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

Abstract

The present application provides a crystal which is at least one crystal selected from the group consisting of a Ra1-type crystal, a Ra2-type crystal and a Ra3-type crystal each having the diffraction peaks described in the specification in powder X-ray diffraction based on Cu-Kα rays, of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide.

Description

TECHNICAL FIELD

[0001] The present application relates to a novel crystal of 3-(difluoromethyl)-l-methyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide having plant disease control effect. BACKGROUND

[0002] 3-(difluoromethyl)-l-methyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide (hereinafter referred to as Compound A) is a crystal having a melting point of 131 to 134°C, and it has been reported that it exhibits a control effect on plant diseases (Patent Literature 1).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: WO 92 / 12970 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] An object of the present application is to provide a novel crystal having physical properties different from those of the known crystal (hereinafter referred to as Ra4-type crystal) described in Patent Literature 1, and further having more excellent plant disease control effect.

[0008] MEANS FOR SOLVING THE PROBLEMS

[0009] The present inventors have found three novel crystals (Ra1-type crystal, Ra2-type crystal and Ra3-type crystal) of Compound A having excellent control effect on plant diseases.

[0010] That is, the present application is as follows.

[0011] [1] A crystal which is at least one crystal selected from the group consisting of 3-(difluoromethyl)-l-methyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide crystals:

[0012] 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 based on Cu-Kα rays,

[0013] 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 based on Cu-Kα rays, and

[0014] 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 based on Cu-Kα rays.

[0015] [2] The crystal described in [1], wherein, in 3-(difluoromethyl)-l-methyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide, it is 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 based on Cu-Kα rays.

[0016] [3] The crystal described in [1], wherein, in 3-(difluoromethyl)-l-methyl-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide, it is 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 based on Cu-Kα rays.

[0017] [4] The crystal as claimed in [1], wherein, in 3-(difluoromethyl)-l-methyl-N-(l,l,3- trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide, it is 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 based on Cu-Kα rays.

[0018] [5] A plant disease control composition comprising one or more crystals as claimed in any one of [1] to [4].

[0019] [6] A method for controlling plant diseases, which comprises treating a plant or soil where a plant grows with an effective amount of one or more crystals as claimed in any one of [1] to [4].

[0020] [7] Use of one or more crystals as claimed in any one of [1] to [4] for controlling plant diseases.

[0021] [8] A composition comprising one or more components selected from Group (a), Group (b), Group (c) and Group (d), and one or more crystals as claimed in any one of [1] to [4]:

[0022] Group (a): a group comprising an insecticidal active ingredient, a miticidal active ingredient and a nematicidal active ingredient;

[0023] Group (b): a fungicidal active ingredient;

[0024] Group (c): a plant growth regulating ingredient;

[0025] Group (d): a repellent ingredient.

[0026] [9] A seed or vegetative propagating organ which retains an effective amount of one or more crystals as claimed in any one of [1] to [4] or the composition as claimed in [7].

[0027] Effects of the Invention

[0028] The present invention provides three novel crystals (Ra1 type crystal, Ra2 type crystal and Ra3 type crystal) of Compound A which show control effects on plant diseases. These crystals show more excellent control effects on plant diseases than the known Ra4 type crystal. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1is a graph showing a powder X-ray diffraction pattern of a crystal of type Ra1. The vertical axis is the intensity of diffraction (unit: cps), and the horizontal axis indicates the diffraction angle 2Θ (unit: °).

[0030] Figure 2 is a graph showing a powder X-ray diffraction pattern of a crystal of type Ra2. The vertical axis is the intensity of diffraction (unit: cps), and the horizontal axis indicates the diffraction angle 2Θ (unit: °).

[0031] Figure 3 is a graph showing a powder X-ray diffraction pattern of a crystal of type Ra3. The vertical axis is the intensity of diffraction (unit: cps), and the horizontal axis indicates the diffraction angle 2Θ (unit: °).

[0032] Figure 4 is a graph showing a powder X-ray diffraction pattern of a crystal of type Ra4. The vertical axis is the intensity of diffraction (unit: cps), and the horizontal axis indicates the diffraction angle 2Θ (unit: °).

[0033] Figure 5 is a graph showing the molecular packing in the crystal lattice of a crystal of type Ra1.

[0034] Figure 6 is a graph showing the molecular packing in the crystal lattice of a crystal of type Ra2.

[0035] Figure 7 is a graph showing the molecular packing in the crystal lattice of a crystal of type Ra3.

[0036] Figure 8 is a graph showing a differential scanning calorimetry (DSC) curve of a crystal of type Ra1. The vertical axis indicates the heat flow (unit: W / g), and the horizontal axis indicates the temperature (unit: °C).

[0037] Figure 9 is a graph showing a differential scanning calorimetry (DSC) curve of a crystal of type Ra2.

[0038] Figure 10 is a graph showing a differential scanning calorimetry (DSC) curve of a crystal of type Ra3.

[0039] Figure 11 is a graph showing a differential scanning calorimetry (DSC) curve of a crystal of type Ra4.

[0040] Figure 12 is a graph showing a spectrum of an infrared spectrum of a crystal of type Ra1. The vertical axis is the transmittance, and the horizontal axis indicates the wave number of the irradiated infrared light.

[0041] Figure 13 is a graph showing a spectrum of an infrared spectrum of a crystal of type Ra2. The vertical axis is the transmittance, and the horizontal axis indicates the wave number of the irradiated infrared light.

[0042] Figure 14 is a graph showing a spectrum of an infrared spectrum of a crystal of type Ra3. The vertical axis is transmittance, and the horizontal axis indicates the wave number of the irradiated infrared light.

[0043] Figure 15 is a graph showing a spectrum of an infrared spectrum of a crystal of type Ra4. The vertical axis is transmittance, and the horizontal axis indicates the wave number of the irradiated infrared light.

[0044] Figure 16 is a graph showing a spectrum of a Raman spectrum of a crystal of type Ra1. The vertical axis is intensity, and the horizontal axis indicates the Raman shift number.

[0045] Figure 17 is a graph showing a spectrum of a Raman spectrum of a crystal of type Ra2. The vertical axis is intensity, and the horizontal axis indicates the Raman shift number.

[0046] Figure 18 is a graph showing a spectrum of a Raman spectrum of a crystal of type Ra3. The vertical axis is intensity, and the horizontal axis indicates the Raman shift number.

[0047] Figure 19 is a graph showing a spectrum of a Raman spectrum of a crystal of type Ra4. The vertical axis is intensity, and the horizontal axis indicates the Raman shift number.

[0048] Figure 20 is a graph showing a photograph of an optical microscope of a crystal of type Ra1.

[0049] Figure 21 is a graph showing a photograph of an optical microscope of a crystal of type Ra2.

[0050] Figure 22 is a graph showing a photograph of an optical microscope of a crystal of type Ra3.

[0051] Figure 23 is a graph showing a photograph of an optical microscope of a crystal of type Ra4. DETAILED DESCRIPTION

[0052] The present application relates to novel crystals of Compound A (crystals of type Ra1, crystals of type Ra2, and crystals of type Ra3). 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 of R and S bodies, and Compound A is an equimolar mixture of them, i.e., a racemate. In addition, crystals in which each of the R and S bodies is regularly arranged in a crystal lattice in an equimolar amount are crystals of the present application, and each becomes a crystal of type Ra1, a crystal of type Ra2, or a crystal of type Ra3 depending on the manufacturing conditions.

[0053] The melting point of the Ra4-type crystal is about 131 to 134°C, and in a powder X-ray diffraction pattern using Cu-Kα rays, as a diffraction peak as a 2θ value (°), there can be mentioned 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.

[0054] Each of the Ra1-type crystal, the Ra2-type crystal, and the Ra3-type crystal has the following physical properties.

[0055] The Ra1-type crystal is a crystal having a melting point of about 134 to 136°C and diffraction peaks as a 2θ value (°) of 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 a powder X-ray diffraction pattern using Cu-Kα rays.

[0056] The Ra1-type crystal can be produced according to the following production method.

[0057] A necessary amount (for example, about 200 mg) of the Ra2-type crystal is heated at about 130°C for a certain period of time (about 2 hours) in a suitable container (for example, a 20 mL sample bottle) to obtain the Ra1-type crystal.

[0058] The Ra2-type crystal is a crystal having a melting point of about 124 to 126°C and diffraction peaks as a 2θ value (°) of 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 a powder X-ray diffraction pattern using Cu-Kα rays.

