JP5830821B2 - N-thioalkylpyrazole-3-carboxamide derivatives and acaricides containing the same as active ingredients - Google Patents

Description

  The present invention relates to an N-thioalkylpyrazole-3-carboxamide derivative and an acaricide containing the same as an active ingredient.

  In the field of agriculture and horticulture, various acaricides for the purpose of controlling various pests have been developed and put into practical use.

However, conventionally used agricultural and horticultural acaricides are not always satisfactory in terms of acaricidal effect or residual effect. Moreover, it cannot be said that the request | requirements, such as the frequency | count of application and reduction of the amount of applied medicine, are satisfied.
In addition, the appearance of various mites that have acquired resistance to conventional acaricides is also a problem.
Development of new acaricides that show sufficient control effects at low doses and have little adverse impact on the environment against various mites that have acquired resistance to conventional agricultural and horticultural acaricides Longed for.

  Various new acaricides for responding to these demands have been proposed, but they do not necessarily meet the above demands.

  The following compounds are disclosed as compound-related compounds of the present invention (for example, Patent Documents 1 and 2). However, these compounds do not show a sufficient acaricidal effect unless a large amount of application dose is used, and lack usefulness as acaricide. In these compounds, a chlorine atom is bonded to the 4-position of the pyrazole ring, and in Patent Documents 1 and 2, a trifluoromethyl group is bonded to the 4-position of the pyrazole ring. Is not described at all.

JP 2011-195543 JP JP 2012-056871 A

  The present invention is to provide a new substance useful for the control of various ticks, and in particular, exhibits a high control effect on various ticks that are resistant to conventional acaricides, The object is to provide a highly safe substance that is effective in dose and has reduced problems such as residual toxicity and environmental pollution.

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that an N-thioalkylpyrazole-3-carboxamide derivative defined by the following formula is a compound having characteristics that can meet the above-mentioned demands. As a result, the present invention has been completed.
That is, the present invention provides the following formula [I],

[Ｉ]

(式中、Ｒ¹は水素原子またはＣ₁〜Ｃ₄のアルキル基を示し、Ｒ²は水素原子、ハロゲン原子、トリフルオロメチル基またはシアノ基を示し、Ｒ³は水素原子またはＣ₁〜Ｃ₄のアルキル基を示し、Ｒ⁴およびＲ⁵はそれぞれ独立に水素原子またはＣ₁〜Ｃ₄のアルキル基を示し、Ｒ⁶は水素原子、Ｃ₁〜Ｃ₄のアルキル基または

を示し、Ｒ⁷は水素原子、ハロゲン原子、Ｃ₁〜Ｃ₄のアルキル基、トリフルオロメチル基またはシアノ基を示し、ｎは0、1または2を示す）で表されるN-チオアルキルピラゾール-３-カルボキサミド誘導体（以下、「本発明の化合物」とも言う）および該誘導体を有効成分として含有する殺ダニ剤に関するものである。

[I]

(Wherein R ¹ represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, R ² represents a hydrogen atom, a halogen atom, a trifluoromethyl group or a cyano group, and R ³ represents a hydrogen atom or C _{1 to} C 4. _{4 represents} an alkyl group, R ⁴ and R ⁵ each independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group, R ⁶ represents a hydrogen atom, a C ₁ -C ₄ alkyl group or

R ⁷ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group, a trifluoromethyl group or a cyano group, and n represents 0, 1 or 2). The present invention relates to a -3-carboxamide derivative (hereinafter also referred to as “the compound of the present invention”) and an acaricide containing the derivative as an active ingredient.

  The compound of the present invention exhibits an excellent control effect and acaricidal effect against mites. Therefore, the compound of the present invention can exert a control effect and an acaricidal effect at a lower dose than conventional drugs.

Hereinafter, the present invention will be described in detail.
In the compound of the present invention represented by the formula [I], examples of the halogen atom represented by R ² and R ⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the C ₁ -C ₄ alkyl group represented by R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, sec-butyl group, and tert-butyl group.
The compound of the present invention is a novel compound not described in any document, and includes two optically active substances when R ⁴ is a hydrogen atom and R ⁵ is a C ₁ -C ₄ alkyl group. This compound can be produced, for example, according to the following reaction formula 1, taking into account the methods described in JP 2011-195543 (Patent Document 1) and JP 2012-056871 (Patent Document 2). it can.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶およびｎは、前記式［Ｉ］で定義した通りであり、Ｘは、塩素原子又は臭素原子を示す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are as defined in the formula [I], and X represents a chlorine atom or a bromine atom.)

