Solid forms of heterocyclic amide derivatives

Abstract

The present invention relates to a crystalline polymorph of a compound of formula (I) having a powder X-ray diffraction pattern comprising at least three 2 [theta] angle values selected from the group consisting of 7.2 + / -0.2 DEG, 10.8 + / -0.2 DEG, 13.8 + / -0.2 DEG, 14.4 + / -0.2 DEG, 14.8 + / -0.2 DEG, 15.9 + / -0.2 DEG, 16.4 + / -0.2 DEG, 19.9 + / -0.2 DEG, 20.7 + / -0.2 DEG, 22.2 + / -0.2 DEG, 22.6 + / -0.2 DEG, 23.9 + / -0.2 DEG, 24.6 + / -0.2 DEG, 26.3 + / -0.2 DEG, 27.5 + / -0.2 DEG, 30.0 + / -0.2 DEG, 32.0 + / -0.2 DEG, and 32.7 + / -0.2 DEG. # imgabs0 #

Description

[0001] The present invention relates to a solid form of a heterocyclic amide derivative, a method for preparing the solid form, a composition comprising the solid form and a method for using the same as a fungicide.

[0002] WO 2007 / 048556 discloses that certain heterocyclic amide derivatives have microbicidal activity, such as fungicidal activity. Specifically, a compound of formula I is disclosed, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methylene-naphthalene-5-yl)-amide:

[0003]

[0004] A new solid form of the compound and its preparation has now been found. Therefore, the present invention relates to a new crystalline form of a heterocyclic amide derivative, which is a crystalline polymorph of a compound of formula I:

[0005]

[0006] The crystalline polymorph according to the invention presents optimized handling and processing, especially on a manufacturing scale. More specifically, the crystalline polymorph can ensure a significant improvement in reducing filtration times.

[0007] More specifically, the crystalline polymorphs of Formula I may be characterized by a powder X-ray diffraction pattern expressed in terms of 2θ angles and / or d-spacings.

[0008] The crystalline polymorph of Formula I may have a powder X-ray diffraction pattern comprising at least three 2θ angle values, preferably at least six 2θ angle values, preferably at least eight 2θ angle values, and more preferably at least ten 2θ angle values ​​selected from the group consisting of: 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 1 5.9±0.2°, 16.4±0.2°, 19.9±0.2°, 20.7±0.2°, 22.2±0.2°, 22.6±0.2°, 23.9±0.2°, 24.6±0.2°, 26.0±0.2°, 26.3±0.2°, 27.5±0.2°, 30.0±0.2°, 32.0±0.2° and 32.7±0.2°.

[0009] In a preferred embodiment, the crystalline polymorph of Formula I may have a powder X-ray diffraction pattern comprising at least three 2θ angle values, preferably at least six 2θ angle values, preferably at least eight 2θ angle values, and more preferably at least ten 2θ angle values ​​selected from the group consisting of: 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 16.4±0.2°, 20.7±0.2°, 22.2±0.2°, 24.6±0.2°, 26.0±0.2°, 27.5±0.2°, 30.0±0.2°, 32.0±0.2°, and 32.7±0.2°.

[0010] More specifically, the crystalline polymorph of Formula I may have a powder X-ray diffraction pattern comprising at least the following 2θ angle values: 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 16.4±0.2°, 20.7±0.2°, 22.2±0.2°, 24.6±0.2°, and 26.0±0.2°; preferably at least the following 2θ angle values: 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 16.4±0.2°, 20.7±0.2°, 22.2±0.2°, 24.6±0.2°, 26.0±0.2°. °, 27.5±0.2°, 30.0±0.2°, 32.0±0.2° and 32.7±0.2°; and more preferably at least the following 2θ angle values: 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 15.9±0.2°, 16.4±0.2°, 19.9±0.2°, 20.7±0.2°, 22.2±0.2°, 22.6±0.2°, 23.9±0.2°, 24.6±0.2°, 26.0±0.2°, 26.3±0.2°, 27.5±0.2°, 30.0±0.2°, 32.0±0.2° and 32.7±0.2°.

