JP4587090B2 - Pyrazole derivative, method for producing the same, and pest control agent comprising the same as an active ingredient - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative and a pest control agent comprising the same as an active ingredient.
[0002]
[Prior art]
Conventionally, in the field of agriculture and horticulture, various pest control agents such as various insecticides for the purpose of controlling various pests have been developed and put into practical use.
For example, pyrazole compounds having insecticidal activity have an amino group which may be substituted at the 5-position in JP-A-62-228065, JP-A-63-316771 and JP-A-3-118369, etc. 3-cyano-1-phenylpyrazole derivatives are disclosed, and JP-A-5-148240 discloses substituted 1-aryl-3-cyano-5- (het) arylmethylideneiminopyrazole derivatives. Further, JP-A No. 64-47768 discloses substituted 1-aryl-5- (het) arylmethylaminopyrazole derivatives.
[0003]
However, the compounds described in the above documents do not satisfy all of the points of insecticidal effect, insecticidal spectrum, safety and the like, and there is a demand for the emergence of new compounds overcoming these problems, so WO98 / 45274 The publication discloses a novel 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative as a highly safe compound.
[0004]
However, in this application, there is no description of specific compounds with respect to a hetero ring having a pyrazine ring, a pyridazine ring or a pyrimidine ring.
[0005]
[Problems to be solved by the invention]
The compounds described in WO 98/45274 and the like have superior insecticidal activity and reduced toxicity compared to known compounds, but in recent years, there has been an increasing demand for safety to living bodies and the environment other than target pests. Moreover, environmental protection measures will be strengthened in the future. Therefore, in order to develop an agrochemical suitable for stricter regulations, it has been an important task to discover compounds with higher safety.
[0006]
In addition, osmotic transfer activity is an important factor in terms of improving the efficiency of drug application methods for pest control and applying it to soil treatment methods that are particularly effective in controlling pests such as sucking pests. The discovery of a new compound having both of the above has been desired.
[0007]
[Means for Solving the Problems]
As a result of diligent efforts to solve the above-described problems, the present inventors have found that in the 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative, which is a pyrazole-based compound, an amino group at the 5-position of the pyrazole ring. It has been found that a compound in which a specific nitrogen-containing hetero 6-membered ring is introduced via a methylene group selectively exhibits high osmotic transfer activity and low environmental toxicity as shown by fish toxicity and the like.
[0008]
In addition, the inventors have found that a higher effect can be obtained by optimizing the combination of the heteroaryl group and the substituent at the 4-position of the pyrazole ring, and have completed the present invention.
That is, the gist of the present invention is
[0009]
[Chemical formula 5]
[0010]
(In the above formula, X represents N or C-halogen, R ¹ Represents an alkyl group, an alkenyl group, an alkynyl group or a haloalkyl group, and R ² Represents a hydrogen atom, an alkyl group or an acyl group, and R ^Three Represents a hydrogen atom or an alkyl group, A is any group represented by the above A-1 to A-4, R ^Four Represents a hydrogen atom, an alkyl group, or a halogen atom, and n represents 0, 1 or 2. Here, when A is A-1 and n = 0, R ¹ Represents a haloalkyl group (excluding a perhaloalkyl group), and when A is A-4, n ≠ 0. 1) -aryl-3-cyano-5-heteroarylalkylaminopyrazole derivatives represented by formula (1)) and a pest control agent comprising the same as an active ingredient.
[0011]
Hereinafter, the present invention will be described in detail.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
[Compound of the present invention]
In the present invention, the substituent R in the compound represented by the above general formula (1) ¹ Is a linear or branched alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group; vinyl group, allyl group, methallyl Linear, branched alkenyl groups such as 2-butenyl group; linear or branched alkynyl groups such as ethynyl group, propargyl group; or fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoro group Ethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl 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- Linear or branched chain such as propyl group, 3,3,4-trichloropropyl group, 4-chlorobutyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group A haloalkyl group, wherein the alkyl group, alkenyl group, alkynyl group, or haloalkyl group is preferably C ₁ ~ C _Four belongs to. Particularly preferably, C ₁ ~ C _Four An alkyl group or C ₁ ~ C _Four Haloalkyl groups of which C ₁ ~ C ₂ An alkyl group or C ₁ ~ C ₂ Haloalkyl groups are preferred, and in particular, C such as fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, etc. ₁ ~ C ₂ The haloalkyl group is preferred.
[0013]
R ² Is a hydrogen atom; a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group; or a methylcarbonyl group, A linear or branched acyl group such as ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, etc. Or as an acyl group, C ₁ ~ C _Four Are preferred. R ² Especially preferably, it is a hydrogen atom.
[0014]
R ^Three Represents a hydrogen atom; or a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group, The alkyl group is C ₁ ~ C _Four Are preferred. R ^Three Especially preferably, it is a hydrogen atom.
A is any group represented by A-1 to A-4, and among these, A-1 is preferable. The present invention is characterized in that the nitrogen-containing hetero 6-membered ring having the specific structure is selected and bonded to the amino group at the 5-position of the pyrazole ring via a methylene group.
[0015]
R ^Four Is a hydrogen atom; a linear or branched alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group; or chlorine atom, fluorine A halogen atom such as an atom or a bromine atom. ₁ ~ C _Four Are preferred. R ^Four Especially preferably, it is a hydrogen atom.
[0016]
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, and preferably n = 0 or 1. However, n is not 0 when A is A-4.
When A is A-1 and n is 0, R ¹ Is a haloalkyl group other than a perhaloalkyl group, and preferably C ₁ ~ C _Four Haloalkyl groups, particularly preferably C ₁ ~ C ₂ And most preferably C such as fluoromethyl group and difluoromethyl group. ₁ Of the fluorinated alkyl group.
[0017]
As the compound of the general formula (1), a compound in which preferred substituents in the description of the substituents are combined is a more preferable compound.
Among these, preferred compounds as a combination of substituents are R ² , R ^Three And R ^Four Is a compound in which 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 ~ C _Four Particularly preferably C ₁ ~ C ₂ A haloalkyl group. When n = 0, R ¹ Is a haloalkyl group other than a perhaloalkyl group, preferably C ₁ ~ C _Four Particularly preferably C ₁ ~ C ₂ Of the fluorinated alkyl group.
[0018]
Above all, R ¹ Is C ₁ When the haloalkyl of the fluoromethyl group, difluoromethyl group or trifluoromethyl group (when n is 0, excluding the trifluoromethyl group) is used as an active ingredient of a pest control agent, particularly an insecticide This is preferable because of its high insecticidal activity and low fish toxicity.
Among the above combinations of substituents, the most preferable compound is 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-fluoromethylthio-5- (pyrazin-2-ylmethyl) represented by the following formula: Amino) pyrazole-3-carbonitrile and 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile It is.
[0019]
[Chemical 6]
[0020]
[Method for producing compound of the present invention]
The method for producing the compound of the present invention represented by the general formula (1) can be produced by forming a pyrazole ring and then adding or changing a substituent as necessary.
Known methods include the methods described in JP-A-63-316771, JP-A-5-148240, and JP-A-64-47768. The production method using these methods includes the following reaction formulas One method is illustrated.
[0021]
[Chemical 7]
[0022]
However, this method has drawbacks such as using an expensive fluorine-containing reagent in the initial stage of the process. Alternatively, the methods of Reaction Schemes 2 and 3 are possible, but there are similar problems such as obtaining raw materials.
[0023]
[Chemical 8]
[0024]
In addition, in WO98 / 45274, pyrazole having a 4-pyridylmethylamino group at the 5-position is obtained by allowing pyrimyl-4-aldehyde to act on the 5-position amino group of the pyrazole derivative at the 4-position to give an imine. It is disclosed that a derivative can be obtained (Scheme 4).
[0025]
[Chemical 9]
[0026]
The compound of the present invention can also be synthesized by the method of the above reaction formula (4). However, as a result of further studies, the present inventors have prepared a method for producing a pyrazole derivative represented by the general formula (1) as follows: 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 the compound of the general formula (1) is produced by the production method.
[0027]
[Chemical Formula 10]
[0028]
(In the above formula, R ² , R ^Three , R ^Four , X has the same meaning as in general formula (1), and R ^Five Represents a hydrogen atom, thiocyanato, a dithio group or a mercapto group bonded to two pyrazole rings. Z represents a halogen atom. )
Hereafter, the manufacturing method of the compound of this invention is described in detail. Reaction methods 5-10 are mentioned as a manufacturing method of the compound of this invention represented by the said General formula (1). In either case R ¹ Is preferably a haloalkyl group having 1 to 2 carbon atoms.
