Crystal of 1,2,4-oxadiazol-5(4H)-one derivative

Abstract

Discovered is a novel crystal form of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridin-2-yl)-4-(4-(trifluoromethyl)pyridin-2-yl)-1,2,4-oxadiazol-5(4H)-one (; compound (1)), which has a control effect on various pests. The crystal has a melting point of 105-115°C and thermodynamically stable physical properties.

Description

Crystal of 1,2,4-oxadiazol-5(4H)-one derivative

[0001] The present invention relates to novel crystals of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridin-2-yl)-4-(4-(trifluoromethyl)pyridin-2-yl)-1,2,4-oxadiazol-5(4H)-one (hereinafter referred to as compound (1)) having pesticidal efficacy. The present invention also relates to a method for producing the crystals and a pesticidal composition containing the crystals.

[0002] For the purpose of pest control, various azole compounds have been developed. Recently, (ethylsulfonyl)pyridine derivatives have attracted attention and many reports have been made. For example, Patent Document 1 describes (ethylsulfonyl)pyridine derivatives having a 1,2,4-oxadiazol-5(4H)-one group. Among them, it is described that compound (1) has a melting point of 53 to 60°C.

[0003] International Publication No. 2023 / 190286

[0004] An object of the present invention is to provide a compound having excellent pesticidal efficacy against pests.

[0005] As a result of investigations to find a compound having excellent pesticidal efficacy against pests, the present inventors have found that compound (1) has excellent pesticidal efficacy against pests, and further, that compound (1) forms novel crystals (hereinafter also referred to as type I crystals).

[0006] In other words, the present invention relates to, but is not limited to, the following: [1] A crystal of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one having a melting point of 105°C to 115°C. [2] A crystal of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one, having diffraction peaks at 2θ = 7.7±0.2°, 16.1±0.2°, 20.1±0.2°, 20.5±0.2°, 23.8±0.2°, 24.7±0.2° and 27.3±0.2° in powder X-ray diffraction by Cu-Kα rays. [3] A crystal of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one, wherein the wavenumber in the infrared absorption spectrum (ATR method) is 1419 ± 4 cm⁻¹. －１ , 1255±4cm －１ , 1171±4cm －１ , 1138±4cm －１ , 1089 ± 4 cm －１ 713±4cm －１ and 532±4cm －１A crystal having a peak at the position of. [4] A method for producing a crystal according to any one of [1] to [3], comprising dissolving 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridin-2-yl)-4-(4-(trifluoromethyl)pyridin-2-yl)-1,2,4-oxadiazol-5(4H)-one in at least one solvent selected from the group consisting of a hydrocarbon solvent, an alcohol solvent, and an ether solvent to obtain a solution, and a step of precipitating crystals of the compound from the obtained solution. [5] A method for producing a crystal according to any one of [1] to [3], comprising heating a suspension of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridin-2-yl)-4-(4-(trifluoromethyl)pyridin-2-yl)-1,2,4-oxadiazol-5(4H)-one and a solvent at 50 to 100 °C. [6] A pest control agent comprising the crystal according to any one of [1] to [3]. [7] A pest control agent comprising the crystal according to any one of [1] to [3] and a surfactant. [8] The pest control agent according to [7], which is a suspension formulation in water.

[0007] According to the present invention, a crystal (type I crystal) of compound (1) can be provided. The type I crystal of compound (1) has a stable solid property and can be used as an agrochemical active ingredient applicable to various formulation forms.

[0008] This figure shows the differential scanning calorimetry (DSC) analysis chart of the amorphous compound (1) obtained in Reference Example 1. The left vertical axis represents the DSC heat flow (unit: mW), the right vertical axis represents the temperature (unit: °C), and the horizontal axis represents time (unit: min). This figure shows the powder X-ray diffraction pattern of the amorphous compound (1) obtained in Reference Example 1. The vertical axis represents the NET intensity (unit: cts), and the horizontal axis represents the diffraction angle 2θ (unit: °). This figure shows the infrared absorption spectrum of the amorphous compound (1) obtained in Reference Example 1. The vertical axis represents the absorbance (unit: Abs), and the horizontal axis represents the wavenumber of the irradiated infrared radiation. This figure shows the DSC analysis chart of the crystal of compound (1) obtained in Example 1. The left vertical axis represents the DSC heat flow (unit: mW), the right vertical axis represents the temperature (unit: °C), and the horizontal axis represents time (unit: min). This is a diagram showing the powder X-ray diffraction pattern of the crystal of compound (1) obtained in Example 1. The vertical axis represents NET intensity (unit: cts), and the horizontal axis represents the diffraction angle 2θ (unit: °). This is a diagram showing the infrared absorption spectrum of the crystal of compound (1) obtained in Example 1. The vertical axis represents absorbance (unit: Abs), and the horizontal axis represents the wavenumber of the irradiated infrared radiation. This is a diagram showing the DSC analysis chart of the crystal of compound (1) obtained in Example 2. The left vertical axis represents DSC heat flow (unit: mW), the right vertical axis represents temperature (unit: °C), and the horizontal axis represents time (unit: min). This is a diagram showing the powder X-ray diffraction pattern of the crystal of compound (1) obtained in Example 2. The vertical axis represents NET intensity (unit: cts), and the horizontal axis represents the diffraction angle 2θ (unit: °). This is a diagram showing the infrared absorption spectrum of the crystal of compound (1) obtained in Example 2. The vertical axis represents absorbance (unit: Abs), and the horizontal axis represents the wavenumber of the irradiated infrared radiation. This is a diagram showing the DSC analysis chart of the crystal of compound (1) obtained in Example 3. The left vertical axis represents DSC heat flow (unit: mW), the right vertical axis represents temperature (unit: °C), and the horizontal axis represents time (unit: min). This is a diagram showing the powder X-ray diffraction pattern of the crystal of compound (1) obtained in Example 3. The vertical axis represents NET intensity (unit: cts), and the horizontal axis represents diffraction angle 2θ (unit: °). This is a diagram showing the infrared absorption spectrum of the crystal of compound (1) obtained in Example 3. The vertical axis represents absorbance (unit: Abs), and the horizontal axis represents the wavenumber of the irradiated infrared radiation.This is a diagram showing the DSC analysis chart of the crystal of compound (1) obtained in Example 5. The left vertical axis represents the DSC heat flow (unit: mW), the right vertical axis represents the temperature (unit: °C), and the horizontal axis represents time (unit: min). This is a diagram showing the powder X-ray diffraction pattern of the crystal of compound (1) obtained in Example 5. The vertical axis represents the NET intensity (unit: cts), and the horizontal axis represents the diffraction angle 2θ (unit: °). This is a diagram showing the infrared absorption spectrum of the crystal of compound (1) obtained in Example 5. The vertical axis represents the absorbance (unit: Abs), and the horizontal axis represents the wavenumber of the irradiated infrared radiation. This is a diagram showing the DSC analysis chart of the crystal of compound (1) obtained in Example 6. The left vertical axis represents the DSC heat flow (unit: mW), the right vertical axis represents the temperature (unit: °C), and the horizontal axis represents time (unit: min). This is a diagram showing the powder X-ray diffraction pattern of the crystal of compound (1) obtained in Example 6. The vertical axis represents NET intensity (unit: cts), and the horizontal axis represents the diffraction angle 2θ (unit: °). This is a diagram showing the infrared absorption spectrum of the crystal of compound (1) obtained in Example 6. The vertical axis represents absorbance (unit: Abs), and the horizontal axis represents the wavenumber of the irradiated infrared radiation.