[0059] The Ra2-type crystal can be produced according to the following production method.

[0060] A necessary amount (for example, about 30 mg) of Compound A is dissolved in a suitable amount (about 80 μL) of an organic solvent (for example, methanol) at about 60°C to prepare a certain amount of a solution having a dissolution concentration (about 375 mg / mL). After the solution is cooled to room temperature, laser light is irradiated under a certain condition, and the solution is left to stand at about 20°C to obtain the Ra2-type crystal.

[0061] The laser light irradiation condition is as follows, but is not limited thereto.

[0062] < femtosecond laser > ​

[0063] Wavelength: 800nm

[0064] Pulse width: 181 fs

[0065] Pulse count: 125 pulses / 10 seconds

[0066] Examples of organic solvents include alcohols, with alkyl solvents having 1 to 3 carbon atoms being preferred. Specifically, these include methanol, ethanol, propanol, and isopropanol, with methanol being the most preferred.

[0067] As for the amount of organic solvent used to dissolve compound A, examples of amounts that achieve a dissolution concentration of about 200 mg / mL to about 1000 mg / mL are given, with a preferred dissolution concentration of about 300 mg / L to about 500 mg / mL, for example, about 375 mg / mL.

[0068] Ra3 type crystals are crystals with melting points of approximately 129–131 °C and diffraction peaks with 2θ values ​​(°) of 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 patterns using Cu-Kα rays.

[0069] Ra3 type crystals can be manufactured according to the following method.

[0070] Add an appropriate amount (e.g., about 1 mL) of organic solvent to the required amount (e.g., about 100 mg) of Ra1 type crystals prepared above, heat the suspension to about 60°C, stir under certain conditions (about 1000 rpm) for a certain period of time (about 2 days), remove the solvent, and obtain Ra3 type crystals.

[0071] Examples of organic solvents include ether-based solvents, with dialkyl ether solvents containing alkyl groups having 1 to 3 carbon atoms being preferred. Specifically, dimethyl ether, diethyl ether, dipropyl ether, and diisopropyl ether are examples, with diisopropyl ether being the most preferred.

[0072] The amount of organic solvent is 5 to 10 parts by weight, preferably 6 to 8 parts by weight, relative to 1 part by weight of the Ra1 type crystals used.

[0073] One or more crystals selected from Ra1 type crystals, Ra2 type crystals and Ra3 type crystals may be used in combination or mixed with one or more components selected from the following groups (a), (b), (c) and (d) (hereinafter referred to as the component).

[0074] The so-called mixed use or combination means that one or more kinds of crystals selected from the group consisting of the Ra1 crystal, the Ra2 crystal and the Ra3 crystal and the present component are used simultaneously or are used with a time interval.

[0075] In the case where one or more kinds of crystals selected from the group consisting of the Ra1 crystal, the Ra2 crystal and the Ra3 crystal and the present component are used simultaneously, the one or more kinds of crystals selected from the group consisting of the Ra1 crystal, the Ra2 crystal and the Ra3 crystal and the present component can be respectively contained in different formulations or can be contained in one formulation.

[0076] One aspect of the present application is a composition containing one or more components selected from the group (a), the group (b), the group (c) and the group (d) and one or more kinds of crystals selected from the group consisting of the Ra1 crystal, the Ra2 crystal and the Ra3 crystal (hereinafter referred to as the present application composition).

[0077] The group (a) is a group containing acetylcholinesterase inhibitors (for example, carbamate-based insecticides, organophosphorus-based insecticides), GABA-agonistic chloride channel antagonists (for example, phenylpyrazole-based insecticides), sodium channel modulators (for example, pyrethroid-based insecticides), nicotinic acetylcholine receptor antagonistic modulators (for example, neonicotinoid-based insecticides), nicotinic acetylcholine receptor allosteric modulators, glutamate-agonistic chloride channel allosteric modulators (for example, macrolide-based insecticides), juvenile hormone analogs, multi-site inhibitors, chordotonal organ TRPV channel modulators, mite growth inhibitors, mitochondrial ATP biosynthesis enzyme inhibitors, oxidative phosphorylation uncouplers, nicotinic acetylcholine receptor channel blockers (for example, nereistoxin-based insecticides), chitin synthesis inhibitors, ecdysis inhibitors, ecdysone receptor agonists, octopamine receptor agonists, mitochondrial electron transport system complex I, II, III and IV inhibitors, voltage-dependent sodium channel blockers, acetyl-CoA carboxylase inhibitors, ryanodine receptor modulators (for example, diamide-based insecticides), chordotonal organ modulators, each active ingredient of microbial insecticides and other insecticidally active ingredients, acaricidally active ingredients, nematocidally active ingredients. They are described in the classification based on the mechanism of action of IRAC.

[0078] Group (b) is a group of components comprising nucleic acid synthesis inhibitors (e.g., phenylamide fungicides, acylamino acid fungicides), cell division and cytoskeletal inhibitors (e.g., MBC fungicides), respiration inhibitors (e.g., QoI fungicides, QiI fungicides), amino acid and protein synthesis inhibitors (e.g., anilinopyrimidine fungicides), signal transduction inhibitors, lipid and membrane synthesis inhibitors, sterol biosynthesis inhibitors (e.g., DMI fungicides such as triazoles), cell wall synthesis inhibitors, melanin synthesis inhibitors, plant defense inducers, multi-site contact activity fungicides, microbial fungicides, and other fungicidally active ingredients. They are described in the FRAC-based classification of mode of action.

[0079] Group (c) is a group of plant growth regulating ingredients (including mycorrhizae and rhizobia).

[0080] Group (d) is a group of repellent ingredients comprising bird repellents and insect repellents.

[0081] Hereinafter, examples of combinations of one or more kinds of crystals selected from the group consisting of Ra1-type crystals, Ra2-type crystals, and Ra3-type crystals and the present ingredient are described. For example, alanycarb + SX means a combination of alanycarb and SX.

[0082] Note that the abbreviated symbol SX means Ra1-type crystals, Ra2-type crystals, or Ra3-type crystals (hereinafter referred to as the present crystals). In addition, the present ingredients described hereinafter are all known ingredients, and can be obtained from commercially available formulations or can be produced by known methods. In the case where the present ingredient is a microorganism, it can also be obtained from a strain deposit institution. Note that the numbers in parentheses indicate CAS RN (registered trademark).

[0083] Combinations of the present ingredients of the above Group (a) and the present crystals:

[0084] abamectin + SX, acephate + SX, acequinocyl + SX, acetamiprid + SX, acetoprole + SX, acrinathrin + SX, 3-endo-[2-propoxy-4-(trifluoromethyl)phenoxy]-9-[5-(trifluoromethyl)-2-pyridyloxy]-9- azabicyclo[3.3.1]nonane + 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, 5-(1,3-dioxan-2-yl)-4-[4-(trifluoromethyl)benzyloxy]pyrimidine + 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, 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, concanamycin A + SX, coumaphos + SX, cryolite + SX, cyanophos + SX, cyantraniliprole + SX, cycloniliprole + 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,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 Dryopteris filix-mas + SX, emamectin-benzoate + SX, empenthrin + SX, endosulfan + SX, EPN (O-ethyl O-(4-nitrophenyl) phenyl thiophosphate) + 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 Cassia nigricans + SX, extract of clitoria ternatea + SX, extract of Symphytum officinale + SX, extracts or simulated blend 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, fenitrothion + SX, fenobucarb + SX, fenoxycarb + SX, fenpropathrin + SX, fenpyroximate + SX, fenthion + SX, fenvalerate + SX, fipronil + SX, 2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]quinolin-4- ylmethyl carbonate (flometoquin) + SX, flonicamid + SX, fluacrypyrim + SX, fluazaindolizine + SX, fluazuron + SX, flubendiamide + SX, flucycloxuron + SX, flucythrinate + SX, fluensulfone + SX, flufenoprox + SX, flufenoxuron + SX, flufiprole + SX, flumethrin + SX, flupyradifurone + SX, N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2- trifluoroacetamide (flupyrimin) + SX, fluralaner + SX, fluvalinate + SX, fluxametamide + SX, formetanate + SX, fosthiazate + SX, furamethrin + SX, furathiocarb + SX, gamma-cyhalothrin + SX, glutamine synthetase-omega / kappa HXTX-Hv1a peptide (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,pyridafenzon + SX, pyridaben + SX, pyridalyl + SX, pyridylfen + SX, pyrimidifen + SX, pyriproxyfen + SX, quinalphos + SX, quinoxyfen + SX, rafoxanide + SX, resmethrin + SX, rotenone + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SX, sabadilla + SX, sabadilla seed + SX, safflower oil + SXpyrethrins + 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 + SX, spinetoram + SX, spinosad + SX, spirodiclofen + SX, spiromesifen + SX, spiropidion + 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, terbufos + SX, terpene constituents of the extract of chenopodium ambrosioides nearambrosioides + SX, tetrachlorantraniliprole + SX, tetrachlorvinphos + SX, tetradifon + SX, tetramethrin + SX, tetronic acids + SX, thiacloprid + SX, thiamethoxam + SX, thiamethoxam-metabolite-I + SX, thiamethoxam-metabolite-II + SX, thiamethoxam-metabolite-III + SX, thiamethoxam-metabolite-IV + SX, thiamethoxam-metabolite-V + SX, thiamethoxam-metabolite-VI + SX, thiamethoxam-metabolite-VII + SX, thiamethoxam-metabolite-VIII + SX, thiamethoxam-metabolite-IX + SX, thiamethoxam-metabolite-X + SX, thiamethoxam-metabolite-XI + SX, thiamethoxam-metabolite-XII + SX, thiamethoxam-metabolite-XIII + SX, thiamethoxam-metabolite-XIV + SX, thiamethoxam-metabolite-XV + SX, thiamethoxam-metabolite-XVI + SX, thiamethoxam-metabolite-XVII + SX, thiamethoxam-metabolite-XVIII + SX, thiamethoxam-metabolite-XIX + SX, thiamethoxam-metabolite-XX + SX, thiamethoxam-metabolite-XXI + SX, thiamethoxam-metabolite-XXII + SX, thiamethoxam-metabolite-XXIII + SX, thiamethoxam-metabolite-XXIV + SX, thiamethoxam-metabolite-XXV + SX, thiamethoxam-metabolite-XXVI + SX, thiamethoxam-metabolite-XXVII + SX, thiamethoxam-metabolite-XXVIII + SX, thiamethoxam-metabolite-XXIX + SX, thiamethoxam-metabolite-XXX + 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, tioxazafen + SX, tolfenpyrad + SX, tralomethrin + SX, transfluthrin + SX, triazamate + SX, triazophos + SX, trichlorfon + SX, triflumezopyrim + SX, triflumuron + SX, trimethacarb + SX, N-[3-chloro-l-(3-pyridinyl)pyrazol-4-yl]-N-ethyl-3-[(3,3,3- trifluoropropyl)thio]propanamide (tyclopyrazoflor) + SX, vamidothion + SX, wood extract of Quassia amara + 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-l,2-oxazol-3-yl]-2-methyl-N-(l- oxothietan-3-yl)benzamide (1241050-20-3) + SX, 3-methoxy-N-(5-{5-(trifluoromethyl)-5-[3- (trifluoromethyl)phenyl]-4,5-dihydro-l,2-oxazol-3-yl}indan-l-yl)propanamide (1118626-57-5) + SX,2-chloro-4-fluoro-5-{[5-(trifluoromethylthio)pentyl]oxy}phenyl 2,2,2-trifluoroethyl sulf oxide (1472050-04-6) + SX, 4-chloro-5-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2- methylphenyl 2,2,2-trifluoroethyl sulf oxide (1632218-00-8) + SX, 4-fluoro-5-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-methylphenyl 2,2,2- trifluoroethyl sulf oxide (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)vinyl 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-oxide (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 (BT crop protein Cry1A.105) + SX, BT crop protein Cry2Ab (BT crop protein Cry2Ab) + SX, BT crop protein Vip3A (BT crop protein Vip3A) + SX, BT crop protein Cry3A (BT crop protein Cry3A) + SX, BT crop protein Cry3Ab (BT crop protein Cry3Ab) + SX, BT crop protein Cry3Bb (BT crop protein Cry3Bb) + SX, BT crop protein Cry34Ab1 / Cry35Ab1 (BT crop protein Cry34Ab1 / Cry35Ab1) + SX,Tea leafroller granulovirus BV-0001 (Adoxophyes oranagranulosis virus BV-0001) + SX, Bean leafroller nucleopolyhedrovirus (Anticarsia gemmatalis mNPV) + SX, Alfalfa leafroller nucleopolyhedrovirus (Autographacalifornica mNPV) + SX, Apple leafroller granulovirus V15 (Cydia pomonella GV strain V15) + SX, Apple leafroller granulovirus V22 (Cydia pomonella GV strain V22) + SX, Apple leafroller heteromorphic granulovirus (Cryptophlebia leucotreta GV) + SX, Pine caterpillar cypovirus (Dendrolimus punctatus cypovirus) + SX, Cotton bollworm nucleopolyhedrovirus BV-0003 (Helicoverpa armigera NPV strain) BV-0003)+SX, Helicoverpa zea NPV+SX, Lymantria dispar NPV+SX, Mamestra brassicae NPV+SX, Mamestraconfigurata NPV+SX, Neodiprion abietis NPV+SX, Neodiprion lecontei NPV+SX, Neodiprion sertifer NPV+SX, Nosema locustae NPV+SX, Orgyia pseudotsugata NPV+SX, Pieris rapae NPV+SX, GV+SX, Plodia interpunctella GV+SX, Spodoptera exigua mNPV+SX, Spodoptera littoralism NPV+SX, Spodoptera litura 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 H5a5b + SX. The following strains were tested: 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, and Bacillus thuringiensis subsp. Aizawai strain GC-91. GC-91)+SX, Bacillus thuringiensis subsp. Aizawai Serotype strain H-7)+SX, Bacillus thuringiensis subsp. Kurstakistrain 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. tenebrionis 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 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 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, Pesteuria thoynei + SX, Serratia entomophila + SX,Verticillium chlamydosporium + SX, Verticillium lecani strain NCIM 1312 + SX, 2-chloro-N-cyclopropyl-5-{1-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1 H- pyrazol-4-yl}-N-methylpyridazine-3-carboxamide (1771741-86-6) + SX, N-{4-chloro-3-[(1 - cyanocyclopropyl)carbamoyl]phenyl}-1 -methyl-4-(methylsulfonyl)-3-(1,1,2,2,2- pentafluoroethyl)-1 H-pyrazole-3-carboxamide (1400768-21-9) + SX, 11-(4-chloro-2,6- dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azaspiro[4.2.4.2]tetradec-11 -ene-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-ene-2-one (1031385-91-7) + SX, N-[3-chloro-1-(pyridin-3-yl)-1 H- pyrazol-4-yl]-2-(methylsulfonyl)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- pyridyl)-2H-indazol-5-yl]-1,2,4-triazolidine-3,5-dione (2171099-09-3) + SX, cyproflanilide + SX.

[0085] The present ingredient of group (b) above in combination with the inventive crystal:

[0086] acibenzolar-S-methyl + SX, aldimorph + SX, ametoctradin + SX, 4- dodecyl-2,6-dimethylmorpholine (aldimorph) + SX, ametoctradin + SX, 4- phenoxybenzyl 2-amino-6-methyl-nicotinate (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, benthivalicarb-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, 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, extract from Melaleuca alternifolia + SX, extract from Reynoutria sachalinensis + SX, extract from the cotyledons of lupine plantlets ("BLAD") + SX, extract of Allium sativum + SX, extract of Equisetum arvense + SX, extract of the roots of the white cedar (Thuja occidentalis) + SX, ferbam + SX, fenhexamid + SX, fenoxanil + SX, fenpiclonil + SX, fenpropidin + SX, fenpropimorph + SX, fthalin + SX, flusulfamide + SX, flutriafol + SX, folpet + SX, formaldehyde + SX, fosetyl + SX, fosetyl-Al + SX, fuberidazole + SX, furalaxyl + SX, guazatine + SX, guazatine-acetate + SX, hymexazol + SX, iminoctad + SX, iprobenfos + SX, iprodione + SX, isoprothiolane + SX, kresoxim-methyl + SX, mancopper (mancozeb + copper sulphate) + SX, maneb (zinc + copper sulphate) + SX, mefenoxam (metalaxyl-M) + SX, mepronil + SX, mercurio-ethanol + SX, mercurio-ketyl + SX, metiram (mancozeb + copper sulphate) + SX, metiram (zinc + copper sulphate) + SX, metrafenone + SX, milneb (wettable granules) + SX, milneb (wettable powders) + SX, morpholine + SX, myclobutanil + SX, nabam (ferbam + zinc sulphate) + SX, nabam (wettable granules) + SX, nabam (wettable powders) + SX, nitrothal-isopropyl + SX, nu-phenamid (dimethomorph + tebuconazole) + SX, octhilinone + SX, ofurace + SX, orysastrobin + SX, oxine-copper + SX, oxolinic acid + SX, pencycuron + SX, penthoxytylium hydroxide + SX, penthrin + SX, phenazine-1-carboxylate + SX, phenazine-1-carb oxylate + SX, phenylmercury acetate + SX, phosdip + SX, phosetyl + SX, phosetyl-Al + SX, phthalide + SX, picoxystrobin + SX, piperalin + SX, polycarbamate + SX, polyoxin B + SX, potassium bicarbonate + SX, potassium carbonate + SX, potassium phosphite + SX, propamocarb + SX, propineb + SX, propomocarb hydrochloride + SX, proquinazid + SX, prothioconazole + SX, pyracarbolid + SX, pyraclostrobin + SX, pyridaben + SX, pyrimethanil + SX, pyrithiobac-sodium + SX, pyroxychlor + SX, pyroxyfur + SX, quinoxyfen + SX, quintozene + SX, spiroxamine + SX, sulphur + SX, tebufloquin + SX, tebuconazole + SX, tecloftalam + SX, tecloftalam + SX, teconazol + SX, tetrahydro-5-imidazolecarboxamidine + SX, thiabendazole + SX, thiamethoxam + SX, thiram + SX, tiadinil + SX, timibenconazole + SX, tolylfluarid + SX, tolylfluarid + SX, tolylfluarid + SX, tridemorph + SX, triforine + SX, trinexamide + SX, unaspur + SX, validamycin + SX, vinclozolin + SX, zineb + SX, ziram + 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, fenpropidin + SX, fenpropimorph + SX, fenpyrazamine + SX, fentin acetate + SX, fentin chloride + SX, fentin hydroxide + SX, ferbam + SX, ferimzone + SX, (1 S)-2,2-bis(4-fluorophenyl)-1 -methyl-ethyl-N-[[3-(acetyloxy)-4-methoxy-2-pyridyl]carbonyl]-L-alanine + 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, fosetyl-aluminium + 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, isofetamid + SX, isoflucypram + SX, isoprothiolane + SX, isopyrazam + SX, isotianil + SX, kasugamycin + SX, kresoxim-methyl + SX, laminarin + SX, leaves and bark of Quercus + 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, oxpoconazolefumarate + SX, oxycarboxin + SX, oxytetracycline + SX, pefurazoate + SX, penconazole + SX, pencycuron + SX, penflufen + SX, penhiopyrad + SX, phenamacril + SX, phosphorous acid acid) + SX, tetrachlorophthalide + SX, picarbutrazox + SX, picoxystrobin + SX, piperalin + SX, polyoxins + SX, potassium hydrogencarbonate + SX, potassium dihydrogen phosphite + SX, probenazole + SX, prochloraz + SX, procymidone + SX, propamidine + SX, propamocarb + SX, propiconazole + SX, propineb + ​​SX, proquinazid + SX, prothiocarb + SX, prothioconazole + SX, pydiflumetofen + SX, pyraclostrobin (pyraclostrobin)+SX, pirametostrobin+SX, piraoxystrobin+SX, pirapropoyne+SX, piraziflumid+SX, pyrazophos+SX, pyribencarb+SX, pyributicarb+SX, pyridachlometyl+SX, pyrifenox+SX, pyrimethanil+SX, pyrimorph+SX, pyriofenone+SX,pyrisoxazole + SX, pyroquilon + SX, Quillaja extract + SX, quinconazole + SX, quinofumelin + SX, quinoxyfen + SX, quintozene + SX, Saponins of Chenopodium quinoa + SX, sedaxane + SX, silthiofam + SX, simeconazole + SX, sodium hydrogen carbonate + SX, spiroxamine + SX, streptomycin + SX, sulfur + SX, tebuconazole + SX, tebufloquin + SX, tecloftalam + 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 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-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'-[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-1 H-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(1 H)-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-(1 H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1394057-11-4) + SX, (1 R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1 H-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)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, 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)-2-2-(difluoromethyl)-N-[1,1,3-trimethyl-2,3-dihydro-1 H-inden-4-yl]pyridine-3- carboxamide (1616239-21 -4) + SX, 2-(difluoromethyl)-N-[3-ethyl-1,1 -dimethyl-2,3- dihydro-1 H-inden-4-yl]pyridine-3-carboxamide (1847460-02-9) + SX, 2-(difluoromethyl)-N- [3-propyl-1,1 -dimethyl-2,3-dihydro-1 H-inden-4-yl]pyridine-3-carboxamide (1847460-05-2) + SX, (2E,3Z)-5-{[1 -(4-chlorophenyl)-1 H-pyrazol-3-yl]oxy}-2- (methoxyimino)-N,3-dimethylpent-3-enamide (1445331 -27-0) + SX, (2E,3Z)-5-{[1 -(2,4- dichlorophenyl)-1 H-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 (Trade Mark) 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 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 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 I strain CC080 + 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 ITEM 908 + 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 IMI 206039 + 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, flubeneteram + SX, N-acetyl-2-(ethylsulfonyl)-N-[2-(methoxycarbonyl)-4- (trifluoromethoxy)phenyl]-4-(trifluoromethyl)benzamide (2043675-28-9) + SX, (2S,3S)-3-(2-methylphenyl)butan-2-yl N-[(3-acetyloxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate (2376210-00-1) + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-[(3-acetyloxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2-yl N-[(3-acetyloxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)butan-2-yl N-[(3-acetyloxy-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-chloro-4-phenoxy-5- methylphenyl)-N-ethyl-N-methylformamidine (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- methoxyphenyl)-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-methoxyphenyl)-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-(acetyloxymethoxy)-4-methoxypyridin-2- yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4- methylpentan-2-yl N-{[3-(acetyloxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L- alaninate + SX,(2S,3S)-3-(2,4-difluorophenyl)-4-methylpentan-2-yl N-{[3-(acetyloxy- methoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2,4- dimethylphenyl)-4-methylpentan-2-yl N-{[3-(acetyloxy-methoxy)-4-methoxypyridin- 2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methoxyphenyl)-4- methylpentan-2-yl N-{[3-(acetyloxy-methoxy)-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-methoxyphenyl)-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-methoxyphenyl)- 4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX.

[0087] The present ingredients of group (c) above in combination with the crystals of the present application:

[0088] 1 -methylcyclopropene + SX, 1,3-diphenylurea + SX, 2,3,5-triiodobenzoic acid + SX, IAA ((1 H-indol-3-yl)acetic acid) + SX, IBA ((4-(1 H-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-(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, choline hydroxide + SX, choline nitrate + SX, choline sulfate + SX, clopyralid + SX, copper carbonate + SX, copper hydroxide + SX, copper oxychloride + SX, copper sulfate + SX, cyanamide + SX, daminozide + SX, dikegulac + SX, endothal + SX, ethephon + SX, fenridazon + SX, gibberellic acid + SX, indole-3-acetic acid + SX, maleic hydrazide + SX, mefluidide + SX, mepiquat-chloride + SX, methionine + SX, methylene bisthio cyanate + SX, naphthaleneacetic acid + SX, nitrophenylacetic acid + SX, paclobutrazol + SX, prohexadione-calcium + SX, prohydrojasmine + SX, prothione + SX, pyriminobac-methyl + SX, thidiazuron + SX, trinexapac-ethyl + SX, uniconazole-P + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5chloride) + 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, gibberellin A3 + SX, inabenfide + SX, kinetin + SX, lipochitooligosaccharide SP104 + SX, maleic hydrazide + SX, mefluidide + SX, mepiquat-chloride + SX, oxidized glutathione + SX, pacrobutrazol + SX, pendimethalin + SX, prohexadione-calcium + SX, prohydrojasmon + SX, pyraflufen-ethyl + SX, sintofen + SX, sodium 1-naphthaleneacetate + SX, sodium cyanate + SX, thidiazuron + SX, trinexapac-ethyl + SX, uniconazole + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2,3,5-tri-iodobenzoic acid + SX, 2cyanamide) + SX, streptomycin + SX, thidiazuron + SX, triapenthenol + SX, tribufos + SX, trinexapac-ethyl + SX, uniconazole-P + SX, 2-(naphthalene-1-yl)acetamide + SX, [4-oxo-4-(2-phenylethyl)amino]butyric acid + SX, 5-(trifluoromethyl)benzo[b]thiophene-2-carboxylic acid methyl ester + 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, Azospirillum oryzae + SX, Azospirillum sp. + SX, Azotobacter chroococcum + SX, Azotobacter vinlandii + SX, Beijerinckia indica + SX, Beijerinckia mobilis + SX, Beijerinckia sp. + SX, Bradyrhizobium japonicum + SX, Methylobacterium nodulosa + SX, Methylobacterium sp. + SX, Methylobacterium zatmanii + SX, Methylobacterium zatmanii + SX, Methylobacterium zatmanii + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, Methylobacterium sp. + SX, MethAzospirillum 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, Rhizobium 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.