[0029]
Embedded image
[0030]
Reaction formula 5 is a general formula (2) (where R ^Five Is a hydrogen atom and Y is Y-3) ¹ S (O) nX ¹ (R ¹ , N has the same meaning as in general formula (1), and X ¹ Represents a chlorine atom or a bromine atom), and shows a method for producing a pyrazole derivative of the general formula (1). X ¹ Is preferably a chlorine atom. Reagent R used when n = 0 ¹ S (O) nX ¹ Preferred examples of trifluoromethylsulfenyl chloride (CF _Three SCl), and the compound obtained in this case is a pyrazole derivative having a trifluoromethylsulfenyl group at the 4-position. Reagent R used when n = 1 ¹ S (O) nX ¹ Preferred examples of trifluoromethylsulfinyl chloride (CF) _Three SOCl), and the resulting compound is a pyrazole derivative having a trifluoromethylsulfinyl group at the 4-position.
[0031]
Hereinafter, this reaction will be described using trifluoromethylsulfenyl chloride and trifluoromethylsulfinyl chloride as representative examples, but the same operation can be performed when other reagents are used.
When trifluoromethylsulfinyl chloride is used, trifluoromethylsulfinyl chloride isolated in advance may be used, or it is generated in the system from sodium or potassium salt of trifluoromethylsulfinic acid and thionyl chloride. May be. Depending on the conditions, pyrazole having a 4-position sulfenylated in the reaction with trifluoromethylsulfinate may be produced.
[0032]
In this reaction, general formula (2) (however, R ^Five R is a hydrogen atom) ₁ S (O) nX ₁ Is used at 0.5 to 10.0 molar equivalents, preferably 0.8 to 5 molar equivalents, and the reaction is carried out at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C. Solvents used in this reaction include aromatic hydrocarbons such as benzene, toluene or xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as chloroform or methylene chloride; polar solvents such as tetrahydrofuran and N, N-dimethylformamide In particular, toluene and dichloromethane are preferable.
[0033]
When trifluoromethylsulfenyl chloride is used, the reaction may be carried out in the absence of a base, but is preferably carried out in the presence of a base, and amines such as pyridine and triethylamine are used. When trifluoromethylsulfinyl chloride or trifluoromethylsulfinate is used, an amine such as dimethylamine, pyridine, 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).
[0034]
Reaction formula 6 is a pyrazole derivative of general formula (1) (where n is 1 or 2), characterized by oxidizing the sulfur atom of the pyrazole derivative of general formula (1) (where n = 0) The manufacturing method is shown. Examples of the oxidation method include a chemical oxidation method using an oxidizing agent and a biochemical oxidation method using enzymes, fungi, and the like, but a chemical oxidation method is generally used. In the chemical oxidation, 0.2 to 5.0 molar equivalents, preferably 0.25 to 2.0 molar equivalents of an oxidizing agent is added in the presence or absence of a solvent to the compound of the general formula (2). In addition, the reaction is performed at a temperature of -20 to 150 ° C, preferably 0 to 120 ° C.
[0035]
Examples of the oxidizing agent used in this reaction include hydrogen peroxide, oxon, m-chloroperbenzoic acid, peracetic acid, sodium periodate, ruthenium tetroxide, ozone, t-butyl hydroperoxide, and nitric acid. Hydrogen peroxide.
As a solvent used in this reaction, an organic solvent generally used for an oxidation reaction can be used, and a hydrocarbon solvent such as toluene and hexane, and a halogenated hydrocarbon solvent such as dichloromethane and chloroform are used.
[0036]
In the present invention, it is particularly preferred to carry out the reaction in the presence of an acid, and examples of the acid used include a proton acid and a Lewis acid, and a proton acid is preferred. Examples of the protic acid include dilute sulfuric acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, formic acid, and trifluoroacetic acid. Preferred are inorganic acids, and more preferred is sulfuric acid. When sulfuric acid is used, dilute sulfuric acid having a concentration of 60 to 90% is used, and preferably 75 to 85% sulfuric acid is used. These acids may be used as a mixture with an organic solvent, but preferably the acid itself is used as a solvent.
[0037]
A preferred combination of oxidizing agent and solvent is a combination of hydrogen peroxide and dilute sulfuric acid.
In this reaction, a catalyst that assists in oxidation may be added as necessary, and as the catalyst, a catalyst that assists in oxidation of sulfide can be generally used, but ruthenium compounds, tungsten compounds, vanadium compounds, Molybdenum compounds and titanium compounds, and more preferably ruthenium compounds. Examples of ruthenium compounds include ruthenium trichloride and ruthenium oxide. The amount of these catalysts used is 0.01 mol% to 100 mol%, preferably 0.1 mol% to 20 mol%, based on the sulfide of the raw material.
[0038]
The reaction is carried out in the range of −30 ° C. to 120 ° C., preferably −10 ° C. to room temperature, and carried out for 1 hour to 48 hours, preferably 1 to 6 hours.
Reaction formula 7 is represented by general formula (2) (where R ^Five Is a thiocyanato group and Y is Y-3) ¹ -X ² (R ¹ Is synonymous with the general formula (1), and X ² Represents a method for producing a pyrazole derivative of the general formula (1) (where n = 0), characterized by reacting with a halogen atom or a trimethylsilyl group.
[0039]
Examples of the reagent used in this reaction include trifluoromethyl bromide, trifluoromethyl iodide, trifluoromethyltrimethylsilane, and the like, and trifluoromethyltrimethylsilane is preferable.
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. Tetrahydrofuran.
[0040]
The reaction is preferably carried out in the presence of a fluorine compound, preferably tetrabutylammonium fluoride or potassium fluoride.
In this reaction, general formula (2) (however, R ^Five Is a hydrogen atom) ¹ -X ² Of 0.5 to 10.0 molar equivalents, preferably 0.8 to 5 molar equivalents, and the reaction is carried out in the range of -20 ° C to 120 ° C, preferably 0 ° C to room temperature, for 1 hour to 24 hours, Preferably it is implemented in 1-4 hours.
[0041]
Reaction formula 8 is represented by general formula (2) (where R ^Five Is a mercapto group and Y is Y-3) ¹ -X ^Three (R ¹ Is synonymous with the general formula (1), and X ^Three Represents a method for producing a pyrazole derivative of the general formula (1) (where n = 0), which is characterized by reacting with a halogen atom.
[0042]
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, and basic solvents such as triethylamine and liquid ammonia, preferably DMF and the like. The polar solvent.
[0043]
The reaction is preferably carried out under trifluoromethyl radical producing conditions, specifically exemplified by light irradiation, the use of a radical initiator or redox agent or an electron transfer agent such as methyl viologen.
The reaction is carried out in the range of −20 ° C. to 120 ° C., preferably 0 ° C. to room temperature, for 1 hour to 24 hours, preferably 1 to 4 hours.
[0044]
The reaction scheme 9 is represented by the general formula (2) (where R ^Five Is a dithio group bonded to two pyrazole rings, and Y is Y-3). ¹ -X ^Four (R ¹ Is synonymous with the general formula (1), and X ^Four Is a halogen atom or SO ₂ General formula (1) (where n = 0, R) ^Three Is a hydrogen atom).
[0045]
Examples of the reagent used include trifluoromethyl bromide, trifluoromethyl iodide, and trifluoromethylsulfinate.
Examples of the solvent include polar solvents such as DMF and DMSO, hydrocarbon solvents such as toluene and hexane, and halogenated hydrocarbon solvents such as dichloromethane and chloroform, with polar solvents such as DMF being preferred.
[0046]
The reaction is preferably carried out under trifluoromethyl radical generating conditions, specifically exemplified by the use of light irradiation, radical initiators or redox agents or electron transfer agents such as methyl viologen.
In the case of trifluoromethyl bromide and trifluoromethyl iodide, it is preferable to use a radical anion generator of sulfur dioxide in combination. As the radical anion generator of sulfur dioxide, sodium dithionate (Na ₂ S ₂ O _Four ), Sodium hydroxymethanesulfinate (Rongalite, NaO) ₂ SCH ₂ OH), zinc hydroxymethanesulfinate, a mixture of sulfur dioxide and zinc, a mixture of sulfur dioxide and formic acid / formate, and the like.
The reaction is carried out in the range of −20 ° C. to 120 ° C., preferably 0 ° C. to room temperature, for 1 hour to 24 hours, preferably 1 to 4 hours.
