JP5570921B2 - N-phenylthioalkylpyrazole-3-carboxamide derivative and acaricide containing the derivative as an active ingredient - Google Patents

Description

  The present invention relates to an N-phenylthioalkylpyrazole-3-carboxamide derivative and an acaricide containing the derivative 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.
It is eager to develop a new acaricide that shows sufficient control effects at low doses and has little adverse impact on the environment, even for various mites that have acquired resistance to conventional agricultural and horticultural acaricides. Has been.

  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 differ from the compounds of the present invention in that the N-substituent of carboxamide is an alkyl group. Moreover, these compounds are only disclosed as bactericidal active compounds, and their usefulness as a miticide is not disclosed at all. In addition, in the technical field of agriculture and horticulture, there is no technical common sense that a compound disclosed as a bactericidal active compound can be applied as it is as an acaricide. Furthermore, pyrazole carboxamide derivatives are known to have insecticidal, acaricidal, bactericidal, herbicidal activity or pharmaceutical activity, respectively, depending on the three substituents on the pyrazole ring and the type of amino group of the carboxamide moiety. Therefore, whether or not the pyrazole carboxamide derivative can be applied as an acaricide needs to be actually confirmed through experiments and the like.

  In addition, compounds similar to these compounds are also disclosed for bactericidal activity (for example, Patent Documents 3 to 7), but no acaricidal activity is disclosed.

  Further, regarding 1-phenylpyrazole-3-carboxamide derivatives, for example, Patent Document 8 reports N-aralkyl-1-phenylpyrazole-3-carboxamide derivatives having insecticidal and acaricidal activity. This compound differs from the compound of the present invention in that the N-substituent of carboxamide is an aralkyl group.

Further, as a substance having a phytotoxicity-reducing action of a herbicide, for example, Patent Document 9 discloses an N-hydroxy-4-halo-5-unsubstituted-1-phenylpyrazole-3-carboxamide derivative. This compound is different from the compound of the present invention in that the N-substituent of carboxamide is an alkyl group or a hydroxyl group.
Further, for example, Patent Document 10 discloses an N-alkyl-4-unsubstituted-5-alkyl-1-phenylpyrazole-3-carboxamide derivative, and this compound has an N-substituent of carboxamide. It is an alkyl group and is different from the compound of the present invention. In addition, this compound is disclosed only as a compound that reduces the phytotoxicity of the herbicide in combination with the herbicide, and the usefulness of the acaricide is not disclosed at all.
Further, for example, Patent Document 11 describes an N-alkyl-4-unsubstituted-1,5-diphenylpyrazole-3-carboxamide derivative. For example, Patent Document 12 describes the herbicidal activity of N-alkyl-4-halo-1,5-diphenylpyrazole-3-carboxamide. These compounds have a phenyl group at the 5-position and relate to herbicidal action, not to acaricides.

  Further, N-alkyl-4-unsubstituted-5-alkoxy-1-phenylpyrazole-3-carboxamide derivatives having pharmacological activity are described in Non-Patent Document 1 and Non-Patent Document 2, but N-alkyl of carboxamide. Unlike the compound of the present invention in the structure of the substituent, there is no description regarding the agrochemical activity of this compound. Further, N-methyl-4-bromo-5-methoxy-1-phenylpyrazole-3-carboxamide is described in, for example, Non-Patent Document 3, but the compound of the present invention in the structure of the N-substituent of carboxamide In addition, this compound not only has no pharmacological activity but also does not describe any pesticidal activity.

