Crystal of 3-(difluoromethyl)-1-methyl-n-(1,1,3-trimethyl-2,3-dihydro-1h-inden-4-yl)-1h-pyrazole-4-carboxamide

Abstract

3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide in at least one crystal form selected from the group consisting of Ra1 form, Ra2 form, and Ra3 form, which respectively show the sets of diffraction peaks given in the description, in analysis by X-ray powder diffractometry with a Cu-Kα line.

Description

Crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide

[0001] The present invention relates to a novel crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide having plant disease control activity.

[0002] 3-(Difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide (hereinafter referred to as Compound A) is a crystal having a melting point of 131 to 134°C, and has been reported to exhibit control efficacy against plant diseases (Patent Document 1).

[0003] WO 92 / 12970

[0004] An object of the present invention is to provide a novel crystal that has physical properties different from those of the known crystal described in Patent Document 1 (hereinafter referred to as Ra4 type crystal) and has superior plant disease control efficacy.

[0005] The present inventors have discovered three novel crystals of Compound A (Ra1 crystal, Ra2 crystal, and Ra3 crystal) that have excellent control efficacy against plant diseases.

[0006] That is, the present invention is as follows: [1] 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, a Ra1 type crystal having diffraction peaks at 2θ=7.1±0.2°, 8.6±0.2°, 8.9±0.2°, 9.1±0.2°, 13.3±0.2°, 14.0±0.2°, 14.3±0.2°, 14.8±0.2°, 16.0±0.2°, 16.4±0.2°, 20.3±0.2°, and 20.6±0.2° in powder X-ray diffraction using Cu-Kα radiation; Ra2 type crystals having diffraction peaks at 2θ=4.3±0.2°, 8.5±0.2°, 10.8±0.2°, 11.4±0.2°, 12.4±0.2°, 12.8±0.2°, 15.1±0.2°, 16.1±0.2°, 16.8±0.2°, and 19.1±0.2° in powder X-ray diffraction using Cu-Kα radiation; and and Ra3 type crystals having diffraction peaks at 2θ = 3.6 ± 0.2°, 7.1 ± 0.2°, 7.4 ± 0.2°, 9.6 ± 0.2°, 11.9 ± 0.2°, 12.5 ± 0.2°, 12.9 ± 0.2°, 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation. [2] In the 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to [1], a Ra1 type crystal having diffraction peaks at 2θ = 7.1 ± 0.2 °, 8.6 ± 0.2 °, 8.9 ± 0.2 °, 9.1 ± 0.2 °, 13.3 ± 0.2 °, 14.0 ± 0.2 °, 14.3 ± 0.2 °, 14.8 ± 0.2 °, 16.0 ± 0.2 °, 16.4 ± 0.2 °, 20.3 ± 0.2 °, and 20.6 ± 0.2 ° in powder X-ray diffraction using Cu-Kα radiation.[3] The 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to [1] has Ra2-type crystals with diffraction peaks at 2θ = 4.3 ± 0.2 °, 8.5 ± 0.2 °, 10.8 ± 0.2 °, 11.4 ± 0.2 °, 12.4 ± 0.2 °, 12.8 ± 0.2 °, 15.1 ± 0.2 °, 16.1 ± 0.2 °, 16.8 ± 0.2 °, and 19.1 ± 0.2 ° in powder X-ray diffraction using Cu-Kα radiation. [4] The 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to [1], having diffraction peaks at 2θ = 3.6 ± 0.2 °, 7.1 ± 0.2 °, 7.4 ± 0.2 °, 9.6 ± 0.2 °, 11.9 ± 0.2 °, 12.5 ± 0.2 °, 12.9 ± 0.2 °, 14.3 ± 0.2 °, 15.7 ± 0.2 °, and 17.9 ± 0.2 ° in powder X-ray diffraction using Cu-Kα radiation. [5] A plant disease control composition comprising one or more crystals according to any one of [1] to [4]. [6] A method for controlling plant diseases, comprising applying an effective amount of one or more crystals according to any one of [1] to [4] to a plant or soil in which the plant grows. [7] Use of one or more crystals according to any one of [1] to [4] for controlling plant diseases. [8] A composition containing one or more components selected from the group consisting of Group (a), Group (b), Group (c), and Group (d) and one or more crystals according to any one of [1] to [4]: ​​Group (a): a group consisting of insecticidal active ingredients, acaricidal active ingredients, and nematicidal active ingredients; Group (b): fungicidal active ingredients; Group (c): plant growth regulator ingredients; Group (d): repellent ingredients. [9] A seed or vegetative reproductive organ holding an effective amount of one or more crystals according to any one of [1] to [4] or the composition according to [7].

[0007] The present invention provides three novel crystals of Compound A (Ra1 crystal, Ra2 crystal, and Ra3 crystal) that exhibit plant disease control efficacy. These crystals exhibit superior plant disease control efficacy to the known Ra4 crystal.

[0008] 1 is a diagram showing the powder X-ray diffraction pattern of the Ra1 type crystal. The vertical axis represents diffraction intensity (unit: cps), and the horizontal axis represents diffraction angle 2θ (unit: °). 2 is a diagram showing the powder X-ray diffraction pattern of the Ra2 type crystal. The vertical axis represents diffraction intensity (unit: cps), and the horizontal axis represents diffraction angle 2θ (unit: °). 3 is a diagram showing the powder X-ray diffraction pattern of the Ra3 type crystal. The vertical axis represents diffraction intensity (unit: cps), and the horizontal axis represents diffraction angle 2θ (unit: °). 4 is a diagram showing the powder X-ray diffraction pattern of the Ra4 type crystal. The vertical axis represents diffraction intensity (unit: cps), and the horizontal axis represents diffraction angle 2θ (unit: °). 5 is a diagram showing molecular packing in the crystal lattice of the Ra1 type crystal. 6 is a diagram showing molecular packing in the crystal lattice of the Ra2 type crystal. 7 is a diagram showing molecular packing in the crystal lattice of the Ra3 type crystal. 1 is a diagram showing a differential scanning calorimetry (DSC) curve of a Ra1 type crystal. The vertical axis represents heat flow (unit: W / g), and the horizontal axis represents temperature (unit: ° C). 2 is a diagram showing a differential scanning calorimetry (DSC) curve of a Ra2 type crystal. 3 is a diagram showing a differential scanning calorimetry (DSC) curve of a Ra3 type crystal. 4 is a diagram showing a differential scanning calorimetry (DSC) curve of a Ra4 type crystal. 5 is a diagram showing an infrared spectrum of a Ra1 type crystal. The vertical axis represents transmittance, and the horizontal axis represents the wave number of the irradiated infrared ray. 6 is a diagram showing an infrared spectrum of a Ra2 type crystal. The vertical axis represents transmittance, and the horizontal axis represents the wave number of the irradiated infrared ray. 7 is a diagram showing an infrared spectrum of a Ra3 type crystal. The vertical axis represents transmittance, and the horizontal axis represents the wave number of the irradiated infrared ray. 8 is a diagram showing an infrared spectrum of a Ra4 type crystal. The vertical axis represents transmittance, and the horizontal axis represents the wave number of the irradiated infrared ray. FIG. 1 is a diagram showing a spectrum diagram of the Raman spectrum of an Ra1 type crystal. The vertical axis represents intensity, and the horizontal axis represents Raman shift number. FIG. 2 is a diagram showing a spectrum diagram of the Raman spectrum of an Ra2 type crystal. The vertical axis represents intensity, and the horizontal axis represents Raman shift number. FIG. 3 is a diagram showing a spectrum diagram of the Raman spectrum of an Ra3 type crystal. The vertical axis represents intensity, and the horizontal axis represents Raman shift number. FIG. 4 is a diagram showing a spectrum diagram of the Raman spectrum of an Ra4 type crystal. The vertical axis represents intensity, and the horizontal axis represents Raman shift number. FIG. 5 is a diagram showing an optical microscope photograph of an Ra1 type crystal. FIG. 6 is a diagram showing an optical microscope photograph of an Ra2 type crystal.1 shows optical microscope photographs of Ra3 type crystals and Ra4 type crystals.