[0009] This invention relates to a crystal (Type I crystal) of compound (1). The Type I crystal of compound (1) can be produced according to the following method.

[0010] (1) The raw material compound (1) is 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one, which can be produced by the method described in International Publication No. 2023 / 190286. In the present invention, it is preferable that compound (1) has a purity suitable for use as a raw material for agricultural chemicals. Specifically, it is preferable that the active ingredient content be 90% or more, more preferably 93% or more, and even more preferably 95% or more. Compound (1) used as a raw material in the present invention may be crystalline or amorphous. Amorphous compound (1) is a solid with a melting point of 53 to 60°C.

[0011] (2) Preparation Method 1 This method involves dissolving compound (1) in a suitable solvent to prepare a solution, precipitating the crystals of compound (1) from this solution, and then isolating them. Methods for precipitating the crystals include cooling (Preparation Method 1-1), adding a poor solvent (Preparation Method 1-2), etc.

[0012] (2-1) Preparation Method 1-1 Compound (1) can be prepared by dissolving compound (1) in a solvent at 30°C to 100°C, gradually cooling the resulting solution (for example, lowering the temperature at 3°C / hr), and precipitating crystals at 0°C to 30°C. In the crystal precipitation operation, seed crystals of compound (1) type I can also be added to a supersaturated solution of compound (1), and crystallization can be performed by gradually cooling the solution as needed (for example, lowering the temperature at 3°C / hr). The amount of seed crystal is preferably 0.0001% to 10% by weight, and more preferably 0.001% to 1% by weight, relative to compound (1). If crystals do not precipitate, the solvent may be partially removed by distillation to reduce the amount of solvent, and then the solution may be gradually cooled again. By separating the precipitated crystals, type I crystals of compound (1) can be obtained. Examples of such separation include filtration and centrifugation.

[0013] The solvent used is preferably at least one selected from the group consisting of hydrocarbon solvents, alcohol solvents, and ether solvents. Two or more of these solvents may be mixed and used, and water or polar solvents may be included in a range that does not inhibit crystal formation. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and tetrahydronaphthalene; halogenated aromatic hydrocarbon solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; nitrated aromatic hydrocarbon solvents such as nitrobenzene; acyclic hydrocarbon solvents such as hexane, heptane, octane, nonane, and decane; and alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, and cycloheptane. Two or more of these may be mixed and used. Among these, toluene and xylene are preferred. Examples of alcohol solvents include acyclic hydrocarbon alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and 3-methyl-1-butanol, and cyclic hydrocarbon alcohol solvents such as cyclohexanol and benzyl alcohol. Two or more of these may be used in mixture. These alcohol solvents may contain water or polar solvents to the extent that they do not inhibit crystal formation. Among these, methanol, ethanol, 1-propanol, and 2-propanol are preferred. Examples of ether solvents include acyclic hydrocarbon ether solvents such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, and 1,2-dimethoxyethane, and cyclic hydrocarbon ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and methoxycyclopentane. Two or more of these may be used in mixture. These ether solvents may contain water or polar solvents to the extent that they do not inhibit crystal formation. Among these, tert-butyl methyl ether, tetrahydrofuran, and 1,4-dioxane are preferred.Examples of polar solvents that may be included in a range that does not inhibit crystal formation include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolinone, and two or more of these may be used in mixture form. The solvent is preferably one or more selected from the group consisting of toluene, xylene, methanol, ethanol, 1-propanol, 2-propanol, tert-butylmethyl ether, tetrahydrofuran, and 1,4-dioxane. The amount of solvent used should be such that compound (1) is completely dissolved upon heating, and it is preferable to use an amount that results in a saturated solution at the heating temperature.