[0047]
Embedded image
[0048]
The method of reaction formula 10 is the general formula (1) (where R ¹ And a pyrazole derivative of an alkyl group containing at least one chlorine atom or bromine atom), and a fluorinating agent selected from the group consisting of hydrogen fluoride, a mixture of hydrogen fluoride and amine, and a metal fluoride. General formula (1) (where R ¹ Is a method for producing a pyrazole derivative of (an alkyl group having one or more fluorine atoms) (in Reaction Scheme 10, R ⁷ Is an alkyl group containing one or more chlorine or bromine atoms, R ⁸ Represents an alkyl group having one or more fluorine atoms).
[0049]
Examples of the reagent used include hydrogen fluoride, a mixture of hydrogen fluoride and organic amines, and metal fluorides such as potassium fluoride, sodium fluoride, and cobalt fluoride. Preferably, hydrogen fluoride and organic amines are used. It is a mixture. As the solvent, a solvent generally used in a halogen exchange fluorination reaction can be used, and a polar solvent such as DMF is preferable. R in raw materials ⁷ Is preferably a trichloromethyl group, and R ⁸ An example of is a trifluoromethyl group.
[0050]
As mentioned above, although the manufacturing method of the pyrazole derivative represented by General formula (1) was described, Preferably the method of Reaction formula 5 and 6 is used.
Next, a method for producing a pyrazole derivative represented by the general formula (2) will be described. When Y is Y-3, a pyrazole represented by the general formula (2) by the method shown in the reaction formulas 11 and 12 using the compounds represented by the general formula (3) and the general formula (4) as raw materials Derivatives can be produced.
[0051]
Embedded image
[0052]
Further, as shown in the above reaction formula 13, the compound of the general formula (3) is first used as a raw material, and A—C (═O) —X ⁷ And an amide compound (a compound in which Y is Y-1 in the general formula (2)) and reduced to give a compound in which Y is Y-3 in the general formula (2). Also, an amide compound (a compound in which Y is Y-1 in the general formula (2)) is converted into a haloimidate compound (a compound in which Y is Y-2 in the general formula (2)), and this is reduced to a pyrazole derivative. A method for obtaining (a compound in which Y is Y-3 in the general formula (2)) can also be exemplified.
[0053]
Examples of the reducing agent used in the reduction reaction include borane THF complex, sodium borohydride, sodium cyanoborohydride, lithium borohydride, and lithium aluminum hydride.
Examples of the solvent used in this reaction include ethers such as diethyl ether, dioxane or tetrahydrofuran; or polar solvents such as alcohols such as methanol, ethanol or propanol.
[0054]
The reaction is carried out in the range of −20 ° C. to 120 ° C., preferably 0 ° C. to room temperature, and carried out for 1 hour to 24 hours, preferably 1 to 4 hours.
Examples of the chlorinating agent used in the formation of halloymidate include phosphorus pentachloride, phosphorus oxychloride, thionyl chloride and the like.
Examples of the solvent used in this reaction include nonpolar solvents such as benzene, toluene and xylene, halogen solvents such as carbon tetrachloride, chloroform and dichloromethane, and ether solvents such as dimethoxyethane and tetrahydrofuran.
[0055]
The reaction is carried out in the range of 0 ° C. to 200 ° C., preferably room temperature to 150 ° C., for 1 hour to 24 hours, preferably 1 to 4 hours.
The compound described in the general formula (1) can be produced by combining the methods described above. The production method of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile is a typical production method. It is shown by the following reaction formula 14.
[0056]
Embedded image
[0057]
[Use of the compound of the present invention]
The pest control agent comprising the compound of the present invention as an active ingredient has an effect of controlling pests, mites and other pests, such as agriculture, forestry, livestock industry, fishery industry, product preservation scenes of these industries, public health, etc. Effective in a wide range of situations, such as repelling, controlling and controlling pests.
In particular, the compounds of the present invention are used in agriculture, forestry, etc., specifically in the cultivation of agricultural crops, pests that damage crops, trees, ornamental plants, etc. Excellent effect as an insecticide and acaricide used in
[0058]
Specific usage scenes, target pests, usage methods and the like are shown below, but the present invention is not limited to the following description. Furthermore, the pests specifically exemplified are not limited to the target pests, and the exemplified pests include adults, larvae, eggs and the like.
(A) Agriculture, forestry scenes, etc .;
Pest control agents comprising the compounds of the present invention as active ingredients are agricultural crops such as edible crops (rice, wheat, corn, potato, sweet potato, beans, etc.), vegetables (cruciferous crops, cucumbers, eggplants, tomatoes, leeks). Etc.), fruit trees (citrus fruits, apples, grapes, peaches, etc.), special crops (cigarettes, tea, sugar beet, sugarcane, cotton, olives, etc.), grass and feed crops (sorghum, grasses, legumes) Etc.) and ornamental plants (herbaceous plants, flowering plants, garden trees, etc.), repelling and controlling pests such as arthropods, molluscs, nematodes and various fungi that damage them It is effective for etc. Furthermore, the compound of the present invention is used to prevent pests when storing harvests from the above-mentioned crops, such as cereals, fruits, nuts, spices and tobacco, and products that have been subjected to treatment such as drying and powdering. It is also effective for extermination. It is also effective in protecting standing trees, fallen trees, processed timber, storage timber, etc. from damage caused by pests such as termites and beetles.
[0059]
Specific pests include, for example, the following as belonging to the arthropod phylum, mollusc phylum, and linear phylum. Examples of the arthropoda insect class include the following.
Lepidoptera, for example, Spodoptera such as Spodoptera litura, Tobacco moth, Spruce moth, Tamanaginuwaba; Spodidae such as Pterodactrum; Spodoptera family such as scallops; Spodoptera family such as oyster moths; Papilionidae; Papilioceae such as Ichimonjiseri; Swallowtail butterflies such as Swallowtail butterflies such as White butterflies; Lycaenidae such as Uramishijimi; Moth family; killer whale pike moth family such as Mont black killer whale pike; Arna Pseudoconspersa tussock family and the like; and the like America white Arctiidae Arctiidae such as.
[0060]
As for Coleoptera, for example, Scarabaeidae such as Douganebububu, Koohanamuguri, Japanese beetle, etc .; Buprestidae such as citrus beetle; Examples include the beetle family; the potato beetle such as the cucurbit beetle, kissing flea beetle, and rice beetle; the beetle family such as the weevil weevil;
[0061]
For example, the order of the half-branch, such as the chame bugs, the sword bugs, and the like; the stag beetles such as the pear bugs; the helicopteres such as the horned bugs; Ganodermaceae such as Nasigunbai; Mekurakamemidae such as Usumimemekuragame; Semicephalidae such as Niiniizemi; Awafukimidae such as Grape Awafuki; Family; leafhopper family such as leafhopper, leafhopper, etc .; planthopper family such as Aobahagoromo; pheasantaceae such as pterfly moth; whitefly family such as whitefly whitefly, silver leaf whitefly; Aphidaceae, such as aphids; Alascidae, such as apple beetles; Aphids, such as cotton aphids, peach aphids, scallop aphids; Spodopteras such as Iceria scales; Examples include the scale insect family;
[0062]
Examples of the thrips include thrips such as citrus thrips, chano thrips, and thrips; and thrips such as thrips and thrips.
Examples of the Hymenoptera include bee departments such as wasps; beetles such as apple bees; bees such as bees; and bees such as rose bees.
[0063]
As for Diptera, for example, Tephritidae, such as soybean Sayatamabaye; Tephritidae, such as Pleuromyidae; Tephritidae, such as Rice moth flies; Drosophila, such as Drosophila; Can be mentioned.
Examples of the order of the scorpionae include grasshoppers such as crickets; crickets such as blue pine beetles; keraceae such as kerats;
[0064]
Examples of the order of the order of the order of the order of the order of the order Coleoptera, for example, a family of D. beetles;
Examples of termites include termites such as taiwan termites, and examples of earworms include carabidaceae such as giant beetles.
[0065]
Examples of the arthropod gate crustacea and the spider can include the following.
Examples of the isopods of the crustacean include the genus Coleoptera, such as okadanagamushi.
As the spider mite, for example, dust mites, such as mite dust mites, cyclamen dust mites; spider mites, such as wheat mites; Examples include the family Acaridaceae such as the black mite;
[0066]
As the mollusc gall footsteps, for example, Sputumurogai, for example, as the middle gastropod of gastropod, and for example, African mussel, slug, Niwako slug, Chakoura slug, Uskawamaimai, etc. .
The following can be illustrated as a linear animal genus class and a tail line class.
For example, the genus Lepidoptera: Anguinaceae such as Imogusaresenchu; Tyrencorinxaceae such as Namiishokusenchu; Platyrenxaceae such as Kitanegususenchu, Minamigusensenchu; Hopiromeidaceae such as Namirasenchu; Potato cyst Examples thereof include heteroderae such as nematodes; meloid gynecaceae such as sweet potato nematodes; crimaceae such as crocodile; nototolenxaceae such as strawberry nematodes; and aferencoides such as strawberry nematodes.