[0089] The present ingredient of group (d) above in combination with the crystals of the present application:

[0090] anthraquinone + SX, deet + SX, icaridin + SX.

[0091] The ratio of the crystal of the present application to the component is not particularly limited, but can be exemplified by 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, in terms of weight ratio (crystal of the present application: component).

[0092] The crystal of the present application can be used in admixture or in combination with chemical fertilizers (ammonium sulfate, ammonium phosphate, amine nitrate, urea, ammonium chloride, and the like).

[0093] The crystal of the present application or the composition of the present application can prevent plant diseases caused by plant pathogenic microorganisms such as fungi, Oomycete, Phytomyxea, bacteria, and the like. As fungi, Ascomycota, Basidiomycota, Blastocladiomycota, Chytridiomycota, Mucoromycota, and Olpidiomycota can be exemplified, for example. As plant diseases, the following examples can be exemplified. The scientific name of the plant pathogenic microorganism causing the disease is indicated in parentheses.

[0094] Diseases of rice: blast (Pyricularia oryzae), leaf scald (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), bakanae disease (Gibberella fujikuroi), yellow dwarf (Sclerophthora macrospora), pseudo-blast and head blight (Epicoccum nigrum), seedling blight (Trichoderma viride, Rhizopus oryzae);

[0095] Diseases of wheat: powdery mildew (Blumeria graminis), scab (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), brown rust (Puccinia graminis), leaf rust (Puccinia recondita), red snow mould (Microdochium nivale, Microdochium majus), snow mould small sclerotium (Typhula incarnata, Typhula ishikariensis), loose smut (Ustilago tritici), smut (Tilletia caries, Tilletia controversa), eye spot (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), glume blotch (Stagonospora nodorum), yellow spot (Pyrenophora tritici-repentis), seedling damping-off caused by Rhizoctonia solani, take-all (Gaeumannomyces graminis), Pyricularia graminis-tritici;

[0096] Diseases of barley: powdery mildew (Blumeria graminis), scab (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Fusarium culmorum), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), stripe rust (Puccinia hordei), loose smut (Ustilago nuda), net blotch (Pyrenophora teres), brown goss' wilt (Cochliobolus sativus), leaf stripe (Pyrenophora graminea), Ramularia leaf spot (Ramularia collo-cygni), seedling blight caused by Rhizoctonia solani (Rhizoctonia solani);

[0097] Diseases of corn: rust (Puccinia sorghi), southern rust (Puccinia polysora), large patch (Setosphaeria turcica), tropical race 1 (Physopella zeae), leaf blight (Cochliobolus heterostrophus), anthracnose (Colletotrichum graminicola), gray leaf spot (Cercospora zeae-maydis), brown spot (Kabatiella zeae), Phaeosphaeria leaf spot (Phaeosphaeria maydis), Diplodia rot (Stenocarpella maydis, Stenocarpella macrospora), stalk rot (Fusarium graminearum, Fusarium verticilioides, Colletotrichum graminicola), smut (Ustilago maydis), stalk rot (Physoderma maydis);

[0098] Diseases of cotton: anthracnose (Colletotrichum gossypii), white mold (Ramularia areola), black spot (Alternaria macrospora, Alternaria gossypii), black root rot (Thielaviopsis basicola);

[0099] Diseases of coffee: rust (Hemileia vastatrix), leaf spot (Cercospora coffeicola);

[0100] Diseases of oilseed rape: sclerotinia (Sclerotinia sclerotiorum), black spot (Alternaria brassicae), root rot (Phoma lingam), light leaf spot (Pyrenopeziza brassicae);

[0101] Sugarcane diseases: Rust (Puccinia melanocephela, Pucciniakuehnii), Smut (Ustilago scitaminea);

[0102] Sunflower diseases: Rust (Puccinia helianthi), downy mildew (Plasmopara halstedii);

[0103] Citrus diseases: black spot (Diaporthe citri), scab (Elsinoe fawcetti), penicillin rot (Penicillium digitatum), penicillin disease (Penicillium italicum), blight (Phytophthora parasitica, Phytophthora citrophthora), aspergillus niger;

[0104] Apple diseases: Blossom rot (Monilinia mali), canker (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), Alternaria alternata (Alternaria alternata apple pathotype), black spot (Venturia inaequalis), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), ring rot (Botryosphaeria berengeriana), blight (Phytophthora cactorum), red spot (Gymnosporangium). (juniperi-virginianae), rust fungus of Malus halliana (Gymnosporangium yamadae);

[0105] Diseases of pear: black spot (Venturia nashicola, Venturia pirina), black leaf spot (Alternaria alternata Japanese pear pathotype), red spot (Gymnosporangium haraeanum);

[0106] Diseases of peach: brown rot (Monilinia fructicola), black spot (Cladosporium carpophilum), brown mottle (Phomopsis rot) (Phomopsis sp.), leaf curl (Taphrina deformans);

[0107] Diseases of grape: black scab (Elsinoe ampelina), late blight (Glomerella cingulata, Colletotrichum acutatum), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), downy mildew (Plasmopara viticola);

[0108] Diseases of persimmon: anthracnose (Gloeosporium kaki, Colletotrichum acutatum), defoliation (Cercospora kaki, Mycosphaerella nawae);

[0109] Diseases of fig: rust (Phakopsora nishidana);

[0110] Diseases of cucurbits: anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), gummy stem blight (Didymella bryoniae), brown spot (Corynespora cassiicola), wilt (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), late blight (Phytophthora capsici), damping-off (Pythium sp.);

[0111] Diseases of tomatoes: ring rot (Alternaria solani), leaf mold (Cladosporium fulvum), brown spot (Pseudocercospora fuligena), late blight (Phytophthora infestans), powdery mildew (Leveillula taurica);

[0112] Diseases of eggplants: brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum);

[0113] Diseases of cruciferous vegetables: black spot (Alternaria japonica), white spot (Cercosporella brassicae), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica), white rust (Albugo candida);

[0114] Diseases of onions: rust (Puccinia allii);

[0115] Diseases of soybean: purple blotch (Cercospora kikuchii), black spot (Elsinoe glycines), black dot (Diaporthe phaseolorum var. sojae), rust (Phakopsora pachyrhizi), brown ring spot (Corynespora cassiicola), anthracnose (Colletotrichum glycines, Colletotrichum truncatum), damping off (Rhizoctonia solani), brown spot (Septoria glycines), target spot ((Cercospora sojina)), sclerotinia (Sclerotinia sclerotiorum), powdery mildew (Microsphaera diffusa), stem blight (Phytophthora sojae), frogeye leaf spot (Peronospora manshurica), sudden death syndrome (Fusarium virguliforme), red crown rot (Calonectria ilicicola), Diaporthe / Phomopsis complex (Diaporthe longicolla);

[0116] Diseases of dry bean: sclerotinia (Sclerotinia sclerotiorum), rust (Uromyces appendiculatus), angular leaf spot (Phaeoisariopsis griseola), anthracnose (Colletotrichum lindemuthianum), root rot (Fusarium solani);

[0117] Diseases of peanut: black spot (Cercospora personata), brown spot (Cercospora arachidicola), southern blight (Sclerotium rolfsii), red crown rot (Calonectria ilicicola);

[0118] Pea diseases: powdery mildew (Erysiphe pisi) and root rot (Fusarium solani).

[0119] Potato diseases: Early blight (Alternaria solani), Phytophthora infestans, Scarlet rot (Phytophthora erythroseptica), Powdery scab (Spongospora subterraneaf.sp.subterranea), Verticillium wilt (Verticillium albo-atrum, Verticillium dahliae, Verticillium nigrescens), Dry rot (Fusarium solani), Canker (Synchytrium endobioticum).