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and methylene chloride; water; methyl acetate and acetic acid Esters such as ethyl; or polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide, for example, 0 ° C. to 30 ° C., preferably 0 ° C. to 5 ° C. The reaction can be carried out in the presence of a base at ° C. As the base, for example, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, or the like can be used. As long as the optically active amine [III] is used, the optically active compound [I] can be easily obtained.

  After the reaction, in order to isolate the compound of the present invention represented by the formula [I], which is the target product, when a solvent dissolved in water was used, the solvent was distilled off under reduced pressure, and water was added. Extracted with water-insoluble benzene, toluene, xylene and other aromatic hydrocarbons; chloroform, methylene chloride and other halogenated hydrocarbons; ethyl acetate and other esters, washed with saturated brine, and anhydrous sodium sulfate After drying with a desiccant such as, the solvent may be distilled off under reduced pressure. In the case of using a solvent insoluble in water, it is separated after adding water, and after washing the organic phase with saturated saline and drying with a desiccant such as anhydrous sodium sulfate, the solvent is distilled off under reduced pressure. good. After evaporation of the solvent, the resulting residue may be sufficiently pure as it is, but if it is impure, it can be washed with a hydrocarbon such as hexane or heptane that does not dissolve the target product, or recrystallized or column chromatographed. Pure product can be obtained by refining by chromatography.

  The starting compound [II] can be synthesized from the following formula [IV] according to the following reaction formula 2.

（式中、Ｒ¹およびＲ²は、前記式［Ｉ］で定義した通りであり、Ｘは、塩素原子又は臭素原子を示す。）

(In the formula, R ¹ and R ² are as defined in the formula [I], and X represents a chlorine atom or a bromine atom.)

When the compound of formula [IV] is reacted with a halogenating agent, a compound of formula [II] is obtained. The above reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as chloroform and dichloromethane. Examples of the halogenating agent include thionyl chloride, thionyl bromide, oxalyl chloride, oxalyl bromide, phosphorus pentachloride, phosphorus pentabromide, phosphorus trichloride, and the like. The reaction temperature is, for example, 5 to 100 ° C, preferably 20 to 90 ° C. After the reaction, in order to isolate the target compound represented by the formula [II], the reaction solution is concentrated under reduced pressure, and the resulting residue is converted into a hydrocarbon such as hexane or heptane that does not dissolve the target object much. And then dry after washing.
The compound of the formula [IV] can be synthesized from the following formula [V] according to the following reaction formula 3.

（式中、Ｒ¹およびＲ²は、前記式［Ｉ］で定義した通りであり、Ｙは、メチル又はエチルを示す。）

(In the formula, R ¹ and R ² are as defined in the formula [I], and Y represents methyl or ethyl.)

  The above reaction can be carried out in the presence or absence of a solvent and in the presence of a base. Examples of the solvent include water; alcohols such as methanol, ethanol, propanol, and ethylene glycol; and mixed solvents of the above solvents. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Examples thereof include alkali metal hydrogen carbonates such as sodium hydrogen and potassium hydrogen carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate. The reaction temperature is 5 to 150 ° C, preferably 10 to 110 ° C. After the reaction, in order to isolate the target compound represented by [IV], acidify with mineral acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and propionic acid, and then filter the precipitate and wash with water. It only needs to be dried afterwards.

The compound of the formula [V] can be synthesized from the following formula [VI] according to the following reaction formula 4. For example, it can be synthesized according to the method described in International Publication No. 2010/051926 pamphlet.
The following [VI] is, for example, Journal of Chemical Society, page 3262 (1958), Journal of Chemical Society, page 2769 (1961), Annalen Der Chemie, volume 716, page 160 (1968), JP-A 63-91373. It can be synthesized according to the method described in Japanese Patent Laid-Open No. 1-283274, Pharmaceutical Journal, Vol. 97, p. 719 (1979), Journal of Medical Chemistry, p. 20, p. 80 (1977).