[0014] (2-2) Preparation Method 1-2 Type I crystals can be prepared by dissolving compound (1) in a solvent at 0°C to 60°C and gradually adding a poor solvent to precipitate the crystals. In the crystal precipitation operation, seed crystals of type I crystals of compound (1) can also be added to a supersaturated solution of compound (1) and crystallized by gradually cooling as needed (for example, decreasing at 3°C / hr). The amount of seed crystals is preferably 0.0001% to 10% by weight, and more preferably 0.001% to 1% by weight, relative to compound (1). If crystals do not precipitate, the amount of solvent can be reduced by partially removing the solvent, and then the poor solvent can be gradually added again. By separating the precipitated crystals, type I crystals of compound (1) can be obtained. Examples of such separation include filtration and centrifugation.

[0015] A good solvent for dissolving compound (1) can be, for example, at least one selected from the group consisting of aromatic solvents, alcohol solvents, ether solvents, and polar solvents. Two or more of these may be used in mixture, and water may be included in a range that does not inhibit the dissolution of the crystals. Examples of aromatic solvents include aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, and nitrated aromatic hydrocarbon solvents. Examples of aromatic hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and tetrahydronaphthalene; halogenated aromatic hydrocarbon solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; and nitrated aromatic hydrocarbon solvents such as nitrobenzene. Two or more of these may be used in mixture. Among these, toluene and xylene are preferred. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1-butanol, cyclohexanol, and benzyl alcohol. Two or more of these solvents may be used in mixtures. These alcohol solvents may contain water to the extent that it does not inhibit the dissolution of the crystals. Methanol, ethanol, 1-propanol, and 2-propanol are preferred. Examples of ether solvents include diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and methoxycyclopentane. Two or more of these solvents may be used in mixtures. These ether solvents may contain water to the extent that it does not inhibit the dissolution of the crystals. Tert-butyl methyl ether, tetrahydrofuran, and 1,4-dioxane are preferred. Examples of polar solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolinone. Two or more of these solvents may be used in mixtures. These polar solvents may contain water to the extent that it does not inhibit the dissolution of the crystals.As a good solvent, an alcohol solvent, a hydrocarbon ether solvent, or a polar solvent is preferred, and one or more selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, tert-butylmethyl ether, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolinone is preferred. The amount of good solvent used should be such that compound (1) is completely dissolved, and it is preferable to use an amount that results in a saturated solution at the dissolution temperature.

[0016] Examples of poor solvents include water and aliphatic hydrocarbon solvents. When the good solvent is a water-miscible solvent such as an alcohol solvent, a cyclic hydrocarbon ether solvent, or a polar solvent, water is preferred as the poor solvent. When the good solvent is a water-immiscible solvent such as an aromatic solvent, an alcohol solvent such as benzyl alcohol, or an acyclic hydrocarbon ether solvent, or a polar solvent, aliphatic hydrocarbon solvents are preferred as the poor solvent. Examples of aliphatic hydrocarbon solvents include acyclic hydrocarbons such as hexane, heptane, octane, nonane, and decane, and cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and cycloheptane. It is preferable to select a poor solvent that is miscible with the good solvent. The amount of poor solvent should be such that crystals precipitate from the compound (1) solution, and can be appropriately set so that the suspended suspension with precipitated crystals is of an appropriate volume.

[0017] (3) Method 2 Compound (1) can be suspended in a solvent and heated and stirred at 50 to 100°C to prepare type I crystals of compound (1). Seed crystals of type I of compound (1) may be added at this time. The amount of seed crystals is preferably 0.0001% to 10% by weight, more preferably 0.001% to 1% by weight, relative to compound (1). The heating temperature is preferably 50 to 100°C, more preferably 60 to 90°C. The heating treatment time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours. After the heating and stirring treatment, the crystal suspension is cooled to 0 to 30°C and the crystals are separated to obtain type I crystals of compound (1). Examples of such separation include filtration and centrifugation.

[0018] The solvent to be used is preferably at least one selected from the group consisting of hydrocarbon solvents, alcohol solvents, and ether solvents. Two or more of these may be used in mixture. These solvents may contain water or polar solvents to the extent that they do not inhibit crystal formation. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and tetrahydronaphthalene; halogenated aromatic hydrocarbon solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; nitrated aromatic hydrocarbon solvents such as nitrobenzene; acyclic hydrocarbon solvents such as hexane, heptane, octane, nonane, and decane; and aliphatic hydrocarbon solvents including alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, and cycloheptane. Two or more of these may be used in mixture. Among these solvents, toluene, xylene, cyclohexane, and methylcyclohexane are preferred. Examples of alcohol solvents include acyclic hydrocarbon alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and 3-methyl-1-butanol, and cyclic hydrocarbon alcohol solvents such as cyclohexanol and benzyl alcohol. Two or more of these may be used in mixture. These alcohol solvents may contain water or polar solvents to the extent that they do not inhibit crystal formation. Examples of ether solvents include acyclic hydrocarbon ether solvents such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, and 1,2-dimethoxyethane, and cyclic hydrocarbon ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and methoxycyclopentane. Two or more of these may be used in mixture. These ether solvents may contain water or polar solvents to the extent that they do not inhibit crystal formation. Among these solvents, diisopropyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane are preferred.The solvent used in method 2 is preferably a hydrocarbon solvent, and more preferably a solvent containing toluene, xylene, cyclohexane, or methylcyclohexane. The solvent for the suspension is preferably one that is insoluble or sparingly soluble in compound (1). If a solvent soluble in compound (1) is used, the suspension should be prepared by applying it at a concentration less than or equal to the solubility of compound (1).

