Crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl) pyridin-2-yl)-5-((trifluoromethyl) sulfinyl) benzo [d] oxazole

Abstract

The present invention provides: a type 1 crystal having an excellent control effect on pests, said type 1 crystal being a type 1 crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl) pyridin-2-yl)-5-((trifluoromethyl) sulfinyl) benzo [d] oxazole represented by formula (1), said type 1 crystal having diffraction peaks at 2 [theta] = 8.5 + / -0.2 degrees, 12.0 + / -0.2 degrees, 15.0 + / -0.2 degrees, 16.6 + / -0.2 degrees, and 20.9 + / -0.2 degrees in powder X-ray diffraction by Cu-K [alpha] rays; a method for producing the crystal; a pest control composition containing the crystal; and a pest control method using the crystal. # imgabs0 #

Description

Technical Field

[0001] This patent application claims priority and benefits under the Paris Convention based on Japanese Patent Application No. 2022-168598 (filed on October 20, 2022), and the entire content described in the above application is incorporated into this specification by reference herein.

[0002] The present invention relates to a novel crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole (hereinafter, referred to as compound (1)) represented by the following formula (1) having a pest control effect. The present invention also relates to a method for producing the crystal, a pest control composition containing the crystal, and a pest control method using the crystal.

[0003] [Chemical formula 1]

[0004] Background Art

[0005] Patent Document 1 describes that compound (1) having a melting point of 58 to 60°C has a pest control effect.

[0006] In addition, Patent Documents 2 and 3 describe methods for producing compound (1).

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: International Publication No. 2017 / 146226

[0010] Patent Document 2: International Publication No. 2019 / 009387

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 2020-172469 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] An object of the present invention is to provide a novel crystal of compound (1) (hereinafter, referred to as type 1 crystal) having excellent pest control effect.

[0014] Means for Solving the Problems

[0015] The inventors of the present application conducted research to find a compound having excellent pest control efficacy, and as a result, it was found that a novel crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole represented by the following formula (1), namely, Form 1 crystal, has excellent pest control efficacy.

[0016] That is, the present invention is as follows.

[0017] 〔1〕A Form 1 crystal, which is a crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole and has diffraction peaks at 2θ = 8.5 ± 0.2°, 12.0 ± 0.2°, 15.0 ± 0.2°, 16.6 ± 0.2° and 20.9 ± 0.2° in powder X-ray diffraction based on Cu-Kα radiation.

[0018] 〔1-1〕A Form 1 crystal, which is a crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole and the diffraction peaks of 2θ in powder X-ray diffraction have a powder X-ray diffraction pattern recorded in Figure 1 、 Figure 3 or Figure 5 any one of them.

[0019] 〔2〕The Form 1 crystal as described in 〔1〕, the lattice constants of which determined by single crystal X-ray diffraction are:

[0020] [Mathematical formula 1]

[0021]

[0022] α = 90°, β = 111.683°,

[0023] and γ = 90°.

[0024] 〔3〕The Form 1 crystal as described in 〔1〕 or 〔2〕, which has peaks at wavenumbers of 1313 ± 4 cm -1 , 1177 ± 4 cm -1 , 1141 ± 4 cm -1 , 1077 ± 4 cm -1 , 845 ± 4 cm -1 , 720 ± 4 cm -1 and 676 ± 4 cm -1 in the infrared absorption spectrum (ATR method).

[0025] 〔4〕The type 1 crystal according to any one of 〔1〕to 〔3〕, having a melting point of 118 to 128 °C.

[0026] 〔5〕The method for producing the type 1 crystal according to any one of 〔1〕to 〔4〕, comprising:

[0027] Dissolving 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole melted in the range of 52 °C to 61 °C in at least one solvent selected from the group consisting of hydrocarbons, alcohols, and ethers,

[0028] Performing crystallization by cooling the resulting solution.

[0029] 〔6〕The method for producing the type 1 crystal according to any one of 〔1〕to 〔4〕, comprising:

[0030] Dissolving 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole melted in the range of 52 °C to 61 °C in an aromatic compound solvent,

[0031] Performing crystallization by mixing the resulting solution with an aliphatic hydrocarbon solvent.

[0032] 〔7〕The pest control composition containing the type 1 crystal according to any one of 〔1〕to 〔3〕.

[0033] 〔8〕The composition containing one or more components selected from the group consisting of group (a), group (b), group (c), and group (d), and the type 1 crystal according to any one of 〔1〕to 〔4〕,

[0034] Group (a): The group consisting of insecticidal active ingredients, acaricidal active ingredients, and nematicidal active ingredients;

[0035] Group (b): Fungicidal active ingredients;

[0036] Group (c): Plant growth regulating ingredients;

[0037] Group (d): Repellent ingredients.

[0038] 〔9〕The method for controlling pests, comprising applying an effective amount of the type 1 crystal according to any one of 〔1〕to 〔4〕 or an effective amount of the pest control composition according to 〔7〕 to the pests or the habitats of the pests.

[0039] 〔10〕The seeds or vegetative propagation organs retaining an effective amount of the type 1 crystal according to any one of 〔1〕to 〔4〕 or an effective amount of the pest control composition according to 〔7〕.

[0040] Use of the type 1 crystal according to any one of

[11] [1] to [4] for controlling pests.

[0041] Advantages of the Invention

[0042] By the present invention, a type 1 crystal of compound (1) having excellent pest control efficacy can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is a drawing showing the powder X-ray diffraction pattern of the type 1 crystal of compound (1) obtained in Example 1. The vertical axis represents the diffraction intensity (unit: cps), and the horizontal axis represents the diffraction angle 2θ (unit: °).

[0044] Figure 2 is a drawing showing the infrared absorption spectrum of the type 1 crystal of compound (1) obtained in Example 1. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of the irradiated infrared rays.

[0045] Figure 3 is a drawing showing the powder X-ray diffraction pattern of the type 1 crystal of compound (1) obtained in Example 2. The vertical axis represents the diffraction intensity (unit: cps), and the horizontal axis represents the diffraction angle 2θ (unit: °).

[0046] Figure 4 is a drawing showing the infrared absorption spectrum of the type 1 crystal of compound (1) obtained in Example 2. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of the irradiated infrared rays.

[0047] Figure 5 is a drawing showing the powder X-ray diffraction pattern of the type 1 crystal of compound (1) obtained in Example 3. The vertical axis represents the diffraction intensity (unit: cps), and the horizontal axis represents the diffraction angle 2θ (unit: °).

[0048] Figure 6 is a drawing showing the infrared absorption spectrum of the type 1 crystal of compound (1) obtained in Example 3. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of the irradiated infrared rays.

[0049] Figure 7 is a drawing showing the molecular packing in the crystal lattice of the type 1 crystal of compound (1) obtained in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0050] The present invention relates to a crystal of compound (1). The type 1 crystal of compound (1) can be produced according to the following production method.

[0051] 1) Production Method 1 ​​​​​​​

[0052] Dissolve the compound (1) synthesized according to the method described in Patent Document 1, Patent Document 2, or Patent Document 3 in a solvent at 40°C to 100°C, and slowly cool the resulting solution (for example, at a rate of 3°C / hr decrease), and crystallize the crystals at 10°C to 30°C. If crystals do not precipitate, after distilling off a part of the solvent to reduce the amount of the solvent, the solution can be slowly cooled again. By separating the precipitated crystals, type 1 crystals of the compound (1) can be obtained. Examples of the separation include filtration and centrifugation.

[0053] As the solvent to be used, at least one selected from the group consisting of hydrocarbons, alcohols, and ethers is preferred.

[0054] Examples of the hydrocarbon include aromatic hydrocarbons such as benzene, toluene, xylene, and tetrahydronaphthalene; halogenated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; nitrated aromatic hydrocarbons such as nitrobenzene; aliphatic hydrocarbons including acyclic hydrocarbons such as hexane, heptane, octane, nonane, and decane, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and cycloheptane; and mixtures of two or more of them. Among these solvents, a mixed solvent of toluene and hexane is particularly preferred.

[0055] Examples of the alcohol include acyclic hydrocarbon alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1-butanol, and cyclic hydrocarbon alcohols such as cyclohexanol and benzyl alcohol. Among them, 2-propanol is preferred.

[0056] Examples of the ether include acyclic hydrocarbon ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, and 1,2-dimethoxyethane, and cyclic hydrocarbon ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and methoxycyclopentane. Among them, tert-butyl methyl ether is preferred.

[0057] 2) Preparation method 2

[0058] Dissolve the compound (1) synthesized according to the method described in Patent Document 1, Patent Document 2, or Patent Document 3 in a good solvent at 10°C to 30°C, slowly add a poor solvent until a solid precipitates, and crystallize the crystals at 10°C to 30°C. If crystals do not precipitate, after distilling off a part of the solvent to reduce the amount of the solvent, the poor solvent can be slowly added again. By separating the precipitated crystals, type 1 crystals of the compound (1) can be obtained. Examples of the separation include filtration and centrifugation.

[0059] As a good solvent, at least one selected from the group consisting of aromatic compounds, alcohols, and ethers can be mentioned. Among them, aromatic compounds are preferred. As the aromatic compound, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrated aromatic hydrocarbons, etc. can be mentioned. As the aromatic hydrocarbon, for example, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydronaphthalene; halogenated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene; nitrated aromatic hydrocarbons such as nitrobenzene; and mixtures of two or more of them can be mentioned. Among them, toluene is preferred. As the alcohol, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol can be mentioned. As the ether, for example, diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, methoxycyclopentane can be mentioned.

[0060] As a poor solvent, for example, aliphatic hydrocarbons can be mentioned. As the aliphatic hydrocarbon, for example, acyclic hydrocarbons such as hexane, heptane, octane, nonane, decane, and cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane can be mentioned. Among them, hexane is preferred.

[0061] Regarding the type 1 crystal of the compound (1) obtained according to the above method, as an example of the diffraction peak of the 2θ value (°) in the powder X-ray diffraction based on Cu-Kα rays, it has Figure 1 the diffraction peaks shown. For example, hereinafter, it has diffraction peaks at 2θ = 8.5 ± 0.2°, 12.0 ± 0.2°, 15.0 ± 0.2°, 16.6 ± 0.2°, and 20.9 ± 0.2°.

[0062] Regarding the type 1 crystal of the compound (1) obtained according to the above method, in the infrared absorption spectrum (ATR method), as an example, it has Figure 2 the peaks shown. For example, hereinafter, at wavenumbers of 1313 ± 4 cm -1 , 1177 ± 4 cm -1 , 1141 ± 4 cm -1 , 1077 ± 4 cm -1 , 845 ± 4 cm -1 , 720 ± 4 cm -1 , and 676 ± 4 cm -1 there are peaks at the positions.

[0063] The melting point of the type 1 crystal of the compound (1) obtained according to the above method is about 118 - 128 °C.

[0064] Regarding the Form 1 crystal of compound (1) obtained according to the above method, when measured by single crystal X-ray diffraction at -172 °C (101 K), as an example, it has the following crystallographic data of a single crystal.

[0065] [Mathematical formula 2]

[0066] Crystal system: Monoclinic crystal

[0067] Space group: P21 / n

[0068] Lattice constants α = 90°, β = 111.683°, = 90°

[0069] Unit cell volume

[0070] Number of molecules in the unit cell: Z = 4

[0071] Density: 1.569 g / cm 3

[0072] The Form 1 crystal of compound (1) can also be obtained by the following method: adding seeds of the Form 1 crystal of compound (1) to a supersaturated solution of compound (1) and slowly cooling (for example, at a rate of 3 °C / hr) as needed for crystallization. As the solvent for preparing the supersaturated solution, a good solvent is sufficient. As good solvents, for example, the good solvents mentioned above can be cited. Among them, 2-propanol is preferred. As the temperature for crystal precipitation, 10 °C to 30 °C is preferred.

[0073] Regarding compound (1), the amount of seeds used in the production of the Form 1 crystal of compound (1) is preferably 0.001 to 10% by weight, more preferably 0.005 to 1% by weight.

[0074] The Form 1 crystal of compound (1) can be mixed or used in combination with one or more components (hereinafter referred to as this component) selected from the group consisting of the following groups (a), (b), (c), and (d).

[0075] The aforementioned mixing or combination means: using the Form 1 crystal of compound (1) and this component simultaneously, separately, or at time intervals.

[0076] When using the Form 1 crystal of compound (1) and this component simultaneously, the Form 1 crystal of compound (1) and this component can be contained in separate preparations or in the same preparation.

[0077] One aspect of the present invention is a composition (hereinafter referred to as Composition A) containing one or more components selected from the group consisting of Group (a), Group (b), Group (c), and Group (d) (i.e., this component) and a Form 1 crystal of Compound (1).

[0078] Group (a) is a group consisting of acetylcholinesterase inhibitors (e.g., carbamate insecticides, organophosphorus insecticides), GABA-gated chloride channel blockers (e.g., phenylpyrazole insecticides), sodium channel modulators (e.g., pyrethroid insecticides), nicotinic acetylcholine receptor competitive modulators (e.g., neonicotinoid insecticides), allosteric modulators of nicotinic acetylcholine receptors, allosteric modulators of glutamate-gated chloride channels (e.g., macrolide insecticides), juvenile hormone mimetics, multi-site inhibitors, chordotonal organ TRPV channel modulators, mite growth inhibitors, insect midgut epithelial membrane disruptors derived from microorganisms, mitochondrial ATP synthase inhibitors, oxidative phosphorylation uncouplers, nicotinic acetylcholine receptor channel blockers (e.g., nereistoxin insecticides), chitin biosynthesis inhibitors, molting inhibitors, ecdysone receptor agonists, octopamine receptor agonists, inhibitors of mitochondrial electron transport chain complexes I, II, III, and IV, voltage-dependent sodium channel blockers, acetyl-CoA carboxylase inhibitors, ryanodine receptor modulators (e.g., diamide insecticides), chordotonal organ modulators, microbial insecticides, and other insecticidal active ingredients, acaricidal active ingredients, and nematicidal active ingredients. These ingredients are described according to the classification of the mode of action based on IRAC.

[0079] Group (b) is a group consisting of nucleic acid synthesis inhibitors (e.g., phenylamide fungicides, acyl amino acid fungicides), cell division and cytoskeleton inhibitors (e.g., MBC fungicides), respiratory inhibitors (e.g., QoI fungicides, QiI fungicides), amino acid synthesis and protein synthesis inhibitors (e.g., anilinopyridine fungicides), signal transduction inhibitors, lipid synthesis and membrane synthesis inhibitors, sterol biosynthesis inhibitors (e.g., DMI fungicides such as triazoles), cell wall biosynthesis inhibitors, melanin synthesis inhibitors, plant defense inducers, multi-site contact-active fungicides, microbial fungicides, and other fungicidal active ingredients. These ingredients are described according to the classification of the mode of action based on FRAC.

[0080] Group (c) is a group of plant growth regulating components (including mycorrhizal fungi and rhizobia).