[0011] d spacing value using The average wavelength is calculated and given in Table 1 above the 2θ angle values.

[0012]

[0013]

[0014] Table 1

[0015] The crystalline polymorphs of the present invention can be characterized by the unit cell parameters of their single crystals as shown in Table 2.

[0016]

[0017] Table 2

[0018] In Table 2, a, b, c are the lengths of the unit cell edges, and α, β, γ are the angles of the unit cell.

[0019] In particular embodiments of the present invention, the crystalline polymorph may have the following lattice parameters: α=70.2±0.2°, β=84.1±0.2°, γ=74.4±0.2°, and

[0020] In another embodiment, the crystalline polymorph according to the present invention may have a melting point ranging from 153° C. to 156° C. (peak position) and preferably ranging from 154° C. to 155° C. (peak position). The melting point is obtained using differential scanning calorimetry (DSC) at a heating rate of 10° C. / min.

[0021] In the context of the present invention, polymorphs are specific crystalline forms of a compound that can exist in more than one crystalline form in the solid state. The crystalline form of a compound includes constituent molecules arranged in an ordered repeating pattern (extending in all three spatial dimensions) (in contrast, amorphous solid forms do not have long-range order in the position of the molecule). Different polymorphs of a compound have different atomic and or molecular arrangements in their crystal structures. When the compound is a biologically active compound such as a fungicide, the differences in crystal structure can result in different polymorphs with different chemical, physical and biological properties. Properties that can be affected include crystal morphology, density, hardness, color, chemical stability, melting point, water absorption, suspension rate, dissolution rate and bioavailability. Thus, a particular polymorph may have properties that make it more advantageous in a particular use relative to another polymorph of the same compound: in particular, the physical, chemical and biological properties listed above may have a significant impact on the development of production methods (especially on a manufacturing scale) and formulations; on the ease with which the compound can be combined in a formulation with other active ingredients and formulation components; and / or on the quality and efficacy of plant treatment agents such as fungicides. It should be noted that it is not possible to predict whether the solid state of a compound may be present as more than one polymorph, nor the properties of any of these crystalline forms.

[0022] By conventional methods known in the art, the solid phase can be measured for the presence of crystals. For example, it is convenient and conventional to use powder X-ray diffraction techniques. Other techniques that can be used include differential scanning calorimetry (DSC), near infrared spectroscopy, mid-infrared spectroscopy, nuclear magnetic resonance (NMR), gas chromatography or high performance liquid chromatography (HPLC). Single crystal X-ray diffraction is particularly useful in identifying crystal structures.

[0023] Another object of the present invention relates to a method for preparing a crystalline polymorph of a compound of formula I, comprising the following steps:

[0024] i. mixing the prodrug compound of formula I with an organic solvent at a temperature of at least 30°C, and more preferably at least 40°C, so as to obtain a saturated solution of the prodrug compound of formula I,

[0025] ii. optionally, filtering the mixture obtained in step i,

[0026] iii. crystallizing the compound obtained in step ii at a temperature of less than 30°C, and preferably up to 25°C, to obtain a suspension, and

[0027] iv. storing the suspension obtained in step iii at a temperature of less than 30°C and preferably up to 25°C for preferably at least 2 hours, preferably at least 4 hours, preferably at least 10 hours, preferably at least 15 days, and more preferably at least 30 days to obtain the crystalline polymorph of the compound of formula I.

[0028] The original drug compound of formula I is a racemic mixture of a compound of formula I (3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-bridged methylene-naphthalen-5-yl)-amide) prepared as described in Example P11 of WO 2012 / 101139 with a purity of at least 98% and more preferably at least 99%.

[0029] The organic solvent may be selected from xylene, isopropanol, chlorobenzene, acetone, methylcyclohexane, ethyl acetate, methanol, acetonitrile, and any mixture thereof.

[0030] In step i, a saturated solution means that no more solute (compound of formula I) can be dissolved in the solvent.

[0031] In step ii, a filtration step can help remove any remaining solid particles, such as, for example, undissolved solids, crystals, and / or dust. This optional step can limit or prevent nucleation sites during the preparation process.