[0019] The type I crystal of compound (1) has a melting point of approximately 105°C to 115°C. The type I crystal of compound (1) obtained according to the above method shows an endothermic peak at 110±5°C in differential scanning calorimetry. On the other hand, the known compound (1) produced according to the method described in Synthesis Examples 1-6 of Patent Document 1 (hereinafter referred to as known compound (1)) has a melting point of approximately 53-60°C, and can be clearly distinguished as a solid physical property.

[0020] The type I crystal of compound (1) exhibits diffraction peaks as shown in Figures 5, 8, 11, 14, and 17, for example, in powder X-ray diffraction using Cu-Kα rays. The crystal is characterized by having diffraction peaks at 2θ = 7.7±0.2°, 16.1±0.2°, 20.1±0.2°, 20.5±0.2°, 23.8±0.2°, 24.7±0.2°, and 27.3±0.2°, as examples of diffraction peaks at 2θ = 11.8±0.2°, 15.6±0.2°, 20.7±0.2°, 21.4±0.2°, and 26.5±0.2°. In one embodiment, the crystal is further characterized by having diffraction peaks at 2θ = 11.8±0.2°, 15.6±0.2°, 20.7±0.2°, 21.4±0.2°, and 26.5±0.2°. In one embodiment, the crystal is further characterized by having diffraction peaks at 2θ = 10.2±0.2°, 15.9±0.2°, 17.1±0.2°, 23.1±0.2°, and 24.1±0.2°. It should be noted that known compound (1) (= the solid obtained in Reference Example 1) was found to be amorphous, as no clear diffraction peaks were observed in powder X-ray diffraction using Cu-Kα rays.

[0021] The type I crystal of compound (1) exhibits absorption spectra shown in FIGS. 6, 9, 12, 15 and 18 as an example in the infrared absorption spectrum (Attenuated Total Reflectance (ATR) method). As an example of the absorption peaks in the infrared absorption spectrum (ATR method), the wavenumbers are 1419 ± 4 cm －１ , 1255 ± 4 cm －１ , 1171 ± 4 cm －１ , 1138 ± 4 cm －１ , 1089 ± 4 cm －１ , 713 ± 4 cm －１ and 532 ± 4 cm －１ and is characterized by having peaks at these positions. In one aspect, the crystal further has peaks at wavenumbers of 1778 ± 4 cm －１ , 1317 ± 4 cm －１ , 1230 ± 4 cm －１ , 856 ± 4 cm －１ and 758 ± 4 cm －１ and is characterized by having peaks at these positions. In one aspect, the crystal further has peaks at wavenumbers of 1328 ± 4 cm －１ , 769 ± 4 cm －１ , 721 ± 4 cm －１ , 667 ± 4 cm －１ and 501 ± 4 cm －１ and is characterized by having peaks at these positions. The type I crystal of compound (1) can be distinguished from the known compound (1) by having peaks at any one or more of the positions of 1419 ± 4 cm －１ and 532 ± 4 cm －１ in the infrared absorption spectrum (ATR method). In one aspect, the type I crystal of compound (1) can be distinguished from the known compound (1) by having peaks at any one or more of the positions of 1328 ± 4 cm －１ , 1230 ± 4 cm －１ and 856 ± 4 cm －１ in the infrared absorption spectrum (ATR method). Incidentally, the known compound (1) is characterized by showing absorption peaks at 1429 ± 4 cm －１ , 1163 ± 4 cm －１ , 542 ± 4 cm －１ in the infrared absorption spectrum (ATR method).

[0022] Compound (1) has control effects against various pests. Furthermore, the type I crystal of compound (1) has a higher melting point and thermodynamically stable solid properties than the known compound (1), resulting in excellent formulation and formulation properties. Therefore, a pest control agent containing the type I crystal of compound (1) can be provided. The target pests of the pest control agent of the present invention include harmful insects, harmful arthropods such as harmful mites, harmful mollusks, and harmful nematodes. It can also be applied to the control of sanitary pests, stored grain pests, clothing pests, household pests, and parasitic pests.

[0023] The pest control agent of the present invention contains type I crystals of compound (1) as an active ingredient, and may be further combined with formulation additives to form various formulations. Examples include aqueous suspension formulations, oily suspension formulations, oil formulations, emulsion formulations, microcapsule formulations, wettable powders, granular wettable powders, powders, granules, etc. In particular, by applying the crystals in a solid formulation, a physicochemically stable pest control formulation can be provided. Preferred formulations include aqueous suspension formulations, wettable powders, granular wettable powders, powders, and granules.

[0024] Examples of additives for formulations include inorganic carriers, solvents, surfactants, and polymer modifiers. Examples of inorganic carriers include clay, talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acid clay, white carbon, ammonium sulfate, vermiculite, and perlite. Examples of solvents include water, alcohols such as ethanol, propanol, benzyl alcohol, propylene glycol, and polyethylene glycol, ketones such as acetone and cyclohexanone, aromatic solvents such as xylene, phenylxylethane, and methylnaphthalene, aliphatic solvents such as hexane and cyclohexane, esters such as ethyl acetate and methyl oleate, ethers such as ethylene glycol dimethyl ether, amides such as N,N-dimethylformamide and N,N-dimethyloctanamide, sulfoxides such as dimethyl sulfoxide, lactams such as N-methylpyrrolidone and N-octylpyrrolidone, and vegetable oils such as soybean oil.

[0025] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, and polyethylene glycol fatty acid esters, and anionic surfactants such as alkyl sulfonates, alkylaryl sulfonates, and alkyl sulfates.

[0026] Other pharmaceutical additives include binders, dispersants, colorants, and stabilizers. Specifically, examples include polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), acidic isopropyl phosphate, and dibutylhydroxytoluene.