[0009] The present invention relates to novel crystals of Compound A (Ra1 crystals, Ra2 crystals, and Ra3 crystals). 3-(Difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide is a compound having two enantiomers, the R- and S-forms, and Compound A is an equal mixture thereof, i.e., a racemate. The crystals of the present invention are those in which equal amounts of the R- and S-forms are regularly arranged in a crystal lattice, and depending on the production conditions, they become Ra1 crystals, Ra2 crystals, or Ra3 crystals, respectively.

[0010] The Ra4 type crystal has a melting point of approximately 131 to 134°C, and in a powder X-ray diffraction pattern using Cu-Kα radiation, the diffraction peaks at 2θ values ​​(°) include 5.8±0.2, 7.2±0.2, 8.6±0.2, 13.8±0.2, 16.3±0.2, 16.7±0.2, 17.4±0.2, 17.7±0.2, 19.4±0.2, 19.8±0.2, and 20.7±0.2.

[0011] The Ra1 type crystal, the Ra2 type crystal, and the Ra3 type crystal each have the following physical properties: The Ra1 type crystal has a melting point of approximately 134 to 136°C, and in a powder X-ray diffraction pattern using Cu-Kα radiation, the following diffraction peaks at 2θ values ​​(°) are present: 7.1±0.2, 8.6±0.2, 8.9±0.2, 9.1±0.2, 13.3±0.2, 14.0±0.2, 14.3±0.2, 14.8±0.2, 16.0±0.2, 16.4±0.2, 20.3±0.2, and 20.6±0.2.

[0012] The Ra1 type crystal can be produced according to the following production method: A required amount (for example, about 200 mg) of the Ra2 type crystal is heated in an appropriate container (for example, a 20 mL sample bottle) at about 130°C for a certain period of time (about 2 hours) to obtain the Ra1 type crystal.

[0013] The Ra2 type crystal is a crystal having a melting point of approximately 124 to 126°C, and in a powder X-ray diffraction pattern using Cu-Kα radiation, the diffraction peaks at 2θ values ​​(°) are 4.3±0.2, 8.5±0.2, 10.8±0.2, 11.4±0.2, 12.4±0.2, 12.8±0.2, 15.1±0.2, 16.1±0.2, 16.8±0.2, and 19.1±0.2.

[0014] The Ra2 type crystal can be produced according to the following production method. A required amount (for example, about 30 mg) of compound A is dissolved in an appropriate amount (about 80 μL) of an organic solvent (for example, methanol) at about 60° C. to prepare a certain dissolved concentration (about 375 mg / mL). After cooling the solution to room temperature, a laser is irradiated under certain conditions, and the solution is allowed to stand at about 20° C. to obtain the Ra2 type crystal. The laser irradiation conditions are as follows, but are not limited thereto. <Femtosecond laser> Wavelength: 800 nm Pulse width: 181 fs Number of pulses: 125 pulses / 10 seconds

[0015] The organic solvent may be, for example, an alcohol solvent, preferably an alkyl solvent having 1 to 3 carbon atoms, specifically methanol, ethanol, propanol, and isopropanol, with methanol being preferred.

[0016] The amount of organic solvent is, for example, an amount that achieves a dissolution concentration of about 200 mg / mL to about 1000 mg / mL relative to the organic solvent used when Compound A is dissolved. The dissolution concentration is preferably about 300 mg / L to about 500 mg / mL, for example, about 375 mg / mL.

[0017] The Ra3 type crystal is a crystal having a melting point of approximately 129 to 131°C, and in a powder X-ray diffraction pattern using Cu-Kα radiation, the diffraction peaks at 2θ values ​​(°) are 3.6±0.2, 7.1±0.2, 7.4±0.2, 9.6±0.2, 11.9±0.2, 12.5±0.2, 12.9±0.2, 14.3±0.2, 15.7±0.2, and 17.9±0.2.

[0018] The Ra3 type crystals can be produced according to the following production method: To a required amount (for example, about 100 mg) of the Ra1 type crystals produced above, an appropriate amount (for example, about 1 mL) of an organic solvent is added, and the resulting suspension is heated to about 60°C and stirred under certain conditions (about 1000 rpm) for a certain time (about 2 days), and then the solvent is removed to obtain the Ra3 type crystals.

[0019] The organic solvent may be, for example, an ether solvent, preferably a dialkyl ether solvent consisting of an alkyl group having 1 to 3 carbon atoms. Specific examples include dimethyl ether, diethyl ether, dipropyl ether, and diisopropyl ether, with diisopropyl ether being preferred.

[0020] The amount of the organic solvent is in the range of 5 to 10 parts by weight, preferably 6 to 8 parts by weight, per part by weight of the Ra1 type crystal used.

[0021] One or more crystals selected from the group consisting of Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals can be mixed or used in combination with one or more components selected from the group consisting of the following groups (a), (b), (c), and (d) (hereinafter referred to as the present component). The mixed or used in combination means that one or more crystals selected from the group consisting of Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals and the present component are used simultaneously, separately, or at intervals. When one or more crystals selected from the group consisting of Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals are used simultaneously with the present component, the one or more crystals selected from the group consisting of Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals and the present component may each be contained in separate preparations, or may be contained in a single preparation. One aspect of the present invention is a composition (hereinafter referred to as the composition of the present invention) containing one or more components selected from the group consisting of group (a), group (b), group (c), and group (d), and one or more crystals selected from the group consisting of Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals.

[0022] Group (a) includes acetylcholinesterase inhibitors (e.g., carbamate insecticides, organophosphate insecticides), GABAergic chloride channel antagonists (e.g., phenylpyrazole insecticides), sodium channel modulators (e.g., pyrethroid insecticides), nicotinic acetylcholine receptor antagonistic modulators (e.g., neonicotinoid insecticides), nicotinic acetylcholine receptor allosteric modulators, glutamatergic chloride channel allosteric modulators (e.g., macrolide insecticides), juvenile hormone mimics, multisite inhibitors, chordotonal organ TRPV channel modulators, mite growth inhibitors, mitochondrial ATP biosynthesis enzyme inhibitors, oxidative phosphorylation uncouplers, nicotinic acetylcholine receptor channel blockers (e.g., nereistoxin insecticides), chitin synthesis inhibitors, molting inhibitors, ecdysone receptor agonists, octopamine receptor agonists, mitochondrial electron transport chain complex I, II, The group consisting of inhibitors of Class III and IV, voltage-dependent sodium channel blockers, acetyl-CoA carboxylase inhibitors, ryanodine receptor modulators (e.g., diamide insecticides), chordotonal organ modulators, active ingredients of microbial insecticides, and other insecticidal, acaricidal, and nematicidal active ingredients, which are described in the IRAC classification based on their mechanism of action.

[0023] Group (b) consists of nucleic acid synthesis inhibitors (e.g., phenylamide fungicides, acylamino 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 synthesis inhibitors, melanin synthesis inhibitors, plant defense inducers, multisite contact-active fungicides, microbial fungicides, and other fungicidal active ingredients. These are listed in the FRAC classification based on the mechanism of action.

[0024] Group (c) is a group of plant growth regulators (including mycorrhizal fungi and rhizobia).

[0025] Group (d) is a group of repellent components consisting of bird repellent components and insect repellent components.

[0026] Below are examples of combinations of the present ingredient with one or more crystals selected from the group consisting of Ra1 crystals, Ra2 crystals, and Ra3 crystals. For example, alanycarb + SX refers to a combination of alanycarb and SX. The abbreviation SX refers to Ra1 crystals, Ra2 crystals, or Ra3 crystals (hereinafter referred to as the crystals of the present invention). The present ingredients described below are all known ingredients and can be obtained from commercially available preparations or produced by known methods. When the present ingredient is a microorganism, it can also be obtained from a bacterial depository. The number in parentheses represents the CAS RN (registered trademark).

