extraction, and the organic layer was subjected to LC analysis. As a result, 1- (2,6
-Dichloro-4-trifluoromethylphenyl) -4-
Trifluoromethylsulfenyl-5- (pyrazine-2
-Ylmethylamino) pyrazole-3-carbonitrile was obtained.

The compounds shown in Table 1 were synthesized according to the methods of Examples 1 to 11. Hereinafter, Compound No. And NMR data are shown. N0.2 ¹ H NMR (CDCl ₃ ): 3.33 (3H, s), 4.19 (2H, d), 7.15 (1H, bt),
7.71 (2H, s), 8.40 (1H, d), 8.42 (1H, d), 8.51 (1H, d) N0.3 1 HNMR (CDCl 3): 1.39 (3H, t), 3.26 (2H, m) , 4.34 (2H, d),
6.83 (1H, t), 7.68 (2H, d), 8.35 (1H, d), 8.47 (1H, d), 8.
^{51 (1H, s) N0.4 1} HNMR (CDCl 3): 4.43 (2H, d), 6.75 (1H, t), 6.78 (1H, t),
7.75 (2H, d), 8.41 (1H, m), 8.50 (2H, m) N0.6 1 HNMR (CDCl 3): 2.56 (3H, s), 4.30 (2H, m), 6.62 (1H, bm) ,
7.72 (2H, d), 8.25 (1H, d), 8.35 (1H, d) N0.7 1 HNMR (CDCl 3): 4.66 (2H, d), 5.27 (1H, b), 5.30 (1H, s) ,
5.61 (1H, s), 7.76 (2H, s), 8.41 (1H, d), 8.49 (1H, d), 8.
^{54 (1H, s) N0.8 1} HNMR (CDCl 3): 4.53 (2H, s), 6.88 (1H, t), 7.71 (2H, s),
8.29 (1H, s), 8.36 (1H, s), 8.39 (1H, s) N0.9 1 HNMR (CDCl 3): 4.35 (2H, m), 6.85 (1H, bs), 7.23 (1H, d) ,
7.74 (2H, d), 8.69 (1H, d), 9.01 (1H, s) N0.10 1 HNMR (CDCl 3): 2.37 (3H, s), 4.90 (2H, d), 5.27 (1H, m) ,
7.45 (2H, m), 7.75 (2H, s), 9.12 (1H, dd) N0.11 1 HNMR (CDCl 3): 4.68 (2H, m), 6.71 (1H, bs), 7.47 (1H, d) ,
7.73 (1H, d), 9.11 (1H, d) N0.12 1 HNMR (CDCl 3): 4.1-4.5 (2H, m), 6.69 (1H, t), 7.10 (2H,
d), 7.21 (1H, t ), 7.77 (2H, s), 8.10 (2H, d) N0.13 1 HNMR (CDCl 3): 4.3 (2H, m), 7.02 (2H, d), 7.70 (2H , s),
^{8.01 (2H, d) N0.15 1} HNMR (CDCl 3): 4.84 (2H, d), 6.35 (1H, b), 7.31 (3H, m),
7.77 (2H, s), 8.15 (1H, m)

[0122]

[Table 1]

Hereinafter, examples of the preparation of agricultural and horticultural insecticides containing the compound of the present invention as an active ingredient are shown, but the form of use of the present invention is not limited to the following. <Formulation Example 1> Wetting agent 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., trade name) ) 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 uniformly mixed and pulverized to obtain a wettable powder containing 20% by weight of the active ingredient. <Formulation Example 2> Dust 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 were 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). Mixture, Toho Chemical Co., trade name) 15 parts by weight, add 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 by 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, mixed well and pulverized to obtain an active ingredient 20.
By weight, a flowable agent was obtained.

Hereinafter, test examples of agricultural and horticultural insecticides containing the compound of the present invention as an active ingredient are shown, but the form of use of the present invention is not limited to the following. Test Example 1: Insecticidal effect on larvae of brown planthoppers Rice sprout seedlings were set on a glass cylinder (inner diameter 3 cm x length 17 cm), and five fourth-stage larvae of brown planthopper 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 agony, and the killing rate (%) was determined by assuming that the agony insects were 死 dead. The results are shown in Table 2 (the compound numbers in the table correspond to Table 1).