[0067]
Examples of the caudate genus Nymphalidae include the Longidoridae such as the giant nematode; and the Trichodolsaceae such as the nematode.
Furthermore, the compound of the present invention is also effective in repelling, controlling and controlling pests that damage or affect trees such as natural forests, artificial forests and urban green spaces. In such a scene, specific pests include the following. Examples of the arthropoda insect class and the spider class include the following.
[0068]
Lepidoptera, for example, Spodoptera, Rana, etc .; Rhizopus, Rhizopus, Rhizopus, Rana, Rana, Rana, Rhizopus, Rhizopus, Rhizopus, Rhizopus And the like, and the like.
[0069]
As for Coleoptera, for example, Scarabaeidae, Nagachakogane, etc .; Scarabaeidae, such as Sphagnum beetle; Examples include the weevil family; the asteraceae family such as pine beetle and itayaki worm;
[0070]
Examples of the semiptera include Aphididae such as Todomatsu Aphid; Casa Aphididae such as Ezomatsusa Abra; Buprestidae such as Sugimaru Aphid; Aphididae such as hornworm.
Examples of the Hymenoptera include a bee family such as a larch bee; a honey bee family such as a pine bee; and a bee family such as a bee.
[0071]
As for Diptera, for example, Crane fly such as Kirigand Gumbo; Drosophila such as Larch fly;
Examples of the mites of the spider class include Suginotani mites and Todomatsu mites.
[0072]
Examples of the linear animal genus genus Lepidoptera include Parasitaferenxaceae such as pine wood nematode.
The pest control agent containing the compound of the present invention as an active ingredient is a preparation effective in the above-mentioned agricultural and forestry situations, and any use form prepared by the preparation, either alone or in other active compounds such as insecticides, insecticides. It can be used in combination with or as a mixture with mites, nematicides, fungicides, synergists, plant regulators, herbicides, poison baits and the like. Specific examples of the other active compounds include the following, but are not limited thereto.
[0073]
Active compounds such as insecticides and acaricides: Examples of organic phosphorus agents include dichlorvos, fenitrothion, malathion, nared, chlorpyrifos, diazinon, tetrachlorbinphos, fenthion, isoxathione, methidathion, salicione, acephate, dimethon-S methyl, disulfone , Monocrotophos, azine phosmesyl, parathion, hosalon, pyrimifosmethyl, prothiophos and the like. Examples of carbamate agents include metorcarb, fenobucarb, propoxur, carbaryl, etiophencarb, 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, acrinatrin, fenvalerate, etofenprox, silafluophene, fulvalinate, flucitrinate, bifenthrin, allethrin, phenothrin, fenpropatrin, ciphenothrin, flamethrin, Resmethrin, transfluthrin, praretrin, flufenprox, halophanprox, imiprotolin and the like can be mentioned. Examples of neonicotinoid agents include imidacloprid, nitenpyram, acetamiprid, tefranitodine, thiamethoxam, thiacloprid and the like.
[0074]
Examples of insect growth control agents such as phenylbenzoyl urea agents include diflubenzuron, chlorofluazuron, triflumuron, flufenoxuron, hexaflumuron, lufenuron, teflubenzuron, buprofezin, tebufenozide, chromafenozide, methoxyphenozide, and cyromazine. .
[0075]
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, and spinosad.
[0076]
Examples of other insecticides include cartap, bensultap, chlorfenapyr, diafenthiuron, nicotine sulfate, metaldehyde, fipronil, pymetrozine, indoxacarb, and tolfenpyrad.
Active compounds of acaricides such as dicophore, phenisobromolate, benzomate, tetradiphone, polynactin complex, amitraz, propargyl, fenbutane oxide, tricyclohexyltin hydroxide, tebufenpyrad, pyridaben, fenpyroximate, pyrimidifene, phenazaquin, clofentezine Hexothiazox, acequinosyl, quinomethionate, phenothiocarb, etoxazole, bifenazate and the like.
[0077]
Examples of the nematicide active compound include methyl isocyanate, phostiazate, oxamyl, mesulfenphos, and the like.
Examples of poison baits include monofluoroacetic acid, warfarin, coumatetralyl, and difacin.
The active compounds of the fungicide include, for example, inorganic copper, organocopper, sulfur, mannebu, thiuram, thiadiazine, captan, chlorothalonil, iprobenfos, thiophanate methyl, benomyl, thiabendazole, iprodione, procymidone, pencyclone, metalaxyl, sandphane, bileton, triflumi Examples thereof include sol, phenalimol, triphorin, dithianone, triazine, fluazinam, probenazole, dietofencarb, isoprothiolane, pyroxylone, iminotadine acetate, echromesole, dazomet, and cresoxime methyl.
[0078]
Examples of the synergist active compound include bis- (2,3,3,3-tetrachloropropyl) ether, N- (2-ethylhexyl) bischloro [2,1,1] hept-5-ene-2, Examples include 3-dicarboximide and α- [2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene.
Examples of active compounds such as herbicides include bialaphos, cetoxydim, trifluralin, mefenacet and the like. Examples of the active compound of the plant regulator include indole butyric acid, ethephon, 4-CPA, and the like.
Examples of repellent active compounds include caran-3,4-diol, N, N-diethyl-m-triamide (Deet), limonene, linalool, citronellal, menthone, hinokitiol, menthol, graniol, eucalyptol, etc. be able to.
[0079]
The use form of the pest control agent of the present invention is arbitrary, and an agricultural chemical adjuvant is added to the compound of the general formula (1), for example, wettable powder, granular wettable powder, aqueous solvent, emulsion, liquid, suspended in water. It is formulated into a flowable agent such as an agent and an emulsion in water, a capsule, a powder, a granule and an aerosol. The content of the active ingredient compound such as the compound of the present invention in these preparations is arbitrary, but is usually selected from the range of 0.001 to 99.5% by weight in terms of the total amount of active ingredients, and various forms such as preparation forms, application methods, etc. It may be appropriately determined depending on the conditions, for example, about 0.01 to 90% by weight, preferably 1 to 50% by weight in wettable powder, wettable powder, water solvent, emulsion, liquid, flowable, capsule, etc. It is manufactured to contain about 0.1 to 50% by weight, preferably 1 to 10% by weight for powders and granules, etc., and about 0.001 to 20% by weight, preferably 0.01 to 2% by weight for aerosols and the like. Is preferred.
[0080]
The agrochemical adjuvants used are for the purpose of improving pest repellent effect, controlling effect, controlling effect, stabilizing and improving dispersibility, for example, carrier (diluent), spreading agent, emulsifier, wet spreading. An agent, a dispersant, a disintegrant, and the like can be used. Examples of liquid carriers include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, Examples include cyclohexane, animal and vegetable oils, and fatty acids. As the solid carrier, 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, higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, anionic surfactants such as lauryl betaine, cations Surfactants, nonionic surfactants, zwitterionic surfactants, and the like can be used. In addition, spreading agents such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl phenyl ether; wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; sodium lignin sulfonate and sodium lauryl sulfate Disintegrants can be used.
[0081]
For example, in the case of a wettable powder, an active ingredient compound of the general formula (I), a solid carrier, a surfactant and the like are mixed to produce a bulk powder. Can be applied diluted. In the case of an emulsion, a stock emulsion can be prepared by mixing a solvent, a surfactant, and the like with the above-mentioned active ingredient compounds. Further, the stock solution can be diluted with water to a predetermined concentration before use. it can. In the case of powders, the above active compound, solid carrier and the like can be mixed and applied as they are. In the case of granules, the active ingredient can be mixed with the solid carrier, surfactant and the like. It can be manufactured by granulating and applied as it is. However, the manufacturing method of each of the above-mentioned preparation forms is not limited to the above-mentioned ones, and can be appropriately selected by those skilled in the art according to the type of active ingredient, application purpose, and the like.
[0082]
The method of use varies depending on the type and amount of pests, the type of target crops and trees, the cultivation form, and the growth state, but for arthropods, gastropods, nematodes, etc. In general, 0.1 to 1000 g, preferably 1 to 100 g of active ingredient per 10 ares may be applied to the place where damage by these pests has occurred or where damage is expected to occur. .
[0083]
Specific application methods include, for example, the above-mentioned wettable powder, granule wettable powder, aqueous solvent, emulsion, liquid, flowable preparation such as suspension in water and emulsion in water, capsules and the like, which are diluted with water. However, it may be applied to crops, trees, etc. in the range of 10 to 1000 liters per 10 ares depending on the type of crops, trees, etc., the cultivation form, and the growth state. In the case of powders, granules, and aerosols, they may be applied to crops, trees, etc. within the range of the above-mentioned usage method in the state of the preparation.