[0027] Combinations of the present ingredient of group (a) above with the crystal of the present invention: abamectin + SX, acephate + SX, acequinocyl + SX, acetamiprid + SX, acetoprole + SX, acrinathrin + SX, acinonapyr + SX, afidopyropen + SX, afoxolaner + SX, alanycarb + SX, aldicarb + SX, allethrin + SX, alpha-cypermethrin + SX, alpha-endosulfan + SX, aluminum phosphide + SX, Amitraz + SX, azadirachtin + SX, azamethiphos + SX, azinphos-ethyl + SX, azinphos-methyl + SX, azocyclotin + SX, Celastrus angulatus bark + 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 phosphide + SX, carbaryl + SX, carbofuran + SX, carbosulfan + SX, cartap hydrochloride + SX, cartap + SX Chinomethionate + 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, concanamycin A A) + SX, coumaphos + SX, cryolite + SX, cyanophos + SX, cyantraniliprole + SX,Cyclaniliprole + SX, cycloprothrin + SX, cycloxaprid + SX, cyenopyrafen + SX, cyflumetofen + SX, cyfluthrin + SX, cyhalodiamide + SX, cyhalothrin + SX, cyhexatin + SX, cypermethrin + SX, cyphenothrin + SX, cyromazine + SX, dazomet + SX, deltamethrin + SX, demeton-S-methyl + SX, Diafenthiuron + SX, diazinon + SX, dichlorvos + SX, dichloromezotiaz + 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 Dryopteris filix (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, ethifencarb + SX, ethion + SX, ethiprole + SX, ethoprophos + SX, etofenprox + SX, etoxazole + SX, Artemisia absinthium extract + SX, Cassia nigricans extract nigricans + SX, Clitoria ternatea extract + SX, Symphytum officinale extract + SX, Chenopodium ambrosioides extract (extracts or simulated blend of Chenopodium ambrosioides) + SX, Tansy extract (Tanacetum vulgare extract) + SX, Urtica dioica extract (Urtica dioica extract) + SX, Viscum album extract (Viscum album extract) + SX, famphur + SX, fenamiphos + SX, fenazaquin + SX, fenbutatin oxide + SX, fenitrothion + 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, flucycloxuron + SX, flucythrinate + SX, fluensulfone + SX, flufenprox + SX, Flufenoxuron + SX, flufiprole + SX, flumethrin + SX, flupyradifurone + SX, flupyrimin + 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 beta acid + SX, hydramethylnon + SX, hydroprene + SX, imicyafos + SX, imidacloprid + SX, imidaclothiz + SX, imiprothrin + 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, 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, milbemycin oxime + SX, momfluorothrin + SX, monocrotophos + SX, moxidectin + SX, naled + SX, neem oil + SX, Nicotine + SX, nicotine sulfate + SX, nitenpyram + SX, novaluron + SX, noviflumuron + SX, Chenopodium anthelminticum seed oil + 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 glycol alginate + 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, ryanodine + SX, sarolaner + SX, selamectin + SX, sigma-cypermethrin + SX, silafluofen + SX, sodium borate + SX, sodium metaborate metaborate + SX, spinetoram + SX, spinosad + SX, spirodiclofen + SX, spiromesifen + SX,Spiropidione + SX, spirotetramat + 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 SX, terbufos + SX, terpene constituents of the extract of chenopodium ambrosioides near ambrosioides + 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 salt + SX, tioxazafen + SX, tolfenpyrad + SX, tralomethrin + SX, transfluthrin + SX, triazamate + SX, triazophos + SX, trichlorfon + SX, triflumezopyrim + SX, triflumuron + SX, trimethacarb + SX, tyclopyrazoflor + SX, vamidothion + SX, Quassia amara wood extract + SX, XMC (3,5-dimethylphenyl N-methylcarbamate + SX, xylylcarb + SX, zeta-cypermethrin + SX, zinc phosphide + 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}indan-1-yl)propanamide (1118626-57-5) + SX, 2-chloro-4-fluoro-5-{[5-(trifluoromethylthio)pentyl]oxy}phenyl 2,2,2-trifluoroethyl sulfoxide (1472050-04-6) + SX, 4-chloro-5-[2,2-difluoro-2-(3,4,2-methylphenyl 2,2,2-trifluoroethyl sulfoxide (1632218-00-8) + SX, 4-fluoro-5-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-methylphenyl 2,2,2-trifluoroethyl sulfoxide (1632217-98-1) + SX, 2-({2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (1445683-71-5) + SX, (1Z)-2-(4-tert-butylphenyl)-2-cyano-1-(1-ethyl-3-methyl-1H-pyrazol-5-yl)ethenyl 2,2-dimethylpropanoate (1253429-01-4) + SX, N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (1644251-74-0) + SX, (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate (2249718-27-0) + SX, BT crop protein Cry1Ab (BT crop protein Cry1Ab) + SX, BT crop protein Cry1Ac (BT crop protein Cry1Ac) + SX, BT crop protein Cry1Fa (BT crop protein Cry1Fa) + SX, BT crop protein Cry1A.105 + SX, BT crop protein Cry2Ab + SX,BT crop protein Vip3A + SX, BT crop protein Cry3A + SX, BT crop protein Cry3Ab + SX, BT crop protein Cry3Bb + SX, BT crop protein Cry34Ab1 / Cry35Ab1 + SX, Adoxophyes orana granulosis virus strain BV-0001 + SX, Anticarsia gemmatalis mNPV + SX, Autographa californica mNPV + SX, Cydia pomonella granulosis virus V15 (GV strain V15) + SX, Cydia pomonella granulosis virus V22 (GV strain V22) + SX, Cryptophlebia leucotreta granulosis virus (GV) + SX, Dendrolimus punctatus cypovirus (Dendrolimus punctatus cypovirus) + SX, Helicoverpa armigera NPV strain BV-0003 + SX, Helicoverpa zea NPV (NPV) + SX, Lymantria dispar NPV (NPV) + SX Mamestra brassicae NPV + SX, Mamestra configurata NPV + SX,Neodiprion abietis nucleopolyhedrosis virus (NPV) + SX, Neodiprion lecontei nucleopolyhedrosis virus (NPV) + SX, Neodiprion sertifer nucleopolyhedrosis virus (NPV) + SX, Nosema locustae + SX, Orgyia pseudotsugata nucleopolyhedrosis virus (NPV) + SX, Pieris rapae granulosis virus (GV) + SX, Plodia interpunctella granulosis virus (GV) + SX, Spodoptera exigua nucleopolyhedrosis virus (NPV) + SX, Spodoptera littoralis mNPV + SX, Spodoptera littoralis NPV + SX, Arthrobotrys dactyloides + SX, Bacillus firmus strain GB-126 + SX, Bacillus firmus strain I-1582 + SX, Bacillus megaterium + SX, Bacillus sp. strain AQ175 + SX, Bacillus sp. strain AQ177 + SX, Bacillus sp. strain AQ178 + SX, Bacillus sphaericus strain 2362 + SX, Bacillus sphaericus strain ABTS1743 + SX, Bacillus sphaericus Serotype strain H5a5b + 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 Serotype strain H-7 + SX, Bacillus thuringiensis subsp. Kurstaki strain ABTS351 + SX, Bacillus thuringiensis subsp. Kurstaki strain BMP123 + SX, Bacillus thuringiensis subsp. Kurstaki strain EG234 + 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. 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 + SX, Beauveria bassiana strain ANT-03 + SX, Beauveria bassiana strain ATCC74040 + SX, Beauveria bassiana strain GHA + SX, Beauveria brongniartii + SX, Burkholderia rinogensis strain A396 + SX, Chromobacterium subtsugae strain PRAA4-1T + SX, Dactyllela ellipsospora + SX, Dactylaria 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 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 thoynei + SX, Serratia entomophila + SX, Verticillium chlamydosporium + SX, Verticillium lecani strain NCIM1312 + SX, 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylpyridine-3-carboxamide (1771741-86-6) + SX,N-{4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl}-1-methyl-4-(methanesulfonyl)-3-(1,1,2,2,2-pentafluoroethyl)-1H-pyrazole-3-carboxamide (1400768-21-9) + SX, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one (907187-07-9) + SX, 3-(4'-fluoro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one (1031385-91-7) + SX, N-[3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl]-2-(methanesulfonyl)propanamide (2396747-83-2) + SX, 2-isopropyl-5-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]-1,3,4-thiadiazole (2058052-95-0) + SX, 1,4-dimethyl-2-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,2,4-triazolidine-3,5-dione (2171099-09-3) + SX, シプロフラニリド(cyproflanilide) + SX。,