[0125]

[Table 2]

Test Example 2: Insecticidal effect on moth larvae A cut cabbage leaf (diameter 6 cm) 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. After immersion, air-dry the plastic cup (7
cm) and five third-instar larvae of the Japanese moth were released into the cup (one concentration, two repetitions). The larvae were kept in a constant temperature room at 25 ° C., and after 4 days from the release, the larvae were examined for viability and agony, and the killing rate (%) was determined by assuming that the agony insects were 頭 dead. Table 3 shows the results
(In the table below, the compound numbers correspond to Table 1).

[0127]

[Table 3]

Test Example 3: Insecticidal effect on the larvae of Spodoptera litura The cut leaf of cabbage (diameter 6 cm) 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. After immersion, air-dry the plastic cup (7
In the cup, five third-instar larvae of Spodoptera litura were released (one concentration, two repetitions). After being kept in a constant temperature room at 25 ° C, 5 days after release, the larvae were examined for viability and agony,
The insecticidal rate (%) was determined by assuming that the writhing insects were 死 dead. The results are shown in Table 4 (in the table below, the compound numbers correspond to Table 1).

[0129]

[Table 4]

Test Example 4: Insecticidal effect of adzuki beetle on adult insects Beans 2 in a glass cylinder (inner diameter 3 cm × length 15 cm)
Individually, 10 adults of Azuki weevil were released. Formulation Example 3
0.3 ml of a water dilution of the agricultural and horticultural insecticide of the present invention produced according to the above formula 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 life and death and writhing, and the killing rate (%) was determined assuming that the writhing larva was １ ／ dead. The results are shown in Table 5 (the compound numbers in the table correspond to Table 1).

[0131]

[Table 5]

Test Example 5: Pesticidal effect of peach aphid on larvae The petiole of a radish leaf was inserted into a screw bottle (capacity: 10 ml) filled with water, and peach peach aphid was applied per leaf.
Five to six animals were inoculated. After inoculation, a glass cylinder (diameter: 0.5c
m, height: 15 cm, with a mesh lid), and aphids were grown in a thermostat 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 radish leaves was examined, 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).

[0133]

[Table 6]

Test Example 6: Insecticidal effect on larvae of brown planthopper through osmotic transferability The roots of rice seedlings (plant height: about 10 cm) planted in plastic cups were washed with water, and the soil was thoroughly washed off without damaging the fine roots. Urethane chips with cuts (diameter 3cm,
(2 cm in height), and insert the root into an Erlenmeyer flask containing 50 ml of a medicinal solution (water dilution of the agricultural and horticultural insecticide of the present invention manufactured according to the formulation of Preparation Example 1) in advance (rice seedling 2). -3 / flask), and a urethane chip was inserted into the mouth of the flask to fix the rice seedlings. A glass tube (diameter 3 cm, height 5 cm) was placed thereon, sandwiched between urethane chips, and fixed with tape. In this state, it was kept in a constant temperature room at 25 ° C. for 3 days. After putting five brown planthopper larvae into this glass tube, cover with a urethane chip,
Was kept in a constant temperature room. (1 concentration, 2 replicates). After processing 4
On the day, the larvae were examined for life and death and agony, and
The insect kill rate (%) was determined as the head. This test was performed for three chemical solutions having different active ingredient concentrations. The results are shown in Table 7 (the compound numbers in the table correspond to Table 1).

As comparative compounds I to V, compounds having the following structures (compound I described in JP-A-63-316771, compounds II and III described in Examples of WO9845274, and WO9845274) Compounds IV and V), which are included in the claims of the publication but not in the claims of the present application, were likewise subjected to a test.

[0136]

Embedded image

[0137]

[Table 7]

The brown planthopper is an important problem pest species that causes harm as described in Test Example 1. However, if the application method such as spraying on the foliage is delayed in discovery or when the drug is not sufficiently distributed to the root, May not be effective enough. Since this species has the characteristic of inhabiting the root of rice etc. and damaging the juice, a more efficient control method is to treat the surface of the soil with a drug (granule treatment) before the occurrence of many this species Is mentioned. However, in order to achieve a high control effect by such a method, it is necessary that the drug has a property of permeating and transferring into a plant as a property of the drug. As is clear from Table 6, the compound of the present invention and the compounds III and IV showed insecticidal activity via high systemic transfer to this species, which is an important problem pest, whereas the compounds I, II and V Due to such a low effect, the effect was clearly inferior to the compound of the present invention. Test Example 7: Fish toxicity test using medaka This test example is an example of a technique for examining environmental safety of an agricultural and horticultural insecticide.