[0084]
When the target pest primarily injures crops, trees, etc. in the soil, for example, wettable powder, granular wettable powder, water solvent, emulsion, liquid, suspension in water, emulsion in water, etc. A flowable agent, capsule or the like may be diluted with water and generally applied in a range of 5 to 500 liters per 10 ares. At this time, the agent may be sprayed on the soil surface so as to be even over the entire application area or may be irrigated in 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. When spraying or irrigating, it may be applied only to the surroundings of seeds, crops, trees, etc. that are to be protected from pest damage, or it may be cultivated during or after spraying to disperse the active ingredients mechanically. Good.
[0085]
Further, a pest control agent containing the compound of the present invention as an active ingredient may be attached around the plant seeds by a known method. Such a treatment not only prevents damage by pests in the soil after sowing of the seeds, but also protects plant stems and leaves, flowers, fruits, etc. from damage by pests after growth. You can also.
[0086]
When protecting the above-mentioned trees, fallen trees, processed wood, storage wood, etc. from damage caused by termites or beetles, for example, oils, emulsions, wettable powders, sols for surrounding soil such as trees and wood Examples of methods include spraying, injecting, irrigating, applying, and spraying medicines in the form of use such as powders and granules. Even in such a situation, the pest control agent containing the compound of the present invention as an active ingredient alone or other active compounds such as insecticide, acaricide, nematicide, bactericidal agent, repellent and synergist, etc. Can be used in combination or as a mixture.
[0087]
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 terms of the total amount of active ingredients, and 0.005 to 10% by weight for oils, powders, granules and the like. %, Emulsion, wettable powder, sol and the like are preferably contained in an amount of 0.01 to 50% by weight. Specifically, for example, when controlling and controlling termites and beetles, 1m ² What is necessary is just to spray 0.01-100 g per soil as an active ingredient compound amount on soil or a wood surface.
(B) Livestock industry, fishery industry scene, etc.
The pest control agent comprising the compound of the present invention as an active ingredient is parasitic inside or outside of animals such as pets bred in the livestock industry, fisheries industry and home, and is used for feeding and blood sucking on the skin etc. Effective for repelling, extermination and control of pests such as arthropods, nematodes, flukes, tapeworms, protozoa, etc. that cause direct harm or damage by spreading diseases, It can also be used to prevent or treat diseases related to these pests.
[0088]
Target animals include vertebrates (eg, livestock such as cattle, sheep, goats, horses, pigs, etc .; farmed fish; birds such as poultry, dogs, cats, mice, rats, hamsters, squirrels, ferrets, etc.) And pets and experimental animals selected from animals and fish).
Among the pests, examples of the arthropoda insect class and the spider class include the following. As for Diptera, for example, Abuidae such as Yamatobu, Tsutsugebuyu, Akaushibu, etc .; Houseflies such as Drosophila, houseflies, and flies; Drosophila such as Drosophila; Bliesidae such as Drosophila; Drosophilidae such as Drosophila; Flea flies; flies flies such as Amanes flies; butterflies such as giant butterflies and flies It can be illustrated.
[0089]
Examples of the culprit include human fleas such as cat fleas and dog fleas.
Examples of the lice include the body lice of pig lice, cattle lice, etc .; the species of porcupine lice such as horse lice; the species of beetle pods such as cattle white lice;
[0090]
Examples of the mite of the arthropod spider mite include, for example, ticks, mites, mites, kingfish mites, mites, mites, etc .; And mites, mites, mites, mites, mite, mite, mite, and the like.
[0091]
The following can be illustrated as a linear animal gate twin line rope.
Examples of the roundworms include cattle worms, pig nematodes, pig lung worms, ciliate nematodes, bovine intestinal nodules and the like. Examples of roundworms include swine roundworms and chicken roundworms.
Examples of the genus Chlamydomonas can include, for example, Schistosoma japonicum, liver tetsu, deer birch fluke, Westermann lung fluke, and Japanese chicken egg fluke.
[0092]
Examples of the tapeworms include foliate tapeworms, extended tapeworms, Beneden tapeworms, square tapeworms, stagnation tapeworms, and ringworms.
In the Protozoan Trichinella, for example, Histomonas is the root flagellate, for example, Leishmania, Trypanosoma, etc., for example, the flagellate, for example Giardia, for example, for Trichomonads, For example, Trichomonas can be mentioned.
[0093]
In addition, examples of the amoeba of the fleshy class include Entamoeba, etc., examples of the sporeworm class Pyroplasma subclass, such as Theilaria, Babesia, etc., examples of the late class sporeworm subclass include Eimeria, Plasmodium, Toxoplasma be able to.
The pest control agent containing the compound of the present invention as an active ingredient is a preparation effective in the above-mentioned livestock industry, fishery industry, etc., and any use form prepared by the preparation, alone or other active compound such as an insecticide. It can be used in combination with or in combination with acaricides, nematicides, fungicides, synergists, plant regulators, herbicides, poison baits and the like. Specific examples of the other active compounds include, but are not limited to, substances exemplified in the section “(A) Agriculture, forestry scene, etc.”.
[0094]
Specific application methods include, for example, mixed pharmaceutical compositions that can be mixed in feed such as livestock and pets, or can be taken orally, such as tablets, pills, and capsules containing pharmaceutically acceptable carriers and coating substances. , Pastes, gels, beverages, medicinal feeds, medicinal drinking water, medicinal supplements, sustained-release large pills, other sustained-release devices designed to be retained in the gastrointestinal tract, or sprays, powders, It can be administered transdermally as grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo and the like.
[0095]
As a method of transdermal administration or local administration, a device (for example, a collar, a medallion, an ear tag, etc.) attached to an animal so as to control an arthropod locally or systemically can be used.
Specific oral administration methods and transdermal administration methods for use as an anthelmintic agent for livestock, pets and the like are shown below, but in the present invention, these administration methods are not necessarily limited to the following descriptions.
[0096]
When administered orally as a pharmaceutical beverage formulation, it is usually a suspension or dispersion dissolved in a suitable non-toxic solvent or water together with a suspending or wetting agent such as bentonite or other excipients. And an antifoaming agent may be contained as necessary. In beverage preparations, the amount of the active ingredient compound is generally 0.01 to 1.0% by weight, preferably 0.01 to 0.1% by weight.
[0097]
When administered orally in a dry solid unit dosage form, capsules, pills or tablets containing a predetermined amount of the active ingredient compound are usually used. These forms of use are prepared by intimately mixing the active ingredient with suitable finely divided diluents, fillers, disintegrants and / or binders such as starch, lactose, talc, magnesium stearate, vegetable gum and the like. Is done. In such a unit use formulation, the weight and content of the anthelmintic agent may be appropriately set according to the type of host animal to be treated, the degree of infection, the type of parasite and the body weight of the host.
[0098]
In the case of administration by feed, there may be mentioned methods such as dispersing the active ingredient compound homogeneously in the feed or using the drug as a top dressing or in the form of pellets. In order to achieve the antiparasitic effect, the active ingredient compound is usually contained in an amount of 0.0001 to 0.05% by weight, preferably 0.0005 to 0.01% by weight, in the final feed.
[0099]
When dissolved or dispersed in a liquid carrier vehicle, it may be administered parenterally to the animal by intragastric, intramuscular, intratracheal or subcutaneous injection. Because of parenteral administration, the active ingredient compound is preferably mixed with vegetable oils such as peanut oil and cottonseed oil. In such pharmaceutical formulations, the active ingredient compound is generally contained in an amount of 0.05 to 50% by weight, preferably 0.1 to 0.2% by weight. In addition, a preparation mixed with a carrier such as dimethyl sulfoxide or a hydrocarbon solvent can be directly and locally administered to the external surface of livestock or pets by spraying or direct injection.
(C) Public health scenes, etc.
The pest control agent comprising the compound of the present invention as an active ingredient is harmful in public health situations such as adversely affecting clothing, food and living environment, further harming the human body, transporting and mediating pathogens, etc. It is also effective for repelling, extermination and control of living organisms to maintain public health. Specifically, the pest control agent of the present invention includes, for example, the house itself, indoor and outdoor wood, processed wood products such as wooden furniture, stored foods, clothing, books, animal products (skin, hair, wool, feathers, etc.) Effective in repelling, extermination and control of lepidoptera, beetles, worms, cockroaches, flies and ticks, etc., which can damage foods and plant products (clothing, paper, etc.) It is. Specific examples of pests in such public health situations include the following.