[0028] Combinations of the present component of the above group (b) with the crystal of the present invention: 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, chinomethionate + SX, chitin + SX, chloroneb + ​​SX, chlorothalonil + SX,Chlozolinate + SX, colletochlorin B + 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 hydrogenphosphite + 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, tea tree extract (from Melaleuca alternifolia) + SX, Japanese knotweed extract (from Reynoutria sachalinensis) + SX, lupine seedling cotyledon extract (BLAD) + SX, garlic extract (from Allium sativum) + SX, horsetail extract (from Equisetum arvense) arvense + SX, nasturtium extract (Tropaeolus majus) + SX, famoxadone + SX, fenamidone + SX, fenaminstrobin + SX, fenarimol + SX, fenbuconazole + SX, fenfuram + SX, fenhexamid + SX, fenoxanil + SX, fenpiclonil + SX, fenpicoxamid + SX, fenpropidin + SX, fenpropimorph + SX, fenpyrazamine + SX, Triphenyltin acetate (fentin acetate) + SX, Triphenyltin chloride (fentin chloride) + SX,Fentin hydroxide + SX, ferbam + SX, ferimzone + SX, florylpicoxamid + SX, fluazinam + SX, fludioxonil + SX, flufenoxystrobin + SX, fluindapyr + SX, flumorph + SX, fluopicolide + SX, fluopyram + SX, fluopimomide + SX, fluoroimide + SX, fluoxapiprolin + SX, fluoxastrobin + SX, Fluquinconazole + SX, flusilazole + SX, flusulfamide + SX, flutianil + SX, flutolanil + SX, flutriafol + SX, fluxapyroxad + SX, folpet + SX, fosetyl + SX, fosetylaluminium + SX, fuberidazole + SX, furalaxyl + SX, furametpyr + SX, guazatine + SX, hexaconazole + SX, hymexazole + SX Imazalil + SX, imibenconazole + SX, iminoctadine + SX, iminoctadine triacetate + SX, inpyrfluxam + SX,Iodocarb + SX, Ipconazole + SX, Ipfentrifluconazole + SX, Ipflufenoquin + SX, Iprobenfos + SX, Iprodione + SX, Iprovalicarb + SX, Isofetamide + SX, Isofleucine + SX, Isoflucypram + SX, Isoprothiolane + SX, Isopyrazam + SX, Isotianil + SX, Kasugamycin + SX, Kresoxim-methyl + SX, Laminarin + SX, Oak Leaves and Bark Quercus bark + SX, mancozeb + SX, mandestrobin + SX, mandipropamid + SX, maneb + ​​SX, mefentrifluconazole + SX, mepanipyrim + SX, mepronil + SX, meptyldinocap + SX, metalaxyl + SX, metalaxyl-M + SX, metconazole + SX, methasulfocarb + SX, metiram + SX, metominostrobin + SX Metrafenone + SX, metyltetraprole + SX, mineral oils + 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 fumarate + 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, pyridaclomethyl + SX, pyrifenox + SX, pyrimethanil + SX, pyrimorph + SX, pyriophenone + SX, Pyrisoxazole + SX, pyroquilon + SX, Quillaja extract + SX, quinconazole + SX, quinofumelin + SX, quinoxyfen + SX, quintozene + SX, quinoa saponins + 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, mustard powder + SX, zinc thiazole + SX, zineb + ​​SX, ziram + SX, zoxamide + SX, N'-[4-({3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl}oxy)-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide (1202781-91-6) + SX, N'-{4-[(4,5-dichlorothiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylmethanimidamide (929908-57-6) + SX, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylmethanimidamide (1052688-31-9) + SX, N'-[5-choro-4-(2-fluorophenoxy)-2-methylphenyl)-N-ethyl-N-methylmethanimidamide (2055589-28-9) + SX, N'-[2-choro-4-(2-fluorophenoxy)-5-methylphenyl)-N-ethyl-N-methylmethanimidamide (2055756-21-1) + SX, N'-[4-(1-hydroxy-1-phenyl-2,2,2-trifluoroethyl)-2- methyl-5-methoxyphenyl)-N-isopropyl-N-methylmethanimidamide (2101814-55-3) + SX, N'-[5-bromo-6-(1-methyl-2-propoxyethoxy)-2-methylpyridin-3-yl)-N-ethyl-N-methylmethanimidamide (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, 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one (1616664-98-2) + SX, ethyl (2Z)-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) + SX, (1R, 2S, 5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-06-2) + SX, (1S, 2R, 5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-07-3) + SX, 2-(chloromethyl)-5-(4-fluorobenzyl)-2-methyl-1-(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)cyclopentan-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, 4-({6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propyl]pyridin-3-yl}oxy)benzonitrile (2046300-61-0) + 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, 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)isoxazolidin-3-one (2098918-25-1) + SX, 5,5-dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one (2098918-26-2) + SX, Agrobacterium radiobactor strain K1026 + SX, Agrobacterium radiobactor strain K84 + SX, Bacillus amyloliquefaciens (Aveo(TM) 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 strain isolate strain B246 + SX, Bacillus amyloliquefaciens strain F727 + 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 + 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 + 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, Pseudomonas fluorescens strain G7090 + SX, Pseudomonas sp. strain CAB-02 + SX, Pseudomonas syringae strain 742RS + SX, Pseudomonas syringae strain MA-4 + SX, Pseudozyma flocculosa strain PF-A22UL + 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 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 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, フルベネテラム(flubeneteram) + SX, N-acetyl-2-(ethanesulfonyl)-N-[2-(methoxycarbonyl)-4-(trifluoromethoxy)phenyl]-4-(trifluoromethyl)benzamide (2043675-28-9) + SX, (2S,3S)-3-(2-methylphenyl)butan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate (2376210-00-1) + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)butan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate (2376209-13-9) + SX, (2S,3S)-3-(2-methylphenyl)butan-2-yl N-({3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate (2376210-02-3) + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-({3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2-yl N-({3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate (2376209-40-2) + SX, (2S,3S)-3-(2,4-dimethylphenyl)butan-2-yl N-({3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate (2376209-15-1) + SX, N'-(2-choro-4-phenoxy-5-methylphenyl)-N-ethyl-N-methylmethanimidamide (2062599-39-5) + SX, (2S,3S)-3-(2-methylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-difluorophenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2 -methoxylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2,4-difluorophenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methoxylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(2,4-difluorophenyl)-4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methoxylphenyl)-4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-difluorophenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methoxylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX。,

[0029] Combination of the present component of group (c) above with the crystal of the present invention: 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, 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, choline chloride + SX, cloprop + SX, cyanamide + SX, cyclanilide + SX Daminozide + SX,Decane-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, gibberellin A3 + SX, inabenfide + SX, kinetin + SX, lipochitooligosaccharide SP104 + SX, maleic hydrazide + SX, mefluidide + SX, mepiquat chloride + SX, oxidized glutathione + SX, paclobutrazol + SX, pendimethalin + SX, prohexandione calcium + SX, prohydrojasmon + SX, pyraflufen-ethyl + SX, sintophen + SX, sodium 1-naphthaleneacetate + SX, sodium cyanate + SX, streptomycin + 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]-1-propanol + SX, Claroideoglomus etunicatum + 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 RTI-801 + SX, Rhizophagus irregularis DAOM 197198 + SX, Azorhizobium caulinodans + SX, Azospirillum amazonense + SX, Azospirillum brasilense XOH + SX, Azospirillum brasilense Ab-V5 + SX, Azospirillum brasilense Ab-V6 + SX, Azospirillum caulinodans + SX, Azospirillum halopraeferens + SX, Azospirillum irakense + SX, Azospirillum lipoferum + SX, Bradyrhizobium elkanii SEMIA 587 + SX, Bradyrhizobium elkanii SEMIA 5019 + SX, Bradyrhizobium japonicum TA-11 + SX,Bradyrhizobium japonicum USDA 110 + SX, Bradyrhizobium liaoningense + SX, Bradyrhizobium lupini + SX, Delftia acidovorans RAY209 + SX, Mesorhizobium ciceri + SX, Mesorhizobium huakii + 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. ,

[0030] Combinations of the present component of the above group (d) with the crystal of the present invention: anthraquinone + SX, deet + SX, icaridin + SX.