10 mg of each compound was dissolved in 1 ml of dimethyl sulfoxide, and 0.05 ml was added to a glass beaker containing 1 liter of distilled water to obtain a 0.5 ppm aqueous solution. This aqueous solution contains medaka (adult, average fish weight: about 36
0 mg) of 5 medaka was observed for survival (retention conditions: 25 ± 2 ° C.), and the mortality after 48 hours was shown as a calculated% (5 fish / beaker in one section, 1 strain). The results are shown in Table 8 (the compound numbers in the table correspond to Table 1).

As a comparative compound, as in Test Example 6,
Compound I, WO984 described in JP-A-3-3167771
Compounds II and III described in the Examples of 5274,
Compounds IV and V included in the claims of WO9845274 but not included in the claims of the present application were subjected to the test.

[0141]

[Table 8]

As is clear from Table 8, the tests using Compounds I to V all showed high values of fish mortality, but none of the compounds of the present invention showed any mortality. The compound can be sufficiently used even in a situation where a controlling agent directly enters an aqueous system such as rice. Test Example 8: Insecticidal effect on cat fleas A chemical solution diluted to a predetermined concentration in a circular filter paper (diameter: 10 cm) was added to a filter paper.
After dropping 7ml and drying, cylinder (diameter: 10cm x height 30cm)
Laid on the bottom. 10 fleas were released in it.
On the second and the second day, life and death were investigated, and the mortality was calculated based on the results. The results are shown in Table 9 (the compound numbers in the table correspond to Table 1).

[0143]

[Table 9]

[0144]

The 1-aryl-3-cyano-5 of the present invention
-A pyrazinylalkylaminopyrazole derivative is a novel compound having excellent insecticidal effect, having a broad insecticidal spectrum, exhibiting a higher penetrating activity, and having reduced toxicity to the environment as shown by fish toxicity. It is a compound and is useful as a pesticide.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 403/12 C07D 403/12 (72) Inventor Toshiki Fukuchi 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Inside Yokohama Research Laboratory Co., Ltd. (72) Inventor Takeshi Ken Tanaka 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Research Co., Ltd. Inside Yokohama Research Laboratory Co., Ltd. No. 1 Inside Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Akiko Miyauchi Hachicho, Ami-cho, Inashiki-gun, Ibaraki Prefecture No. 3 No. 1 Mitsubishi Chemical Corporation Tsukuba the laboratory (72) inventor Akiko Yabe Inashiki-gun, Ibaraki Ami-cho, central eight-chome third No. 1 Mitsubishi Chemical Corporation Tsukuba the laboratory

Claims (20)