[0032] Step iv can advantageously be carried out under stirring and preferably under constant stirring. The stirring can be gentle stirring, and more particularly constant gentle stirring. In the present invention, gentle stirring means stirring sufficient to suspend the solids.

[0033] Step iv may be followed by a filtration step v of the stored suspension in order to separate the crystals produced in step iv from their solvent(s) and to use them as solid seeds.

[0034] The polymorphs of the invention can be applied in unaltered form, but are more preferably applied by conventional means incorporated into an agrochemical composition. Therefore, a further object according to the invention relates to an agrochemical composition comprising the crystalline polymorph as defined in the invention and at least one agriculturally acceptable carrier or diluent. The agrochemical composition comprising the crystalline polymorph of the invention can be used to control phytopathogenic fungi on a variety of plant species.

[0035] Another object of the present invention relates to a method for preventing or controlling fungal infections on plants or plant propagation materials, which comprises treating the plants or plant propagation materials with said agrochemical composition, and preferably with a fungicidally effective amount of said agrochemical composition.

[0036] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0037] The term "plant propagation material" is understood to mean all reproductive parts of a plant, such as seeds, which can be used for the latter's proliferation, including vegetative plant materials, such as cuttings. Seeds (strictly speaking), roots, fruits, tubers, bulbs, rhizomes, parts of plants can be mentioned as plant propagation materials. Germinating plants and young plants that will be transplanted after germination or after emergence can also be mentioned. These young plants can be treated completely or partially by dipping and protected before transplanting. Before sowing or planting the plant propagation material, the material can be treated with the composition of the present invention. Alternatively, during sowing or planting, the plant propagation material can be treated with the composition of the present invention. In addition, before or during the planting of plant propagation material, the composition of the present invention can be applied to the plant propagation material previously treated. The composition of the present invention can be applied during the sowing of seeds. The composition can also be used for plant propagation materials derived from plants grown in greenhouses and / or during transplanting.

[0038] More preferably, plant propagation material is plant seed.For the purpose of germination and growth of plant, seed treatment can occur in unsown seed, and term " unsown seed " means to comprise the seed of any period between the harvest of seed and the sowing of seed in the soil.For the processing of unsown seed, it is not intended to comprise that wherein these compositions are applied to those practices in the soil but to comprise any application practice that seed is targeted during the sowing / planting process.The treated plant propagation material of the present invention can be processed in the same manner as conventional plant propagation material.These treated plant propagation materials can be stored, processed, sown and cultivated in the same manner as the material processed with any other pesticide.

[0039] The agricultural chemical composition of the present invention can be used to control plant pathogenic fungi belonging to the following classes: Ascomycetes (for example, Venturia, Psoralea, Erysiphe, Corythuja, Mycosphaeria, Uncinaria); Basidiomycetes (for example, Hemileia, Rhizoctonia, Puccinia, Puccinia, Ustilago, Tilletia); Deuteromycetes (also known as Deuteromycetes, for example, Botrytis, Helminthosporium, Rhizoctonia, Fusarium, Septoria, Cercospora, Alternaria, Pyrospora and Pseudocercospora); Oomycetes (for example, Phytophthora, Peronospora, Pseudocercospora, Albugo, Discoideum, Pythium, Pseudocercoideum and Monoparana).