[0031] The ratio of the crystal of the present invention to the present component is not particularly limited, and examples thereof include a weight ratio (crystal of the present invention:present component) of 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, and the like.

[0032] The crystal of the present invention can be mixed with or used in combination with chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.).

[0033] The crystals or compositions of the present invention can control plant diseases caused by plant pathogenic microorganisms such as fungi, oomycetes, Phytomyxea, and bacteria. Examples of fungi include Ascomycota, Basidiomycota, Blasocladiomycota, Chytridiomycota, Mucoromycota, and Olpidiomycota. Plant diseases include the following. The scientific name of the plant pathogenic microorganism that causes the disease is shown in parentheses.

[0034] Rice diseases: blast (Pyricularia oryzae), brown spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), bakanae disease (Gibberella fujikuroi), yellow dwarf disease (Sclerophthora macrospora), stunt and ear blight (Epicoccum nigrum), damping-off (Trichoderma viride, Rhizopus oryzae); wheat diseases: powdery mildew (Blumeria graminis), head blight (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), red rust (Puccinia recondita), pink snow rot (Microdochium nivale, Microdochium majus), snow rot small-grain sclerotide (Typhula incarnata, Typhula ishikariensis), bare smut (Ustilago tritici), tilletia smut (Tilletia caries, Tilletia controversa), eye spot disease (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), bacterial blight (Stagonospora) nodorum), yellow spot (Pyrenophora tritici-repentis), seedling damping off caused by Rhizoctonia fungi (Rhizoctonia solani), damping off (Gaeumannomyces graminis), rice blast (Pyricularia graminis-tritici);Barley diseases: powdery mildew (Blumeria graminis), head blight (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), small rust (Puccinia hordei), ear bunt (Ustilago nuda), scald (Rhynchosporium secalis), net blotch (Pyrenophora teres), leaf spot (Cochliobolus sativus), leaf spot (Pyrenophora graminea), leaf spot (Ramularia collo-cygni), seedling damping-off (Rhizoctonia solani); corn diseases: rust (Puccinia sorghi), southern rust (Puccinia polysora), Setosphaeria blight (Setosphaeria turcica), tropical rust (Physopella zeae), whole-leaved leaf blight (Cochliobolus heterostrophus), anthracnose (Colletotrichum graminicola), gray leaf spot (Cercospora zeae-maydis), brown spot (Kabatiella zeae), Phaeosphaeria leaf spot (Phaeosphaeria maydis), Diplodia disease (Stenocarpella maydis, Stenocarpella macrospora), stalk rot (Fusarium graminearum, Fusarium verticilioides, Colletotrichum graminicola), smut (Ustilago maydis), Physoderma maydis; cotton diseases: anthracnose (Colletotrichum gossypii), white mold (Ramularia areola), black spot (Alternaria macrospora, Alternaria gossypii), Black root rot (Thielaviopsis basicola);Coffee diseases: rust (Hemileia vastatrix), leaf spot (Cercospora coffeicola); rapeseed diseases: sclerotinia sclerotiorum, black spot (Alternaria brassicae), root rot (Phoma lingam), light leaf spot (Pyrenopeziza brassicae); sugarcane diseases: rust (Puccinia melanocephela, Puccinia kuehnii), smut (Ustilago scitaminea); sunflower diseases: rust (Puccinia helianthi), downy mildew (Plasmopara halstedii); citrus diseases: black spot (Diaporthe citri), scab (Elsinoe fawcetti), green mold (Penicillium digitatum), blue mold (Penicillium italicum), late blight (Phytophthora parasitica, Phytophthora citrophthora), Aspergillus niger; Apple diseases: Monilinia mali, canker (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), leaf spot (Alternaria alternata apple pathotype), scab (Venturia inaequalis), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), ring spot (Botryosphaeria berengeriana), late blight (Phytophtora cactorum), red spot (Gymnosporangium juniperi-virginianae, Gymnosporangium yamadae);Pear diseases: black spot (Venturia nashicola, Venturia pirina), black spot (Alternaria alternata Japanese pear pathotype), red spot (Gymnosporangium haraeanum); peach diseases: brown spot (Monilinia fructicola), black spot (Cladosporium carpophilum), phomopsis rot (Phomopsis sp.), leaf crinkle (Taphrina deformans); grape diseases: black rot (Elsinoe ampelina), late rot (Glomerella cingulata, Colletotrichum acutatum), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), downy mildew (Plasmopara viticola); persimmon diseases: anthracnose (Gloeosporium kaki, Colletotrichum acutatum), leaf drop (Cercospora kaki, Mycosphaerella nawae); Fig diseases: rust (Phakopsora nishidana); Cucurbit diseases: anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), vine blight (Didymella bryoniae), brown spot (Corynespora cassiicola), vine wilt (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), late blight (Phytophthora capsici), seedling damping-off (Pythium sp.); Tomato diseases: ring spot (Alternaria solani), leaf mold (Cladosporium fulvum), leaf mold (Pseudocercospora fuligena), late blight (Phytophthora infestans), powdery mildew (Leveillula taurica); Eggplant diseases: brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum);Diseases of cruciferous vegetables: black spot (Alternaria japonica), white spot (Cercosporella brassicae), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica), white rust (Albugo candida); diseases of leeks: rust (Puccinia allii); diseases of soybeans: purple spot (Cercospora kikuchii), black rot (Elsinoe glycines), black spot (Diaporthe phaseolorum var. sojae), rust (Phakopsora pachyrhizi), brown ring spot (Corynespora cassiicola), anthracnose (Colletotrichum glycines, Colletotrichum truncatum), leaf rot (Rhizoctonia solani), brown spot (Septoria glycines), leaf spot (Cercospora sojina), Sclerotinia sclerotiorum, Powdery mildew (Microsphaera diffusa), Stem rot (Phytophthora sojae), Downy mildew (Peronospora manshurica), Sudden death (Fusarium virguliforme), Black root rot (Calonectria ilicicola), Diaporthe / Phomopsis complex (Diaporthe longicolla); Diseases of common beans: Sclerotinia sclerotiorum, Rust (Uromyces appendiculatus), Angular spot (Phaeoisariopsis griseola), Anthracnose (Colletotrichum lindemuthianum), Root rot (Fusarium solani); Diseases of peanuts: Black spot (Cercospora personata), Brown spot (Cercospora arachidicola), Southern blight (Sclerotium rolfsii), black root rot (Calonectria ilicicola); Pea diseases: powdery mildew (Erysiphe pisi), root rot (Fusarium solani);Potato diseases: summer blight (Alternaria solani), late blight (Phytophthora infestans), scarlet rot (Phytophthora erythroseptica), powdery scab (Spongospora subterranea f. sp. subterranea), verticillium wilt (Verticillium albo-atrum, Verticillium dahliae, Verticillium nigrescens), dry rot (Fusarium solani), canker (Synchytrium endobioticum); strawberry diseases: powdery mildew (Sphaerotheca humuli); tea diseases: net blight (Exobasidium reticulatum), white spot (Elsinoe leucospila), ring spot (Pestalotiopsis sp.), anthracnose (Colletotrichum theae-sinensis); tobacco diseases: red spot (Alternaria longipes), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), late blight (Phytophthora nicotianae); sugar beet diseases: brown spot (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root rot (Aphanomyces cochlioides), rust (Uromyces betae); rose diseases: black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa); chrysanthemum diseases: brown spot (Septoria chrysanthemi-indici), white rust (Puccinia horiana); onion diseases: white spot leaf blight (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa), gray rot (Botrytis allii), Botrytis squamosa;Diseases of various crops: gray mold (Botrytis cinerea), sclerotinia sclerotiorum, damping-off (Pythium aphanidermatum, Pythium irregulare, Pythium ultimum); diseases of radish: black spot (Alternaria brassicicola); diseases of turfgrass: dollar spot (Sclerotinia homoeocarpa), brown patch, large patch (Rhizoctonia solani), red blight (Pythium aphanidermatum); diseases of banana: Sigatoka (Mycosphaerella fijiensis, Mycosphaerella musicola); diseases of lentil: Ascochyta (Ascochyta lentis); diseases of chickpea: Ascochyta (Ascochyta rabiei); diseases of bell pepper: anthracnose (Colletotrichum scovillei); mango diseases: anthracnose (Colletotrichum acutatum); fruit tree diseases: white root rot (Rosellinia necatrix), purple root rot (Helicobasidium mompa); postharvest fruit diseases of apples, pears, etc.: mucor rot (Mucor piriformis); seed diseases or diseases in the early stages of growth caused by species of the genera Aspergillus, Penicillium, Fusarium, Gibberella, Tricoderma, Thielaviopsis, Rhizopus, Mucor, Corticium, Phoma, Rhizoctonia, Diplodia, etc.; viral diseases: big vein disease of lettuce transmitted by Olpidium brassicae, viral diseases of various crops transmitted by species of the Polymyxa genus (e.g., Polymyxa betae and Polymyxa graminis);Diseases caused by bacteria: rice seedling blight (Burkholderia plantarii), cucumber spot (Pseudomonas syringae pv. Lachrymans), eggplant bacterial wilt (Ralstonia solanacearum), citrus canker (Xanthomonas citri), Chinese cabbage soft rot (Erwinia carotovora), potato scab (Streptomyces scabiei), corn Goss's wilt (Clavibacter michiganensis), grape, olive, peach, etc. Pierce's disease (Xylella fastidiosa), and crown gall disease (Agrobacterium tumefaciens) of Rosaceae plants such as apples, peaches, and cherries;