Japanese Patent Laid-Open No. 11-171867 Japanese Patent Laid-Open No. 11-199566 Japanese Unexamined Patent Publication No. 2000-103784 JP 2000-169453 A JP 2001-240592 A JP 2002-205985 A Japanese Patent Laid-Open No. 2002-265452 JP-A 64-25763 Japanese Unexamined Patent Publication No. 63-91373 Japanese Unexamined Patent Publication No. 1-283274 JP 63-115867 A Japanese Patent Laid-Open No. 8-12654

Pharmaceutical Journal, 97, 719 (1977) Journal of Medical Chemistry, 20, 80 (1977) Nagoya City University Faculty of Pharmaceutical Sciences Annual Report, 29, 25 (1981)

  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-mentioned problems, the present inventors have found that an N-phenylthioalkylpyrazole-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],

（式中、Ｒ¹およびＲ²はそれぞれ独立に、水素原子、ハロゲン原子、メチル基、トリフルオロメチル基、メトキシ基、シアノ基またはニトロ基を示し、Ｒ³は水素原子、Ｃ₁〜Ｃ₄のアルキル基またはＣ₁〜Ｃ₄のアルコキシ基を示し、Ｘは水素原子またはハロゲン原子を示し、或いは、Ｒ³とＸは一緒になって、

を形成し（式中、Ｒ¹⁰およびＲ¹¹は水素原子、ハロゲン原子、Ｃ₁〜Ｃ₄のアルキル基またはＣ₁〜Ｃ₄のアルコキシ基を示す。）、Ｒ⁴は水素原子またはＣ₁〜Ｃ₄のアルキル基を示し、Ｒ⁵、Ｒ⁶、Ｒ⁷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、Ｒ⁸およびＲ⁹はそれぞれ独立に、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、メチルチオ基、メチルスルホニル基、トリフルオロメトキシ基、シアノ基、ニトロ基またはエトキシカルボニル基を示し、ｎは0、1または2を示す。）で表されるN-フェニルチオアルキルピラゾール-３-カルボキサミド誘導体（本明細書において、「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。

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, a methoxy group, a cyano group or a nitro group, and R ³ represents a hydrogen atom, C _{1 to} C _4. An alkyl group or a C ₁ -C ₄ alkoxy group, X represents a hydrogen atom or a halogen atom, or R ³ and X together,

Wherein R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group, and R ⁴ is a hydrogen atom or C _1- C _{4 represents} an alkyl group, R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, and R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, alkyl C ₁ -C _4, a trifluoromethyl group, methylthio group, methylsulfonyl group, a trifluoromethoxy group, a cyano group, a nitro group or an ethoxycarbonyl group, n represents 0, 1 or 2. N-phenylthioalkylpyrazole-3-carboxamide derivatives (also referred to herein as “compounds of the present invention”), and acaricides containing the derivatives as active ingredients.

  The compound of the present invention exhibits an excellent control effect and acaricidal effect against mites.

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 ¹ , R ² , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and X include a fluorine atom, a chlorine atom and a bromine atom. And iodine atom. Examples of the C ₁ -C ₄ alkyl group represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. Examples of the C _{1 to} C ₄ alkoxy group represented by R ³ , R ¹⁰ and R ¹¹ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec- Examples include butoxy group and tert-butoxy group.

The compound of the present invention is a novel compound not described in any literature, and includes two optically active substances when R ⁵ and R ⁷ are hydrogen atoms and R ⁶ is a C ₁ -C ₄ alkyl group. Further, a R ⁵ is a hydrogen atom, when R ⁶ and R ⁷ is an alkyl group of C ₁ -C _4, including four optically active forms. This compound can be produced, for example, according to the following Reaction Scheme 1.

Reaction formula 1

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , X and n are defined in the above formula [I]. And Y 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 above 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] as a target product, when a solvent that dissolves 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, the mixture is separated after adding water, and the organic phase is washed with saturated brine and dried with a drying agent such as anhydrous sodium sulfate, and then the solvent is distilled off under reduced pressure. It ’s fine. After evaporation of the solvent, the resulting residue may be sufficiently pure as it is, but if it is impure, it may be washed with a hydrocarbon such as hexane or heptane that does not dissolve the target product so much, or recrystallization or column chromatography. 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. The following [IV] 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. Gazette (Patent Document 9) and JP-A-1-283274 (Patent Document 10), Journal of Pharmaceutical Sciences, 97, 719 (1979) (Non-patent Document 1), Journal of Medical Chemistry, 20, 80 (1977) ) (Non-Patent Document 2).