[0040] The agrochemical compositions of the present invention are suitable for controlling such diseases on a variety of plants and their propagation materials, including but not limited to the following target crops: cereals (wheat, barley, rye, oats, corn (including field corn, popcorn and sweet corn), rice, sorghum and related crops); beets (sugar beets and fodder beets); legumes (beans, lentils, peas, soybeans); oil crops (rapeseed, mustard, sunflower); cucumber plants (zucchini, cucumber, cantaloupe); fiber plants (cotton, flax, hemp, jute); vegetables vegetables (spinach, lettuce, asparagus, cabbage, carrots, eggplant, onions, peppers, tomatoes, potatoes, red peppers, okra); cultivated crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals (flowers, shrubs, broadleaf trees and evergreens such as pines and cypresses); and other plants such as vines, shrub fruits (such as blueberries), caneberries, cranberries, mint, rhubarb, sugarcane, and turf grasses, including but not limited to cool-season turf grasses (e.g., bluegrasses, Poa canina, and bluegrasses). L.), such as Kentucky bluegrass (Poa pratensis L.), rough bluegrass (Poa trivialis L.), Canada bluegrass (Poa compressa L.), and annual bluegrass (Poa annua L.); bentgrasses (Agrostis L.), such as creeping bentgrass (Agrostis palustris Huds.), colonial bentgrass (Agrostis tenius Sibth.), velvet bentgrass (Agrostis canina L.), and redtop (Agrostis alba L.); fescues (Festuca L.), such as tall fescue (Festuca arundinacea). fescue, Festuca arundinacea Schreb.), meadow fescue, Festuca elatior L., and fine fescue such as creeping red fescue, Festuca rubra L., chewing fescue, Festuca rubra var. commutata Gaud., sheep fescue, Festuca ovina L.) and hard fescue (Festuca longifolia); and ryegrasses (Lolium L.), such as perennial ryegrass (Lolium perenne L.) and annual (Italian) ryegrass (Lolium multiflorum Lam.)) and warm-season turfgrasses (e.g., Bermudagrasses (Cynodon LCRich), including hybrid and common Bermudagrasses; Zoysiagrasses (Zoysia Willd.), St. Augustinegrass (Stenotaphrum secundatum (Walt.) Kuntze); and centipedegrass (Eremochloa ophiuroides) (Munro.) Hack.)).

[0041] In addition, "crops" are understood to include those crops that have been tolerant to pests and pesticides (including various herbicides or various classes of herbicides) as a result of conventional methods of breeding or genetic engineering. Tolerance to, for example, herbicides means that the sensitivity to damage caused by a particular herbicide is reduced compared to conventional crop species. Crops can be modified or bred so as to be tolerant, for example, to HPPD inhibitors, such as mesotrione, or EPSPS inhibitors, such as glyphosate.

[0042] In particular, the compositions according to the invention are particularly effective against powdery mildew; rust; leaf spot species; early blight and mold; in particular against Septoria, Puccinia, Powdery Mildew, Pyrococcus and Tapesia in cereals; Puccinia in soybeans; Puccinia in coffee; Puccinia in roses; Alternaria in potatoes, tomatoes and cucurbits; Sclerotinia in turf, vegetables, sunflowers and rapeseed; black rot, red fire, powdery mildew, gray mold and vine blight in vines; Botrytis cinerea in fruit; Monilinia spp. in fruit and Penicillium spp. in fruit.

[0043] Furthermore, the compositions according to the invention are particularly effective against seedborne and soilborne diseases, such as Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurogenum, Cochliobolus graminearum, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium gloeosporium, graminis, Helminthosporium spp., Pyrenophora graminea, Pyrithosporium spp., Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Ustilago spp., Tilletia spp., Typhula incarnata, Ustilago spp., Ustilago spp. or Verticillium spp.; in particular against cereals, such as wheat, barley, rye or oats; corn; rice; cotton; soybeans; turf; sugar beet; rapeseed; potatoes; pulse crops, such as peas, lentils or chickpeas; and sunflower pathogens.

[0044] Furthermore, the compositions according to the invention are particularly effective against post-harvest diseases such as Botrytis cinerea, Colletotrichum lunulata, Fusarium semitecum, Geotrichum candidum, Psoralea corylifolia, Psoralea sylvestris, Sclerotinia sclerotiorum, Mucor pyriformis, Penicillium italicum, Penicillium sepium, Penicillium digitatum or Penicillium expansum; in particular against pathogens of fruits such as pome fruits (e.g. apples and pears), stone fruits (e.g. peaches and plums), citrus, melon, papaya, kiwi, mango, berries (e.g. strawberries), avocados, pomegranates and bananas, and nuts.