[0035] The method for controlling plant diseases of the present invention is carried out by applying an effective amount of the crystals or composition of the present invention to plants or soil. Treatment methods include, for example, foliage treatment, soil treatment, and seed treatment.

[0036] The crystals of the present invention or the composition of the present invention are usually mixed with an inert carrier such as a solid carrier or a liquid carrier, and if necessary, a surfactant or other formulation adjuvants are added to prepare solid preparations, aqueous suspension preparations, etc. These preparations usually contain the crystals of the present invention or the composition of the present invention in an amount of 0.0001 to 99% by weight.

[0037] Examples of solid carriers include clays (kaolin clay, diatomaceous earth, bentonite, acid clay, etc.), dry silica, wet silica, talc, ceramics, other inorganic minerals (fine powders and granules such as sericite, quartz, sulfur, activated carbon, calcium carbonate, etc.), and synthetic resins (polyester resins such as polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene terephthalate, etc.; nylon resins such as nylon-6, nylon-11, nylon-66, etc.; polyamide resins, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymers, etc.).

[0038] Examples of liquid carriers include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, diesel, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate, etc.), and the like. nitrile, propylene glycol monomethyl ether acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), propylene carbonate, and vegetable oils (soybean oil, cottonseed oil, etc.).

[0039] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, and polyethylene glycol fatty acid esters, and anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl sulfates. Specific examples include Nimbus (registered trademark), Assist (registered trademark), Aureo (registered trademark), Iharol (registered trademark), Silwet L-77 (registered trademark), BreakThru (registered trademark), Sundance II (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).

[0040] Other formulation adjuvants include thickeners, antifoaming agents, preservatives, and antifreeze agents.

[0041] Examples of thickeners include natural polysaccharides such as xanthan gum, rhamsan gum, locust bean gum, guar gum, carrageenan, welan gum, alginic acid, alginates, and tragacanth gum; mineral powders such as aluminum silicate, magnesium aluminum silicate, smectite, bentonite, hectorite, synthetic hydrous silica, and dry silica; and alumina sol. When the composition of the present invention contains a thickener, the total content thereof is usually 0.1 to 5% by weight, based on 100% by weight of the composition of the present invention.

[0042] Examples of the defoaming agent include Antifoam C Emulsion (trade name of Dow Corning Toray Co., Ltd.), Antifoam CE (trade name of Dow Corning Toray Co., Ltd.), Antifoam A Compound (trade name of Dow Corning Toray Co., Ltd.), FS Antifoam 1266 (trade name of Dow Corning Toray Co., Ltd.), KM-98 (trade name of Shin-Etsu Chemical Co., Ltd.), KS-530 (trade name of Shin-Etsu Chemical Co., Ltd.), KS-538 (trade name of Shin-Etsu Chemical Co., Ltd.), Break-Through AF5503 (trade name of Evonik Industries AG), Antifoam E-20 (Hana Examples of suitable antifoaming agents include silicone-based antifoaming agents such as TSA730 (trade name of Momentive Performance Materials Japan LLC), TSA731 (trade name of Momentive Performance Materials Japan LLC), TSA732 (trade name of Momentive Performance Materials Japan LLC), and YMA6509 (trade name of Momentive Performance Materials Japan LLC); and fluorine-based antifoaming agents such as FluoWet PL80 (trade name of Clariant); and Foamstar W220 (trade name of Cognis Japan Co., Ltd.). When the composition of the present invention contains an antifoaming agent, the total content thereof is usually 0.05 to 0.5% by weight, based on 100% by weight of the composition of the present invention.

[0043] Examples of preservatives include p-hydroxybenzoic acid esters, salicylic acid derivatives, 1,2-benzisothiazolin-3-ones (e.g., Proxel GXL (trade name, manufactured by Lonza)), and isothiazolin-3-one derivatives (e.g., Biohope L (trade name, manufactured by K.I. Kasei)). When the composition of the present invention contains a preservative, the total content thereof is usually 0.01 to 3 wt % relative to 100 wt % of the composition of the present invention.

[0044] Examples of the antifreezing agent include water-soluble glycols such as ethylene glycol, propylene glycol, etc. When the composition of the present invention contains an antifreezing agent, the total content thereof is usually 1 to 20% by weight based on 100% by weight of the composition of the present invention.

[0045] In the present invention, plants include whole plants and specific parts of plants, such as stems, leaves, flowers, spikes, fruits, trunks, branches, crowns, seeds, vegetative reproductive organs, and seedlings.

[0046] Vegetative reproductive organs refer to plant roots, stems, leaves, and other parts that can grow when separated from the main body and placed in soil. Examples of vegetative reproductive organs include tuberous roots, creeping roots, bulbs, corms (or solid bulbs), tubers, rhizomes, stolons, rhizophores, cane cuttings, propagules, and vine cuttings. Stolons are sometimes called runners, and propagules are also called bulbils and are divided into broad buds and bulbils. Vines refer to shoots (a collective term for leaves and stems) of plants such as sweet potatoes and Japanese yams. Bulbs, corms, tubers, rhizomes, stem fragments, rhizophores, and tuberous roots are collectively called bulbils. Potato cultivation begins by planting tubers in the soil, and the tubers used are generally called seed potatoes.

[0047] The application amount of the crystals or composition of the present invention varies depending on weather conditions, formulation, application time, application method, application location, target disease, target crop, etc., but in the case of foliage application or soil application, it is generally 1000 ml 2 The amount is usually 1 to 500 g per kg of seeds. In the case of seed treatment, the amount of the crystals of the present invention or the composition of the present invention is usually 0.001 to 100 g per kg of seeds. When the crystals of the present invention or the composition of the present invention are formulated as an emulsifiable concentrate, wettable powder, flowable concentrate or the like, they are usually applied after being diluted with water to an active ingredient concentration of 0.01 to 10,000 ppm, and dusts, granules and the like are usually applied as they are.