[0081] Group (d) is a group of repellent components consisting of bird repellent components, insect repellent components, etc.

[0082] Examples of combinations of the present ingredient and the Form 1 crystal of compound (1) are described below. For example, alanycarb + SX means the combination of alanycarb and SX.

[0083] It should be noted that the abbreviation SX refers to the Form 1 crystal of compound (1). In addition, all of the present ingredients described below are known ingredients and can be obtained from commercially available preparations or manufactured by known methods. When the present ingredient is a microorganism, it can also be obtained from a microorganism preservation institution. It should be noted that the numbers in parentheses represent CAS RN (registered trademark).

[0084] Combinations of the present ingredient of the above group (a) and the Form 1 crystal of compound (1):

[0085] Abamectin + SX, Acephate + SX, Acequinocyl + SX, Acetamiprid + SX, Acetoprole + SX, Acrinathrin + SX, Acynonapyr + SX, Afidopyropen + SX, Afoxolaner + SX, Alanycarb + SX, Aldicarb + SX, Allethrin + SX, Alpha-cypermethrin + SX, Alpha-endosulfan + SX, Aluminium phosphide + SX, Amitraz + SX, Azadirachtin + SX, Azamethiphos + SX, Azinphos-ethyl + SX, Azinphos-methyl + SX, Azocyclotin + SX, Bark of Celastrus angulatus + SX, Bendiocarb + SX, Benfluthrin + SX, Benfuracarb + SX, Bensultap + SX, Benzoximate + SX, Benzpyrimoxan + SX, Beta-cyfluthrin + SX, Beta-cypermethrin + SX, Bifenazate + SX, Bifenthrin + SX, Bioallethrin + SX, Bioresmethrin + SX, Bistrifluron + SX, Borax + SX, Boric acid + SX, Broflanilide + SX, Bromopropylate + SX, Buprofezin + SX, Butocarboxim + SX, Butoxycarboxim + SX, Cadusafos + SX, Calcium phosphidephosphide)+SX, carbaryl+SX, carbofuran+SX, carbosulfan+SX, cartap hydrochloride+SX, cartap+SX, chinomethionat+SX, chlorantraniliprole+SX, chlordane+SX, chlorethoxyfos+SX, chlorfenapyr+SX, chlorfenvinphos+SX, chlorfluazuron+SX, chlormephos+SX, chloropicrin+SX, chlorpyrifos+SX, chlorpyrifos-methyl+SX, chromafenozide+SX, clofentezine+SX, clothianidin+SX, concanamycinA) +SX, coumaphos +SX, cryolite +SX, cyanophos +SX, cyantraniliprole +SX, cyclaniliprole +SX, cyclobutrifluram +SX, cycloprothrin +SX, cycloxaprid +SX, cyenopyrafen +SX, cyetpyrafen +SX, cyflumetofen +SX, cyfluthrin +SX, cyhalodiamide +SX, cyhalothrin +SX, cyhexatin +SX, cypermethrin +SX, cyphenothrin +SX, cyproflanilide +SX, cyromazine +SX, dazomet +SX, deltamethrin +SX, demeton-S-methyl +SX, diafenthiuron +SX, diazinon +SX, dichlorvos +SX, dicloromezotiaz +SX, dicofol +SX, dicrotophos +SX, diflovidazin +SX, diflubenzuron +SX, dimefluthrin +SX, dimethoate +SX, dimethylvinphos +SX, dimpropyridaz +SX, dinotefuran +SX, disodium octaborate +SX, disulfoton +SX, DNOC (2-methyl-4,6-dinitrophenol +SX, doramectin +SX, dried leaves of Dryopterisfilix-mas)+SX, emamectin-benzoate)+SX, empenthrin)+SX, endosulfan)+SX, EPN (O-ethyl O-(4-nitrophenyl)phenylphosphonothioate)+SX, epsilon-metofluthrin)+SX, epsilon-momfluorothrin+SX, esfenvalerate)+SX, ethiofencarb)+SX, ethion)+SX, ethiprole)+SX, ethoprophos)+SX, etofenprox)+SX, etoxazole)+SX, extract of Artemisia absinthium)+SX, extract of Azadirachta indica)+SX, extract of Cassia nigricans)+SX, extract of clitoria ternatea)+SX, extract of Symphytum officinale)+SX, extract of Chenopodium ambrosioides)+SX, extract of Tanacetum vulgare)+SX, extract of Urtica dioica)+SX, extract of Viscum album)+SX, famphur)+SX, fenamiphos)+SX, fenazaquin)+SX, fenbutatin oxide)+SX,

[0086] Fenitrothion + SX, Fenmezoditiaz + SX, Fenobucarb + SX, Fenoxycarb + SX, Fenpropathrin + SX, Fenpyroximate + SX, Fenthion + SX, Fenvalerate + SX, Fipronil + SX, Flometoquin + SX, Flonicamid + SX, Fluacrypyrim + SX, Fluazaindolizine + SX, Fluazuron + SX, Flubendiamide + SX, Fluchlordiniliprole + SX, Flucycloxuron + SX, Flucythrinate + SX, Fluensulfone + SX, Flufenoprox + SX, Flufenoxuron + SX, Flufiprole + SX, Flumethrin + SX, Flupentiofenox + SX, Flupyradifurone + SX, Flupyrimin + SX, Flupyroxystrobin + SX, Fluralaner + SX, Fluvalinate + SX, Fluxametamide + SX, Formetanate + SX, Fosthiazate + SX, Furamethrin + SX, Furathiocarb + SX, Gamma - Cyhalothrin + SX, GS - omega / kappa HXTX - Hv1a peptide + SX, Halfenprox + SX, Halofenozide + SX, Heptafluthrin + SX, Heptenophos + SX, Hexaflumuron + SX, Hexythiazox + SX, Potassium salt of hop betaacid)+SX, hydramethylnon)+SX, hydroprene)+SX, imicyafos)+SX, imidacloprid)+SX, imidaclothiz)+SX, imiprothrin)+SX, indazapyroxamet)+SX, indoxacarb)+SX, isocycloseram+SX, isofenphos)+SX, isoprocarb)+SX, isopropyl-O-(methoxyaminothiophosphoryl)salicylate)+SX, isoxathion)+SX, ivermectin)+SX, kadethrin)+SX, kappa-tefluthrin)+SX, kappa-bifenthrin)+SX, kinoprene)+SX, lambda-cyhalothrin)+SX, ledprona+SX, lenoremycin)+SX, lepimectin)+SX, lime sulfur)+SX, lotilaner)+SX, lufenuron)+SX, machine oil)+SX, malathion)+SX, mecarbam)+SX, meperfluthrin)+SX, metaflumizone)+SX, metam)+SX, methamidophos)+SX, methidathion)+SX, methiocarb)+SX, methomyl)+SX, methoprene)+SX, methoxychlor)+SX, methoxyfenozide)+SX, methyl bromide)+SX, metofluthrin)+SX, metolcarb)+SX, metoxadiazone)+SX, mevinphos)+SX, milbemectin)+SX, milbemycinoxime) + SX, mivorilaner + SX, modoflaner + SX, momfluorothrin + SX, monocrotophos + SX, moxidectin + SX, naled + SX, nicofluprole + SX, nicotine + SX, nicotine-sulfate + SX, nitenpyram + SX, novaluron + SX, noviflumuron + SX, oil of the seeds of Chenopodium anthelminticum + SX, omethoate + SX, oxamyl + SX, oxazosulfyl + SX, oxydemeton-methyl + SX, parathion + SX, parathion-methyl + SX, permethrin + SX, phenothrin + SX, phenthoate + SX, phorate + SX, phosalone + SX, phosmet + SX, phosphamidon + SX, phosphine + SX, phoxim + SX, pirimicarb + SX, pirimiphos-methyl + SX, prallethrin + SX, profenofos + SX, profluthrin + SX, propargite + SX, propetamphos + SX, propoxur + SX, propylene glycolalginate)+SX, prothiofos)+SX, pyflubumide+SX, pymetrozine)+SX, pyraclofos)+SX, pyrethrins)+SX, pyridaben)+SX, pyridalyl)+SX, pyridaphenthion)+SX, pyrifluquinazone)+SX, pyrimidifen)+SX, pyriminostrobin)+SX, pyriprole)+SX, pyriproxyfen)+SX, quinalphos)+SX, resmethrin)+SX, rotenone)+SX,

[0087] Ryanodine + SX, Sarolaner + SX, Selamectin + SX, Sigma-cypermethrin + SX, Silafluofen + SX, Sodium borate + SX, Sodium metaborate + SX, Spidoxamat + SX, Spinetoram + SX, Spinosad + SX, Spirobudifen + SX, Spirodiclofen + SX, Spiromesifen + SX, Spiropidion + SX, Spirotetramat + SX, Sulfiflumin + SX, Sulfluramid + SX, Sulfotep + SX, Sulfoxaflor + SX, Sulfur + SX, Sulfuryl fluoride + SX, Tartar emetic + SX, Tau-fluvalinate + SX, Tebufenozide + SX, Tebufenpyrad + SX, Tebupirimfos + SX, Teflubenzuron + SX, Tefluthrin + SX, Temephos + SX, Terbufos + SX, Terpene constituents of the extract of Chenopodium ambrosioides nearambrosioides)+SX, tetrachlorantraniliprole+SX, tetrachlorvinphos+SX, tetradifon+SX, tetramethrin+SX, tetramethylfluthrin+SX, tetraniliprole+SX, theta-cypermethrin+SX, thiacloprid+SX, thiamethoxam+SX, thiocyclam+SX, thiodicarb+SX, thiofanox+SX, thiometon+SX, thiosultap-disodium+SX, thiosultap-monosodium+SX, tigolaner+SX, tiorantraniliprole+SX, tioxazafen+SX, tolfenpyrad+SX, tralomethrin+SX, transfluthrin+SX, triazamate+SX, triazophos+SX, trichlorfon+SX, trifluenfuronate+SX, triflumezopyrim+SX, triflumuron+SX, trimethacarb+SX, tyclopyrazoflor+SX, umifoxolaner+SX, vamidothion+SX, wood extract of Quassia amara+SX, XMC (3,5-dimethylphenyl N-methylcarbamate, N-methylaminoformic acid 3,5-dimethylphenyl ester)+SX, xylylcarb+SX, zeta-cypermethrin+SX, zincphosphide) + SX, 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide (1241050-20-3) + SX, 3-methoxy-N-(5-{5-(trifluoromethyl)-5-[3-(trifluoromethyl)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}inden-1-yl)propanamide (1118626-57-5) + SX, N-{4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl}-1-methyl-4-(methylsulfonyl)-3-(1,1,2,2,2-pentafluoroethyl)-1H-pyrazole-3-carboxamide (1400768-21-9) + SX, N-[3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl]-2-(methylsulfonyl)propanamide (2396747-83-2) + SX, N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide + SX, 1,4-dimethyl-2-[2-(pyridin-3-yl)-2H-indazol-5-yl]-1,2,4-triazolidine-3,5-dione (2171099-09-3) + SX, 2-isopropyl-5-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]-1,3,4-thiadiazole (2058052-95-0) + SX, N-({2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methyl)cyclopropanecarboxamide + SX, 7-fluoro-N-[1-(methylthio)-2-methylpropan-2-yl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide + SX, 7-fluoro-N-[1-(methanesulfinyl)-2-methylpropan-2-yl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide + SX, 7-fluoro-N-[1-(methylsulfonyl)-2-methylpropan-2-yl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide + SX, N-[1-(difluoromethyl)cyclopropyl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide + SX, 2,9-dihydro-9-(methoxymethyl)-2-(pyridin-3-yl)-10H-pyrazolo[3,4-f]pyrido[2,3-b][1,4]oxazepin-10-one (2607927-97-7) + SX, BT crop protein Cry1Ab + SX, BT crop protein Cry1Ac + SX, BT crop protein Cry1Fa + SX, BT cropprotein Cry1Fa)+SX, BT crop protein Cry1A.105)+SX, BT crop protein Cry2Ab)+SX, BT crop protein Vip3A)+SX, BT crop protein mCry3A)+SX, BT crop protein Cry3Ab)+SX, BT crop protein Cry3Bb)+SX, BT crop protein Cry34Ab1 / Cry35Ab1)+SX, Adoxophyes orana GV (granulovirus) strain BV-0001)+SX, Anticarsia gemmatalis MNPV (multiple nucleocapsid nucleopolyhedrovirus))+SX, Autographa californica MNPV)+SX, Cydia pomonella GV strain V15)+SX, Cydia pomonella GV strain V22)+SX, Cryptophlebia leucotreta GV)+SX, Dendrolimus punctatus cypovirus)+SX, Helicoverpa armigera NPV (nucleopolyhedrovirus) strain BV-0003)+SX, Helicoverpa zea NPV)+SX, Lymantria dispar NPV)+SX, Mamestra brassicae NPV)+SX, Mamestra configurata NPV)+SX, Neodiprion abietisNPV)+SX, Neodiprion lecontei NPV)+SX, Neodiprion sertifer NPV)+SX, Nosema locustae)+SX, Orgyia pseudotsugata NPV)+SX, Pieris rapae GV)+SX, Plodia interpunctella GV)+SX, Spodoptera exigua MNPV)+SX, Spodoptera littoralis MNPV)+SX,