[0100]
Examples of the arthropoda insect class include the following. Lepidoptera, for example, stag beetles such as Mongolian moth, moths such as squirrel moths, moths such as Aura moth, moths such as bamboo moths, moths such as sand moths, sand moths, moths, etc. Can be mentioned.
[0101]
Examples of the order of Coleoptera include, for example, the red beetle, such as the red beetle; the long-nosed family, such as the bean scorpion; the beetle family, such as the red-winged beetle; the weevil family, such as the weevil, scallop weevil; Leguminosidae; Buprestidae such as Physcomitridae; Scarabaeidae, Scarabaeidae, etc .; Scarabaeidae such as Tobacco beetle, Jinsanbanbushi, etc .; Examples include leopard hornworms such as hornworms; Nagasinkidae such as Cittatakena cinnamon beetles and wiltworms; Kill.
[0102]
Examples of the Hymenoptera include hornets such as killer whales; antaceae such as giant clams;
As for Diptera, for example, mosquitoes such as Yamatoyabuka; scorpiones such as Nukaka; Chironomidae such as Sesuji Yurika; scorpionaceae such as Ashimadarabyu; abu family such as Abububu; houseflies such as housefly; And the like, and the like, and the like, and the like.
[0103]
Examples of the culprit include a flea family such as a human flea.
Examples of the myxomycetes include the beetle family such as purple beetles.
Examples of cockroaches include German cockroaches such as German cockroaches and American cockroaches; cockroach such as American cockroaches, black cockroaches, and cockroaches.
[0104]
Examples of the straight eye include the Colagiidae such as Madarakamadoma and Kamadouma.
Examples of the louse include human lice such as head lice; lice such as lice.
Examples of the hemiptera include bedbugs such as bed bugs; and sand turtles such as giant turtles.
[0105]
Examples of the termites include, but are not limited to, the white termites such as the Yamato termite and the termites; the lepidoptera such as the white termites, and the chatteridae such as the cochasaceae such as tsuchachaate; it can. Examples of the blemishes include stains such as Yamato Shimi and Shiro Amida.
[0106]
Examples of arthropod arachnids include the following.
As for the mite, for example, a tick family such as Schulze mite; a house mite family such as house dust mite; a tick family such as white tick mite; a lice mite family such as lice mite; a mite family such as a mite mite; a dust mite family such as a leopard mite; Examples include the tsutsugamushi family such as the red tsutsugamushi; the mite family such as the stag beetle mite and the white mite mite; the sugar mite family such as the sugar mite.
[0107]
Examples of the genuine spider are the genus Spider, such as the spider spider; the spider spider, such as the spider spider; the spider spider, such as the spider spider, the spider spider; the flat spider spider, such as the spider spider; .
Examples of the scorpion include oleanders such as the spotted scorpion.
[0108]
As other arthropod gates, examples of the labrum pods include omdeidae such as tobism cadets and aorth cadets, and examples of gegots include geidae such as geji. Further, examples of the Arthropoda bipoda Obiyasude include a zelkova family such as Toyake Yasude, and examples of the Arthropoda crustacea include an Alaska family, such as the crabs. Furthermore, examples of the annelid genus Lepidoptera include the Yamaviridae such as Yamavir.
[0109]
The pest control agent comprising the compound of the present invention as an active ingredient is a preparation effective in the public health situation described above, and any use form prepared by the preparation, alone or in other active compounds such as insecticides and acaricides. , Nematicides, fungicides, synergists, plant regulators, herbicides, poison baits and the like can be used in combination or as a mixture. Specific examples of the other active compounds may include substances exemplified in the section “(A) Agriculture, forestry scene, etc.”, but are not necessarily limited thereto.
[0110]
The use form of the pest control agent of the present invention is arbitrary. For example, when protecting the above-mentioned animal products, plant products, etc., spraying of oils, emulsions, wettable powders, powders, etc., installation of resin transpiration agents, etc. It can be controlled by methods such as treatment with smoke and fumes, installation of granules, tablets and poisonous bait, aerosol spraying and the like. The amount of the active ingredient compound in these preparations is preferably 0.0001 to 95% by weight.
[0111]
Application methods include pests such as arthropods that cause direct harm and arthropods that are disease vectors. Spraying, injection, irrigation, application, etc., fumigation, fumigant, mosquito coil, self-combustion smoke, chemical reaction smoke, etc., smoke, fogging smoke, ULV, etc. The method of processing with the preparation of the above can be mentioned. Alternatively, these can be applied by other methods such as dropping them into waterways, wells, reservoirs, water tanks and other running water or detained water. That's fine.
[0112]
In addition, it is possible to control stag beetles, etc., which are also pests in agriculture and forestry, in the same manner as described in “(A) Agriculture, forestry scenes, etc.”. For example, a method for mixing active ingredients in feces by mixing in livestock feed, and a method for volatilizing mosquitoes etc. to the air with an electric mosquito trap etc. are also effective.
[0113]
These forms of use can also be present as a mixture with other active compounds as described above, for example insecticides, acaricides, nematicides, fungicides, repellents or synergists. In these preparations, the active ingredient compounds are preferably contained in a total amount of 0.0001 to 95% by weight. In addition, it is also possible to use together with another active compound at the time of use.
[0114]
When protecting houses and wooden furniture from damage caused by termites or beetles, for example, spraying, injecting, irrigating and applying oils, emulsions, wettable powders, sols, powders, The method of spraying a chemical | medical agent by the usage form, such as a granule, etc. can be mentioned. Even in such situations, the compounds of the present invention are used alone or in combination with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents, synergists, etc. I can do it.
[0115]
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 terms of the total amount of active ingredients, and 0.005 to 10% by weight for oils, powders, granules and the like. %, Emulsion, wettable powder, sol and the like are preferably contained in an amount of 0.01 to 50% by weight. Specifically, for example, when controlling or controlling termites or beetles, 1 m ² What is necessary is just to spray 0.01-100g as an active ingredient compound amount per circumference | surroundings or the surface directly.
[0116]
In addition to the above, in addition to the above, appropriate orally ingested formulated pharmaceutical compositions, etc., such as pharmaceutical preparations, should be used to avoid harmful organisms such as causing harm to the human body and transporting or transmitting pathogens. Retained in tablets, pills, capsules, pastes, gels, beverages, medicinal feeds, medicinal drinking water, medicinal supplements, sustained release large pills and other gastrointestinal tracts containing acceptable carriers and coating substances It can be administered orally as a sustained release device, or transdermally administered as a spray, powder, grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo and the like.
The specific formulation and the like can be formulated in the same manner as the method described in the section “(B) Livestock industry, fishery industry scene, etc.”.
[0117]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
Example 1 1- (2,6-Dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile (Compound No. 1) 5) Production
To a mixture 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- Toluenesulfonic acid monohydrate (0.1 g) was added, and the mixture was heated to reflux for 10 hours while removing the 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-carbohydrate. Nitrile was obtained.
[0118]
100 ml solution of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylideneimino) pyrazole-3-carbonitrile obtained above in methanol To the solution, 0.9 g of sodium borohydride was gradually added. After stirring at room temperature for 1 hour, ice and ethyl acetate were added for extraction. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography to obtain 7.0 g of the compound (No. 5) described in Table 1 below. Melting point 169 ℃
¹ HNMR (CDCl _Three ): 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-carbonitrile (Compound No. 1) Manufacturing of
P-Toluenesulfonic acid in a mixture of 5.6 g of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl-4-methylsulfinylpyrazole-3-carbonitrile, 2.0 g of formylpyrazine and 60 ml of toluene 20 mg of monohydrate was added, and the mixture was heated to reflux for 3 hours while removing generated water, cooled to room temperature, extracted with 0.1 ml of triethylamine and 30 ml of ice water, and the organic layer was dried over anhydrous sodium sulfate. Was distilled off under reduced pressure to give crude 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinyl-5- (pyrazin-2-ylmethylideneimino) pyrazole-3-carbonitrile.
Got.
[0119]
Hydrogen was added to a solution of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinyl-5- (pyrazin-2-ylmethylideneimino) pyrazole-3-carbonitrile obtained above in 50 ml of methanol. 0.7 g of sodium borohydride was gradually added. After stirring at room temperature for 1 hour, ice and ethyl acetate were added for extraction. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography to obtain 5.1 g of the compound (No. 1) described in Table 1 below. Melting point 198 ℃,
¹ HNMR (CDCl _Three ): 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- (1-oxy-pyridin-3-ylmethylamino) pyrazole-3-carbonitrile (Compound No. 14) )Manufacturing of
Suspend 0.1 g of 60% sodium hydride in 10 ml of N, N-dimethylformamide, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinylpyrazole-3-carbonitrile 1 g was gradually added. After stirring at room temperature for 20 minutes, 3 drops of 15-crown-5-ether and then 0.3 g of 3-chloromethylpyridine-1-oxide were added and stirred at room temperature. After standing overnight, water and ethyl acetate were added and neutralized with 1N hydrochloric acid. After separation, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography to obtain 0.9 g of the compound (No. 14) described in Table 1 below.