[0120] Strawberry diseases: powdery mildew (Sphaerotheca humuli);

[0121] Tea diseases: Net cake disease (Exobasidium reticulatum), white spot disease (Elsinoe leucospila), ring spot disease (Pestalotiopsis sp.), anthracnose (Colletotrichum theae-sinensis);

[0122] Tobacco diseases: Red spot disease (Alternaria longipes), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), blight (Phytophthora nicotianae);

[0123] Diseases of beet: Cercospora leaf spot (Cercospora beticola), leaf blight (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root (aphanomyces root rot) (Aphanomyces cochlioides), rust (Uromyces betae);

[0124] Diseases of rose: black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa);

[0125] Diseases of chrysanthemum: brown spot (Septoria chrysanthemi-indici), white rust ((Puccinia horiana));

[0126] Diseases of onion: botrytis leaf blight (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa), grey mould (Botrytis allii), neck rot (Botrytis squamosa);

[0127] Diseases of various crops: grey mould (Botrytis cinerea), sclerotinia (Sclerotinia sclerotiorum), damping off (Pythium aphanidermatum, Pythium irregulare, Pythium ultimum);

[0128] Diseases of radish: black spot (Alternaria brassicicola);

[0129] Diseases of turf grass: dollar spot (Sclerotinia homoeocarpa), brown patch, large patch (Rhizoctonia solani), pythium blight (Pythium aphanidermatum);

[0130] Banana diseases: Banana leaf spot (Sigatoka disease) (Mycosphaerella fijiensis, Mycosphaerella musicola));

[0131] Diseases of lentils: Ascochyta (Ascochyta lentis);

[0132] Chickpea diseases: Ascochyta rabiei blight (chickpea ascochyta rabiei);

[0133] Diseases of bell peppers: Anthracnose (Colletotrichum scovillei);

[0134] Mango diseases: Anthracnose (Colletotrichum acutatum);

[0135] Fruit tree diseases: white root rot (Rosellinia necatrix), purple root rot (Helicobasidium mompa);

[0136] Post-harvest diseases of fruits such as apples and pears: Mucor rot diseases (Mucorpiriformis);

[0137] Seed diseases or diseases in the early stages of growth caused by fungi such as Aspergillus, Penicillium, Fusarium, Gibberella, Trichoderma, Thieviopsis, Rhizopus, Mucor, Corticium, Phona, Rhizoctonia, and Diplodia;

[0138] Viral diseases: Giant vein disease of lettuce mediated by Olpidium brassicae; and various viral diseases of crops mediated by Polymyxa species (e.g., Polymyxa betae and Polymyxa graminis).

[0139] Diseases caused by bacteria: bacterial seedling blight of rice (Burkholderia plantarii), bacterial angular leaf spot of cucumber (Pseudomonas syringae pv. Lachrymans), bacterial wilt of eggplant (Ralstonia solanacearum), bacterial canker of citrus (Xanthomonas citri), bacterial soft rot of Chinese cabbage (Erwinia carotovora), bacterial scab of potato (Streptomyces scabiei), bacterial wilt of corn (Clavibacter michiganensis), crown gall of grape, olive, peach, and the like (Xylella fastidiosa), and bacterial crown gall of Rosaceae plants such as apple, peach, and cherry (Agrobacterium tumefaciens).

[0140] As the plant disease control method of the present application, it can be performed by treating a plant or soil with an effective amount of the crystal of the present application or the composition of the present application. As the treatment method, for example, there can be mentioned stem-leaf treatment, soil treatment, and seed treatment.

[0141] The crystal of the present application or the composition of the present application is usually mixed with a non-active carrier such as a solid carrier and a liquid carrier, and, if necessary, a surfactant, other formulation auxiliary agent is added, and formulated into a solid preparation, an aqueous suspension preparation, and the like, and used. In these formulations, the crystal of the present application or the composition of the present application is usually contained in an amount of 0.0001 to 99% by weight.

[0142] As the solid carrier, for example, there can be mentioned clay (kaolin clay, diatomaceous earth, bentonite, acid clay, and the like), dry silica, wet silica, talc, ceramic, other inorganic minerals (micropowder and granular substance of sericite, quartz, sulfur, activated carbon, calcium carbonate, and the like), and synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate, polyester resin such as polyethylene terephthalate, nylon resin such as nylon-6, nylon-11, and nylon-66, polyamide resin, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer, and the like).

[0143] As the liquid carrier, for example, water, alcohols (methanol, ethanol, isopropanol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxy ethanol, and the like), ketones (acetone, methyl ethyl ketone, cyclohexanone, and the like), aromatic hydrocarbons (toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, and the like), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, ligroin, and the like), esters (ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, and the like), nitriles (acetonitrile, isobutyronitrile, and the like), 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, and the like), amides (N,N-dimethylformamide, N,N-dimethylacetamide, and the like), sulfoxides (dimethyl sulfoxide, and the like), propylene carbonate, and vegetable oils (soybean oil, cottonseed oil, and the like) can be given.

[0144] As the surface active agent, for example, nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyethylene glycol fatty acid ester, and anionic surface active agents such as alkyl sulfonate, alkylbenzenesulfonate, alkyl sulfate can be given. Specifically, 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) and the like can be given.

[0145] As other formulation auxiliary agents, thickening agents, antifoaming agents, preservatives, and antifreezing agents and the like can be given.

[0146] As the thickening agent, for example, natural polysaccharides such as xanthan gum, rhamnose gum, locust bean gum, guar gum, carrageenan, welan gum, alginic acid, alginate, tragacanth gum, and the like; mineral powders such as aluminum silicate, magnesium aluminum silicate, smectite, bentonite, hectorite, synthetic hydrated silicic acid, dry silica, and the like; and aluminum sol can be given.

[0147] In the case where the composition of the present application contains a thickening agent, the total content thereof is usually 0.1 to 5% by weight, relative to 100% by weight of the composition of the present application.

[0148] As the defoaming agent, for example, silicone-based defoaming agents such as ANTIFOAM C emulsion (trade name of Toray Dowcorning Co., Ltd.), ANTIFOAM CE (trade name of Toray Dowcorning Co., Ltd.), ANTIFOAM A COMPOUND (trade name of Toray Dowcorning Co., Ltd.), FS ANTIFOAM 1266 (trade name of Toray Dowcorning 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.), BREAKTHRU AF5503 (trade name of Evonik Industries AG), ANTIFOAM E-20 (trade name of Kao Corp.), TSA730 (trade name of Momentive Performance Materials Japan KK), TSA731 (trade name of Momentive Performance Materials Japan KK), TSA732 (trade name of Momentive Performance Materials Japan KK), YMA6509 (trade name of Momentive Performance Materials Japan KK), and the like; and fluorine-based defoaming agents such as FLUOWET PL80 (trade name of Clariant), and the like; FoamStar 220 (trade name of Cognis Japan Co., Ltd.) can be mentioned.

[0149] In the case where the composition of the present application contains a defoaming agent, the total content thereof is usually 0.05 to 0.5% by weight, relative to 100% by weight of the composition of the present application.

[0150] As the preservative, for example, p-hydroxybenzoic acid esters, salicylic acid derivatives, 1,2-benzisothiazolin-3-one (for example, Proxel GXL (trade name of Lonza), and isothiazolin-3-one derivatives (for example, Biohope L (trade name of KI Chemical Co., Ltd.)) can be mentioned.

[0151] In the case where the composition of the present application contains a preservative, the total content thereof is usually 0.01 to 3% by weight, relative to 100% by weight of the composition of the present application.

[0152] As the antifreezing agent, for example, water-soluble glycols such as ethylene glycol and propylene glycol can be given.

[0153] In the case where the composition of the present application contains an antifreezing agent, the total content thereof is usually 1 to 20% by weight, relative to 100% by weight of the composition of the present application.

[0154] In the present application, the whole plant and specific parts of the plant are included. As the specific parts of the plant, for example, stems and leaves, flowers, ears, fruits, trunks, branches, canopies, seeds, vegetative propagation organs, and seedlings can be given.

[0155] The vegetative propagation organ refers to a part among roots, stems, leaves, and the like of a plant, which has the ability to grow when the part is set in soil by cutting it from the main body. As the vegetative propagation organ, for example, tuberous roots, creeping roots, bulbs, corms or solid bulbs, tubers, rhizomes, stolons, rhizophores, cane cuttings, propagules, and vine cuttings can be given. Note that the stolon is also called runner, and the propagule is also called bulbil, which is classified into broad bud and bulbil. The vine cutting refers to a seedling (total of leaves and stems, shoot) of Dioscorea alata, Dioscorea japonica, and the like, which has no root. The bulb, corm, tuber, rhizome, cane cutting, rhizophore, or tuberous root is collectively called a bulbous root. The cultivation of potatoes is started by planting tubers in soil, but the tuber used is generally called a seed potato.