[0088] Spodoptera litura NPV + SX, Arthrobotrys dactyloides + SX, Bacillus firmus strain GB-126 + SX, Bacillus firmus strain I-1582 + SX, Bacillus firmus strain NCIM2637 + SX, Bacillus megaterium + SX, Bacillus sp. strain AQ175 + SX, Bacillus sp. strain AQ177 + SX, Bacillus sp. strain AQ178 + SX, Bacillus sphaericus strain 2362 serotype H5a5b + SX, Bacillus sphaericus strain ABTS1743 + SX, Bacillus thuringiensis strain AQ52 + SX, Bacillus thuringiensis strain BD#32 + SX, Bacillus thuringiensis strain CR-371 + SX, Bacillus thuringiensis subsp. Aizawai strain ABTS-1857 + SX, Bacillus thuringiensis subsp. Aizawai strain AM65-52 + SX, Bacillus thuringiensis subsp. Aizawai strain GC-91 + SX, Bacillus thuringiensis subsp. Aizawai strain NB200 + SX, Bacillus thuringiensis subsp.Aizawai strain NB200)+SX, Bacillus thuringiensis subsp. Aizawai Serotype strain H-7)+SX, Bacillus thuringiensis subsp. Kurstaki strain ABTS351)+SX, Bacillus thuringiensis subsp. Kurstaki strain BMP123)+SX, Bacillus thuringiensis subsp. Kurstaki strain CCT1306)+SX, Bacillus thuringiensis subsp. Kurstaki strain EG2348)+SX, Bacillus thuringiensis subsp. Kurstaki strain EG7841)+SX, Bacillus thuringiensis subsp. Kurstaki strain EVB113-19)+SX, Bacillus thuringiensis subsp. Kurstaki strain F810)+SX, Bacillus thuringiensis subsp. Kurstaki strain HD-1)+SX, Bacillus thuringiensis subsp. Kurstaki strain PB54)+SX, Bacillus thuringiensis subsp. Kurstaki strain SA-11)+SX, Bacillus thuringiensis subsp. Kurstaki strain SA-12)+SX, Bacillus thuringiensis subsp.Bacillus thuringiensis subsp. kurstaki strain SA-12)+SX, Bacillus thuringiensis subsp. tenebriosis strain NB176)+SX, Bacillus thuringiensis subsp. thuringiensis strain MPPL002)+SX, Bacillus thuringiensis subsp. morrisoni)+SX, Bacillus thuringiensis var. colmeri)+SX, Bacillus thuringiensis var. darmstadiensis strain 24-91)+SX, Bacillus thuringiensis var. dendrolimus)+SX, Bacillus thuringiensis var. galleriae)+SX, Bacillus thuringiensis var. israelensis strain BMP144)+SX, Bacillus thuringiensis var. israelensis serotype strain H-14)+SX, Bacillus thuringiensis var. japonensis strain buibui)+SX, Bacillus thuringiensis var. san diego strain M-7)+SX, Bacillus thuringiensis var. 7216)+SX, Bacillus thuringiensis var. aegypti)+SX, Bacillus thuringiensis var. T36)+SXT36)+SX, Beauveria bassiana strain ANT-03+SX, Beauveria bassiana strain ATCC74040+SX, Beauveria bassiana strain GHA+SX, Beauveria brongniartii+SX, Burkholderia rinojensis strain A396+SX, Chromobacterium subtsugae strain PRAA4-1T+SX, Dactyllela ellipsospora+SX, Dectylaria thaumasia+SX, Hirsutella minnesotensis+SX, Hirsutella rhossiliensis+SX, Hirsutella thompsonii+SX, Lagenidium giganteum+SX, Lecanicillium lecanii strain KV01+SX, Lecanicillium lecanii conidia of strain DAOM198499+SX, Lecanicillium lecanii conidia of strain DAOM216596+SX, Lecanicillium muscarium strain Ve6+SX, Metarhizium anisopliae strain F52+SX, Metarhizium anisopliae var. acridum+SX, Metarhizium anisopliae var. anisopliae var. BIPESCO 5 / F52 strainBeauveria anisopliae BIPESCO 5 / F52)+SX, Metarhizium flavoviride)+SX, Monacrosporium phymatopagum+SX, Paecilomyces fumosoroseus Apopka strain 97)+SX, Paecilomyces lilacinus strain 251)+SX, Paecilomyces tenuipes strain T1)+SX, Paenibacillus popilliae)+SX, Pasteuria nishizawae strain Pn1)+SX, Pasteuria penetrans)+SX, Pasteuria usgae+SX, Pasteuria thornei)+SX, Serratia entomophila)+SX, Verticillium chlamydosporium)+SX, Verticillium lecani strain NCIM1312)+SX, Wolbachia pipientis)+SX.

[0089] The combination of the component of group (b) above and the type 1 crystal of compound (1):

[0090] acibenzolar-S-methyl + SX, aldimorph + SX, ametoctradin + SX, aminopyrifen + SX, amisulbrom + SX, anilazine + SX, azaconazole + SX, azoxystrobin + SX, basic copper sulfate + SX, benalaxyl + SX, benalaxyl-M + SX, benodanil + SX, benomyl + SX, benthiavalicarb + SX, benthiavalicarb-isopropyl + SX, benzovindiflupyr + SX, binapacryl + SX, biphenyl + SX, bitertanol + SX, bixafen + SX, blasticidin-S + SX, Bordeaux mixture + SX, boscalid + SX, bromothalonil + SX, bromuconazole + SX, bupirimate + SX, captafol + SX, captan + SX, carbendazim + SX, carboxin + SX, carpropamid + SX, chinomethionat + SX, chitin + SX, chloroinconazide + SX, chloroneb + SX, chlorothalonil + SX, chlozolinate + SX, colletochlorinB + SX, copper(II) acetate + SX, copper(II) hydroxide + SX, copper oxychloride + SX, copper(II) sulfate + SX, coumoxystrobin + SX, cyazofamid + SX, cyflufenamid + SX, cymoxanil + SX, cyproconazole + SX, cyprodinil + SX, dichlobentiazox + SX, dichlofluanid + SX, diclocymet + SX, diclomezine + SX, dicloran + SX, diethofencarb + SX, difenoconazole + SX, diflumetorim + SX, dimethachlone + SX, dimethirimol + SX, dimethomorph + SX, dimoxystrobin + SX, diniconazole + SX, diniconazole-M + SX, dinocap + SX, dipotassium hydrogen phosphite + SX, dipymetitrone + SX, dithianon + SX, dodecylbenzenesulphonic acid bisethylenediamine copper(II) salt + SX, dodemorph + SX, dodine + SX, edifenphos + SX, enoxastrobin + SX, epoxiconazole + SX, etaconazole + SX, ethaboxam + SX, ethirimol + SX, etridiazole + SX, extract of Allium sativum + SX, extract of the cotyledons of lupineplantlets(“BLAD”)) + SX, extract of Equisetum arvense + SX, extract of Melaleuca alternifolia + SX, extract of Reynoutria sachalinensis + SX, extract of Tropaeolum majus + SX, famoxadone + SX, fenamidone + SX, fenaminstrobin + SX, fenarimol + SX, fenbuconazole + SX, fenfuram + SX, fenhexamid + SX, fenoxanil + SX, fenpiclonil + SX, fenpicoxamid + SX,

[0091] Fenpropidin + SX, Fenpropimorph + SX, Fenpyrazamine + SX, Fentin acetate + SX, Fentin chloride + SX, Fentin hydroxide + SX, Ferbam + SX, Ferimzone + SX, Florylpicoxamid, Fluazinam, Flubeneteram, Fludioxonil, Flufenoxadiazam, Flufenoxystrobin, Fluindapyr, Flumetylsulforim, Flumorph, Fluopicolide, Fluopyram, Fluopimomide, Fluoroimide, Fluoxapiprolin, Fluoxastrobin, Fluoxytioconazole, Fluquinconazole, Flusilazole, Flusulfamide, Flutianil, Flutolanil, Flutriafol, Fluxapyroxad, Folpet, Fosetyl, Fosetyl - aluminium, Fuberidazole, Furalaxyl, Furametpyr, Guazatine, Hexaconazole, Hymexazole, Imazalil, Imibenconazole, Iminoctadine, Iminoctadine triacetatetriacetate)+SX, inpyrfluxam+SX, iodocarb)+SX, ipconazole)+SX, ipfentrifluconazole)+SX, ipflufenoquin+SX, iprobenfos)+SX, iprodione)+SX, iprovalicarb)+SX, isofetamid)+SX, isoflucypram+SX, isoprothiolane)+SX, isopyrazam)+SX, isotianil)+SX, kasugamycin)+SX, kresoxim-methyl)+SX, laminarin)+SX, leaves and bark ofQuercus)+SX, mancozeb)+SX, mandestrobin+SX, mandipropamid)+SX, maneb)+SX, mefentrifluconazole)+SX, mepanipyrim)+SX, mepronil)+SX, meptyldinocap)+SX, metalaxyl)+SX, metalaxyl-M)+SX, metarylpicoxamid+SX, metconazole)+SX, methasulfocarb)+SX, metiram)+SX, metominostrobin)+SX, metrafenone)+SX, metyltetraprole+SX, myclobutanil)+SX, naftifine)+SX, nuarimol)+SX, octhilinone)+SX, ofurace)+SX, orysastrobin)+SX, oxadixyl)+SX, oxathiapiprolin)+SX, oxine-copper)+SX, oxolinic acid)+SX, oxpoconazole)+SX, oxpoconazole fumaratefumarate)+SX, oxycarboxin)+SX, oxytetracycline)+SX, pefurazoate)+SX, penconazole)+SX, pencycuron)+SX, penflufen)+SX, penthiopyrad)+SX, phenamacril)+SX, phosphorous acid)+SX, phthalide)+SX, picarbutrazox)+SX, picoxystrobin)+SX, piperalin)+SX, polyoxins)+SX, potassium hydrogencarbonate)+SX, potassium dihydrogenphosphite)+SX, probenazole)+SX, prochloraz)+SX, procymidone)+SX, propamidine)+SX, propamocarb)+SX, propiconazole)+SX, propineb)+SX, proquinazid)+SX, prothiocarb)+SX, prothioconazole)+SX, pydiflumetofen)+SX, pyraclostrobin)+SX, pyrametostrobin)+SX, pyraoxystrobin)+SX, pyrapropoyne+SX, pyraziflumid)+SX, pyrazophos)+SX, pyribencarb)+SX, pyributicarb)+SX, pyridachlometyl+SX, pyrifenox)+SX, pyrimethanil)+SX, pyrimorph)+SX, pyriofenone)+SX, pyrisoxazole)+SX,

[0092] Pyroquilon + SX, Quillaja extract + SX, Quinconazole + SX, Quinofumelin + SX, Quinoxyfen + SX, Quintozene + SX, Saponins of Chenopodium quinoa + SX, Seboctylamine + SX, Sedaxane + SX, Silthiofam + SX, Simeconazole + SX, Sodium hydrogencarbonate + SX, Spiroxamine + SX, Streptomycin + SX, Sulfur + SX, Tebuconazole + SX, Tebufloquin + SX, Teclofthalam + SX, Tecnazene + SX, Terbinafine + SX, Tetraconazole + SX, Thiabendazole + SX, Thifluzamide + SX, Thiophanate + SX, Thiophanate-methyl + SX, Thiram + SX, Thymol + SX, Tiadinil + SX, Tolclofos-methyl + SX, Tolfenpyrad + SX, Tolprocarb + SX, Tolylfluanid + SX, Triadimefon + SX, Triadimenol + SX, Triazoxide + SX, Triclopyricarb + SX, Tricyclazole + SX, Tridemorph + SX, Trifloxystrobin + SX, Triflumizole + SX, Triforine + SX, Triticonazole + SX, Validamycin + SX, Valifenalate + SX, Vinclozolin + SX, Yellow mustardpowder)+SX, zoxamide zinc + SX, zineb + SX, ziram + SX, zoxamide + SX,

[0093] N’-[4-({3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl}oxy)-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine (1202781-91-6) + SX, N’-{4-[(4,5-dichlorothiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylformamidine (929908-57-6) + SX, N’-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine (1052688-31-9) + SX, N’-[5-chloro-4-(2-fluorophenoxy)-2-methylphenyl]-N-ethyl-N-methylformamidine (2055589-28-9) + SX, N’-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformamidine (2055756-21-1) + SX, N’-(2-chloro-4-phenoxy-5-methylphenyl)-N-ethyl-N-methylformamidine (2062599-39-5) + SX, N’-[4-(1-hydroxy-1-phenyl-2,2,2-trifluoroethyl)-2-methyl-5-methoxyphenyl]-N-isopropyl-N-methylformamidine (2101814-55-3) + SX, N’-[5-bromo-6-(1-methyl-2-propoxyethoxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylformamidine (1817828-69-5) + SX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine (1362477-26-6) + SX, 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline (1257056-97-5) + SX, (2Z)-ethyl 3-amino-2-cyano-3-phenylacrylate (39491-78-6) + SX, N-[(2-chlorothiazol-5-yl)methyl]-N-ethyl-6-methoxy-3-nitropyridin-2-amine (1446247-98-8) + SX, 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1394057-11-4), (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-06-2), (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-07-3), 2-(chloromethyl)-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-(1H-1,2,4-Triazol-1-ylmethyl)cyclopentan-1-ol (1394057-13-6) + SX, (1R,2S,5S)-2-(Chloromethyl)-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-08-4) + SX, (1S,2R,5R)-2-(Chloromethyl)-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-09-5) + SX, Methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentane-1-carboxylate (1791398-02-1) + SX, 1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)-1-[1-(4-bromo-2,6-difluorophenoxy)cyclopropyl]ethanol (2019215-86-0) + SX, 1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)-1-[1-(4-chloro-2,6-difluorophenoxy)cyclopropyl]ethanol (2019215-84-8) + SX, 1-[2-(1-Chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]-1H-imidazole-5-carbonitrile (2018316-13-5) + SX, 1-[2-(1-Chlorocyclopropyl)-3-(2,3-difluorophenyl)-2-hydroxypropyl]-1H-imidazole-5-carbonitrile (2018317-25-2) + SX, 2-[6-(4-Bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol (2082661-43-4) + SX,