[0045] The compositions according to the invention are particularly useful for controlling the following diseases on the following crops: Alternaria species on fruits and vegetables; Ascochyta species on legumes; Botrytis cinerea on strawberries, tomatoes, sunflowers, legumes, vegetables and grapes, such as Botrytis cinerea on grapes; Brown spot on peanuts; Corytomyces graminearum on cereals; Colletotrichum species on legumes; Powdery mildew species on cereals, such as B. tritici on wheat and B. graminearum on barley; Powdery mildew on cucurbits and B. graminearum on cucumbers; Fusarium species on cereals and corn; Graminoides graminearum on cereals and lawns graminis); Helminthosporium species on corn, rice, and potatoes; Psoralea coffeae on coffee; Psoralea nivalis species on wheat and rye; Psoralea graminis in bananas; Phakopsora species in soybeans, such as Psora pachyrhizi in soybeans; Puccinia species on broadleaf crops and perennials; such as Puccinia tritici on wheat, Puccinia streak on wheat, and Puccinia tritici on barley; Pseudocercospora species in cereals, such as Puccinia tritici on wheat; Puccinia brevis on roses; Powdery mildew species on fruit; Pyricularia species in barley, such as Pyricularia rotundifolia on barley; Pyricularia oryzae on rice; Cygnus cylindrica on barley; Rhizoctonia solani in cotton, soybeans, cereals, maize, potatoes, rice, and turf, such as Rhizoctonia solani on potatoes, rice, barley, and cotton; Pseudomonas solani on barley, Pseudomonas solani on rye; Turf, lettuce, Sclerotinia species in vegetables and oilseed rape, such as Sclerotinia sclerotiorum on rapeseed and Sclerotinia sclerotiorum on turf; Septoria species in cereals, soybeans and vegetables, such as Septoria tritici on wheat, Septoria glumensis on wheat and Septoria sojae on soybeans; Ustilago officinalis on corn; Tinderella species on cereals; Uncinaria, Botrytis cinerea and Phomopsis viticola on vines; Ustilago officinalis on rye; Ustilago officinalis species in beans; Ustilago officinalis species on cereals and corn; Venturia species in fruits, such as Venturia inaequalis on apples; Sclerotinia sp. on fruits; Penicillium species on citrus and apples.

[0046] The application rate of the agricultural chemical composition of the present invention depends on the specific type of fungi to be controlled, the required control degree and the application time arrangement and method and can be easily determined by a person of ordinary skill in the art. Usually, the composition of the present invention can be applied at an application rate between 0.005 kilograms per hectare (kg / ha) and about 5.0 kg / ha based on the total amount of active fungicides in the composition. The application rate between about 0.1 kg / ha and about 1.5 kg / ha is preferred, and the application rate between about 0.3 kg / ha and 0.8 kg / ha is particularly preferred.

[0047] In fact, the agrochemical compositions comprising the polymorphs of the present invention are applied as formulations containing a variety of adjuvants and carriers known or used in industry. Therefore, they can be formulated into granules, wettable powders, emulsifiable concentrates, suspension concentrates (including oil dispersions), powders or dusts, flowables, solutions, suspensions or emulsions or suspoemulsions, or formulated into controlled release forms, such as microcapsules. Suitably, the agrochemical compositions of the present invention can be formulated into suspension concentrates, suspoemulsions, emulsion concentrates or wet granules. These formulations are described in more detail below and can contain active ingredients as low as about 0.5% by weight to as much as about 95% by weight or more of the polymorph form. The optimum amount depends on the formulation, the application device, and the properties of the plant pathogenic fungi to be controlled.

[0048] Wettable powders are in the form of finely dispersed particles that are easily dispersed in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin, silica and other easily wettable organic or inorganic solids. Wettable powders typically contain from about 5% to about 95% by weight of the active ingredient plus a small amount of a wetting agent, dispersant or emulsifier.

[0049] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquids and are usually applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% by weight of the suspension concentrate.

[0050] Suspension concentrates are preparations in which highly dispersed solid particles of the active compound are stably suspended. These solid particles can be suspended in an aqueous solution or in oil (as an oil dispersion). Such preparations contain anti-settling agents and dispersants, and may further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. When used, these concentrates are diluted in water and are usually applied to the area to be treated as a spray. The amount of active ingredient can range from about 0.5% to about 95% by weight of the suspension concentrate.