[0156] The application amount of the crystal of the present application or the composition of the present application also varies depending on the weather condition, the formulation form, the application timing, the application method, the application site, the target disease, the target crop, and the like, and in the case of foliage treatment or soil treatment, it is usually 1 to 500 g per 1000 m 2 of the application site. In the case of seed treatment, the amount of the crystal of the present application or the composition of the present application is usually 0.001 to 100 g per 1 kg of seeds. In the case where the crystal of the present application or the composition of the present application is formulated as an emulsion, a wettable powder (Japanese: suiwai agent), a suspension, or the like, it is usually diluted with water so that the effective ingredient concentration becomes 0.01 to 10000 ppm, and then applied, and the powder, granules, and the like are usually applied directly.

[0157] As seed treatment, for example, there can be mentioned treatment of seeds or vegetative propagation organs with the crystal of the present application or the composition of the present application, specifically, for example, there can be mentioned spray treatment in which a suspension of the crystal of the present application or the composition of the present application is atomized and sprayed onto the surface of seeds or vegetative propagation organs, coating treatment in which the crystal of the present application or the composition of the present application is applied to seeds or vegetative propagation organs, dipping treatment in which seeds are dipped in a solution of the crystal of the present application or the composition of the present application for a certain period of time, and a method in which seeds or vegetative propagation organs are coated with a carrier containing the crystal of the present application or the composition of the present application (encapsulation treatment, pellet coating treatment, etc.). As the vegetative propagation organs mentioned above, tubers can be particularly mentioned.

[0158] In the case where seeds or vegetative propagation organs are treated with the composition of the present application, the composition of the present application can be prepared into one formulation and the seeds or vegetative propagation organs can be treated with the one formulation, or the composition of the present application can be prepared into different formulations and the seeds or vegetative propagation organs can be treated with the different formulations in multiple times. As the method in which the composition of the present application is prepared into different formulations and the seeds or vegetative propagation organs are treated in multiple times, for example, there can be mentioned a method in which the seeds or vegetative propagation organs are treated with a formulation containing only the crystal of the present application as an effective ingredient, the seeds or vegetative propagation organs are allowed to dry, and then the seeds or vegetative propagation organs are treated with a formulation containing the ingredient, and a method in which the seeds or vegetative propagation organs are treated with a formulation containing the crystal of the present application and the ingredient as effective ingredients, the seeds or vegetative propagation organs are allowed to dry, and then the seeds or vegetative propagation organs are treated with a formulation containing the ingredient other than the treated ingredient.

[0159] The so-called seeds or vegetative propagation organs having the crystal of the present application or the composition of the present application in the present application means a substance in a state in which the crystal of the present application or the composition of the present application is attached to the surface of seeds or vegetative propagation organs. The seeds or vegetative propagation organs having the crystal of the present application or the composition of the present application mentioned above can have a material other than the crystal of the present application or the composition of the present application attached thereto before or after the crystal of the present application or the composition of the present application is attached to the seeds or vegetative propagation organs.

[0160] In addition, in the case where the composition of the present application is attached to the surface of seeds or vegetative propagation organs in a layer, the layer is formed of one layer or multiple layers. In addition, in the case where the layer is formed of multiple layers, each layer is a layer containing one or more effective ingredients, or is formed of a layer containing one or more effective ingredients and a layer not containing an effective ingredient.

[0161] The seeds or vegetative propagation organs having the crystal of the present application or the composition of the present application can be obtained, for example, by applying a formulation containing the crystal of the present application or the composition of the present application to seeds or vegetative propagation organs by the seed treatment method mentioned above.

[0162] The crystal of the present application or the composition of the present application can be used as an agent for preventing or treating plant diseases in agricultural lands such as upland fields, paddy fields, lawns, orchards, and the like. As the plants, for example, the following plants can be mentioned:

[0163] corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rape, sunflower, sugarcane, tobacco, Solanaceae vegetables (eggplant, tomato, green pepper, hot pepper, potato, and the like), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, and the like), Cruciferae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower, and the like), Asteraceae vegetables (burdock, chrysanthemum, artichoke, lettuce, and the like), Liliaceae vegetables (onion, garlic, asparagus, and the like), Umbelliferae vegetables (carrot, parsley, celery, parsnip, and the like), Chenopodiaceae vegetables (spinach, Swiss chard, and the like), Labiatae vegetables (perilla, mint, basil, and the like), strawberry, sweet potato, Japanese yam, taro, pome fruits (apple, European pear, Japanese pear, Shaddock, Japanese mountain-ash, and the like), stone fruits (peach, plum, nectarine, green plum, cherry, apricot, prune, and the like), citrus fruits (Unshiu mandarin, orange, lemon, lime, grapefruit, and the like), nuts (chestnut, walnut, hazelnut, almond, pistachio, cashew nut, macadamia nut, and the like), berry fruits (blueberry, small red fruit, blackberry, raspberry, and the like), grape, persimmon, olive, loquat, banana, coffee, date, coconut, tea, mulberry, ornamental plants, forest plants, lawn grasses, and pasture grasses.

[0164] Among the above plants, genetically modified crops are also included.

[0165] Examples

[0166] Hereinafter, the present application will be described more specifically by giving manufacturing examples, reference manufacturing examples, formulation examples, and test examples, but the present application is not limited to these examples. Note that "%" and "parts" in the examples mean "wt%" and "wt parts" unless otherwise specified.

[0167] In addition, the manufactured crystal of the present application was measured for various physical properties using the following apparatus (with measurement conditions).

[0168] Powder XRD

[0169] Powder X-ray diffractometer: SmartLab (manufactured by Rigaku Corporation)

[0170] X-ray output: Cu-Ka, 45 kV, 200 mA

[0171] Sampling width: 0.02°

[0172] Scanning range: 2° to 50°

[0173] Measurement temperature: room temperature

[0174] Single crystal XRD

[0175] (Ra1 type crystal)

[0176] Apparatus: R-AXIS RAPID (manufactured by Rigaku Corporation)

[0177] X-ray source: Mo-Ka

[0178] Measurement temperature: room temperature

[0179] Solve: SHELXT

[0180] Refinement: SHELXL

[0181] (Ra2 type crystal)

[0182] Apparatus: R-AXIS RAPID (manufactured by Rigaku Corporation)

[0183] X-ray source: Mo-Ka

[0184] Measurement temperature: room temperature

[0185] Solve: SIR2014

[0186] Refinement: SHELXL

[0187] (Ra3 type crystal)

[0188] Apparatus: XtaLAB Synergy (manufactured by Rigaku Corporation)

[0189] X-ray source: Cu-Ka

[0190] Measurement temperature: 100 K

[0191] Solve: SHELXT

[0192] Refinement: SHELXL

[0193] DSC

[0194] Apparatus: DSC Q2000 (manufactured by TA Instruments)

[0195] Temperature increase rate: 2°C / min

[0196] Sample amount: 0.5 to 5 mg

[0197] Measurement atmosphere: nitrogen

[0198] Fourier transform infrared spectroscopy (FT-IR)

[0199] Apparatus: Nicolet iS50 (manufactured by Thermo Fisher Scientific Inc.)

[0200] Method: Diamond ATR method

[0201] Micro-Raman spectroscopy

[0202] Apparatus: NRS-5100 (manufactured by Japan Spectroscopic Co., Ltd.)

[0203] Laser wavelength: 532 nm

[0204] Optical microscopy

[0205] Optical microscope: Leica Z16 APO (manufactured by Leica Microsystems)

[0206] Camera: Leica MC170 HD (manufactured by Leica Microsystems)

[0207] Magnification: 115 times

[0208] A production example of the crystal of the present application is described.

[0209] Production Example 1

[0210] (Ra2-type crystal production)

[0211] 30 mg of Compound A was dissolved in methanol at 60°C to prepare 375 mg / mL. After the solution was cooled to room temperature, laser light was irradiated under the following conditions, and then left to stand at 20°C to obtain an Ra2-type crystal.

[0212] The laser irradiation conditions were set as follows.

[0213] < femtosecond laser >

[0214] Wavelength: 800 nm

[0215] Pulse width: 181 fs

[0216] Number of pulses: 125 pulses / 10 seconds

[0217] Production Example 2

[0218] (Ra1-type crystal production)

[0219] Ra2-type crystal 200 mg obtained in Production Example 1 was measured in a 20 mL volumetric sample bottle, and heated at 130°C for 2 hours to obtain an Ra1-type crystal.