[0094] 2-[6-(4-Chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol (2082660-27-1) + SX, Methyl ({2-methyl-5-[1-(4-methoxy-2-methylphenyl)-1H-pyrazol-3-yl]phenyl}methyl)carbamate (1605879-98-8) + SX, 2-(Difluoromethyl)-N-[1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1616239-21-4) + SX, 2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1847460-02-9) + SX, 2-(Difluoromethyl)-N-[3-propyl-1,1-dimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1847460-05-2) + SX, (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide (1445331-27-0) + SX, (2E,3Z)-5-{[1-(2,4-dichlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide (1445331-54-3) + SX, 5-Chloro-4-({2-[6-(4-chlorophenoxy)pyridin-3-yl]ethyl}amino)-6-methylpyrimidine (1605340-92-8) + SX, N-(1-Benzyl-1,3-dimethylbutyl)-8-fluoroquinoline-3-carboxamide (2132414-04-9) + SX, N-(1-Benzyl-3,3,3-trifluoro-1-methylpropyl)-8-fluoroquinoline-3-carboxamide (2132414-00-5) + SX, 4,4-Dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolin-3-one (2098918-25-1) + SX, 5,5-Dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolin-3-one (2098918-26-2) + SX, N-Ethyl-2-methyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, N,2-Dimethoxy-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, N-Methoxy-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)cyclopropanecarboxamide + SX, N-Methoxy-N'-methyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl}methyl)urea + SX, N'-ethyl-N-methoxy-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea + SX, N,N'-dimethoxy-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea + SX, N-acetyl-2-(ethylsulfonyl)-N-[2-(methoxycarbonyl)-4-(trifluoromethoxy)phenyl]-4-(trifluoromethyl)benzamide (2043675-28-9) + SX, N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alanine 3-(4-bromo-7-fluoroindol-1-yl)but-2-yl ester + SX, N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alanine 3-(7-bromoindol-1-yl)but-2-yl ester + SX, N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alanine 3-(7-bromo-4-fluoroindol-1-yl)but-2-yl ester + SX, N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alanine 3-(3,5-dichloropyridin-2-yl)but-2-yl ester + SX, N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alanine 3-(3,5-dichloropyridin-2-yl)but-2-yl ester + SX, N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alanine (1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl ester ((1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate) + SX, N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alanine (1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl ester ((1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate) + SX, N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alanine (1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl ester ((1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate) + SX, N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl}methyl)cyclopropanecarboxamide + SX, N-allyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)acetamide + SX, N-allyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, 3,3,3-trifluoro-N-({2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, 3,3,3-trifluoro-N-({3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, 3,3,3-trifluoro-N-({2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide + SX, N-({2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)butyramide + SX, N-methoxy-N-methyl-N'-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea + SX, N,N-diethyl-N'-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea + SX, N-methyl-N'-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea + SX, 1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)pyrrolidin-2-one + SX, 1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)piperidin-2-one + SX, 4-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)morpholin-3-one + SX, 2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolin-3-one + SX, 3,3-dimethyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)piperidin-2-one + SX, 2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1,2-oxazinan-3-one + SX, 1-({3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)azepan-2-one + SX, 4,4-dimethyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)pyrrolidin-2-one + SX, 5-methyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl}methyl)pyrrolidin-2-one + SX, ethyl 1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxylate + SX, N-methyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide + SX, N-propyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide + SX, N-methoxy-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide + SX, N-methoxy-N-methyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide + SX, N,N-dimethyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-1,2,4-triazol-3-amine + SX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + SX, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propionate + SX, ethyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propionate + SX, methyl 2-[2-(trifluoromethyl)-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propionate + SX, 1-(2,3-dimethylpyridin-5-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline + SX, 1-[2-(difluoromethyl)-3-methylpyridin-5-yl]-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline + SX, 2,2-difluoro-N-[6-({[1-(1-methyl-1H-tetrazol-5-yl)benzimidazol-2-yl]oxy}methyl)pyridin-2-yl]-2-phenoxyacetamide + SX, 1-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]-1H-imidazole-5-carbonitrile + SX, ethyl 1-[(4-{[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy}phenyl)methyl]-1H-pyrazole-4-carboxylate + SX, ethyl 1-[(4-{[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy}phenyl)methyl]-1H-pyrazole-4-carboxylate + SX, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-(Difluoroethyl)-5-methylpyridazine-4-carboxamide + SX, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide + SX, 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide + SX, 2-[Cyano(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-[Cyano(2,6-difluoropyridin-4-yl)amino]-N-(spiro[3.4]octan-1-yl)-5-methylthiazole-4-carboxamide + SX, 2-[Cyano(2,6-difluoropyridin-4-yl)amino]-N-hexyl-5-methylthiazole-4-carboxamide + SX, 2-[Acetyl(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-[(2-Methoxyacetyl)(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-[(2-Methylpropanoyl)(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-[(2,6-Difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-{[(Oxetan-3-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-{[(Oxolane-3-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 2-{[(Oxan-4-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methylthiazole-4-carboxamide + SX, 5-[5-(Difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)ethyl]pyrimidin-2-amine + SX, 5-[5-(Difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)ethyl]pyrimidin-2-amine + SX, 5-[5-(Difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin-2-amine + SX, 5-[5-(Difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(6-chloropyridin-3-yl)ethyl]pyrimidin-2-amine + SX, 5-[5-(Difluoromethyl)-1,3,4-Oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine + SX, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine + SX, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2-fluoro-3-methoxyphenyl)cyclopropyl]pyrimidin-2-amine + SX, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-2-{[1-(2,6-difluorophenyl)cyclopropyl]oxy}pyrimidine + SX, 3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine + SX, (5S)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine + SX, 3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(4-bromo-2-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine + SX, 3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2-chloro-4-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine + SX, (5S)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2-chloro-4-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine + SX, (5R)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2-chloro-4-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine + SX, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}-3-methylbutan-2-yl)-2-methylpropanamide + SX, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}-3-methylbutan-2-yl)-2,2-dimethylpropanamide + SX, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}propan-2-yl)-2-methylpropanamide + SX, N-((2S)-1-{3-[2-(2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}propan-2-yl)-2-methylpropanamide + SX, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-(2-cyanoethoxy)ethyl]-5-[1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}propan-2-yl)-2-methylpropanamide + SX, ({5-[1-(2,6-difluoro-4-isopropylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl}methyl)methylcarbamate + SX, ({5-[1-(2,6-difluoro-4-cyclopropylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl}methyl)methylcarbamate + SX, ({5-[1-(2,6-difluoro-4-methoxyphenyl)-1H-pyrazol-3-yl]-2-methylphenyl}methyl)methylcarbamate + SX, (Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-methoxy-2-methylacrylate + SX, (Z)-2-(5-cyclohexyl-2-methylphenoxy)-3-methoxy-2-methylacrylate + SX, (Z)-2-[(3-isopropyl-1H-pyrazol-1-yl)-2-methylphenoxy]-3-methoxy-2-methylacrylate + SX, 1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline + SX, 1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinoline + SX, 1-(pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline + SX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-6-fluoro-3,3-dimethylisoquinolin-4(3H)-one + SX, (2Z)-3-methoxy-2-[(4-methyl[1,1'-biphenyl]-3-yl)oxy]-2-methylacrylate + SX,

[0095] Agrobacterium radiobactor strain K1026 + SX, Agrobacterium radiobactor strain K84 + SX, Bacillus amyloliquefaciens strain PTA - 4838 (Aveo (trademark) EZ Nematicide) + SX, Bacillus amyloliquefaciens strain AT332 + SX, Bacillus amyloliquefaciens strain B3 + SX, Bacillus amyloliquefaciens strain D747 + SX, Bacillus amyloliquefaciens strain DB101 + SX, Bacillus amyloliquefaciens strain DB102 + SX, Bacillus amyloliquefaciens strain GB03 + SX, Bacillus amyloliquefaciens strain FZB24 + SX, Bacillus amyloliquefaciens strain FZB42 + SX, Bacillus amyloliquefaciens strain IN937a + SX, Bacillus amyloliquefaciens strain MBI600 + SX, Bacillus amyloliquefaciens strain QST713 + SX, Bacillus amyloliquefaciens isolate strain B246 + SX, Bacillus amyloliquefaciens strain F727F727)+SX, Bacillus amyloliquefaciens subsp. plantarum strain D747)+SX, Bacillus licheniformis strain HB-2)+SX, Bacillus licheniformis strain SB3086)+SX, Bacillus pumilus strain AQ717)+SX, Bacillus pumilus strain BUF-33)+SX, Bacillus pumilus strain GB34)+SX, Bacillus pumilus strain QST2808)+SX, Bacillus simplex strain CGF2856)+SX, Bacillus subtilis strain AQ153)+SX, Bacillus subtilis strain AQ743)+SX, Bacillus subtilis strain BU1814)+SX, Bacillus subtilis strain D747)+SX, Bacillus subtilis strain DB101)+SX, Bacillus subtilis strain FZB24)+SX, Bacillus subtilis strain GB03)+SX, Bacillus subtilis strain HAI0404)+SX, Bacillus subtilis strain IAB / BS03)+SX, Bacillus subtilis strain MBI600)+SX, Bacillus subtilis strain QST30002 / AQ30002 strain (Bacillus subtilis strainBacillus subtilis strain QST30002 / AQ30002)+SX, Bacillus subtilis strain QST30004 / AQ30004)+SX, Bacillus subtilis strain QST713)+SX, Bacillus subtilis strain QST714)+SX, Bacillus subtilis var. Amyloliquefaciens strain FZB24)+SX, Bacillus subtilis strain Y1336)+SX, Burkholderia cepacia)+SX, Burkholderia cepacia type Wisconsin strain J82)+SX, Burkholderia cepacia type Wisconsin strain M54)+SX, Candida oleophila strain O)+SX, Candida saitoana)+SX, Chaetomium cupreum)+SX, Clonostachys rosea)+SX, Coniothyrium minitans strain CGMCC8325)+SX, Coniothyrium minitans strain CON / M / 91-8)+SX, cryptococcus albidus)+SX, Erwinia carotovora subsp. carotovora strain CGE234M403)+SX, Fusarium oxysporum strain Fo47)+SX, Gliocladium catenulatum strain J1446)+SX, Paenibacillus polymyxa strain AC-1)+SXAC-1)+SX, Paenibacillus polymyxa strain BS-0105+SX, Pantoea agglomerans strain E325+SX, Phlebiopsis gigantea strain VRA1992+SX, Pseudomonas aureofaciens strain TX-1+SX, Pseudomonas chlororaphis strain 63-28+SX, Pseudomonas chlororaphis strain AFS009+SX, Pseudomonas chlororaphis strain MA342+SX, Pseudomonas fluorescens strain 1629RS+SX, Pseudomonas fluorescens strain A506+SX, Pseudomonas fluorescens strain CL145A+SX,

[0096] Pseudomonas fluorescens strain G7090 + SX, Pseudomonas sp. strain CAB-02 + SX, Pseudomonas syringae strain 742RS + SX, Pseudomonas syringae strain MA-4 + SX, Pseudozyma flocculosa PF-A22UL strain + SX, Pseudomonas rhodesiae strain HAI-0804 + SX, Pythium oligandrum strain DV74 + SX, Pythium oligandrum strain M1 + SX, Streptomyces griseoviridis strain K61 + SX, Streptomyces lydicus strain WYCD108US + SX, Streptomyces lydicus strain WYEC108 + SX, Talaromyces flavus strain SAY-Y-94-01 + SX, Talaromyces flavus strain V117b + SX, Trichoderma asperellum strain ICC012 + SX, Trichoderma asperellum SKT-1 + SX, Trichoderma asperellum strain T25 + SX, Trichoderma asperellum strain T34 + SX, Trichoderma asperellum strain TV1 + SX, Trichoderma atroviride strain CNCM 1-1237 + SX, Trichoderma atroviride strain LC52strain LC52)+SX, Trichoderma atroviride strain IMI 206040)+SX, Trichoderma atroviride strain SC1)+SX, Trichoderma atroviride strain SKT-1)+SX, Trichoderma atroviride strain T11)+SX, Trichoderma gamsii strain ICC080)+SX, Trichoderma harzianum strain 21)+SX, Trichoderma harzianum strain DB104)+SX, Trichoderma harzianum strain DSM 14944)+SX, Trichoderma harzianum strain ESALQ-1303)+SX, Trichoderma harzianum strain ESALQ-1306)+SX, Trichoderma harzianum strain IIHR-Th-2)+SX, Trichoderma harzianum strain ITEM908)+SX, Trichoderma harzianum strain kd)+SX, Trichoderma harzianum strain MO1)+SX, Trichoderma harzianum strain SF)+SX, Trichoderma harzianum strain T22)+SX, Trichoderma harzianum strain T39)+SX, Trichoderma harzianum strain T78)+SX, Trichoderma harzianum strain TH35)+SX, Trichoderma harzianum strainTH35)+SX, Trichoderma polysporum strain IMI206039+SX, trichoderma stromaticum+SX, Trichoderma virens strain G-41+SX, Trichoderma virens strain GL-21+SX, Trichoderma viride+SX, Variovorax paradoxus strain CGF4526+SX, Harpin protein+SX.

[0097] The combination of the present component of group (c) and the type 1 crystal of compound (1):

[0098] 1-methylcyclopropene + SX, 1,3-diphenylurea + SX, 2,3,5-triiodobenzoic acid + SX, IAA ((1H-indol-3-yl) acetic acid) + SX, IBA (4-(1H-indol-3-yl) butyric acid) + SX, MCPA (2-(4-chloro-2-methylphenoxy) acetic acid) + SX, MCPB (4-(4-chloro-2-methylphenoxy) butyric acid) + SX, 4-CPA (4-chlorophenoxyacetic acid) + SX, 5-aminolevulinic acid hydrochloride + SX, 6-benzylaminopurine + SX, abscisic acid + SX, AVG (aminoethoxyvinylglycine) + SX, anisiflupurin + SX, ancymidol + SX, butralin + SX, calcium carbonate + SX, calcium chloride + SX, calcium formate + SX, calcium peroxide + SX, calcium polysulfide + SX, calcium sulfate + SX, chlormequat-chloride + SX, chlorpropham + SX, cholinechloride)+SX, cloprop)+SX, cyanamide)+SX, cyclanilide)+SX, daminozide)+SX, decan-1-ol)+SX, dichlorprop)+SX, dikegulac)+SX, dimethipin)+SX, diquat)+SX, ethephon)+SX, ethychlozate)+SX, flumetralin)+SX, flurprimidol)+SX, forchlorfenuron)+SX, formononetin)+SX, Gibberellin A)+SX, GibberellinA3)+SX, inabenfide)+SX, Kinetin)+SX, lipochitooligosaccharide)SP104+SX, maleic hydrazide)+SX, mefluidide)+SX, mepiquat-chloride)+SX, oxidizedglutathione)+SX, paclobutrazol)+SX, pendimethalin)+SX, prohexadione-calcium)+SX, prohydrojasmon)+SX, pyraflufen-ethyl)+SX, sintofen)+SX, sodium 1-naphthaleneacetate)+SX, sodium cyanate)+SX, thidiazuron)+SX, triapenthenol)+SX, tribufos)+SX, trinexapac-ethyl)+SX, uniconazole-P)+SX, 2-(naphthalen-1-yl)acetamide)+SX, [4-oxo-4-(2-phenylethyl)amino]butyric acid+SX, methyl 5-(trifluoromethyl)benzo[b]thiophene-2-carboxylate+SX, 3-[(6-chloro-4-phenylquinazolin-2-yl)amino]propan-1-ol+SX, Claroideoglomusetunicatum)+SX, Claroideoglomus claroideum)+SX, Funneliformis mosseae)+SX, Gigaspora margarita)+SX, Gigaspora rosea)+SX, Glomus aggregatum)+SX, Glomus deserticola)+SX, Glomus monosporum)+SX, Paraglomus brasillianum)+SX, Rhizophagus clarus)+SX, Rhizophagus intraradices strain RTI-801)+SX, Rhizophagus irregularis strain DAOM 197198)+SX, Azorhizobium caulinodans)+SX, Azospirillum amazonense)+SX, Azospirillum brasilense strain XOH)+SX, Azospirillum brasilense strain Ab-V5)+SX, Azospirillum brasilense strain Ab-V6)+SX, Azospirillum caulinodans+SX, Azospirillum halopraeferens)+SX, Azospirillum irakense)+SX, Azospirillum lipoferum)+SX, Bradyrhizobium elkanii strain SEMIA 587)+SX, Bradyrhizobium elkanii strain SEMIA 5019)+SX, Bradyrhizobium japonicum strain TA-11)+SX, Bradyrhizobium japonicum strain USDA 110)+SX, Bradyrhizobium liaoningense)+SX, Bradyrhizobium lupini)+SX, Delftia acidovorans strain RAY209)+SX, Mesorhizobium ciceri)+SX, Mesorhizobium huakuiiHuakii)+SX, Mesorhizobium loti)+SX, Rhizobium etli)+SX, Rhizobium galegae)+SX, Rhizobium leguminosarum bv. Phaseoli)+SX, Rhizobium leguminosarum bv. Trifolii)+SX, Rhizobium leguminosarum bv. Viciae)+SX, Rhizobium trifolii)+SX, Rhizobium tropici)+SX, Sinorhizobium fredii)+SX, Sinorhizobium meliloti)+SX, Zucchini Yellow Mosaik Virus weak strain)+SX.