(式中、Ｒ¹及びＲ²は、前記式［Ｉ］で定義した通りであり、Ｙは、前記式［Ｖ］で定義した通りであり、Ｚは臭素原子又はヨウ素原子を示す。）

(In the formula, R ¹ and R ² are as defined in the formula [I], Y is as defined in the formula [V], and Z represents a bromine atom or an iodine atom.)

  The starting thioalkylamine derivative [III] is, for example, Japanese Patent Application Laid-Open No. 2001-163854, Japanese Patent Application Laid-Open No. 2006-89469, Japanese Patent Application Publication No. 2005-526858, Japanese Patent Application Publication No. 6640444, U.S. Patent Application Publication 2002/0055631, U.S. Patent Application Publication 2002/0086887, U.S. Patent Application Publication 2005/0272744, JP 2002-105046 A, Journal of American Chemical Society, Vol. 73, 2121 (1951), Journal of Organic Chemistry, 28, 2587 (1963), Tetrahedron letters, 24, 2131 (1983), Tetrahedron, 48, 2359 (1992), Journal of Organic Chemistry, 57 6257 (1992), Journal of Medicinal Chemistry, 27, 1354 (1984).

  The compound of the present invention can be used for agricultural crops such as food crops (rice, barley, wheat, rye, oats and other wheat, corn, potato, sweet potato, taro, soybeans, red beans, broad beans, peas, beans, peanuts, etc. Bean, etc.), vegetables (cabbage, Chinese cabbage, radish, persimmon, broccoli, cauliflower, cruciferous crops such as komatsuna, pumpkins, cucumbers, watermelons, mushrooms, melons and other cucumbers, eggplants, tomatoes, peppers, peppers , Okura, spinach, lettuce, lotus root, carrot, burdock, garlic, onion, green onion, etc.), fruit trees / fruits (apple, citrus, pear, strawberry, peach, plum, cherry peach, walnut, chestnut, almond, Bananas, strawberries, etc.), fragrances and other crops for viewing (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), special crops (cigarettes, tea, sugar beet, sugarcane) Bi, hop, cotton, hemp, olive, rubber, coffee, etc.), forage and feed crops (Timothy, clover, alfalfa, corn, sorghum, orchard grass, grass, legume, etc.), turf Turf, bentgrass, etc.), forest trees (Todomatsu, Ezo pine, pine, hiba, cedar, cocoon, etc.) and ornamental plants (kiku, rose, carnation, orchid, herbaceous, florets, ginkgo, cherry, Aoki, etc.) It can also be used to control pests such as arthropods that cause damage to garden trees.

  Specific pests include Acari, Arthropoda spiders, for example, Polyphagotarsonemus latus, Phytonemus pallidus, Penthaleus major, etc. Grape spider mite (Brevipalpus lewisi), Southern spider spider mite (Brevipalpus phoenicis) etc. viennensis), Oligonychus ununguis, Eotetranychus kankitus, Clover spider mite (Bryobia praetiosa), etc. Grape ticks (Colomerus vitis) Preferable examples include adults, larvae, eggs, and the like, such as tick, mite (Aculus fockeui), and prickly tick (Calacarus carinatus), and the like.

The compounds of the invention having the formula [I] can also be used as a mixture with other active compounds. In particular, harmful to arthropods, gastropods, nematodes, etc. that damage plants by using them in combination with compounds (insecticides) having insecticidal activity, acaricidal activity, horticultural horticultural use, nematocidal activity With respect to the control of living organisms, it is possible to expand the number of pests to be controlled, and a synergistic effect such as a reduction in dosage can be expected.
The form of the agricultural and horticultural acaricide in the form of a composition produced using agrochemical adjuvants widely used in the industry is not particularly limited. For example, emulsions, wettable powders, powders, flowables, fine granules It is preferable to use a form such as an agent, a granule, a tablet, an oil, a spray, and an aerosol. One or more of the above compounds can be blended as an active ingredient.

  The agrochemical adjuvant used for producing the agricultural and horticultural acaricide can be used for the purpose of, for example, improving the effect, stabilizing, and improving dispersibility of the agricultural and horticultural acaricide. For example, a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersing agent, a disintegrating agent, 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, and methylnaphthalene. , Cyclohexane, animal and vegetable oils, fatty acids and the like. 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.