[0027] A pest control agent containing type I crystals of compound (1) preferably further contains a surfactant. Specifically, it is preferable that the agent contains type I crystals of compound (1) and a surfactant in the form of a powder, granules, wettable powder, granular wettable powder, or aqueous suspension formulation.

[0028] When applying type I crystals of compound (1) to a powder formulation, the crystals can be mixed with an inorganic carrier and a surfactant, and then appropriately ground to prepare the powder. Alternatively, the crystals, inorganic carrier, and surfactant can be ground and mixed, water can be added and kneaded thoroughly, then granulated and dried, and then ground again to prepare the powder. The composition of the powder is preferably 1 to 30 parts by mass of type I crystals of compound (1), 30 to 95 parts by mass of a solid carrier, and 0.1 to 10 parts by mass of any surfactant.

[0029] When applying type I crystals of compound (1) to a granular formulation, the crystals can be mixed with an inorganic carrier, a surfactant, and any other additives, and then appropriately ground to prepare the granular formulation. Alternatively, the crystals, inorganic carrier, and surfactant can be ground and mixed, water can be added and kneaded thoroughly, then granulated, dried, and appropriately sized. The composition of the granular formulation is preferably 10 to 50 parts by mass of type I crystals of compound (1), 30 to 95 parts by mass of a solid carrier, and 0.1 to 10 parts by mass of any surfactant.

[0030] When applying type I crystals of compound (1) to a wettable powder, the crystals can be mixed with an inorganic carrier, a surfactant, water, and any other additives, and then appropriately ground to prepare the powder. Alternatively, the crystals, inorganic carrier, surfactant, and any other additives can be ground and mixed, water can be added and kneaded thoroughly, then granulated and dried, and then ground again to prepare the powder. The composition of the wettable powder is preferably 10 to 50 parts by mass of type I crystals of compound (1), 30 to 80 parts by mass of a solid carrier, and 0.1 to 10 parts by mass of a surfactant.

[0031] When applying type I crystals of compound (1) to a granular wettable powder, the crystals can be mixed with an inorganic carrier, a surfactant, water, and any other additives, and then appropriately ground to prepare the powder. Alternatively, the crystals, inorganic carrier, surfactant, and any other additives can be ground and mixed, water can be added and kneaded thoroughly, then granulated, dried, and appropriately sized to prepare the powder. The composition of the granular wettable powder is preferably 10 to 50 parts by mass of type I crystals of compound (1), 30 to 80 parts by mass of a solid carrier, and 0.1 to 10 parts by mass of a surfactant.

[0032] When type I crystals of compound (1) are used in an aqueous suspension formulation, the crystals can be prepared by mixing them with a surfactant, water, any other additives, and water, and then wet grinding as appropriate. The composition of the aqueous suspension formulation is preferably a formulation in which 0.5 to 50 parts by mass of type I crystals of compound (1) and 1 to 10 parts by mass of a surfactant are suspended in water.

[0033] Since the type I crystals of compound (1) have thermodynamically stable properties, it is preferable to apply them to aqueous suspension formulations. A aqueous suspension formulation is also called a flowable formulation, and is a formulation in which fine particles of the active ingredient are dispersed in an aqueous medium. That is, it is a formulation in which fine particles of type I crystals of compound (1) are suspended and dispersed in an aqueous medium. The aqueous suspension formulation is a formulation containing type I crystals of compound (1), a surfactant, and water.

[0034] Examples of surfactants include nonionic surfactants and anionic surfactants. Examples of nonionic surfactants include polyoxyalkylene castor oils such as polyoxyethylene castor oil, polyoxyalkylene hydrogenated castor oils such as polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymer type surfactants such as polyoxyethylene polyoxypropylene block copolymer, polyoxyalkylene (poly)arylphenyl ethers such as polyoxyethylene tristyrylphenyl ether and polyoxyethylene distyrylphenyl ether, formaldehyde condensates of polyoxyalkylene (poly)arylphenyl ethers such as formaldehyde condensates of polyoxyethylene distyrylphenyl ether, polyoxyalkylene fatty acid esters such as polyoxyethylene fatty acid esters, polyoxyalkylene sugar fatty acid esters such as polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene (poly)arylaryl phosphate esters such as polyoxyethylene tristyrylphenyl phosphate diesters, glycerin fatty acid esters, polyglycerin fatty acid esters, and sucrose fatty acid esters. Preferred nonionic surfactants include one or more nonionic surfactants selected from the group consisting of polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymer type surfactants such as polyoxyethylene polyoxypropylene block copolymers, polyoxyalkylene (poly)arylphenyl ethers such as polyoxyethylene tristyrylphenyl ether and polyoxyethylene distylylphenyl ether, and polyoxyalkylene fatty acid esters such as polyoxyethylene fatty acid esters. These may be used individually or in mixtures.

[0035] Examples of anionic surfactants include alkylbenzene sulfonates, aryl sulfonates such as naphthalene sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, lignin sulfonates, salts of polyoxyalkylene (poly)arylphenyl ether sulfates such as polyoxyethylene distyrylphenyl ether sulfate, salts of polyoxyalkylene (poly)arylphenyl ether phosphates such as polyoxyethylene tristyrylphenyl ether phosphate, salts of polyoxyalkylene alkylaryl phosphates such as polyoxyethylene alkylaryl phosphate, and salts of polyoxyalkylene alkyl phosphates such as polyoxyethylene alkyl phosphate. These may be used individually or in mixtures. Preferably, the anionic surfactant is one or more selected from alkylbenzene sulfonates, aryl sulfonates such as naphthalene sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, or lignin sulfonates. These may be used individually or in mixtures.