[0220] Production Example 3

[0221] (Manufacturing of Ra3 type crystals)

[0222] 100 mg of Ra1 type crystals obtained in Manufacturing Example 2 was added to 1 mL of diisopropyl ether. The suspension was heated to 60 °C and stirred at 1000 rpm for 2 days. The solvent was then removed to obtain Ra3 type crystals.

[0223] Reference Manufacturing Example 1

[0224] (Manufacturing of Ra4 type crystals)

[0225] The Ra4 type crystal is manufactured by dissolving compound A in toluene and then recrystallizing it, as described in WO 92 / 12970 (Patent Document 1).

[0226] The physical properties of the crystal of the present invention are shown below.

[0227] Ra1-type crystal

[0228] IR characteristic peaks: 2933.0, 1648.4, 1632.0, 1606.6, 1554.6, 1338.8, 1082.9, and 1036.5 cm⁻¹ -1 .

[0229] Raman characteristic peaks: 2946, 2927, 2858, 1649, 1631 and 1397 cm⁻¹ -1 Nearby peaks.

[0230] XRD characteristic peaks:

[0231] right Figure 1 The characteristic diffraction peaks in the powder X-ray diffraction pattern shown are represented in Table 1 as diffraction peaks in the form of diffraction angles (2θ ± 0.2°), but are not limited to them.

[0232] Table 1

[0233] Table 1

[0234]

[0235] Typical diffraction peaks 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.

[0236] Ra2-type crystal

[0237] IR characteristic peaks: 3292.4, 2957.1, 2927.5, 1659.1, 1642.0, 1544.1, 1133.5, and 1123.2 cm -1 .

[0238] Raman characteristic peaks: 3118, 2924, 2876, 1658, and 1641 cm -1 nearby peaks.

[0239] XRD characteristic peaks:

[0240] For the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 2, the diffraction peak values in the form of diffraction angles (2Θ ± 0.2°) are shown in Table 2, but are not limited thereto. Figure 2 Table 2

[0241]

Table 2

[0242]

[0243] As typical diffraction peak values, 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 shown in Table 2 above can be cited.

[0244]

[0245] 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 .

[0246] Raman characteristic peaks: 3046, 2928, 1652, 1588, and 1545 cm -1 nearby peaks.

[0247] XRD characteristic peaks:

[0248] For the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 3, the diffraction peak values in the form of diffraction angles (2Θ ± 0.2°) are shown in Table 3, but are not limited thereto.

[0249] Figure 3 Table 3

[0250]

Table 3

[0251]

[0252] ​​

[0253] As typical diffraction peak values, 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 shown in Table 3 can be mentioned.

[0254] For comparison with the Ra1 type crystal, the Ra2 type crystal, and the Ra3 type crystal of the present application, the various spectral values of the Ra4 type crystal are shown below.

[0255] Ra4-type crystal

[0256] IR characteristic peaks: 2953.8, 1635.5, 1608.7, 1553.2, 1138.7, 1066.8, 1034.2, and 1012.3 cm -1 .

[0257] Raman characteristic peaks: 2928, 2859, 1491, 1398, and 1311 cm -1 nearby.

[0258] XRD characteristic peaks

[0259] For Figure 4 The characteristic diffraction peaks in the powder X-ray diffraction pattern shown in Table 4 are expressed as diffraction peak values in the form of diffraction angles (2θ ± 0.2°), but are not limited thereto.

[0260] Table 4

[0261]

Table 4

[0262]

[0263] As typical diffraction peak values, 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 shown in Table 4 can be mentioned.

[0264] For the crystal of the present application, the crystallographic data of the single crystal are shown in Table 5 below.

[0265] Table 5

[0266]

Table 5

[0267]

[0268] The plant disease control efficacy of the crystal of the present application was determined using the following test examples.

[0269] Test Example 1

[0270] A mixture (weight ratio 1 : 1) of 5 parts of the Ra1 type crystal or the Ra4 type crystal as a comparative object, white carbon black and polyoxyethylene alkyl ether sulfate ammonium salt, and 60 parts of water was mixed, and micro-pulverized by a wet type pulverization method, whereby a preparation was obtained. A dilute solution was obtained by adding water to the preparation so that the concentration of the Ra1 type crystal or the Ra4 type crystal was 2 ppm.

[0271] A plastic pot was filled with soil, and soybeans (variety: Black Kidney) were sown therein, and grown in a greenhouse for 15 days. Thereafter, a water suspension of spores of Phakopsora pachyrhizi was sprayed and inoculated. After the inoculation, it was left at 23°C under a high humidity condition for 1 night, and then cultivated in a greenhouse for 3 days, and then the above dilute solution was foliar-sprayed in a manner so as to be sufficiently adhered to the leaf surface of the above soybeans. After the spraying, the plants were air-dried, and left under a high humidity condition only at night, and the lesion area was investigated 7 days after the spraying.

[0272] On the other hand, in the untreated area, the same operation as in the treated area was performed except that the Ra1 type crystal or the Ra4 type crystal was not used, and the lesion area of the soybean rust in the untreated area (untreated area lesion area) was investigated.

[0273] From the lesion areas of the treated area and the untreated area, respectively, the efficacy of the treated area was calculated by using the following "Formula 1".

[0274] The results thereof are shown in Table 6.

[0275] "Formula 1"

[0276] Efficacy (%) = [1 - (treated area lesion area / untreated area lesion area)] x 100

[0277] Table 6

[0278] [Table 6]

[0279] Test crystal Potency (%) Ra1-type crystal 72 Ra4-type crystal 54

[0280] It was found that the Ra1 type crystal showed a higher efficacy than the Ra4 type crystal.

[0281] Test Example 2

[0282] Five parts of Ra2-type crystals, Ra3-type crystals, or Ra4-type crystals (as a comparison), 35 parts of a mixture of silica and polyoxyethylene alkyl ether ammonium sulfate (weight ratio 1:1), and 60 parts of water were mixed and micronized using a wet milling method to obtain a formulation. Water was then added to this formulation to make the Ra2-type crystals, Ra3-type crystals, or Ra4-type crystals 50 ppm, to obtain a diluent.

[0283] Soil was filled into plastic pots, and rice (variety: Hinohikari) was sown in them and grown in a greenhouse for 17 days. The diluted solution was sprayed onto the foliage of the rice plants, ensuring it adhered fully to the leaves. After spraying, the plants were air-dried and then cultivated outdoors for 8 days. Subsequently, under greenhouse conditions of 24°C during the day and 20°C at night with high humidity, the sprayed rice plants were placed in contact with rice seedlings infected with Pyricularia oryzae for 11 days, and the area of ​​lesions (lesion area in the treated area) was investigated.

[0284] On the other hand, in the untreated area, the same operation as in the treated area was performed except that Ra2-type crystals, Ra3-type crystals, or Ra4-type crystals were not used for treatment, and the lesion area of ​​rice blast in the untreated area (lesion area of ​​the untreated area) was investigated.

[0285] The effectiveness of the treatment area is determined using Equation 1 above, based on the lesion area of ​​the treated and untreated areas.

[0286] The results are shown in Table 7.

[0287] Table 7

[0288] Table 7

[0289] Test crystal Potency (%) Ra2-type crystal 85 Ra3-type crystal 75 Ra4-type crystal 50

[0290] It can be seen that Ra2 and Ra3 crystals exhibit higher efficiency than Ra4 crystals.

[0291] Industrial availability

[0292] The crystals of this invention (Ra1 type crystals, Ra2 type crystals and Ra3 type crystals) show excellent control effects on plant diseases.

Claims

1. A crystal, which is a racemic mixture of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, is 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 Cu-Kα ray-based powder X-ray diffraction.

2. A plant disease control composition comprising the crystals of claim 1.

3. A method for preventing and controlling plant diseases, comprising the step of treating the plant or the soil in which the plant grows with an effective amount of the crystals as described in claim 1.

4. Use of the crystal according to claim 1 for the prevention and control of plant diseases.

5. A composition comprising one or more ingredients selected from group (a), group (b), group (c) and group (d), and the crystal of claim 1. Group (a): Groups containing insecticidal, acaricidal, and nematicidal active ingredients; Group (b): Bactericidal active ingredients; Group (c): Plant growth regulators; Group (d): Repellent component.

6. A method for treating a seed or vegetative reproductive organ, wherein the crystal of claim 1 or the composition of claim 2 is applied to the surface of the seed or vegetative reproductive organ in an effective amount.

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