[Claims] 1. A 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative represented by the following general formula (1). Embedded image (In the above formula, X represents N or C-halogen, R ¹ represents an alkyl group, alkenyl group, alkynyl group or haloalkyl group, R ² represents a hydrogen atom, an alkyl group or an acyl group, and R ³ represents hydrogen. Represents an atom or an alkyl group;
Is any of the groups represented by A-1 to A-4,
R ⁴ represents a hydrogen atom, an alkyl group, or a halogen atom;
Represents 0, 1 or 2. Where A is A-1 and n
When = 0, R ¹ represents a haloalkyl group (excluding a perhaloalkyl group), and when A is A-4, n ≠
Indicates 0. ) 2. The 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative according to claim 1, wherein A is A-1 and R ⁴ represents a hydrogen atom or an alkyl group. . 3. The 1-aryl-3-cyano-5 according to claim 1, wherein R ¹ is an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms.
-Heteroarylalkylaminopyrazole derivatives. 4. The 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative according to claim 1, wherein R ¹ is a haloalkyl group having 1 to 2 carbon atoms. . 5. 1- (2,6-Dichloro-4-trifluoromethylphenyl) -4-fluoromethylthio-5
(Pyrazin-2-ylmethylamino) pyrazole-3-
Carbonitrile and 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile. 6. The method according to claim 1, wherein
A pest control agent comprising an aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative as an active ingredient. 7. 1- according to claim 1, wherein
An insecticide comprising an aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative as an active ingredient. 8. A pyrazole derivative represented by the following general formula (2). Embedded image (In the above formula, X, R ² , R ³ and R ⁴ have the same meanings as in the general formula (1), and R ⁵ represents a hydrogen atom, thiocyanato, a dithio group bonded to two pyrazole rings, or a mercapto group. Z
Represents a halogen atom. ) 9. formula (2) (wherein R ⁵ is a hydrogen atom, Y is Y-3 is a) a pyrazole derivative R ¹ S of
(O) nX ¹ (R ¹ has the same meaning as in general formula (1), and n is 0
Or X ¹ is a chlorine atom or a bromine atom), wherein the pyrazole derivative of the general formula (1) is produced. 10. The general formula (1) (where n is 0)
A method for producing a pyrazole derivative of the general formula (1), wherein n is 1 or 2, wherein a sulfur atom of the pyrazole derivative is oxidized. 11. A pyrazole derivative represented by the general formula (2) (wherein R ⁵ is a thiocyanato group and Y is Y-3) is represented by the formula R ¹ -X ² (R ¹ is the same as defined in the general formula (1)). , X ² represents a halogen atom or a trimethylsilyl group), a method for producing a pyrazole derivative of the general formula (1) (where n is 0). 12. A pyrazole derivative represented by the general formula (2) (wherein R ⁵ is a mercapto group and Y is Y-3) is represented by the formula R ¹ -X ³ (R ¹ has the same meaning as in the general formula (1)). , X ³ is a halogen atom) and a pyrazole derivative of the general formula (1) (where n is 0). 13. A pyrazole derivative represented by the general formula (2) (wherein R ⁵ is a dithio group bonded to two pyrazole rings and Y is Y-3) is represented by the formula R ¹ -X ⁴ (where R ¹ is Has the same meaning as in formula (1), and X ⁴ is a halogen atom or SO ₂ M
(M represents an alkali metal), wherein n is 0 and R ³
Is a hydrogen atom). 14. A pyrazole derivative of the general formula (1) (wherein R ¹ is an alkyl group containing at least one chlorine atom or bromine atom) comprises hydrogen fluoride, a mixture of hydrogen fluoride and an amine, and a metal fluoride. A fluorinating agent selected from the group consisting of a compound represented by the following general formula (1):
Wherein ¹ has one or more fluorine atoms). 15. The method for producing a pyrazole derivative according to claim 9, wherein R ¹ is a haloalkyl group having 1 to 2 carbon atoms. 16. A pyrazole derivative represented by the following general formula (3) (X is as defined in the formula (1)), and A-CH
(—R ³ ) —X ⁵ (A is as defined in the general formula (1), and X ⁵
Represents a halogen atom, a lower alkylsulfonyloxy group or an arylsulfonyloxy group), and reacts with a nitrogen-containing hetero 6-membered ring compound represented by the general formula (2) (where Y is Y-3, R ² is hydrogen) Which is an atom). Embedded image 17. The following general formula (4) (X is the formula (1):
R ⁵ has the same meaning as in formula (2), and X ⁶ represents a halogen atom, a lower alkylsulfonyloxy group or an arylsulfonyloxy group. ) And A-CH (R ³ ) -NH ₂ (A, R
³ has the same meaning as in formula (1))
General formula (2) characterized by acting a membered ring compound
(Where Y is Y-3 and R ² is a hydrogen atom). Embedded image 18. A pyrazole derivative represented by the general formula (3) and AC (＝ O) X ⁷ (A is the same as the general formula (1), X ⁷ is a hydroxyl group, and has 1 to 6 carbon atoms. A method for producing an amide compound of the general formula (2) (where Y is Y-1 and R ² is a hydrogen atom) by reacting a nitrogen-containing hetero 6-membered ring compound represented by an alkoxy group or a halogen atom. 19. An amide compound represented by the general formula (2) (where Y is Y-1 and R ² is a hydrogen atom): phosphorus pentachloride, phosphorus bromochloride, phosphorus oxychloride, phosphorus oxybromide, General formula (2) characterized by acting with thionyl chloride and thionyl bromide (where Y is Y-2 and Z is
Is a chlorine atom or a bromine atom). 20. A method of reducing an amide compound or a haloimidate compound represented by the following general formula (2), wherein Y is Y-1 or Y-2, wherein Y is Y: -3, and R ³ is a hydrogen atom).