As the emulsifier and the dispersant, a normal surfactant can be used. For example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, etc. Cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used. Further, spreading agents; wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; disintegrating agents such as sodium lignin sulfonate and sodium lauryl sulfate can be used.
The content of the active ingredient in the agricultural and horticultural acaricide of the present invention is, for example, 0.01 to 99.5% by mass, for example, selected from the range of 0.5 to 90% by mass, and various conditions such as formulation form, application method, etc. For example, in the case of a powder, about 0.5 to 20% by mass, preferably about 1 to 10% by mass, and in the case of a wettable powder, about 1 to 90% by mass, preferably about 10 to 80% by mass. In the case of an emulsion, it is preferable to produce the emulsion so that it contains about 1 to 90% by mass, preferably 10 to 40% by mass of the active ingredient.

  For example, in the case of an emulsion, the compound of the present invention, which is an active ingredient, can be mixed with a solvent and a surfactant to produce a stock emulsion, and this stock solution is diluted with water to a predetermined concentration when used. Can be applied. In the case of a wettable powder, the compound of the present invention as an active ingredient, a solid carrier, and a surfactant are mixed to produce a stock solution, which can be further diluted with water to a predetermined concentration before use. . In the case of powders, the compound of the present invention, which is an active ingredient, and a solid carrier can be mixed and applied as it is. In the case of granules, the compound of the present invention as an active ingredient, a solid carrier, and a surfactant It can be produced by mixing and granulating an agent 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.

The agricultural and horticultural acaricides of the present invention include other fungicides, insecticides, acaricides, herbicides, insect growth regulators, fertilizers, soil improvers, etc. in addition to the compounds of the present invention which are active ingredients. Arbitrary active ingredients may be blended. The application method of the acaricide of the present invention is not particularly limited, and can be applied by any method such as foliage spraying or soil treatment. For example, in the case of foliage spraying, for example, a solution having a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm can be used at an application rate of, for example, about 100 to 700 liters per 10 ares. In the case of soil treatment, a solution having a concentration range of 5 to 1000 ppm can be used at an application rate of about 1 to 10 liters per 1 m ² .

  Hereinafter, the present invention is further described in detail using Examples, Formulation Examples, and Test Examples, but the scope of the present invention is not limited by these Examples, Formulation Examples, and Test Examples.

Example 1 N- [1- (4-Chlorophenyl) thio-2-methyl-2-propyl] -1- (4-chlorophenyl) -5-methyl-4- (trifluoromethyl) pyrazole-3-carboxamide (1) Synthesis of ethyl 1- (4-chlorophenyl) -5-methyl-4- (trifluoromethyl) pyrazole-3-carboxylate 1- (4-chlorophenyl) -5-methyl-4-iodopyrazole- To a solution of 1.95 g of ethyl 3-carboxylate in 15 ml of DMF, 2.84 g of trimethyl (trifluoromethyl) silane, 2.86 g of copper iodide and 0.69 g of potassium fluoride were added and stirred at 80 ° C. for 12 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography to obtain 1.22 g of the desired product. Melting point (mp) 90-91 ° C.
(2) Synthesis of 1- (4-chlorophenyl) -5-methyl-4- (trifluoromethyl) pyrazole-3-carboxylic acid 1- (4-chlorophenyl) -5-methyl- obtained in (1) above To a mixed solution of 5 ml of water of 0.82 g of ethyl 4- (trifluoromethyl) pyrazole-3-carboxylate and 0.3 ml of ethanol was added 0.29 g of sodium hydroxide, and the mixture was heated to reflux for 1 hour. After cooling to room temperature, the reaction solution was poured into ice water and acidified with hydrochloric acid. The precipitate was collected by filtration, washed with water and dried to obtain 0.67 g of the desired product. Melting point (mp) 135-136 ° C.
(3) Synthesis of N- [1- (4-chlorophenyl) thio-2-methyl-2-propyl] -1- (4-chlorophenyl) -5-methyl-4- (trifluoromethyl) pyrazole-3-carboxamide 0.11 g of 1- (4-chlorophenyl) -5-methyl-4- (trifluoromethyl) pyrazole-3-carboxylic acid obtained in (2) above was heated under reflux in 5 ml of thionyl chloride for 1 hour and then concentrated under reduced pressure. did. The obtained residue was added to a solution of 0.11 g of 1- (4-chlorophenylthio) -2-methyl-2-propylamine and 0.15 g of triethylamine in 5 ml of ethyl acetate and stirred at room temperature for 1 hour. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography to obtain 0.15 g of the compound (No. 1) of the present invention described in Table 1. In addition, the compound of the present invention (No. 2-24) was prepared in the same manner as in Example 1 except that each substituent in the compound was adjusted as described in Table 1. Table 1 below lists the compounds of the present invention that were produced.