[0036] The aqueous suspension formulation contains type I crystals of compound (1), a surfactant, and water, and is a formulation in which fine particles of type I crystals of compound (1) are dispersed in water. The aqueous suspension formulation can be prepared by adding type I crystals of compound (1) together with a surfactant to water and then performing a desired micronization treatment on a wet grinder such as a batch-type bead mill or a dyno mill to obtain a slurry. The fine particles in the slurry preferably have a particle size of 0.1 to 10.0 μm. Preferably, the slurry contains fine particles with a particle size of 0.5 to 5.0 μm. The particle size is the average particle size on a volume basis, and is the particle size at the point where the cumulative curve reaches 50% when the total volume of the fine particle population is taken as 100%. The particle size can be measured using a laser diffraction particle size distribution analyzer, for example, SALD-2200 (manufactured by Shimadzu Corporation).

[0037] The aqueous suspension formulation may optionally contain known additives such as thickeners, antifreeze agents, preservatives, defoamers, and crystal growth inhibitors. Examples of thickeners include natural polysaccharides such as xanthan gum and locust beam, bentonites such as magnesium aluminum silicate, and semi-synthetic polysaccharides such as carboxymethylcellulose. Examples of antifreeze agents include glycols such as ethylene glycol and propylene glycol, and urea. Examples of preservatives include 1,2-benzoisothiazolin-3-one and 2-methylisothiazolin-3-one. Examples of defoamers include silicone resins.

[0038] The present invention will be described in more detail below with reference to manufacturing examples, formulation examples, and test examples, but the present invention is not limited to these examples.

[0039] The conditions for measuring the melting point, differential scanning calorimetry, powder X-ray diffraction, FT-IR, and particle size are as follows. (Melting point measurement conditions) Melting point analyzer: MP70 (METTLER TOLEDO) Heating rate: 1°C / min (Differential scanning calorimetry conditions) Differential scanning calorimeter: DSC-60A Plus (Shimadzu Corporation) Heating rate: 10°C / min Atmosphere: Nitrogen Cell: Aluminum sealed cell (Powder X-ray diffraction measurement conditions) Powder X-ray diffractometer: X'PRO MPD (PANAlytical) X-ray output: Cu-Kα, 45kV, 40mA Step size: 0.017° Scan range: 5.0° to 100.0° (Infrared absorption spectrum measurement conditions) FT-IR spectrometer: IR Affinity-1S (Shimadzu Corporation) Measurement method: Attenuated Total Reflection (ATR) method Number of integrations: 20 Resolution: 4cm －１ (Particle size measurement conditions) Laser diffraction particle size distribution analyzer: SALD-2200 (manufactured by Shimadzu Corporation) Particle size: Median diameter

[0040] [Reference Example 1] Compound (1) was prepared according to the method described in Synthesis Examples 1-6 of Patent Document 1 (International Publication No. 2023 / 190286). 10 g of the obtained compound (1) was mixed with 100 mL of dichloromethane and completely dissolved. The solution was concentrated under reduced pressure and vacuum dried to obtain the solid of Reference Example 1.

[0041] The melting point of the solid in Reference Example 1 was measured, and it began to melt at 53°C and melted completely at 60°C. Furthermore, differential scanning calorimetry of the solid in Reference Example 1 revealed an endothermic peak with a peak top at 50.97°C (Figure 1). Table 1 shows the obtained DSC peak (°C), onset (°C), and heat quantity (mJ, J / g).

[0042] Powder X-ray diffraction using Cu-Kα radiation was measured for the solid in Reference Example 1. The measurement results are shown in Figure 2. As no X-ray diffraction peaks were observed, it was determined that the solid was amorphous.

[0043] The FT-IR measurement of the solid in Reference Example 1 yielded the spectrum shown in Figure 3. A typical specific peak was 1782.23 cm⁻¹. －１ 1429.25cm －１ , 1319.31cm －１ , 1251.80cm －１ 1163.08 cm －１ , 1136.07cm －１ 715.59cm －１ and 542.00 cm －１ It had a peak. The wavenumber (cm) of the obtained peak －１ The values ​​of the relative correction area and the corresponding area are shown in Table 2.

[0044] [Example 1] 2.24 g of compound (1) obtained in Reference Example 1 was added to 16 mL of methanol and heated to 60°C until completely dissolved. The mixture was allowed to stand at room temperature to precipitate crystals. The solid was filtered from the resulting mixture and dried to obtain 1.10 g of the crystals of Example 1.

[0045] The melting point of the crystal in Example 1 was measured to be 107–115°C. Furthermore, differential scanning calorimetry revealed an endothermic peak with a peak top at 112.48°C (Figure 4). Table 3 shows the obtained DSC peak (°C), onset (°C), and heat quantity (mJ, J / g).

[0046] Powder X-ray diffraction of the crystal from Example 1 using Cu-Kα radiation was measured, and the diffraction angles (2θ) of the obtained diffraction peaks are shown in Figure 5. Typical specific diffraction peaks were 7.7°, 16.1°, 20.1°, 20.5°, 23.8°, 24.6°, and 27.3°. The diffraction angles (2θ) and NET intensity (cts) values ​​of the main diffraction peaks obtained are shown in Table 4.

[0047] The infrared absorption spectrum of the crystal from Example 1 was measured and showed the peaks shown in Figure 6. A typical specific peak was 1419.61 cm⁻¹. －１ , 1255.66cm －１ 1170.79cm －１ , 1138.00cm －１ , 1089.78cm －１ 713.66 cm －１ and 534.28 cm －１ It had a peak. The wavenumber (cm) of the obtained peak －１ The values ​​of the relative correction area and the corresponding area are shown in Table 5.