[0099] Combination of the present component of group (d) and the type 1 crystal of compound (1):

[0100] Anthraquinone)+SX, Deet)+SX, Icaridin)+SX.

[0101] The ratio of the type 1 crystal of compound (1) to the present component is not particularly limited, and examples include 1000:1 to 1:1000, 500:1 to 1:500, 100:1 to 1:100, 50:1, 20:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:20, 1:50, etc. in terms of weight ratio (type 1 crystal of compound (1): present component).

[0102] The type 1 crystal of compound (1) can control harmful arthropods such as harmful insects and harmful mites, harmful mollusks, and harmful nematodes. Examples of harmful arthropods, harmful mollusks, and harmful nematodes include the following animals.

[0103] Hemiptera: Delphacidae such as Laodelphax striatellus, Nilaparvata lugens, Sogatella furcifera, Peregrinus maidis, Javesella pellucida, Perkinsiella saccharicida, Tagosodes orizicolus, Stenocranus pacificus, etc.; Cicadellidae such as Nephotettix cincticeps, Nephotettix virescens, Nephotettix nigropictus, Recilia dorsalis, Empoasca onukii, Empoasca fabae, Dalbulus maidis, Cofana spectra, Amrasca biguttula biguttula, etc.; Aphrophoridae such as Philaenus spumarius; Cercopidae such as Mahanarva posticata, Mahanarva fimbriolata, etc.Aphididae such as *Aphis fabae*, *Aphis glycines*, *Aphis gossypii*, *Aphis pomi*, *Aphis spiraecola*, *Myzus persicae*, *Brachycaudus helichrysi*, *Brevicoryne brassicae*, *Dysaphis plantaginea*, *Lipaphis erysimi*, *Macrosiphum euphorbiae*, *Aulacorthum solani*, *Nasonovia ribisnigri*, *Rhopalosiphum padi*, *Rhopalosiphum maidis*, *Toxoptera citricida*, *Hyalopterus pruni*, *Melanaphis sacchari*, *Tetraneura nigriabdominalis*, *Ceratovacuna lanigera*, *Eriosoma lanigerum*, *Sitobion avenae*; Phylloxeridae such as *Daktulosphaira vitifoliae*, *Phylloxera devastatrix*, *Phylloxera notabilis*, *Phylloxera russelae*; Adelgidae such as *Adelges tsugae*, *Adelges piceae*, *Aphrastasia pectinatae*;Pentatomidae such as Scotinophara lurida, Scotinophara coarctata, Nezara antennata, Eysarcoris aeneus, Eysarcoris lewisi, Eysarcoris ventralis, Eysarcoris annamita, Halyomorpha halys, Nezara viridula, Euschistus heros, Piezodorus guildinii, Oebalus pugnax, Dichelops melacanthus, Piezodorus hybneri, etc.; Cydnidae such as Scaptocoris castanea; Alydidae such as Riptortus clavatus, Leptocorisa chinensis, Leptocorisa acuta; Coreidae such as Cletus punctiger, Leptoglossus australis; Lygaeidae such as Cavelerius saccharivorus, Togohemipterus, Blissus leucopterus; Miridae such as Trigonotylus caelestialium, Stenotus rubrovittatus, Stenodema calcarata, Lygus lineolaris; Aleyrodidae such as Trialeurodes vaporariorum, Bemisia tabaci, Dialeurodes citri, Aleurocanthus spiniferus, Aleurocanthus camelliae, Pealius euryaeAbgrallaspis cyanophylli, Aonidiella aurantii, Diaspidiotus perniciosus, Pseudaulacaspis pentagona, Unaspis yanonensis, Unaspis citri, etc. of the family Diaspididae; Ceroplastes rubens of the family Coccidae; Icerya purchasi, Icerya seychellarum, etc. of the family Margarodidae; Phenacoccus solani, Phenacoccus solenopsis, Planococcus kraunhiae, Pseudococcus comstocki, Planococcus citri, Pseudococcus calceolariae, Pseudococcus longispinus, Brevennia rehi, etc. of the family Pseudococcidae; Diaphorina citri, Trioza erytreae, Cacopsylla pyrisuga, Cacopsylla chinensis, Bactericera cockerelli, Cacopsylla pyricola, etc. of the family Psyllidae; Corythucha ciliata, Corythucha marmorata, Stephanitis nashi, Stephanitis pyrioides, etc. of the family Tingidae; Cimex lectularius, Cimex hemipterus, etc. of the family Cimicidae; Quesada gigas of the family Cicadidae;Triatomine bugs such as Triatoma infestans, Triatoma rubrofasciata, Triatoma dimidiata, Rhodnius prolixus, etc. (Reduviidae);

[0104] Lepidoptera: Crambidae such as Chilo suppressalis, Chilopolychrysus, Scirpophaga innotata, Scirpophaga incertulas, Rupela albina, Cnaphalocrocis medinalis, Marasmiapatnalis, Marasmia exigua, Notarcha derogata, Ostrinia furnacalis, Ostrinia nubilalis, Hellulaundalis, Herpetogramma luctuosale, Parapediasiateterrellus, Nymphula depunctalis, Diatraea saccharalis, Leucinodes orbonalis, etc.; Pyralidae such as Elasmopalpuslignosellus, Plodia interpunctella, Euzophera batangensis, Cadra cautella, etc.Spodoptera litura, Spodoptera exigua, Mythimna separata, Mamestra brassicae, Sesamia inferens, Spodoptera mauritia, Naranga aenescens, Spodoptera frugiperda, Spodoptera exempta, Spodoptera cosmioides, Spodoptera eridania, Agrotis ipsilon, Agrotis segetum, Autographa nigrisigna, Plusia festucae, Chrysodeixis includens, Trichoplusia spp., Heliothis virescens and other Heliothis spp., Helicoverpa armigera, Helicoverpa zea and other Helicoverpa spp., Anticarsia gemmatalis, Alabama argillacea, Hydraecia immanis and other Noctuidae; Pieris rapae and other Pieridae;Tortricidae such as Grapholita molesta, Grapholita dimorpha, Leguminivora glycinivorella, Matsumuraeses azukivora, Adoxophyes orana fasciata, Adoxophyes honmai, Homona magnanima, Archips fuscocupreanus, Cydia pomonella, Tetramoera schistaceana, Bean Shoot Borer (Epinotia aporema), Citripestis sagittiferella, Lobesia botrana, etc.; Gracillariidae such as Caloptilia theivora, Phyllonorycter ringoniella, etc.; Carposinidae such as Carposina sasakii, etc.; Lyonetiidae such as Leucoptera coffeella, Lyonetia clerkella, Lyonetia prunifoliella, etc.; Lymantriidae such as Lymantria dispar of Lymantria spp., Euproctis pseudoconspersa of Euproctis spp., etc.; Plutellidae such as Plutella xylostella, etc.; Gelechiidae such as Anarsia lineatella, Helcystogramma triannulella, Pectinophora gossypiella, Phthorimaea operculella, Tuta absoluta, etc.; Arctiidae such as Hyphantria cunea, etc.; Castniidae such as Telchin licus, etc.Cossidae such as Cossus insularis; Geometridae such as Ascotis selenaria; Limacodidae such as Parasalepida; Stathmopodidae such as Stathmopoda masinissa; Sphingidae such as Acherontia lachesis; Sesiidae such as Nokonaferalis, Synanthedon hector, Synanthedon tenuis; Hesperiidae such as Parnara guttata; Tineidae such as Tinea translucens, Tineola bisselliella.

[0105] Thysanoptera: Thripidae such as Frankliniella occidentalis, Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, Stenchaetothrips biformis, Echinothrips americanus, Scirtothrips perseae; Phlaeothripidae such as Haplothrips aculeatus.

[0106] Diptera: Anthomyiidae such as Delia platura, Delia antiqua, Pegomya cunicularia, etc.; Ulidiidae such as Tetanops myopaeformis, etc.; Agromyzidae such as Agromyza oryzae, Liriomyza sativae, Liriomyza trifolii, Chromatomyia horticola, etc.; Chloropidae such as Chlorops oryzae, etc.; Tephritidae such as Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera latifrons, Bactrocera oleae, Bactrocera tryoni, Ceratitis capitata, Rhagoletis pomonella, Rhacochlaena japonica, etc.; Ephydridae such as Hydrellia griseola, Hydrellia philippina, Hydrellia sasakii, etc.; Drosophilidae such as Drosophila suzukii, Drosophila melanogaster, etc.; Phoridae such as Megaselia spiracularis, etc.; Psychodidae such as Clogmia albipunctata, etc.; Sciaridae such as Bradysia difformis, Bradysia odoriphaga, etc.; Cecidomyiidae such as Mayetiola destructor, Orseolia oryzae, etc.; Diopsidae such as Diopsis macrophthalma, etc.Glossina palpalis, Glossina morsitans, etc. of the family Glossinidae; Simulium japonicum, Simulium damnosum, etc. of the family Simuliidae; subfamily Phlebotominae; Tipula aino, Tipula oleracea, Tipula paludosa, etc. of the family Tipulidae; Culex pipiens pallens, Culex tritaeniorhynchus, Culex pipiens f. molestus, Culex quinquefasciatus, Culex pipiens pipiens, Culex vishnui, Aedes albopictus, Aedes aegypti, Anopheles sinensis, Anopheles gambiae, Anopheles stephensi, Anopheles coluzzii, Anopheles albimanus, Anopheles sundaicus, Anopheles arabiensis, Anopheles funestus, Anopheles darlingi, Anopheles farauti, Anopheles minimus, etc. of the family Culicidae; Prosimulium yezoensis, Simulium ornatum, etc. of the family Simuliidae; Tabanus trigonus of the family Tabanidae; Musca domestica, Muscina stabulans, Stomoxys calcitrans, Haematobia irritans, etc. of the family Muscidae; family Calliphoridae; family Sarcophagidae;Chironomidae such as Chironomus plumosus, Chironomus yoshimatsui, Glyptotendipes tokunagai, etc.; Fannidae;

[0107] Coleoptera: Diabrotica spp. (such as Diabrotica virgifera virgifera, Diabrotica undecimpunctata howardi, Diabrotica barberi, Diabrotica virgifera zeae, Diabrotica balteata, Cucurbit Beetle (Diabrotica speciosa), etc.), Cerotoma trifurcata, Oulema melanopus, Aulacophora femoralis, Phyllotreta striolata, Phyllotreta cruciferae, Phyllotreta pusilla, Psylliodes chrysocephala, Psylliodes punctulata, Leptinotarsa decemlineata, Oulema oryzae, Colaspis brunnea, Chaetocnema pulicaria, Chaetocnema confinis, Epitrix cucumeris, Dicladispa armigera, Myochrous denticollis, Laccoptera quadrimaculata, Epitrix hirtipennis, Phaedon brassicae, Medythia nigrobilineata, etc. of Chrysomelidae; Seedcorn beetle (Stenolophus lecontei), Clivina impressifrons, etc. of Carabidae;Scarabaeidae such as Anomala cuprea, Anomala rufocuprea, Anomala albopilosa, Popillia japonica, Heptophyllapicea, Rhizotrogus majalis, Tomarus gibbosus, Holotrichia spp., Phyllophaga crinita and other Phyllophaga spp., Diloboderus abderus and other Diloboderus spp.; Anthriibidae such as Araecerus coffeae; Aponidae such as Cylas formicarius; Bruchidae such as Zabrotes subfasciatus; Scolytidae such as Tomicus piniperda, Hypothenemus hampei; Curculionidae such as Euscepes postfasciatus, Hypera postica, Sitophilus zeamais, Sitophilus oryzae, Sitophilus granarius, Echinocnemus squameus, Lissorhoptrus oryzophilus, Rhabdoscelus lineaticollis, Anthonomus grandis, Sphenophorus venatus, Sphenophorus callosus, Sternechus subsignatus, Sphenophorus levis, Scepticus griseus, Scepticus uniformis, Aracanthus mourei and other Aracanthus spp., Eutinobothrus brasiliensis and other Curculionidae;Tenebrionidae such as Tribolium castaneum, Tribolium confusum, Alphitobius diaperinus, etc.; Coccinellidae such as Epilachna vigintioctopunctata, etc.; Bostrychidae such as Lyctus brunneus, Rhizopertha dominica, etc.; Ptinidae; Cerambycidae such as Anoplophora malasiaca, Migdolus fryanus, Aromia bungii, etc.; Elateridae such as Melanotus okinawensis, Agriotes fuscicollis, Melanotus legatus, Anchastus spp., Conoderus spp., Ctenicera spp., Limonius spp., Aeolus spp., etc.; Staphylinidae such as Paederus fuscipes, etc.; Dermestidae such as Anthrenus verbasci, Dermestes maculates, Trogoderma granarium, etc.; Anobiidae such as Lasioderma serricorne, Stegobium paniceum, etc.; Laemophloeidae such as Cryptolestes ferrugineus, etc.; Silvanidae such as Oryzaephilus surinamensis, etc., Nitidulidae such as Brassicogethes aeneus, etc.

[0108] Orthoptera: Acrididae such as Locusta migratoria, Dociostaurus maroccanus, Chortoicetes terminifera, Nomadacris septemfasciata, Locustana pardalina, Anacridium melanorhodon, Calliptamus italicus, Melanoplus differentialis, Melanoplus bivittatus, Melanoplus sanguinipes, Melanoplus femurrubrum, Camnula pellucida, Schistocerca gregaria, Yellow-winged locust (Gastrimargus musicus), Spur-throated locust (Austracris guttulosa), Oxya yezoensis, Oxya japonica, Patanga succincta, etc.; Gryllotalpidae such as Gryllotalpa orientalis; Gryllidae such as Acheta domestica, Teleogryllus emma; Tettigoniidae such as Anabrus simplex.

[0109] Hymenoptera: Tenthredinidae such as Athalia rosae and Athalia japonica; Solenopsis spp. such as Solenopsis invicta and Solenopsis geminata, Atta spp. such as Brown leaf-cutting ant (Attacapiguara), Acromyrmex spp., Paraponera clavata, Ochetellus glaber, Monomorium pharaonis, Linepithema humile, Formica japonica, Pristomyrmex punctutus, Pheidole noda, Pheidole megacephala, Camponotus japonicus, Camponotus obscuripes and other Camponotus spp., Pogonomyrmex occidentalis and other Pogonomyrmex spp., Wasmania auropunctata and other Wasmania spp., Anoplolepis gracilipes and other Formicidae; Vespidae such as Vespa mandarinia, Vespa simillima, Vespa analis, Vespa velutina, Polistes jokahamae; Siricidae such as Urocerus gigas; Bethylidae.