Table 1

  In Table 1 above, the numbers in parentheses given to “oil” in the “mp” column correspond to the numbers in the following parentheses, and each means a compound represented by the following NMR data.

1) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.51 (6H, s), 2.37 (3H, s), 3.48 (2H, s), 6.70 (1H, bs), 7.07 (2H, d
), 7.27 (2H, d), 7.32 (2H, d), 7.53 (2H, d).
2) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (6H, s), 2.42 (3H, s), 3.49 (2H, s), 6.68 (1H, bs), 7.06 (2H, d), 7.30 (2H , d), 7.54 (2H, d), 7.84 (2H, d).
3) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.53 (6H, s), 2.34 (3H, s), 3.58 (2H, s), 6.70 (1H, bs), 7.28 (2H, d), 7.35 (2H) , d), 7.44 (2H, d), 7.52 (2H, d).
4) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.53 (6H, s), 2.39 (3H, s), 3.61 (2H, s), 6.68 (1H, bs), 7.32 (2H, d), 7.34 (2H , d), 7.40 (2H, d), 7.53 (2H, d).
5) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.58 (6H, s), 2.37 (3H, s), 3.30 (2H, s), 7.82 (1H, bs), 7.34 (2H, d), 7.49 (2H d). (The proton of mercapto group could not be observed)
6) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.62 + 1.64 (6H, s), 2.39 (3H, s), 2.62 (3H, 2), 2.87 (1H, d), 3.74 (1H, d), 7.14 (1H, bs), 7.34 (2H, d), 7.52 (2H, d).
7) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.56 (6H, s), 2.34 (3H, s), 2.97 (3H, s), 3.75 (2H, s), 7.20 (2H, d), 7.34 (2H , d), 7.38 (2H, d), 7.49 (2H, d).
8) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.56 (6H, s), 3.49 (2H, s), 6.78 (1H, bs), 7.04 (2H, d), 7.30 (2H, d), 7.45 (2H , d), 7.59 (2H, d), 8.12 (1H, s).
9) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.56 (6H, s), 2.23 (3H, s), 3.42 (2H, s), 6.72 (1H, bs), 7.11 (2H, d), 7.31 (2H , d), 7.42 (1H, dd), 7.48 (1H, ddd), 7.53 (1H, ddd), 7.59 (1H, dd).
10) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (6H, s), 2.37 (3H, s), 3.52 (2H, s), 6.80 (1H, bs), 7.06 (1H, ddd), 7.13 (1H , dd), 7.27 (1H, dd), 7.32 (1H, ddd), 7.35 (2H, d), 7.52 (2H, d).
11) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.51 (6H, s), 2.39 (3H, s), 3.48 (2H, s), 6.70 (1H, bs), 7.10 (2H, d), 7.34 (2H , d), 7.39 (2H, d), 7.52 (2H, d).

  Next, formulation examples are shown. In addition, a part represents a mass part.

Formulation Example 1 Emulsion Compound of the present invention (10 parts), xylene (60 parts), N-methyl-2-pyrrolidone (20 parts) and Solpol 3005X (mixture of nonionic surfactant and anionic surfactant, Toho Chemical Industry Co., Ltd. (trade name) (10 parts) was uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 2 Wetting Agent-1
Compound of the present invention (20 parts), Nipseal NS-K (white carbon, Tosoh Silica Co., Ltd., trade name) (20 parts), Kaolin clay (Kaolinite, Takehara Chemical Co., Ltd., trade name) (50 parts) , Sun Extract P-252 (sodium lignin sulfonate, Nippon Paper Chemical Co., Ltd., trade name) (5 parts) and Lunox P65L (alkyl allyl sulfonate, Toho Chemical Co., Ltd., trade name) (5 parts) The mixture was pulverized and mixed uniformly to obtain a wettable powder.