[0048] [Example 2] 2.24 g of compound (1) obtained in Reference Example 1 was added to 32 mL of methylcyclohexane and heated and stirred at 80°C for 2 hours. The resulting suspension was then cooled to room temperature, the solid was filtered, and the mixture was dried to obtain 2.13 g of the crystals of Example 2.

[0049] The melting point of the crystal in Example 2 was measured to be 105–113°C. Furthermore, differential scanning calorimetry revealed an endothermic peak with a peak top at 109.12°C (Figure 7). The obtained DSC peak (°C), onset (°C), and heat quantity (mJ, J / g) values ​​are shown in Table 6.

[0050] Powder X-ray diffraction using Cu-Kα rays was measured for the crystal of Example 2. The diffraction angles (2θ) of the obtained diffraction peaks are shown in Figure 8. Typical specific diffraction peaks were 7.7°, 16.1°, 20.1°, 20.5°, 23.8°, 24.7°, and 27.3°. Table 7 shows the diffraction angles (2θ) and NET intensity (cts) values ​​of the main diffraction peaks obtained.

[0051] The infrared absorption spectrum of the crystal from Example 2 was measured and showed the peaks shown in Figure 9. A typical specific peak was 1419.61 cm⁻¹. －１ , 1255.66cm －１ 1170.79cm －１ , 1138.00cm －１ , 1089.78cm －１ 713.66 cm －１ and 532.35 cm －１ It had a peak. The wavenumber (cm) of the obtained peak －１ The values ​​of the relative correction area and the corresponding area are shown in Table 8.

[0052] [Example 3] 104.08 g of compound (1) obtained in Reference Example 1 was added to 598 mL of methanol and heated to 45°C until completely dissolved. 29 mL of water was gradually added, then the temperature was lowered to 30°C, and 25 mg of compound (1) obtained in Example 1 was added as a seed crystal to confirm crystal precipitation. Subsequently, 152 mL of water was gradually added, the temperature was lowered to below 10°C, and the resulting mixture was filtered to obtain 96.35 g of crystals for Example 3.

[0053] The melting point of the crystal in Example 3 was measured to be 107–115°C. Furthermore, differential scanning calorimetry revealed an endothermic peak with a peak top at 114.54°C (Figure 10). The obtained DSC peak (°C), onset (°C), and heat quantity (mJ, J / g) values ​​are shown in Table 9.

[0054] Powder X-ray diffraction using Cu-Kα rays was measured for the crystal of Example 3. The diffraction angles (2θ) of the obtained diffraction peaks are shown in Figure 11. Typical specific diffraction peaks were 7.7°, 16.1°, 20.1°, 20.4°, 23.8°, 24.7°, and 27.3°. Table 10 shows the diffraction angles (2θ) and NET intensity (cts) values ​​of the main diffraction peaks obtained.

[0055] The infrared absorption spectrum of the crystal from Example 3 was measured and showed the peaks shown in Figure 12. A typical specific peak was 1419.61 cm⁻¹. －１ 1257.59cm －１ 1170.79cm －１ , 1138.00cm －１ , 1089.78cm －１ 713.66 cm －１ and 532.35 cm －１ It had a peak. The wavenumber (cm) of the obtained peak －１ The values ​​of the relative correction area and the corresponding area are shown in Table 11.

[0056] [Example 4] 1.1 parts by mass of type I crystals of compound (1), 0.5 parts by mass of sodium dioctyl sulfosuccinate (Takemoto Oil & Fat Co., Ltd.; product name New Calgen EP-70G), 1.5 parts by mass of sodium lignin sulfonate (Nippon Paper Industries Ltd.; product name Sun Extract P252), 1.0 part by mass of silicone resin (Kao Corporation; product name Antifoam E-20), and 46.4 parts by mass of water were mixed, and then ground at 3000 rpm for 1 hour using a bead mill type wet grinder to obtain a slurry with a particle size of approximately 2 μm. Subsequently, the beads were removed using a 36-mesh sieve, and 10 parts by weight of propylene glycol (AGC Inc.), 0.3 parts by weight of xanthan gum (product name Roadpol 23), 0.3 parts by weight of 1,2-benzisothiazoline 3-one (Lonza Corporation; product name PROXEL GXL(S)), and 38.9 parts by weight of water were added to the slurry and mixed to obtain a suspension formulation in water.

[0057] [Comparative Example 1] In Example 4, instead of the type I crystal of compound (1), the solid (amorphous) of Reference Example 1 was used to obtain an aqueous suspension formulation containing fine particles with a particle size of approximately 2 μm.

[0058] [Example of Formulation Stability Test] 10 mL of the aqueous suspension formulations of Example 4 and Comparative Example 1 were added to No. 4 glass vials and stored in a constant temperature bath set to 54±2°C for 24 hours. After that, the presence or absence of sedimentation or separation was checked by the appearance of the contents. The particle size of the contents was also checked and the rate of change from the initial value was calculated. Rate of change = ((Particle size after storage) / (Initial particle size) - 1) × 100 (%) As a result, no change in appearance was observed in the formulation of Example 4, and the rate of change in particle size was 0%. On the other hand, a large amount of sediment was observed in the formulation of Comparative Example 1 after storage, and the particle size increased in size, with a rate of change of 147% (increase to 2.47 times the size).

[0059] [Example 5] 5.00 g of compound (1) obtained in Reference Example 1 was mixed with 18 mL of methanol, 2.7 mL of N,N-dimethylacetamide, and 2.5 mL of water, and the mixture was heated to 58°C until completely dissolved. Subsequently, the mixture was cooled to 28°C over 20 minutes while stirring, and the precipitation of crystals was confirmed. The mixture was then cooled to 10°C in an ice bath and stirred at 0-10°C for 10 minutes. The solid was filtered from the resulting mixture, the crystals were washed with 9 mL of 44% methanol water, and dried to obtain 4.60 g of the crystals of Example 5.