[0110] Order Blattodea: Ectobiidae such as Blattella germanica; Blattidae such as Periplaneta fuliginosa, Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Blatta orientalis; Termitidae such as Reticulitermes speratus, Coptotermes formosanus, Incisitermes minor, Cryptotermes domesticus, Odontotermes formosanus, Neotermes koshunensis, Glyptotermes satsumensis, Glyptotermes nakajimai, Glyptotermes fuscus, Hodotermopsis sjostedti, Coptotermes guangzhouensis, Reticulitermes amamianus, Reticulitermes miyatakei, Reticulitermes kanmonensis, Nasutitermes takasagoensis, Pericapritermes nitobei, Sinocapritermes mushae, Cornitermes cumulans.

[0111] Order Siphonaptera: Pulicidae such as Pulex irritans, Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Echidnophaga gallinacea; Hectopsyllidae such as Tunga penetrans; Ceratophyllidae such as Nosopsyllus fasciatus.

[0112] Psocodea: Pediculidae such as Pediculus humanus capitis; Pthiridae such as Pthirus pubis; Haematopinidae such as Haematopinus eurysternus and Haematopinus suis; Linognathidae such as Linognathus vituli, Linognathus ovillus, and Solenopotes capillatus; Bovicoliidae such as Bovicola bovis, Bovicola ovis, Bovicola breviceps, Damalinia forficula, and Werneckiella spp.; Trichodectidae such as Trichodectes canis and Felicola subrostratus; Menoponidae such as Menopon gallinae, Menacanthus stramineus, and Trinoton spp.; Trimenoponidae such as Cummingsia spp.; Trogiidae such as Trogium pulsatorium; Liposcelididae or Liposcelididae such as Liposcelis corrodens, Liposcelis bostrychophila, Liposcelis pearmani, and Liposcelis entomophila.

[0113] Thysanura: Lepismatidae such as Ctenolepisma villosa and Lepisma saccharina.

[0114] Acari: Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai, Tetranychus evansi, Panonychus citri, Panonychus ulmi, Oligonychus spp.; Eriophyidae such as Aculops pelekassi, Phyllocoptruta citri, Aculops lycopersici, Calacarus carinatus, Acaphylla theavagrans, Eriophyes chibaensis, Aculus schlechtendali, Aceria diospyri, Aceria tosichella, Shevtchenkella sp.; Tarsonemidae such as Polyphagotarsonemus latus; Tenuipalpidae such as Brevipalpus phoenicis; TuckerellidaeHard ticks of the family Ixodidae, such as Haemaphysalis longicornis, Haemaphysalis flava, Haemaphysalis japonica, Haemaphysalis campanulata, Dermacentor variabilis, Dermacentor taiwanensis, Dermacentor andersoni, Dermacentor reticulatus, Ixodes ovatus, Ixodes persulcatus, Ixodes scapularis, Ixodes pacificus, Ixodes holocyclus, Ixodes ricinus, Amblyomma americanum, Amblyomma maculatum, Rhipicephalus microplus, Rhipicephalus annulatus, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus decoloratus, etc.; soft ticks of the family Argasidae, such as Argas persicus, Ornithodoros hermsi, Ornithodoros turicata, etc.; flour mites of the family Acaridae, such as Tyrophagus putrescentiae, Tyrophagus similis, etc.; house dust mites of the family Pyroglyphidae, such as Dermatophagoides farinae, Dermatophagoides pteronyssinus, etc.; predatory mites of the family Cheyletidae, such as Cheyletus eruditus, Cheyletus malaccensis, Chelacaropsis moorei, Cheyletiella yasguri, etc.;Psoroptidae such as Psoroptes ovis, Psoroptes equi, Knemidocoptes mutans, Otodectes cynotis, Chorioptes spp.; Sarcoptidae such as Notoedres cati, Notoedres muris, Sarcoptes scabiei; Listrophoridae such as Listrophorus gibbus; Dermanyssidae such as Dermanyssus gallinae; Macronyssidae such as Ornithonyssus sylviarum, Ornithonyssus bacoti; Varroidae such as Varroa jacobsoni; Demodicidae such as Demodex canis, Demodex cati; Trombiculidae such as Leptotrombidium akamushi, Leptotrombidium pallidum, Leptotrombidium scutellare.

[0115] Order Araneae: Eutichuridae such as Cheiracanthium japonicum; Theridiidae such as Latrodectus hasseltii.

[0116] Order Polydesmida: Paradoxosomatidae such as Oxidus gracilis, Nedyopus tambanus.

[0117] Order Isopoda: Armadillidiidae such as Armadillidium vulgare.

[0118] Chilopoda: Scutigeridae such as Thereuonema hilgendorfi; Scolopendridae such as Scolopendra subspinipes; Ethopolyidae such as Bothropolys rugosus.

[0119] Gastropoda: Limacidae such as Limax marginatus and Limax flavus; Philomycidae such as Meghimatium bilineatum; Ampullariidae such as Pomacea canaliculata; Lymnaeidae such as Austropeplea ollula.

[0120] Nematoda: Aphelenchoididae such as Aphelenchoides besseyi; Pratylenchidae such as Pratylenchus coffeae, Pratylenchus brachyurus, Pratylenchus neglectus, Radopholus similis; Heteroderidae such as Meloidogyne javanica, Meloidogyne incognita, Meloidogyne enterolobii, Meloidogyne hapla, Heterodera glycines, Globodera rostochiensis, Globodera pallida, Meloidogyne chitwoodi; Hoplolaimidae such as Rotylenchulus reniformis; Anguinidae such as Nothotylenchus acris, Ditylenchus dipsaci; Tylenchulidae such as Tylenchulus semipenetrans; Longidoridae such as Xiphinema index; Trichodoridae; Parasitaphelenchidae such as Bursaphelenchus xylophilus.

[0121] Harmful arthropods such as harmful insects and harmful mites, harmful mollusks, and harmful nematodes can also be harmful insects, harmful mites and other harmful arthropods, harmful mollusks, and harmful nematodes that have reduced susceptibility to pesticides, acaricides, molluscicides, or nematicides, or are highly resistant.

[0122] As the method for controlling harmful arthropods of the present invention, it can be implemented by directly applying an effective amount of the type 1 crystal of compound (1) or composition A to harmful arthropods and / or to the habitats of harmful arthropods (plants, soil, indoors of houses, animals, etc.). Examples of the method for controlling harmful arthropods of the present invention include foliar treatment, soil treatment, root treatment, spraying treatment, fumigation treatment, water surface treatment, and seed treatment.

[0123] For the type 1 crystal of compound (1) or composition A, non-active carriers such as solid carriers, liquid carriers, and gaseous carriers, and surfactants are usually mixed, and formulation aids such as binders, dispersants, and stabilizers are further added as needed, and formulated into aqueous suspension formulations, oily suspension formulations, oil formulations, emulsion formulations, emulsion preparations, microemulsion formulations, microcapsule formulations, wettable powders, water-dispersible granules, powders, granules, tablets, aerosol formulations, resin formulations, etc. for use. It is not limited to these formulations, and it can be formulated into the dosage forms described in Manual on development and use of FAO and WHO Specifications for pesticides, FAO Plant Production and Protection Papers - 271~276, prepared by the FAO / WHO Joint Meeting on Pesticide Specifications (Manual on development and use of FAO and WHO Specifications for pesticides, FAO Plant Production and Protection Papers - 271~276, prepared by the FAO / WHO Joint Meeting on Pesticide Specifications), 2016, ISSN: 0259 - 2517 for use.

[0124] In these formulations, the type 1 crystal of compound (1) or composition A is usually contained in an amount of 0.0001 to 99% by weight.

[0125] Examples of the solid carrier include clays (pyrophyllite clay, kaolin clay, etc.), talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acid clay, attapulgite, silica white, ammonium sulfate, vermiculite, perlite, pumice, silica sand, fine powders and granules of chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), and resins (polyethylene, polypropylene, polyester, polyurethane, polyamide, polyvinyl chloride, etc.).

[0126] Examples of the liquid carrier include water, alcohols (ethanol, cyclohexanol, benzyl alcohol, propylene glycol, polyethylene glycol, etc.), ketones (acetone, cyclohexanone, etc.), aromatic hydrocarbons (xylene, phenylxylene ethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), esters (ethyl acetate, methyl oleate, propylene carbonate, etc.), nitriles (acetonitrile, etc.), ethers (ethylene glycol dimethyl ether, etc.), amides (N,N-dimethylformamide, N,N-dimethyloctanamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), lactams (N-methylpyrrolidone, N-octylpyrrolidone, etc.), fatty acids (oleic acid, etc.), and vegetable oils (soybean oil, etc.).

[0127] Examples of the gaseous carrier include fluorocarbons, butane gas, LPG (liquefied petroleum gas), dimethyl ether, nitrogen, and carbon dioxide.

[0128] Examples of the surfactant include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyethylene glycol fatty acid ester, etc.) and anionic surfactants (alkyl sulfonate, alkyl aryl sulfonate, alkyl sulfate, etc.).

[0129] Examples of the other adjuvants for the preparation include binders, dispersants, colorants, stabilizers, etc. Specific examples include polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), isopropyl acid phosphate, and butylated hydroxytoluene.

[0130] In addition, as a component for enhancing or assisting the efficacy of the type 1 crystal of the compound (1), an adjuvant can be used. Specifically, examples include Nimbus (registered trademark), Assist (registered trademark), Aureo (registered trademark), Iharol (registered trademark), Silwet L-77 (registered trademark), BreakThru (registered trademark), SundanceII (registered trademark), Induce (registered trademark), Penetrator (registered trademark), AgriDex (registered trademark), Lutensol A8 (registered trademark), NP-7 (registered trademark), Triton (registered trademark), Nufilm (registered trademark), Emulgator NP7 (registered trademark), Emulad (registered trademark), TRITON X 45 (registered trademark), AGRAL 90 (registered trademark), AGROTIN (registered trademark), ARPON (registered trademark), EnSpray N (registered trademark), and BANOLE (registered trademark), etc.

[0131] In the present invention, examples of the plant include the whole plant, stems and leaves, flowers, spikes, fruits, trunks, branches, crowns, seeds, vegetative propagation organs, and seedlings.

[0132] The vegetative propagation organ refers to a part of the root, stem, leaf, etc. of a plant that has the ability to grow when the part is cut off from the main body and placed in the soil. Examples of the vegetative propagation organ include, for example, tuberous root, creeping root, bulb, corm (or solid bulb), tuber, rhizome, stolon, rhizophore, cane cuttings, propagule, and vine cutting. It should be noted that a stolon is sometimes also referred to as a runner, and a propagule is also referred to as a bulblet, which is divided into a broad bud and a bulbil. A vine cutting refers to a slender shoot (a general term for leaves and stems, a shoot without roots) such as sweet potato and Japanese yam. Bulbs, corms, tubers, rhizomes, cane cuttings, rhizophores, or tuberous roots are also collectively referred to as bulbs. The cultivation of potatoes starts by implanting tubers into the soil, but the tubers used are usually referred to as seed potatoes.

[0133] As a method of applying the type 1 crystal of compound (1) or composition A in an effective amount to soil for controlling harmful arthropods, for example, there can be mentioned: a method of applying the type 1 crystal of compound (1) or composition A in an effective amount to the soil before or after transplanting plants; a method of applying the type 1 crystal of compound (1) or composition A in an effective amount to the rhizosphere of crops (intended to be protected from damage such as feeding caused by harmful arthropods); and a method of controlling harmful arthropods that feed on plants by allowing the type 1 crystal of compound (1) or composition A in an effective amount to penetrate and migrate from the roots, etc. into the interior of the plant body. More specifically, for example, there can be mentioned hole treatment (hole spraying, hole soil mixing), root treatment (root spraying, root soil mixing, root irrigation, late-stage root treatment during seedling raising), furrow treatment (furrow spraying, furrow soil mixing), ditch treatment (ditch spraying, ditch soil mixing, ditch spraying during the growth period), furrow treatment at sowing (furrow spraying at sowing, furrow soil mixing at sowing), overall treatment (whole soil spraying, whole soil mixing), side treatment in ridge cultivation, water surface treatment (water surface application, water surface application after water storage), other soil spraying treatments (granule foliar spraying during the growth period, spraying under the canopy or around the main trunk, soil surface spraying, soil surface mixing, hole spraying, surface spraying on the ridge, inter-plant spraying), other irrigation treatments (soil irrigation, irrigation during seedling raising, liquid injection treatment, plant base irrigation, drip irrigation of liquid medicine, chemical solution irrigation), seedling box treatment (seedling box spraying, seedling box irrigation, liquid medicine accumulation in seedling box), seedling tray treatment (seedling tray spraying, seedling tray irrigation, liquid medicine accumulation in seedling tray), seedbed treatment (seedbed spraying, seedbed irrigation, seedbed spraying in paddy field seedbed, seedling dipping), bed soil mixing treatment (bed soil mixing, bed soil mixing before sowing, spraying before covering soil at sowing, spraying after covering soil at sowing, covering soil mixing), and other treatments (cultivated soil mixing, turning in, topsoil mixing, soil mixing at the rain dripping part, planting position treatment, granule calyx spraying, paste fertilizer mixing).

[0134] As seed treatment, for example, there can be mentioned the treatment of seeds or vegetative propagation organs with the type 1 crystal of compound (1) or composition A. Specifically, for example: spraying treatment in which a suspension of the type 1 crystal of compound (1) or composition A is atomized and sprayed onto the surface of seeds or vegetative propagation organs; coating treatment in which the type 1 crystal of compound (1) or composition A is coated on seeds or vegetative propagation organs; dipping treatment in which seeds or vegetative propagation organs are dipped in a liquid medicine of the type 1 crystal of compound (1) or composition A for a certain period of time; a method of coating seeds or vegetative propagation organs with a carrier containing the type 1 crystal of compound (1) or composition A (coating treatment, granule coating treatment, etc.). As the above-mentioned vegetative propagation organs, seed potatoes can be particularly mentioned.

[0135] When treating seeds or vegetative propagation organs with Composition A, Composition A can be formulated into a single preparation for treating seeds or vegetative propagation organs, or can be formulated into different multiple preparations for treating seeds or vegetative propagation organs in several times. As a method of formulating Composition A into different multiple preparations for treating in several times, for example, there can be mentioned: treating with a preparation containing only the type 1 crystal of Compound (1) as the active ingredient, allowing the seeds or vegetative propagation organs to air-dry, and then treating with a preparation containing this ingredient; and treating with a preparation containing the type 1 crystal of Compound (1) and this ingredient as the active ingredient, allowing the seeds or vegetative propagation organs to air-dry, and then treating with a preparation containing this ingredient except for the ingredient that has been treated.

[0136] The seeds or vegetative propagation organs holding the type 1 crystal of Compound (1) or Composition A in the present invention refer to: seeds or vegetative propagation organs in a state where the type 1 crystal of Compound (1) or Composition A is adhered to the surface of the seeds or vegetative propagation organs. For the above-mentioned seeds or vegetative propagation organs holding the type 1 crystal of Compound (1) or Composition A, materials other than the type 1 crystal of Compound (1) or Composition A can be adhered before and after adhering the type 1 crystal of Compound (1) or Composition A to the seeds or vegetative propagation organs.