[0048] Seed treatments include, for example, treatment of seeds or vegetative reproductive organs with the crystals or composition of the present invention. More specifically, examples include spray treatments in which a suspension of the crystals or composition of the present invention is sprayed onto the surface of seeds or vegetative reproductive organs in a mist; smear treatments in which seeds or vegetative reproductive organs are coated with the crystals or composition of the present invention; immersion treatments in which seeds are immersed in a solution of the crystals or composition of the present invention for a certain period of time; and methods of coating seeds or vegetative reproductive organs with a carrier containing the crystals or composition of the present invention (film coating treatments, pellet coating treatments, etc.). Seed potatoes are particularly examples of such vegetative reproductive organs. When treating seeds or vegetative reproductive organs with the composition of the present invention, the composition can be applied to the seeds or vegetative reproductive organs as a single formulation, or the composition can be applied to the seeds or vegetative reproductive organs in multiple separate applications as different formulations. Examples of methods for treating the composition of the present invention in multiple separate formulations include treating the seeds or vegetative reproductive organs with a formulation containing only the crystal of the present invention as an active ingredient, air-drying the seeds or vegetative reproductive organs, and then treating with a formulation containing this ingredient; and treating the seeds or vegetative reproductive organs with a formulation containing both the crystal of the present invention and this ingredient as active ingredients, air-drying the seeds or vegetative reproductive organs, and then treating with a formulation containing an ingredient other than the ingredient already treated. In the present invention, the term "seeds or vegetative reproductive organs bearing the crystal of the present invention or the composition of the present invention" refers to seeds or vegetative reproductive organs to which the crystal of the present invention or the composition of the present invention is attached. The seeds or vegetative reproductive organs bearing the crystal of the present invention or the composition of the present invention may have materials other than the crystal of the present invention or the composition of the present invention attached to them before or after the crystal of the present invention or the composition of the present invention is attached to the seeds or vegetative reproductive organs. Furthermore, when the composition of the present invention is attached to the surface of the seeds or vegetative reproductive organs in layers, the layers may consist of one layer or multiple layers. Furthermore, when the composition of the present invention consists of multiple layers, each layer may contain one or more active ingredients, or may consist of a layer containing one or more active ingredients and a layer containing no active ingredients. Seeds or vegetative reproductive organs carrying the crystals or compositions of the present invention can be obtained, for example, by applying a formulation containing the crystals or compositions of the present invention to the seeds or vegetative reproductive organs using the seed treatment method described above.

[0049] The crystals or compositions of the present invention can be used as agents for controlling plant diseases in agricultural lands such as fields, paddy fields, lawns, orchards, etc. Examples of plants include the following.

[0050] Corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, Solanaceae vegetables (eggplant, tomato, bell pepper, chili pepper, potato, etc.), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), Cruciferae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard greens, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, garland chrysanthemum, artichoke, lettuce, etc.), Liliaceae vegetables (leeks, onions, garlic, asparagus, etc.), Umbelliferae vegetables (carrots, parsley, celery, parsley, etc.), Chenopodiaceae vegetables (horseshoe, etc.) vegetables (perilla, mint, basil, etc.), strawberries, sweet potatoes, yams, taro, pome fruits (apples, European pears, Japanese pears, quince, quince, etc.), stone fruits (peaches, plums, nectarines, plums, cherries, apricots, prunes, etc.), citrus fruits (unshu mandarins, oranges, lemons, limes, grapefruit, etc.), nuts (chestnuts, walnuts, hazelnuts, almonds, pistachios, cashew nuts, macadamia nuts, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons, olives, loquats, bananas, coffee, dates, coconuts, tea, mulberry, ornamental plants, forest plants, lawn grass, pasture grass.

[0051] The above plants also include genetically modified crops.

[0052] The present invention will be explained in more detail below by showing Production Examples, Reference Production Examples, Formulation Examples, and Test Examples, but the present invention is not limited to these examples. In the examples, "%" and "parts" mean "% by weight" and "parts by weight" unless otherwise specified. Furthermore, various physical properties of the produced crystals of the present invention were measured using the following apparatus (with measurement conditions).

[0053] Powder XRD Powder X-ray diffractometer: SmartLab (Rigaku Corporation) X-ray output: Cu-Kα, 45 kV, 200 mA Sampling width: 0.02° Scanning range: 2° to 50° Measurement temperature: room temperature

[0054] Single crystal XRD (Ra1 type crystal) Apparatus: R-AXIS RAPID (Rigaku Corporation) X-ray source: Mo-Kα Measurement temperature: room temperature Solve: SHELXT Refinement: SHELXL

[0055] (Ra2 type crystal) Equipment: R-AXIS RAPID (manufactured by Rigaku Co., Ltd.) X-ray source: Mo-Kα Measurement temperature: Room temperature Solve: SIR2014 Refinement: SHELXL

[0056] (Ra3 type crystal) Apparatus: XtaLAB Synergy (manufactured by Rigaku Corporation) X-ray source: Cu-Kα Measurement temperature: 100 K Solve: SHELXT Refinement: SHELXL

[0057] DSC equipment: DSC Q2000 (manufactured by TA instruments) Heating rate: 2°C / min Sample amount: 0.5 to 5 mg Measurement atmosphere: nitrogen

[0058] Fourier transform infrared spectroscopy (FT-IR) Apparatus: Nicolet iS50 (manufactured by Thermo Fisher Scientific Inc.) Measurement method: Diamond ATR method

[0059] Microscopic Raman spectroscopy: Apparatus: NRS-5100 (manufactured by JASCO) Laser wavelength: 532 nm

[0060] Optical microscope Optical microscope: Leica Z16 APO (Leica Microsystems) Camera: Leica MC170 HD (Leica Microsystems) Magnification: 115x

[0061] An example of the production of the crystal of the present invention will be described.

[0062] Production Example 1 (Production of Ra2-type crystals) 30 mg of compound A was dissolved in methanol at 60°C to prepare a solution of 375 mg / mL. After cooling this solution to room temperature, it was irradiated with a laser under the following conditions, and then allowed to stand at 20°C to obtain Ra2-type crystals. The laser irradiation conditions were as follows: <Femtosecond laser> Wavelength: 800 nm Pulse width: 181 fs Number of pulses: 125 pulses / 10 seconds

[0063] Production Example 2 (Production of Ra1 type crystals) 200 mg of the Ra2 type crystals obtained in Production Example 1 were weighed into a 20 mL sample bottle and heated at 130° C. for 2 hours to obtain Ra1 type crystals.

[0064] Preparation Example 3 (Preparation of Ra3-type crystals) 1 mL of diisopropyl ether was added to 100 mg of the Ra1-type crystals obtained in Preparation Example 2, and the resulting suspension was heated to 60°C and stirred at 1000 rpm for 2 days. Thereafter, the solvent was removed to obtain Ra3-type crystals.

[0065] Reference Production Example 1 (Production of Ra4 Crystal) The Ra4 crystal was produced by dissolving Compound A in toluene and recrystallizing it according to the method described in WO 92 / 12970 (Patent Document 1).

[0066] The physical property data of the crystal of the present invention are shown below. Ra1 type crystal IR characteristic peaks: 2933.0, 1648.4, 1632.0, 1606.6, 1554.6, 1338.8, 1082.9, and 1036.5 cm －1 Raman characteristic peaks: 2946, 2927, 2858, 1649, 1631, and 1397 cm －1 XRD characteristic peaks: Regarding the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 1, the diffraction peak values ​​as diffraction angles (2θ±0.2°) are shown in Table 1, but are not limited thereto. Table 1

[0067]

[0068] Typical diffraction peak values ​​include, for example, 7.1±0.2, 8.6±0.2, 8.9±0.2, 9.1±0.2, 13.3±0.2, 14.0±0.2, 14.3±0.2, 14.8±0.2, 16.0±0.2, and 16.4±0.2 as shown in Table 1.

[0069] Ra2 type crystal IR characteristic peaks: 3292.4, 2957.1, 2927.5, 1659.1, 1642.0, 1544.1, 1133.5, and 1123.2 cm －1 Raman characteristic peaks: 3118, 2924, 2876, 1658, and 1641 cm －1 XRD characteristic peaks: Regarding the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 2, the diffraction peak values ​​as diffraction angles (2θ±0.2°) are shown in Table 2, but are not limited thereto.

[0070]

[0071] Typical diffraction peak values ​​include, for example, 4.3±0.2, 8.5±0.2, 10.8±0.2, 11.4±0.2, 12.4±0.2, 12.8±0.2, 15.1±0.2, 16.1±0.2, 16.8±0.2, and 19.1±0.2, as shown in Table 2 above.