Reaction formula 2

(In the above formula, R ¹ , R ² , R ³ , R ¹⁰ , R ¹¹ and X are as defined in the formula [I], and Y 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.

  Further, the phenylthioalkylamine derivative [III] as a starting material is disclosed in JP 2001-163854 A, JP 2005-526858 A, Lankoku Patent Application Publication No. 6464444, US Patent Application Publication No. 2002-55631. Specification, U.S. Patent Application Publication No. 2002-86887, U.S. Patent Application Publication No. 2005-272744, JP 2002-105046 A, Journal of American Chemical Society, Vol. 73, p. 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 It can be synthesized according to the method described in 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. 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, methyl Mention may be made of naphthalene, 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%, and is selected from a range of 0.5 to 90%, for example, as appropriate depending on various conditions such as formulation form and application method. For example, for powders, about 0.5 to 20% by mass, preferably 1 to 10% by mass, for wettable powders, about 1 to 90% by mass, preferably 10 to 80% by mass, The emulsion is preferably prepared so as to contain 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 Synthesis of N- [1- (4-chlorophenyl) thio-2-methyl-2-propyl] -1- (4-chlorophenyl) -4-chloro-5-methylpyrazole-3-carboxamide 1- 0.41 g of (4-chlorophenyl) -4-chloro-5-methylpyrazole-3-carboxylic acid was heated to reflux in 5 ml of thionyl chloride for 1 hour and then concentrated under reduced pressure. The obtained residue was added to a solution of 0.32 g of 1- (4-chlorophenylthio) -2-methyl-2-propylamine and 0.30 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 washed with hexane to obtain 0.65 g of the compound (No. 1) of the present invention described in Table 1. The melting point was 123-125 ° C. In the same manner, the compound of the present invention was prepared in the same manner. Table 1 below lists the compounds of the present invention prepared as in Example 1.

Table 1

  The numbers in parentheses given to “oil” in the “mp” column in the above table correspond to the numbers in the following parentheses.

1) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.51 (6H, s), 2.32 (3H, s), 3.50 (2H, s), 6.66 (1H, bs), 7.07 (2H, d
), 7.32 (2H, d), 7.36-7.39 (1H, m), 7.46-7.51 (3H, m).
2) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.04 (3H, t), 1.51 (6H, s), 2.24 (3H, s), 2.61 (2H, q), 3.51 (2H, s), 6.82 (1H , bs), 7.09 (2H, d), 7.30 (2H, d), 7.32 (2H, d), 7.48 (2H, d).
3) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.35 (6H, d), 1.48 (6H, s), 2.95 (1H, qq), 3.49 (2H, s), 6.71 (1H, bs), 7.12 (2H , d), 7.24 (2H, d), 7.34 (2H, d), 7.51 (2H, d).
4) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.33 (3H, t), 1.55 (6H, s), 3.50 (2H, s), 4.32 (2H, q), 6.73 (1H, bs), 7.12 (2H , d), 7.33 (2H, d), 7.45 (2H, d), 7.61 (2H, d).
5) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.51 (6H, s), 1.78-1.82 (4H, m), 2.61-2.69 (2H, m), 2.71-2.80 (2H, m), 3.51 (2H, s), 6.75 (1H, bs), 7.05 (2H, d), 7.32 (2H, d), 7.46 (2H, d), 7.48 (2H, d).
6) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.49 + 1.51 (6H, s), 1.84-1.94 (1H, m), 1.99-2.05 (1H, m), 2.60-2.71 (1H, m), 2.78- 2.89 (2H, m), 2.91-3.09 (2H, m), 3.38 + 3.56 (2H, d), 3.42 (3H, s), 3.70-3.79 (1H, m), 6.79 (1H, bs), 7.07 ( 2H, d), 7.31 (2H, d), 7.40 (2H, d), 7.42 (2H, d).
7) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.60 (6H, s), 2.32 (3H, s), 3.06 (3H, s), 3.77 (2H, s), 7.21 (2H, d), 7.36 (2H) , d), 7.39 (2H, d), 7.45 (2H, d).
8) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.58 (6H, s), 2.31 (3H, s), 3.51 (2H, s), 6.73 (1H, bs), 7.06-7.12 (2H, m), 7.35 -7.40 (1H, m), 7.41 (2H, d), 7.52 (2H, d).
9) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (6H, s), 2.33 (3H, s), 3.50 (2H, s), 6.64 (1H, bs), 7.12 (2H, d), 7.36 (2H , d), 7.41 (2H, d), 7.50 (2H, d).
10) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.55 (6H, s), 2.26 (3H, s), 2.87 (3H, s), 3.62 (2H, s), 6.67 (1H, bs), 7.38 (2H , d), 7.49 (2H, d), 7.52 (2H, d), 7.66 (2H, d).
11) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (6H, s), 2.32 (3H, s), 3.51 (2H, s), 6.58 (1H, s), 6.75 (1H, bs), 7.11 (2H , d), 7.32 (2H, d), 7.39 (2H, d), 7.48 (2H, d).
12) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.55 (6H, s), 2.09-2.32 (2H, m), 2.83-2.87 (2H, m), 3.22-3.38 (2H, m), 6.68 (1H, bs), 7.05 (2H, d), 7.31 (2H, d), 7.42 (2H, d), 7.49 (2H, d).
13) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (3H, s), 2.29 (3H, s), 3.50 (2H, s), 6.69 (1H, bs), 7.07 (2H, d), 7.31 (2H , d), 7.34-7.43 (2H, m), 7.48-7.54 (3H, m).
14) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (6H, s), 2.29 (3H, s), 3.51 (2H, s), 6.65 (1H, bs), 7.07 (2H, d), 7.30 (2H , d), 7.33 (2H, d), 7.60 (2H, d).
15) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.52 (6H, s), 2.28 (3H, s), 3.51 (2H, s), 6.55 (1H, bs), 7.08 (2H, d), 7.31 (2H , d), 7.36 (2H, d), 7.49 (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 (nonionic and anionic surfactants) And Toho Chemical Co., Ltd. (trade name) (10 parts) were 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) (20 parts) Sun extract P-252 (sodium lignin sulfonate, Nippon Paper Chemical Co., Ltd., trade name) (5 parts) and Lunox P-65L (alkyl allyl sulfonate, Toho Chemical Co., Ltd., trade name) (5 parts) Was uniformly mixed and ground with an air mill 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. The compounds of the present invention are indicated by the compound numbers shown in Table 1.

Test Example 1: An insecticidal test against a spider mite

  A 90 ml capacity polyethylene cup filled with water 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 life and death of the adults and the bitter melon were investigated under the binocular. The results are shown in Table 2 (in the following table, the compound numbers correspond to the numbers in Table 1).

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 remarkably high acaricidal activity.

Claims (2)

The following formula [I]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, a methoxy group, a cyano group or a nitro group, and R ³ represents a hydrogen atom, C _{1 to} C _4. An alkyl group or a C ₁ -C ₄ alkoxy group, X represents a hydrogen atom or a halogen atom, or R ³ and X together,

Wherein R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group, and R ⁴ is a hydrogen atom or C _1- C _{4 represents} an alkyl group, R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, and R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, alkyl C ₁ -C _4, a trifluoromethyl group, methylthio group, methylsulfonyl group, a trifluoromethoxy group, a cyano group, a nitro group or an ethoxycarbonyl group, n represents 0, 1 or 2. N-phenylthioalkylpyrazole-3-carboxamide derivatives represented by   An acaricide comprising the N-phenylthioalkylpyrazole-3-carboxamide derivative represented by the formula [I] according to claim 1 as an active ingredient.