[0137] In addition, when Composition A forms a layer and adheres to the surface of the seeds or vegetative propagation organs, the layer is formed by one layer or multiple layers. In addition, when formed by multiple layers, each layer is a layer containing one or more active ingredients, or is formed by a layer containing one or more active ingredients and a layer not containing active ingredients.

[0138] The seeds or vegetative propagation organs holding the type 1 crystal of Compound (1) or Composition A can be obtained, for example, by the following method: applying a preparation containing the type 1 crystal of Compound (1) or Composition A to the seeds or vegetative propagation organs by using the aforementioned seed treatment method.

[0139] When using the type 1 crystal of Compound (1) or Composition A for controlling harmful arthropods in the agricultural field, the application rate is usually 1 to 10000 g based on the amount of the type 1 crystal of Compound (1) per 10000 m 2 In the case of treating seeds or vegetative propagation organs, the amount of the type 1 crystal of Compound (1) is usually applied in the range of 0.001 to 100 g relative to 1 Kg of the seeds or vegetative propagation organs. When the type 1 crystal of Compound (1) or Composition A is formulated into an emulsion, wettable powder, suspension agent, etc., it is usually diluted with water so that the active ingredient concentration becomes 0.01 to 10000 ppm and then applied, and granule agents, powder agents, etc. are usually applied directly.

[0140] In addition, the type 1 crystal of compound (1) or composition A can also be applied by methods such as winding resin preparations processed into sheets or lines around crops, stretching them near crops, or laying them on the root soil.

[0141] When the type 1 crystal of compound (1) or composition A is used for controlling harmful arthropods inhabiting in houses, for the application amount, in the case of surface treatment, based on the amount of the type 1 crystal of compound (1) per 1 m 2 of the treatment area, it is usually 0.01 - 1000 mg. In the case of space treatment, based on the amount of the type 1 crystal of compound (1) per 1 m 3 of the treatment space, it is usually 0.01 - 500 mg. When the type 1 crystal of compound (1) or composition A is formulated into an emulsion, wettable powder, suspension agent, etc., it is usually diluted with water so that the active ingredient concentration becomes 0.1 - 10000 ppm and then applied, and oil agents, aerosol agents, fumigants, bait agents, etc. are applied directly.

[0142] When the type 1 crystal of compound (1) or composition A is used for controlling external parasites of livestock such as cattle, horses, pigs, sheep, goats, chickens, and small animals such as dogs, cats, rats, and mice, it can be used for animals by methods known in veterinary medicine. As specific usage methods, for the purpose of systemic inhibition, it is administered by, for example, tablets, incorporation into feed, suppositories, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.). For the purpose of non-systemic inhibition, it is used by methods such as spraying an oil agent or aqueous liquid, pouring treatment or drip treatment, washing the animal with a shampoo preparation, or making resin preparations into collars and ear tags for the animal to wear. The amount of the type 1 crystal of compound (1) or composition A when administered to an animal is usually in the range of 0.1 - 1000 mg per 1 kg of the animal's body weight.

[0143] The type 1 crystal of compound (1) or composition A can be used as a control agent for harmful arthropods in agricultural fields such as dry fields, paddy fields, lawns, and orchards. Examples of plants are as follows.

[0144] Maize (dent corn, flint corn, soft corn, pop corn, waxy corn, sweet corn, non-sweet corn), rice (long-grain rice, short-grain rice, medium-grain rice, japonica rice, tropical japonica rice, indica rice, javanica rice, paddy rice, upland rice, floating rice, direct seeding, transplantation, glutinous rice), wheat (bread wheat (hard, soft, medium, red wheat, white wheat), durum wheat, spelt wheat, club wheat, their respective winter wheat types, spring wheat types), barley (two-row barley (= brewing barley), six-row barley, naked barley, glutinous barley, their respective winter barley types, spring barley types), rye (winter rye type, spring rye type), triticale (winter triticale type, spring triticale type), oats (winter oat type, spring oat type), sorghum, cotton (upland cotton, pima cotton), soybeans (mature seed harvest varieties, edamame varieties, green manure varieties, their respective indeterminate growth types, determinate growth types, semi-determinate growth types), peanuts, buckwheat, sugar beets (for sugar production, for feed, root vegetables, leaf vegetables, for fuel), rapeseed (winter rapeseed type, spring rapeseed type), canola (winter canola type, spring canola type), sunflowers (for oil extraction, for food, for ornamental purposes), sugarcane, tobacco, tea plants, mulberries, solanaceous vegetables (eggplants, tomatoes, green peppers, chili peppers, potatoes, etc.), cucurbitaceous vegetables (cucumbers, pumpkins, zucchinis, watermelons, melons, etc.), cruciferous vegetables (radishes, turnips, horseradishes, kohlrabi, Chinese cabbages, cabbages, mustards, broccoli, cauliflowers, etc.), asteraceous vegetables (burdocks, spring chrysanthemums, artichokes, lettuces, etc.), liliaceous vegetables (scallions, onions, garlics, asparagus, etc.), umbelliferous vegetables (carrots, parsley, celery, parsnips, etc.), chenopodiaceous vegetables (spinaches, chards, etc.), labiatae vegetables (perillas, mints, basils, etc.), strawberries, sweet potatoes, Japanese yams, taros, pome fruits (apples, European pears, Japanese pears, white pears, Chinese flowering quinces, quinces, etc.), stone fruits (peaches, plums, nectarines, ume plums, cherries, apricots, prunes, etc.), citrus fruits (Satsuma mandarins, oranges, lemons, limes, grapefruits, etc.), nuts (chestnuts, walnuts, hazelnuts, almonds, pistachios, cashews, macadamias, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons, figs, olives, loquats, bananas, coffee, dates, coconuts, ornamental plants, forest plants, lawn grasses, forage grasses.

[0145] The above-mentioned plants may be any commonly cultivated varieties without any particular limitation. The above-mentioned plants also include plants that can be produced by natural cross-breeding, plants that can be generated by mutation, F1 hybrid plants, and genetically modified crops. Examples of genetically modified crops include plants that have been given tolerance to HPPD (4-hydroxyphenylpyruvate dioxygenase) inhibitors such as isoxaflutole, ALS (acetolactate synthase) inhibitors such as imazethapyr and thifensulfuron-methyl, EPSP (5-enolpyruvylshikimate-3-phosphate synthase) inhibitors, glutamine synthetase inhibitors, PPO (protoporphyrinogen oxidase) inhibitors, herbicides such as bromoxynil or dicamba; plants that can synthesize selective toxins known in Bacillus species such as Bacillus thuringiensis; plants that can confer specific insecticidal activity by synthesizing gene fragments partially identical to endogenous genes from harmful insects and inducing gene silencing (RNAi; RNA interference) in the target harmful insects.

[0146] Examples

[0147] Hereinafter, the present invention will be described in more detail by means of production examples, formulation examples, and test examples, but the present invention is not limited to these examples only.

[0148] The powder X-ray diffraction measurement conditions, FT-IR measurement conditions, and melting point measurement conditions are as described below.

[0149] (Powder X-ray diffraction measurement conditions)

[0150] Powder X-ray diffractometer: XtaLAB Synergy-i (manufactured by Rigaku Corporation)

[0151] X-ray output: CuKα, 50 kV, 40 mA

[0152] Step width: 0.01°

[0153] Scanning range: 0° to 118.1°

[0154] (Single crystal X-ray diffraction measurement conditions)

[0155] [Mathematical formula 3]

[0156] Powder X-ray diffractometer: XtaLAB Synergy-i (manufactured by Rigaku Corporation)

[0157] Detector: HPC detector (HyPix-Bantam)

[0158] X-ray output: 50 kV, 40 mA

[0159] Measured temperature: 101 K

[0160] Structure analysis: ShelXT (Sheldrick, G.M. (2015).

[0161] Acta Cryst. A71, 3 - 8.)

[0162] Refinement: ShelXL (Sheldrick, G.M. (2015)

[0163] Acta Cryst. A71, 3 - 8.)

[0164] (FT - IR measurement conditions)

[0165] FT - IR spectroscopic analysis device: IRSpirit (manufactured by Shimadzu Corporation)

[0166] Measurement method: Attenuated Total Reflection

[0167] Number of accumulations: 40

[0168] Resolution: 4 cm -1

[0169] (Melting point measurement conditions)

[0170] Melting point measurement device: M - 565 (Buchi Japan Co., Ltd.)

[0171] Heating condition: 0.5 °C / min

[0172] Reference Example 1

[0173] Compound (1) was prepared according to the method described in Reference Example 4 of Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2020 - 172469). The obtained compound (1) started to melt at 52 °C and was completely melted at 61 °C.

[0174] Example 1

[0175] To 1.26 g of the compound (1) obtained in Reference Example 1, 70 mL of 2 - propanol was added, and the mixture was heated to 60 °C to completely dissolve it. The mixture was allowed to stand at room temperature, and the solid was filtered from the obtained mixture to obtain Form 1 crystals of the compound (1).

[0176] Powder X - ray diffraction based on Cu - Kα radiation was measured for the obtained Form 1 crystals of the compound (1). As a result, the diffraction angles (2θ) of the obtained diffraction peaks were as Figure 1As shown. As typical and specific diffraction peaks, they are 8.5°, 12.0°, 14.9°, 16.6° and 20.7°, but not limited thereto. The values of the diffraction angle (2θ) and the integrated intensity (cps°) of the obtained diffraction peaks are shown in Table 1A. In addition, FT-IR was measured, and the results showed peaks as shown in Figure 2 As shown. As typical and specific peaks, there are peaks at 1313 cm -1 , 1177 cm -1 , 1141 cm -1 , 1077 cm -1 , 845 cm -1 , 720 cm -1 and 676 cm -1 , but not limited thereto. In addition, the melting point was measured, and the result was 118 - 127 °C.

[0177] [Table 1]

[0178] Table 1A

[0179] 2θ Integrated intensity (cps°) 8.50 3.1 11.95 17.0 14.90 13.8 16.59 7.4 18.28 69.7 20.67 14.5 22.92 11.5

[0180] Example 2

[0181] 15 mL of toluene was added to 0.704 g of the compound (1) obtained in Reference Example 1 and completely dissolved. 80 mL of hexane was slowly added. After confirming the precipitation of a solid, the mixture was allowed to stand at room temperature. The solid was filtered from the obtained mixture, and thus a type 1 crystal of the compound (1) was obtained.

[0182] Powder X-ray diffraction based on Cu-Kα rays was measured for the obtained type 1 crystal of the compound (1), and the diffraction angle (2θ) of the obtained diffraction peaks was as shown in Figure 3 As shown. As typical and specific diffraction peaks, they are 8.4°, 12.1°, 15.0°, 16.7° and 21.1°, but not limited thereto. The values of the diffraction angle (2θ) and the integrated intensity (cps°) of the obtained diffraction peaks are shown in Table 2A. In addition, FT-IR was measured, and the results showed peaks as shown in Figure 4 As shown. As typical and specific peaks, there are peaks at 1313 cm -1 , 1174 cm -1 , 1138 cm -1 , 1077 cm -1 , 845 cm -1 , 720 cm -1 and 676 cm -1 , but not limited thereto. In addition, the melting point was measured, and the result was 118 - 127 °C.

[0183] [Table 2]

[0184] Table 2A

[0185] 2θ Integrated intensity (cps°) 8.44 19.8 12.06 89.4 15.01 16.1 16.65 63.6 17.69 30.8 21.09 74.7 23.50 94.6

[0186] Example 3

[0187] To 1 g of the compound (1) obtained in Reference Example 1, 50 mL of tert-butyl methyl ether was added, and the mixture was heated to 60 °C to completely dissolve it. The mixture was allowed to stand at room temperature, and the solid was filtered from the resulting mixture to obtain Form 1 crystals of the compound (1).

[0188] The powder X-ray diffraction based on Cu-Kα radiation was measured for the obtained Form 1 crystals of the compound (1). As a result, the diffraction angles (2θ) of the obtained diffraction peaks were as Figure 5 shown. As typical and specific diffraction peaks, they were 8.5°, 12.0°, 15.0°, 16.6°, and 21.0°, but not limited thereto. The values of the diffraction angles (2θ) and integrated intensities (cps°) of the obtained diffraction peaks are shown in Table 3A. In addition, FT-IR was measured, and as a result, peaks as Figure 6 shown were exhibited. As typical and specific peaks, peaks were present at 1313 cm -1 , 1174 cm -1 , 1138 cm -1 , 1076 cm -1 , 843 cm -1 , 720 cm -1 , and 676 cm -1 , but not limited thereto. In addition, the melting point was measured, and the result was 120 to 128 °C. For the obtained Form 1 crystals, single crystal X-ray diffraction was measured. As a result, the crystallographic data of the obtained single crystal are shown in Table 3B.

[0189] [Table 3A]

[0190] Table 3A

[0191] 2θ Integrated intensity (cps°) 7.98 9.1 8.54 7.1 12.00 54.8 15.01 11.7 16.56 37.6 17.70 27.0 19.25 11.4 20.95 69.0 23.36 75.3

[0192] [Table 3B]

[0193] Table 3B

[0194]

[0195] Reference Example 2

[0196] To 0.8 g of the compound (1) obtained in Reference Example 1, 10 mL of acetone was added to completely dissolve it. The solution was concentrated under reduced pressure and dried in vacuo to obtain a solid. The powder X-ray diffraction based on Cu-Kα radiation was measured for the obtained solid. As a result, no X-ray diffraction peak was confirmed, and it was thus found that the solid was amorphous.

[0197] Next, a formulation example of the Form 1 crystal of Compound (1) is shown. It should be noted that "parts" represents parts by weight.

[0198] Formulation Example 1

[0199] 35 parts of a mixture of ammonium polyoxyethylene alkyl ether sulfate and silica (weight ratio 1:1), 10 parts of the Form 1 crystal of Compound (1), and 55 parts of water were mixed and micro-ground by a wet grinding method to obtain a formulation.

[0200] Formulation Example 2

[0201] 50 parts of the Form 1 crystal of Compound (1), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of silica were ground and mixed to obtain a formulation.

[0202] Formulation Example 3

[0203] 5 parts of the Form 1 crystal of Compound (1), 9 parts of polyoxyethylene styrylphenyl ether, 5 parts of polyoxyethylene decyl ether (ethylene oxide addition number: 5), 6 parts of calcium dodecylbenzenesulfonate, and 75 parts of xylene were mixed to obtain a formulation.

[0204] Formulation Example 4

[0205] 2 parts of the Form 1 crystal of Compound (1), 1 part of silica, 2 parts of calcium lignosulfonate, 30 parts of bentonite, and 65 parts of kaolin clay were ground and mixed, an appropriate amount of water was added, kneaded, granulated by a granulator, and then dried to obtain a formulation.

[0206] Formulation Example 5

[0207] 10 parts of the Form 1 crystal of Compound (1) was mixed into a mixture of 18 parts of benzyl alcohol and 9 parts of DMSO, 6.3 parts of GERONOL (registered trademark) TE250, 2.7 parts of Ethylan (registered trademark) NS-500LQ, and 54 parts of solvent naphtha were added thereto, and mixed to obtain a formulation.