[0120]
Melting point 189 ~ 191 ℃
¹ HNMR (CDCl _Three ): 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 Preparation of N- [3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazol-5-yl] pyrazine-2-carboxamide
5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole-3-carbonitrile 0.5 g (1.6 mmol), methyl pyrazinecarboxylate 0.24 g (1.7 mmol) and acetonitrile 0 .28% CH at room temperature in 5 ml mixture _Three ONa / CH _Three 0.3 g (1.6 mmol) of OH was gradually 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, whereby crystals were precipitated. 10 ml of ethyl acetate was added for extraction, and the organic layer was washed with saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off and concentrated, and the resulting crystals were filtered. The crystals were washed with a small amount of hexane and ethyl acetate, dried, and N- [3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazol-5-yl] pyrazine-2-carboxamide. 5 g (yield 77%) was obtained.
Example 5 Preparation of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylchloromethylimino) pyrazole-3-carbonitrile
N- [3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazol-5-yl] pyrazine-2-carboxamide 139 g (0.33 mol), phosphorus pentachloride 72.6 g (0.35 mol) and A mixture of 300 ml of toluene was heated to reflux for 2 hours. An additional 5 g of phosphorus pentachloride was added and heated to reflux for 1 hour. Cool to room temperature and let stand overnight. After stirring for 30 minutes, the crystals were filtered and washed with toluene. The crystals were dissolved in 1 l of chloroform and extracted by adding water. The organic layer was washed twice with water, washed with saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crystals were washed with hexane, and 112.3 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylchloromethylimino) pyrazole- 3-carbonitrile (yield 79%) was obtained.
Example 6 Production of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile
To a suspension of 85 mg (2.2 mmol) of sodium borohydride in 2 ml of ethanol, 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylchloromethylimino) pyrazole-3- Carbonitrile 0.5 g (1.1 mmol) was gradually added at 20 ° C. or lower. After stirring at room temperature for 1 hour, the mixture was gradually poured into 40 ml of water to precipitate crystals. After stirring for 30 minutes, the mixture was filtered, and the crystals were washed with water until the pH of the furnace liquid reached 6. The obtained crystals were dissolved in ethyl acetate and extracted with saturated brine. After anhydrous magnesium sulfate was added to the organic layer and dried, it was separated in a furnace, 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 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile. 42 g (yield 92%) were obtained.
Example 7 Preparation of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole
To a solution of 3.0 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole dissolved in 30 ml of dehydrated methylene chloride under a nitrogen atmosphere 14 ml of a dehydrated methylene chloride solution of sulfenyl chloride was added dropwise at room temperature over about 1 hour and 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 was performed, and 3.59 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole was added. Obtained.
Example 8 Preparation of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile
234 mg (1.3 mmol) of potassium trifluoromethanesulfinate, 358 mg (1.6 mmol) of p-toluenesulfonic acid dimethylamine salt, 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazine-2 -Ilmethylamino) pyrazole-3-carbonitrile (413 mg, 1.0 mmol) was suspended in 1.0 ml of 1,2-dichloroethane, and 301 mg (2.5 mmol) of thionyl chloride was added under water cooling. After raising the temperature to 60 ° C. and stirring for 30 minutes, the reaction mixture was analyzed by high performance liquid chromatography. As a result, 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-5- (Pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile was produced in a yield of 11%. The conversion of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile was 95%.
Example 9 Preparation of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile
1.725 g (10.0 mmol) of potassium trifluoromethanesulfinate, 895 mg (4.1 mmol) of p-toluenesulfonic acid dimethylamine salt, 951 mg (5.0 mmol) of p-toluenesulfonic acid monohydrate were added to 1,2- The suspension was suspended in 5.0 ml of dichloroethane, and 1.506 g (12.6 mmol) of thionyl chloride was added under ice cooling. 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 mixture was heated to 40 ° C. and 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 distilling off 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 (38% yield) of 2-ylmethylamino) pyrazole-3-carbonitrile were isolated.
Example 10 Preparation of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile
7.89 g (8.88 mmol) bis (1- (2,6-dichloro-4-trifluoromethylphenyl) -3-carbonitrile-5- (pyrazin-2-ylmethylamino) pyrazol-4-yl) -disulfide ), 5.44 g (31.6 mmol) of potassium trifluoromethylsulfinate and 0.40 g (1.24 mmol) of dioxobis (acetylacetonato) molybdenum are dissolved in 350 ml and 110 ml of acetonitrile, and an 80% t-butyl hydroperoxide solution is dissolved. 3.4 ml (27.2 mmol) was added dropwise at room temperature. Further, the addition of 5.44 g (31.6 mmol) of potassium trifluoromethylsulfinate and 3.4 ml (27.2 mmol) of 80% t-butyl hydroperoxide solution was repeated twice every 4 hours, and then 15 ml at room temperature. Stir for hours. Thereafter, 5.44 g (31.6 mmol) of potassium trifluoromethylsulfenate and 3.4 ml (27.2 mmol) of 80% t-butyl hydroperoxide solution were added again and stirred for 6 hours. After the precipitated light brown crystals were filtered off, acetonitrile was distilled off from the filtrate under reduced pressure, and ethyl acetate was added thereto for extraction. After the organic layer is washed with water, the solvent is removed under reduced pressure, and column chromatography purification (Hex / AcOEt = 5/2) is performed to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfate. 0.88 g (1.7 mmol) of a light yellow crystal of phenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile was obtained in a yield of 9.6%.
Example 11 Preparation of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile
1- (2,6-dichloro-4-trifluoromethylphenyl) -4-thiocyanato-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile 50 mg (0.11 mmol) of methanol under nitrogen atmosphere To the 1.5 ml solution was added 10.1 mg (0.24 ml) of sodium borohydride, and the mixture was stirred at room temperature for 2 hours. After distilling off the solvent from the reaction solution under reduced pressure, 2 ml of DMF was added under nitrogen, followed by cooling in a dry ice-acetone bath, and then 54.5 mg (0 of trifluoromethylating agent MEC-12 manufactured by Daicel Chemical Industries). .11 mmol) in DMF (0.5 ml) 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. Methylphenyl) -4-trifluoromethylsulfenyl-5- (pyrazin-2-ylmethylamino) pyrazole-3-carbonitrile was obtained.
[0121]
The compounds listed in Table 1 were synthesized according to the methods of Examples 1-11. Compound Nos. And NMR data are shown.
N0.2
¹ HNMR (CDCl _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 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 _Three ): 4.3 (2H, m), 7.02 (2H, d), 7.70 (2H, s), 8.01 (2H, d)
N0.15
¹ HNMR (CDCl _Three ): 4.84 (2H, d), 6.35 (1H, b), 7.31 (3H, m), 7.77 (2H, s), 8.15 (1H, m)
[0122]
[Table 1]
[0123]
Hereinafter, although the formulation example of the agricultural and horticultural insecticide which contains the compound of this invention as an active ingredient is shown, the usage form of this 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 Pharmaceutical Co., Ltd., trade name), 52 parts by weight of ST kaolin clay (Kaolinite, Tsuchiya Kaolin, trade name), Solpol 9047K ( Anionic surfactant, Toho Chemical Co., Ltd., trade name) 5 parts by weight, Lunox P65L (anionic surfactant, Toho Chemical Co., Ltd., trade name) 3 parts by weight, mixed and ground uniformly, effective A wettable powder containing 20% by weight of ingredients was obtained.
<Formulation example 2> Powder
2 parts by weight of the compound of the present invention, 93 parts by weight of clay (manufactured by Nippon Talc Co., Ltd.) and 5 parts by weight of Carplex # 80 (white carbon, Shionogi Pharmaceutical Co., Ltd., trade name) are uniformly mixed and ground to obtain active ingredient 2 A weight percent powder was produced.
<Formulation example 3> Emulsion
20 parts by weight of the compound of the present invention is dissolved in a mixed solvent consisting of 35 parts by weight of xylene and 30 parts by weight of dimethylformamide, and Solpol 3005X (a mixture of a nonionic surfactant and an anionic surfactant, Toho Chemical Co., Ltd.) (Trade name) 15 parts by weight was added to obtain an emulsion containing 20% by weight of the active ingredient.