[0060] The melting point of the crystal in Example 5 was measured to be 110–112°C. Furthermore, differential scanning calorimetry revealed an endothermic peak with a peak top at 111.07°C (Figure 13). The obtained DSC peak (°C), onset (°C), and heat quantity (mJ, J / g) values ​​are shown in Table 12.

[0061] Powder X-ray diffraction using Cu-Kα rays was measured for the crystal of Example 5. The diffraction angles (2θ) of the obtained diffraction peaks are shown in Figure 14. Typical specific diffraction peaks were 7.7°, 16.1°, 20.1°, 20.5°, 23.8°, 24.7°, and 27.3°. Table 13 shows the diffraction angles (2θ) and NET intensity (cts) values ​​of the main diffraction peaks obtained.

[0062] The infrared absorption spectrum of the crystal from Example 5 was measured and showed the peaks shown in Figure 15. A typical specific peak was 1419.61 cm⁻¹. －１ , 1255.66cm －１ 1170.79cm －１ , 1138.00cm －１ , 1089.78cm －１ 713.66 cm －１ and 532.35 cm －１ It had a peak. The wavenumber (cm) of the obtained peak －１ The values ​​of the relative correction area and the corresponding area are shown in Table 14.

[0063] [Example 6] 5.00 g of compound (1) obtained in Reference Example 1 was mixed with 2.7 mL of N,N-dimethylacetamide and 18 mL of methanol, and the mixture was heated to 50°C until completely dissolved. The mixture was then cooled to 25°C, 1 mL of water was slowly added, and 10 mg of type I crystals of compound (1) were added as seed crystals. The mixture was stirred at the same temperature for 15 minutes, and crystal precipitation was confirmed. Further, 8 mL of water was gradually added while stirring. The solid was filtered from the resulting mixture, washed with 9 mL of 44% methanol water, and dried to obtain 4.94 g of crystals for Example 6.

[0064] The melting point of the crystal according to Example 6 was measured to be 109–112°C. Furthermore, differential scanning calorimetry revealed an endothermic peak with a peak top at 109.89°C (Figure 16). Table 15 shows the obtained DSC peak (°C), onset (°C), and heat quantity (mJ, J / g).

[0065] Powder X-ray diffraction using Cu-Kα rays was measured for the crystal of Example 6. The diffraction angles (2θ) of the obtained diffraction peaks are shown in Figure 17. Typical specific diffraction peaks were 7.7°, 16.1°, 20.1°, 20.5°, 23.7°, 24.6°, and 27.3°. Table 16 shows the diffraction angles (2θ) and NET intensity (cts) values ​​of the main diffraction peaks obtained.

[0066] The infrared absorption spectrum of the crystal from Example 6 was measured and showed the peaks shown in Figure 18. A typical specific peak was 1419.61 cm⁻¹. －１ 1257.59cm －１ 1170.79cm －１ , 1138.00cm －１ , 1089.78cm －１ 713.66 cm －１ and 532.35 cm －１ It had a peak. The wavenumber (cm) of the obtained peak －１ The values ​​of the relative correction area and the corresponding area are shown in Table 17.

[0067] [Biological Test Example] Control Test for Spodoptera litura (Stem and Leaf Immersion Treatment) Cabbage leaves were cut to a diameter of 8.0 cm, and these cabbage leaf pieces were immersed in 20 mL of a diluted solution of Example 4 or Comparative Example 1, which was diluted with water to a concentration of compound (1) of 0.1 ppm, and then air-dried. After air-drying, the cabbage leaf pieces were placed in a plastic cup, five second-instar Spodoptera litura larvae were released into it, and the cup was covered and reared in a constant temperature room at 25°C. After 5 days of treatment, the survival rate of the larvae was observed, and the mortality rate was calculated. As a result, the sample used in Example 4 showed a mortality rate of 100%. On the other hand, Comparative Example 1 showed a mortality rate of 20%.

Claims

1. A crystal of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one having a melting point of 105°C to 115°C.

2. A crystal of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one, having diffraction peaks at 2θ = 7.7±0.2°, 16.1±0.2°, 20.1±0.2°, 20.5±0.2°, 23.8±0.2°, 24.7±0.2° and 27.3±0.2° in powder X-ray diffraction using Cu-Kα rays.

3. A crystal of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one, with a wavenumber of 1419 ± 4 cm in the infrared absorption spectrum (ATR method). －１ , 1255±4cm －１ , 1171±4cm －１ , 1138±4cm －１ , 1089 ± 4 cm －１ 713±4cm －１ and 532±4cm －１ A crystal with a peak at the position indicated.

4. A method for producing crystals according to any one of claims 1 to 3, comprising the steps of: dissolving 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one in a solvent containing at least one selected from the group consisting of hydrocarbon solvents, alcohol solvents and ether solvents to obtain a solution; and precipitating crystals of the compound from the obtained solution.

5. A method for producing the crystal according to any one of claims 1 to 3, comprising the step of heating a suspension of 3-(3-(ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyridine-2-yl)-4-(4-(trifluoromethyl)pyridine-2-yl)-1,2,4-oxadiazole-5(4H)-one and a solvent at 50 to 100°C.

6. A pest control agent comprising the crystals described in any one of claims 1 to 3.

7. A pest control agent comprising the crystal and surfactant described in any one of claims 1 to 3.

8. The pest control agent according to claim 7, which is a suspension formulation in water.

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