Formulation Example 3 Wetting Agent-2
Compound of the present invention (20 parts), nip seal NS-K (20 parts), kaolin clay (50 parts), LUNOX 1000C (naphthalene sulfonate condensate, Toho Chemical Co., Ltd., trade name) (5 parts) and Solpol 5276 (nonionic surfactant, Toho Chemical Co., Ltd., trade name) (5 parts) was uniformly mixed and pulverized with an air mill to obtain a wettable powder.

Formulation Example 4 Flowable Agent-1
Premixed propylene glycol (5 parts), Solpol 7933 (anionic surfactant, Toho Chemical Co., Ltd., trade name) (5 parts), compound of the present invention (20 parts) in water (50 parts) Was dispersed into a slurry mixture, and then this slurry mixture was wet pulverized with Dynomill (Shinmaru Enterprises Co., Ltd.), and then xanthan gum (0.2 parts) was mixed and dispersed in water (19.8 parts) in advance. Was added to obtain a flowable agent-1.

Formulation Example 5 Flowable Agent-2
Compound of the present invention (20 parts), Newkalgen FS-26 (mixture of dioctylsulfosuccinate and polyoxyethylene tristyryl phenyl ether, Takemoto Yushi Co., Ltd., trade name) (5 parts), propylene glycol (8 parts), Water (50 parts) was mixed in advance, and this slurry-like mixture was wet-pulverized with a Dynomill (Shinmaru Enterprises). Next, xanthan gum (0.2 parts) was thoroughly mixed and dispersed in water (16.8 parts) to prepare a gel-like material, which was thoroughly mixed with the pulverized slurry to obtain a flowable agent-2.

  Next, it is shown by test examples that the compound of the present invention is useful as an active ingredient of a tick control agent. In addition, the compound of this invention is shown with the compound number of Table 1, and the compound used for the comparison control is shown with the following compound symbols (compound A and B).

Test Example 1: An insecticidal test against nymph spider mites A 90 ml capacity polyethylene cup was capped with a hole (diameter about 5 mm) in the center. A notch with a width of about 5 mm was cut into a circular filter paper having a diameter of 6.5 cm, and a strip-like portion hanging downward was inserted so as to be immersed in the water in the cup through a hole in the lid, and absorbent cotton was placed on the filter paper. In this way, four leaf discs (diameter 20 mm) made from the initial leaves of kidney bean were placed on the cotton wool that had been constantly replenished with water in the cup, and four female nymph mite females were inoculated on the leaf disc. did. This cup was placed in an acrylic cylinder having a height of 50 cm and a diameter of 10 cm, and 1.35 ml of a water-diluted solution of the compound of the present invention was sprayed per cup using an air brush (one concentration, one repetition). After spraying, it was kept in a constant temperature room at 25 ° C. Three days after the treatment, the mortality and bitterness of adult worms were investigated under a binocular, and the mortality rate (%) was determined by dying the bitter worms. The results are shown in Table 2 (in the following table, the compound numbers correspond to Table 1).

化合物Ａ

化合物Ｂ

Compound A

Compound B

Table 2
Mortality rate (%) = [Number of dead insects / (Number of dead insects + Number of surviving insects)] x 100

  As shown in Table 2 above, the compounds of the present invention have significantly higher acaricidal activity than Compounds A and B.

Claims (2)

The following formula [I]

[I]
(Wherein R ¹ represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, R ² represents a hydrogen atom, a halogen atom, a trifluoromethyl group or a cyano group, and R ³ represents a hydrogen atom or C _{1 to} C 4. _{4 represents} an alkyl group, R ⁴ and R ⁵ each independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group, R ⁶ represents a hydrogen atom, a C ₁ -C ₄ alkyl group or

R ⁷ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group, a trifluoromethyl group or a cyano group, and n represents 0, 1 or 2). -3-Carboxamide derivatives.   An acaricide comprising the N-thioalkylpyrazole-3-carboxamide derivative according to claim 1 as an active ingredient.