<Formulation example 4> Flowable agent
30 parts by weight of the compound of the present invention, 5 parts by weight of Solpol 9047K, 3 parts by weight of sorbon T-20 (nonionic surfactant, Toho Chemical Co., Ltd., trade name), 8 parts by weight of ethylene glycol and 44 parts by weight of water (Shinmaru Enterprises Co., Ltd.) mixed and pulverized, 10 parts by weight of a 1% by weight xanthan gum (natural polymer) aqueous solution was added to this slurry mixture, mixed and pulverized well to obtain a flowable agent having an active ingredient of 20% by weight. It was.
[0124]
Hereinafter, although the test example of the agricultural and horticultural insecticide which contains the compound of this invention as an active ingredient is shown, the usage form of this invention is not limited to the following.
Test Example 1: Insecticidal effect on brown larvae
Rice seedling seedlings were set in a glass cylinder (inner diameter: 3 cm × length: 17 cm), and five brown planthopper 4th instar larvae 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 Preparation Example 3 was sprayed onto the glass cylinder using a spray tower (manufactured by Mizuho Rika) (1 concentration, 2 repetitions). It was kept in a thermostatic chamber at 25 ° C., and after 5 days of treatment, the mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined with the bitter insects killed by half. The results are shown in Table 2 (compound numbers in the table correspond to Table 1).
[0125]
[Table 2]
[0126]
Test Example 2: Insecticidal effect on larvae
Cabbage cut leaves (6 cm in diameter) were immersed for 1 minute in an aqueous diluted solution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Preparation Example 1. After immersion, it was air-dried and placed in a plastic cup (inner diameter: 7 cm), and 5 third instar larvae were released in this cup (1 concentration, 2 repetitions). It was kept in a constant temperature room at 25 ° C., and after 4 days of larvae, mortality and bitterness of larvae were investigated, and an insecticidal rate (%) was determined by dying the bitter worms in half. The results are shown in Table 3 (in the following table, the compound numbers correspond to Table 1).
[0127]
[Table 3]
[0128]
Test Example 3: Insecticidal effect on larvae of Spodoptera litura
Cabbage cut leaves (6 cm in diameter) were immersed for 1 minute in an aqueous diluted solution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Preparation Example 1. After soaking, it was air-dried and placed in a plastic cup (inner diameter 7 cm), and 5 third-instar larvae of the scallop were released (1 concentration, 2 repetitions). It was kept in a constant temperature room at 25 ° C., and after 5 days of larvae, mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined with the half of the bitter worms dead. The results are shown in Table 4 (in the following table, the compound numbers correspond to Table 1).
[0129]
[Table 4]
[0130]
Test Example 4: Insecticidal effect on adult weevil weevil
Two red beans were placed in a glass cylinder (inner diameter: 3 cm × length: 15 cm), and 10 adult weevil was released. 0.3 ml of a water-diluted solution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Formulation Example 3 was sprayed on the glass cylinder using a spray tower (manufactured by Mizuho Rika) (1 concentration, 2 repetitions). It was kept in a thermostatic chamber at 25 ° C., and after 4 days of treatment, the mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined with the half of the bitter worms dead. The results are shown in Table 5 (compound numbers in the table correspond to Table 1).
[0131]
[Table 5]
[0132]
Test Example 5: Insecticidal effect on larvae of peach aphid
The petioles of daikon leaves were inserted into a water-filled screw bottle (volume: 10 ml), and 5 to 6 peach aphids were inoculated per leaf. After inoculation, they were placed in a glass cylinder (diameter: 0.5 cm, height: 15 cm, with mesh lid), and aphids were grown in a thermostatic chamber at 25 ° C. for 3 days. After removing the aphid adults on the daikon leaves, the leaves were immersed in a water-diluted solution of the agricultural and horticultural insecticide of the present invention produced according to the formulation of Preparation Example 3 (about 5 seconds) and returned to the glass cylinder ( 1 concentration, 2 repetitions). It was kept in a constant temperature room at 25 ° C., and the number of aphids on the cocoon leaves was investigated on the 4th day after the treatment, and the insecticidal rate (%) was determined based on the results. The results are shown in Table 6 (compound numbers in the table correspond to Table 1).
[0133]
[Table 6]
[0134]
Test Example 6: Insecticidal effect through penetration and transferability to brown larvae
The roots of rice seedlings (plant height of about 10 cm) planted with plastic cups were washed with water, and the soil was thoroughly washed away so as not to damage the fine roots. Triangle with a cut portion of urethane chips (diameter 3 cm, height 2 cm) and 50 ml of a chemical solution (a dilute water solution of the agricultural and horticultural insecticide of the present invention manufactured according to the formulation of Preparation Example 1) in advance. The roots were inserted into the flask (2-3 rice seedlings / flask), and a urethane chip was sandwiched between the mouths 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 in this glass tube, it was covered with a urethane chip and kept in a constant temperature room at 25 ° C. (1 concentration, 2 repetitions). On the 4th day after the treatment, the mortality and bitterness of the larvae were investigated, and the insecticidal rate (%) was determined with 1/2 of the bitter worms. This test was performed on three chemical solutions having different active ingredient concentrations. The results are shown in Table 7 (compound numbers in the table correspond to Table 1).
[0135]
As comparative compounds I to V, each compound having the structure shown below (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 but not in the claims of this application, were also subjected to testing.
[0136]
Embedded image
[0137]
[Table 7]
[0138]
The brown planthopper is an important pest species that causes harm as described in Test Example 1, but it is sufficient if the application method such as spraying on the foliage is delayed in discovery or if the drug does not reach the root sufficiently. May not be effective.
Since this species has the feature that it inhabits the roots of rice and the like and absorbs juice, a more efficient control method is to treat the soil surface (granule treatment) before the occurrence of this species. Is mentioned. However, in order to increase the high control effect by such a method, a property of penetrating and transferring into the plant body is necessary as a property of the drug. As is clear from Table 6, the compounds of the present invention and compounds III and IV showed high insecticidal activity via high osmotic transferability against this species, which is an important problem pest, but compounds I, II and V were Since such an action is low, the effect is clearly inferior to that of the compound of the present invention.
Test Example 7: Fish toxicity test using Himedaka
This test example is an example of a technique for examining the environmental safety of agricultural and horticultural insecticides.
[0139]
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. Five medaka (adult fish, average fish weight: about 360 mg) were put into this aqueous solution, and the mortality of the medaka was observed (retention condition: 25 ± 2 ° C.), and the mortality after 48 hours was shown as a calculated percentage (1 ward). 5 fish / beaker, 1 continuous). The results are shown in Table 8 (compound numbers in the table correspond to Table 1).
[0140]
As comparative compounds, as in Test Example 6, compound I described in JP-A-63-316771, compounds II and III described in the examples of WO98445274, and claims of WO98445274 are included. Compounds IV and V not included in the claims of this application were subjected to the test.
[0141]
[Table 8]
[0142]
As is clear from Table 8, in the tests using compounds I to V, all showed high values of fish mortality, whereas none of the compounds of the present application showed death, It can be used well even in the situation where the control chemical enters the water system directly like paddy rice.
Test Example 8: Insecticidal effect on cat fleas
0.7 ml of a chemical solution diluted to a predetermined concentration was dropped onto a circular filter paper (diameter: 10 cm), dried, and then spread on the bottom of a cylinder (diameter: 10 cm × height 30 cm). Ten fleas were released, and on the 1st and 2nd day after treatment, life and death were investigated, and mortality was calculated based on the results. The results are shown in Table 9 (compound numbers in the table correspond to those in Table 1).
[0143]
[Table 9]
[0144]
【The invention's effect】
The 1-aryl-3-cyano-5-pyrazinylalkylaminopyrazole derivative of the present invention is excellent in insecticidal effect, has the performance of a broad insecticidal spectrum, exhibits a higher osmotic transfer activity, and has fish toxicity and the like. It is a novel compound with reduced environmental toxicity as shown, and is useful as a pesticidal agent.

Claims (6)

1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivatives represented by the following general formula (1).
(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. An atom or an alkyl group , R ⁴ represents a hydrogen atom or an alkyl group, and n represents 0, 1 or 2. Here, when n = 0, R ¹ represents a haloalkyl group (provided that a perhaloalkyl group the excluding) indicates be.) The ¹ -aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative 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. The ¹ -aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative according to claim 1 or 2 , wherein R ¹ is a haloalkyl group having 1 to 2 carbon atoms.   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. A pest control agent comprising the 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative according to any one of claims 1 to 4 as an active ingredient. An insecticide containing the 1-aryl-3-cyano-5-heteroarylalkylaminopyrazole derivative according to any one of claims 1 to 4 as an active ingredient.