[0072] Ra3 type crystal IR characteristic peaks: 3301.7, 2959.1, 2858.1, 1654.4, 1644.3, 1545.6, 1518.3, 1133.9, 1123.3, and 1032.8 cm －1 Raman characteristic peaks: 3046, 2928, 1652, 1588, and 1545 cm －1 XRD characteristic peaks: Regarding the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 3, the diffraction peak values ​​as diffraction angles (2θ±0.2°) are shown in Table 3, but are not limited thereto.

[0073]

[0074] Typical diffraction peak values ​​include, for example, 3.6±0.2, 7.1±0.2, 7.4±0.2, 9.6±0.2, 11.9±0.2, 12.5±0.2, 12.9±0.2, 14.3±0.2, 15.7±0.2, and 17.9±0.2 as shown in Table 3.

[0075] For comparison with the Ra1 type crystal, Ra2 type crystal, and Ra3 type crystal of the present invention, various spectral values ​​of the Ra4 type crystal are shown below. Ra4 type crystal IR characteristic peaks: 2953.8, 1635.5, 1608.7, 1553.2, 1138.7, 1066.8, 1034.2, and 1012.3 cm －1 Raman characteristic peaks: 2928, 2859, 1491, 1398, and 1311 cm －1 Regarding the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 4, the diffraction peak values ​​as diffraction angles (2θ±0.2°) are shown in Table 4, but are not limited thereto.

[0076]

[0077] Typical diffraction peak values ​​include, for example, 5.8±0.2, 7.2±0.2, 8.6±0.2, 13.8±0.2, 16.3±0.2, 16.7±0.2, 17.4±0.2, 17.7±0.2, 19.5±0.2, 19.8±0.2 and 20.7±0.2 as shown in Table 4.

[0078] The crystallographic data of the single crystal of the present invention is shown in Table 5 below.

[0079]

[0080] The plant disease control efficacy of the crystals of the present invention was measured by the following test examples.

[0081] Test Example 1: 5 parts of Ra1 crystals or Ra4 crystals for comparison, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (1:1 by weight), and 60 parts of water were mixed and finely pulverized by wet milling to obtain a formulation. Water was added to this formulation so that the concentration of Ra1 crystals or Ra4 crystals was 2 ppm to obtain a diluted solution. Plastic pots were filled with soil, and soybeans (variety: Kurosengoku) were sown and grown in a greenhouse for 15 days. An aqueous suspension of soybean rust fungus (Phakopsora pachyrhizi) spores was then sprayed and inoculated. After inoculation, the plants were left overnight at 23°C under humid conditions and further cultivated in a greenhouse for 3 days. The diluted solution was sprayed on the stems and leaves of the soybeans so that it adhered well to the leaf surface. After spraying, the plants were air-dried, placed under humid conditions only overnight, and the lesion area was examined 7 days after spraying (lesion area in the treatment area). On the other hand, in the untreated area, the same procedure as in the treated area was carried out except that the Ra1 type crystals or Ra4 type crystals were not applied, and the lesion area of ​​soybean rust in the untreated area was investigated (lesion area in the untreated area). From the lesion areas in the treated and untreated areas, the efficacy of the treated area was calculated using the following "Equation 1". The results are shown in Table 6. "Equation 1" Efficacy (%) = [1 - (lesion area in the treated area / lesion area in the untreated area)] x 100

[0082] Table 6

[0083] It was found that the Ra1 crystal exhibited higher efficacy than the Ra4 crystal.

[0084] Test Example 2 5 parts of Ra2 crystals, Ra3 crystals, or Ra4 crystals for comparison, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1:1), and 60 parts of water were mixed and finely pulverized by wet grinding to obtain a formulation. Water was added to this formulation so that the Ra2 crystals, Ra3 crystals, or Ra4 crystals were 50 ppm to obtain a diluted solution. Soil was filled into a plastic pot, and rice (variety: Hinohikari) was sown therein and grown in a greenhouse for 17 days. The diluted solution was sprayed on the stems and leaves of the rice so that it adhered sufficiently to the leaf surface. After spraying, the plants were air-dried and cultivated outdoors for 8 days. The treated rice plants were then placed in contact with rice seedlings infected with rice blast fungus (Pyricularia oryzae) in a greenhouse at 24°C during the day and 20°C at night under humid conditions for 11 days, and the lesion area was then measured (lesion area in the treated area). The untreated area was subjected to the same procedures as the treated area, except that no Ra2, Ra3, or Ra4 crystals were applied, and the lesion area of ​​rice blast in the untreated area was measured (lesion area in the untreated area). The efficacy of the treated area was calculated from the lesion areas in the treated and untreated areas using the above formula 1. The results are shown in Table 7.

[0085] Table 7

[0086] It was found that the Ra2 and Ra3 crystals exhibited higher efficacy than the Ra4 crystal.

[0087] The crystals of the present invention (Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals) exhibit excellent control effects against plant diseases.

Claims

1. In 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, an Ra1-type crystal having diffraction peaks at 2θ = 7.1 ± 0.2°, 8.6 ± 0.2°, 8.9 ± 0.2°, 9.1 ± 0.2°, 13.3 ± 0.2°, 14.0 ± 0.2°, 14.3 ± 0.2°, 14.8 ± 0.2°, 16.0 ± 0.2°, 16.4 ± 0.2°, 20.3 ± 0.2°, and 20.6 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation, an Ra2-type crystal having diffraction peaks at 2θ = 4.3 ± 0.2°, 8.5 ± 0.2°, 10.8 ± 0.2°, 11.4 ± 0.2°, 12.4 ± 0.2°, 12.8 ± 0.2°, 15.1 ± 0.2°, 16.1 ± 0.2°, 16.8 ± 0.2°, and 19.1 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation, and an Ra3-type crystal having diffraction peaks at 2θ = 3.6 ± 0.2°, 7.1 ± 0.2°, 7.4 ± 0.2°, 9.6 ± 0.2°, 11.9 ± 0.2°, 12.5 ± 0.2°, 12.9 ± 0.2°, 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation, at least one crystal selected from the group consisting of these crystals.

2. The 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to claim 1, which is an Ra1-type crystal having diffraction peaks at 2θ = 7.1 ± 0.2°, 8.6 ± 0.2°, 8.9 ± 0.2°, 9.1 ± 0.2°, 13.3 ± 0.2°, 14.0 ± 0.2°, 14.3 ± 0.2°, 14.8 ± 0.2°, 16.0 ± 0.2°, 16.4 ± 0.2°, 20.3 ± 0.2°, and 20.6 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation.

3. In the 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to claim 1, a Ra2-type crystal having diffraction peaks at 2θ = 4.3 ± 0.2°, 8.5 ± 0.2°, 10.8 ± 0.2°, 11.4 ± 0.2°, 12.4 ± 0.2°, 12.8 ± 0.2°, 15.1 ± 0.2°, 16.1 ± 0.2°, 16.8 ± 0.2°, and 19.1 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation.

4. In the 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to claim 1, a Ra3-type crystal having diffraction peaks at 2θ = 3.6 ± 0.2°, 7.1 ± 0.2°, 7.4 ± 0.2°, 9.6 ± 0.2°, 11.9 ± 0.2°, 12.5 ± 0.2°, 12.9 ± 0.2°, 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2° in powder X-ray diffraction using Cu-Kα radiation.

5. A plant disease control composition comprising one or more crystals according to any one of claims 1 to 4.

6. A method for controlling plant diseases, comprising treating an effective amount of one or more crystals according to any one of claims 1 to 4 to a plant or the soil in which the plant grows.

7. Use of one or more crystals according to any one of claims 1 to 4 for controlling plant diseases.

8. A composition comprising one or more components selected from the group consisting of group (a), group (b), group (c), and group (d) and one or more crystals according to any one of claims 1 to 4: Group (a): a group consisting of an insecticidal active ingredient, an acaricidal 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 seed or vegetative reproductive organ holding an effective amount of the crystal according to any one of claims 1 to 4 or the composition according to claim 7.

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