[0208] Formulation Example 6

[0209] 0.1 part of the Form 1 crystal of Compound (1) and 39.9 parts of kerosene were mixed and dissolved, filled into an aerosol container, and 60 parts of liquefied petroleum gas (a mixture of propane, butane, and isobutane; saturated vapor pressure: 0.47 MPa (25 °C)) was filled therein to obtain a formulation.

[0210] Formulation Example 7

[0211] 0.2 parts of Form 1 crystals of compound (1), 50 parts of pyrethrum extract meal powder, 30 parts of Machilus thunbergii powder, and 19.8 parts of wood powder were mixed, an appropriate amount of water was added, kneaded, and then fed into an extruder to form a plate-like sheet, which was formed into a spiral shape using a punching machine to obtain a preparation.

[0212] Next, the efficacy of Form 1 crystals of compound (1) against harmful arthropods was illustrated by experiments. In the following experimental examples, the experiments were carried out at 25 °C.

[0213] Test method 1

[0214] The test compound was prepared into a preparation according to the method described in Preparation Example 1, and water containing 0.03% by volume of Shindain (registered trademark) was added thereto to prepare a dilution containing a specified concentration of the test compound.

[0215] About 30 cotton aphids (all stages) were inoculated onto cucumber (Cucumis sativus) seedlings (at the stage when the second true leaf was unfolded) planted in a container. One day later, the dilution was sprayed onto the seedlings at a ratio of 10 mL / seedling. Further, five days later, the number of surviving insects was investigated, and the control value was calculated from the following formula.

[0216] Control value (%) = {1 - (Cb × Tai) / (Cai × Tb)} × 100

[0217] It should be noted that the letters in the formula represent the following meanings.

[0218] Cb: Number of test insects in the untreated area

[0219] Cai: Number of surviving insects at the time of investigation in the untreated area

[0220] Tb: Number of test insects in the treated area

[0221] Tai: Number of surviving insects at the time of investigation in the treated area

[0222] Here, the untreated area refers to the area where the same operations as the treated area are carried out except that the test compound is not used.

[0223] Test example 1-1

[0224] When the specified concentration was 500 ppm and Form 1 crystals of compound (1) were used as the test compound, the test was carried out according to Test method 1. As a result, Form 1 crystals of compound (1) showed a control value of more than 90%.

[0225] Test method 2

[0226] The test compound was formulated according to the method described in Preparation Example 1, and water containing 0.03% by volume of Shindain (registered trademark) was added thereto to prepare a dilution containing the test compound at a specified concentration.

[0227] The dilution was sprayed onto cabbage (Brassicae oleracea) seedlings (at the stage where the second to third true leaves were unfolded) planted in containers at a rate of 20 mL / seedling. Then, the stem and leaf parts of the seedlings were cut and placed in a container lined with filter paper. Five second-instar larvae of Spodoptera litura were placed therein. After 5 days, the number of surviving insects was counted, and the mortality rate was calculated using the following formula.

[0228] Mortality rate (%) = (1 - number of surviving insects / 5) × 100

[0229] Test Example 2-1

[0230] The specified concentration was 500 ppm, and the type 1 crystal of compound (1) was used as the test compound. The test was conducted according to Test Method 2. As a result, the type 1 crystal of compound (1) showed a mortality rate of 80% or more.

[0231] Test Method 3

[0232] The test compound was formulated according to the method described in Preparation Example 1, and water was added thereto to prepare a dilution containing the test compound at a specified concentration.

[0233] The dilution was sprayed onto cabbage (Brassicae oleracea) seedlings (at the stage where the second to third true leaves were unfolded) planted in containers at a rate of 20 mL / seedling. Then, the stem and leaf parts of the seedlings were cut and placed in a container lined with filter paper. Five second-instar larvae of Plutella xylostella were placed therein. After 5 days, the number of surviving insects was counted, and the mortality rate was calculated using the following formula.

[0234] Mortality rate (%) = (1 - number of surviving insects / 5) × 100

[0235] Test Example 3-1

[0236] The specified concentration was 500 ppm, and the type 1 crystal of compound (1) was used as the test compound. The test was conducted according to Test Method 3. As a result, the type 1 crystal of compound (1) showed a mortality rate of 80% or more.

[0237] Test Method 4

[0238] The test compound was formulated according to the method described in Preparation Example 1, and water was added thereto to prepare a dilution containing the test compound at a specified concentration.

[0239] Put 30 final-instar larvae of Culex pipiens pallens into this diluent. After 1 day, investigate the state of the Culex pipiens pallens larvae and calculate the mortality rate. The mortality rate is calculated by the following formula.

[0240] Mortality rate (%) = (Number of dead insects / Number of test insects) × 100

[0241] Test Example 4-1

[0242] Make the specified concentration 3.5 ppm, use the type 1 crystal of Compound (1) as the test compound, and conduct the test according to Test Method 4. As a result, the type 1 crystal of Compound (1) showed a mortality rate exceeding 90%.

[0243] Test Method 5

[0244] Prepare the test compound into a preparation according to the method described in Preparation Example 1, add water containing 0.03% by volume of Shindain (registered trademark) thereto, and prepare a diluent containing the test compound at a specified concentration.

[0245] Spray this diluent onto rice (Oryza sativa) seedlings (at the stage when the second leaf is unfolded) planted in a container at a ratio of 10 mL / seedling. Then, put 20 third-instar larvae of Nilaparvata lugens. After 6 days, investigate the number of surviving insects, and calculate the mortality rate by the following formula.

[0246] Mortality rate (%) = {1 - Number of surviving insects / 20} × 100

[0247] Test Example 5-1

[0248] Make the specified concentration 500 ppm, use the type 1 crystal of Compound (1) as the test compound, and conduct the test according to Test Method 5. As a result, the type 1 crystal of Compound (1) showed a mortality rate of over 90%.

[0249] Test Method 6

[0250] Prepare the test compound into a preparation according to the method described in Preparation Example 1, add water containing 0.02% by volume of Shindain (registered trademark) thereto, and prepare a diluent containing the test compound at a specified concentration.

[0251] Only leave the second true leaf of cucumber (Cucumis sativus) seedlings (at the stage when the third true leaf is unfolded) planted in a container and cut off the other leaves. Spray this diluent onto the seedlings at a ratio of 10 mL / seedling. After the diluent has dried after treatment, use an artificial rainfall device to apply rainfall of 10 mm / h to the cucumber seedlings for 1 hour. After 1 day, inoculate 10 cotton aphids (female adults) onto the cucumber seedlings. Further, after 5 days, investigate the number of surviving insects, and calculate the control value by the following formula.

[0252] Control efficacy (%) = {1 - (Cb × Tai) / (Cai × Tb)} × 100

[0253] It should be noted that the words in the formula have the following meanings.

[0254] Cb: Number of test insects in the untreated area

[0255] Cai: Number of surviving insects at the time of investigation in the untreated area

[0256] Tb: Number of test insects in the treated area

[0257] Tai: Number of surviving insects at the time of investigation in the treated area

[0258] Here, the untreated area refers to the area where the same operations as the treated area are carried out except that the test compound is not used.

[0259] Test Example 6-1

[0260] Using the type 1 crystal of compound (1) and the amorphous form of compound (1) as test compounds at a specified concentration of 0.5 ppm, and conducting tests according to Test Method 6. As a result, the type 1 crystal of compound (1) showed a control efficacy of 55.7%. On the other hand, the amorphous form of compound (1) showed a control efficacy of 32.4%.

[0261] Test Method 7

[0262] Prepare a preparation of the test compound according to the method described in Formulation Example 1, add 1.8 g of sucrose, and add 3% sugar water thereto to prepare a dilution containing the test compound at a specified concentration.

[0263] Lay a filter paper of the same size on the inner bottom of a cup with a diameter of 5.5 cm, drop 0.7 mL of the dilution onto the filter paper, put 10 worker ants of Argentine ants into the cup, and cover the lid. After 6 days, investigate the number of dead and knockdown individuals of Argentine ants, and calculate the knockdown and death rate (%) from the following formula. It should be noted that a dead individual refers to an individual that has completely stopped moving, and a knockdown individual refers to an individual that cannot get up and walk when turned on its back.

[0264] Knockdown and death rate (%) = {(Number of dead individuals + Number of knockdown individuals) / Number of test insects} × 100

[0265] Test Example 7-1

[0266] Using the type 1 crystal of compound (1) and the amorphous form of compound (1) as test compounds at a specified concentration of 0.2 ppm, and conducting tests according to Test Method 7. As a result, the type 1 crystal of compound (1) showed a knockdown and death rate of 95%. On the other hand, the amorphous form of compound (1) showed a knockdown and death rate of 30%.

[0267] Test Method 8

[0268] The test compound was formulated according to the method described in Preparation Example 1, 1.8 g of sucrose was added, and 3% sucrose water was added thereto to prepare a dilution containing a predetermined concentration of the test compound.

[0269] A filter paper of the same size was laid on the inner bottom of a cup with a diameter of 5.5 cm, 0.7 mL of the dilution was dripped onto the filter paper, 10 small yellow house ant workers were placed in the cup, and the lid was closed. After 2 days, the number of deaths and knockdown individuals of the small yellow house ant workers was investigated, and the knockdown death rate (%) was calculated by the following formula. It should be noted that the dead individual refers to an individual that has completely stopped moving, and the knockdown individual refers to an individual that cannot get up and cannot walk if it is turned on its back.

[0270] Knockdown rate (%) = {(number of dead individuals + number of knockdown individuals) / number of test insects} × 100

[0271] Test Example 8-1

[0272] The test was conducted according to Test Method 8 using the type 1 crystal of compound (1) and the amorphous form of compound (1) as test compounds at a predetermined concentration of 0.05 ppm. As a result, the type 1 crystal of compound (1) showed a 100% knockdown rate. On the other hand, the amorphous form of compound (1) showed a 15% knockdown rate.

[0273] Test method 9

[0274] The test compound was formulated according to the method described in Preparation Example 1, 1.8 g of sucrose was added, and 3% sucrose water was added thereto to prepare a dilution containing a predetermined concentration of the test compound.

[0275] Filter paper of the same size was laid on the inner bottom of a cup with a diameter of 5.5 cm, 0.7 mL of the diluent was dripped onto the filter paper, 5 male adults of German cockroaches were placed in the cup, and the lid was closed. After 5 days, the death and knockdown individual numbers of male adults of German cockroaches were investigated, and the knockdown dead insect rate (%) was calculated by the following formula. It should be noted that the dead individual refers to the individual that completely stops moving, and the knockdown individual refers to the individual that cannot climb up and cannot walk if it is turned on its back.

[0276] Knockdown rate (%) = {(number of dead individuals + number of knockdown individuals) / number of test insects} × 100

[0277] Test Example 9-1

[0278] The specified concentration was made 0.2 ppm, and the type 1 crystal of compound (1) and the amorphous form of compound (1) were used as test compounds. The test was conducted according to Test Method 9. As a result, the type 1 crystal of compound (1) showed a knockdown kill rate of 100%. On the other hand, the amorphous form of compound (1) showed a knockdown kill rate of 0%.

[0279] Test Method 10

[0280] The test compound was formulated according to the method described in Formulation Example 1. 1.8 g of sucrose was added, and 3% sugar water was added thereto to prepare a dilution containing the test compound at the specified concentration.

[0281] A filter paper of the same size was placed on the inner bottom of a cup with a diameter of 5.5 cm, 0.7 mL of the dilution was dropped onto the filter paper, and 5 female adult Culex pipiens pallens were placed in the cup and covered with a lid. After 2 days, the number of dead and knockdown individuals of the female adult Culex pipiens pallens was investigated, and the knockdown kill rate (%) was calculated by the following formula. It should be noted that a dead individual refers to an individual that has completely stopped moving, and a knockdown individual refers to an individual that cannot fly and cannot walk.

[0282] Knockdown kill rate (%) = {(number of dead individuals + number of knockdown individuals) / number of test insects} × 100

[0283] Test Example 10-1

[0284] The specified concentration was made 0.8 ppm, and the type 1 crystal of compound (1) and the amorphous form of compound (1) were used as test compounds. The test was conducted according to Test Method 10. As a result, the type 1 crystal of compound (1) showed a knockdown kill rate of 100%. On the other hand, the amorphous form of compound (1) showed a knockdown kill rate of 20%.

[0285] Industrial Applicability

[0286] The type 1 crystal of compound (1) shows an excellent control effect against harmful arthropods.

Claims

Type 1 crystal, which is a type 1 crystal of 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole having diffraction peaks at 2θ = 8.5 ± 0.2°, 12.0 ± 0.2°, 15.0 ± 0.2°, 16.6 ± 0.2° and 20.9 ± 0.2° in powder X-ray diffraction based on Cu-Kα rays.

2. The type 1 crystal according to claim 1, wherein the lattice constants determined by single crystal X-ray diffraction are: [Mathematical formula 1] α = 90°, β = 111.683°, and γ = 90°.

3. The type 1 crystal according to claim 1 or claim 2, which has peaks at wavenumbers of 1313 ± 4 cm -1 , 1177 ± 4 cm -1 , 1141 ± 4 cm -1 , 1077 ± 4 cm -1 , 845 ± 4 cm -1 , 720 ± 4 cm -1 and 676 ± 4 cm -1 in the infrared absorption spectrum (ATR method).

4. The type 1 crystal according to any one of claims 1 to 3, having a melting point of 118 to 128 °C.

5. A method for producing the type 1 crystal according to any one of claims 1 to 4, comprising: dissolving 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole melted in the range of 52 °C to 61 °C in at least one solvent selected from the group consisting of hydrocarbons, alcohols and ethers, and performing crystallization by cooling the obtained solution.

6. A method for producing the type 1 crystal according to any one of claims 1 to 4, comprising: dissolving 2-(5-cyclopropyl-3-(ethylsulfonyl)pyridin-2-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole melted in the range of 52 °C to 61 °C in an aromatic compound solvent, and performing crystallization by mixing the obtained solution with an aliphatic hydrocarbon solvent.

7. A pest control composition, which contains the type 1 crystal according to any one of claims 1 to 4.

8. A composition, which contains one or more components selected from the group consisting of group (a), group (b), group (c) and group (d), and the type 1 crystal according to any one of claims 1 to 4, Group (a): a group consisting of an insecticidal active ingredient, a miticidal active ingredient and a nematicidal active ingredient; Group (b): a bactericidal active ingredient; Group (c): a plant growth regulating ingredient; Group (d): a repellent ingredient.

9. A method for controlling pests, which comprises applying an effective amount of the type 1 crystal according to any one of claims 1 to 4 or an effective amount of the pest control composition according to claim 7 to the pests or the habitats of the pests.

10. A seed or vegetative propagation organ, which retains an effective amount of the type 1 crystal according to any one of claims 1 to 4 or an effective amount of the composition according to claim 7.

11. Use of the type 1 crystal according to any one of claims 1 to 4 for controlling pests.

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