[0051] Granular formulations include both extrudates and relatively coarse granules and can be applied undiluted to areas where control of phytopathogenic fungi is desired, or dispersed in a spray tank, for example, prior to application. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that absorb or can be coated with active compounds. Granular formulations used undiluted typically contain from about 5% to about 25% by weight of active ingredients, which may include surfactants, such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrins, glues, or synthetic resins. When these granules are dispersed in a spray tank before application, the active ingredient content can be increased to 80% by weight.

[0052] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

[0053] Microcapsules are typically droplets or particles of active ingredients encapsulated in an inert porous shell that allows the encapsulated material to escape into the environment at a controlled rate. Encapsulated droplets are typically from about 1 to about 50 microns in diameter. The encapsulated liquid typically constitutes about 50% to 95% of the capsule weight and may include solvents in addition to the active compound. Encapsulated particles are usually porous particles, wherein the porous membrane seals the particle pores and retains the active species in liquid form inside the particle pores. The diameter of the particles is typically in the range of from 1 mm to 1 cm (and preferably from 1 to 2 mm). The particles are formed by extrusion, coagulation or spheroidization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon fine particles. Shell or membrane materials include natural and synthetic rubbers, fiber materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0054] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent (such as acetone, alkylated naphthalenes, xylene and other organic solvents) in which the active ingredient is completely soluble at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in finely divided form due to evaporation of a low-boiling dispersant solvent carrier.

[0055] Many of these formulations include wetting agents, dispersants or emulsifiers. Examples are alkyl and alkylaryl sulfonates and sulfates and their salts, polyols; polyethoxylated alcohols, esters and fatty amines. These agents, when used, typically comprise from 0.1% to 40% by weight of the formulation.

[0056] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the invention in the above-mentioned formulation types are well known to those skilled in the art. Suitable examples of different categories are found in the following non-limiting list.

[0057] Liquid carriers that may be used include water and any solution in which the polymorph has no solubility or limited solubility, for example, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosin acid ester, diethylene glycol butyl ether , diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate , monoacetin, triacetin, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene Benzene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, and the like. Water is generally the carrier of choice for diluting the concentrates.

[0058] Suitable solid carriers include talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.

[0059] A wide range of surfactants may be advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These surfactants may be anionic, cationic, nonionic or polymeric in nature and may act as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products such as tridecanol-C.sub.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates.

[0060] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, opacifiers, compatibilizing agents, defoamers, masking agents, neutralizing and buffering agents, corrosion inhibitors, dyes, flavor enhancers, spreading agents, penetration aids, micronutrients, emollients, lubricants, fixatives, and the like.

[0061] Each of the above formulations can be prepared as a package containing the fungicide together with the other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.) The formulations can also be prepared by a tank mix process, where the ingredients are obtained separately and combined at the growing site.

[0062] These preparations can be applied to the area of ​​wishing to control by conventional methods. For example, powders and liquid compositions can be applied by using a power duster, a tube sprayer and a hand sprayer and a spray duster. The preparation can also be applied from an airplane as a dusting agent or a spray, or applied by a rope core. Both solid and liquid preparations can also be applied to the soil of the plant site to be treated, thereby allowing the active ingredient to penetrate into the plant through the root. The preparation of the present invention can also be used for the dressing application on the plant propagation material, so that the plant propagation material is provided with antifungal infection protection, and the protection of the plant pathogenic fungi occurring in the soil. Suitably, by impregnating the plant propagation material (particularly seed) with the liquid preparation of the fungicide, or coating with a solid preparation, the active ingredient can be applied to the plant propagation material to be protected. In special cases, it is also possible for other types to be applied, for example, special treatment is carried out on plant cuttings or twigs used as breeding.

[0063] Suitably, the agrochemical compositions and formulations of the invention are applied prior to disease development. The rates and frequencies of application of these formulations are conventional in the art and depend on the risk of infection by the fungal pathogen.

[0064] The compositions and formulations of the present invention can also be used in combination with other active ingredients (compound II), for example other fungicides, and / or insecticides, and / or miticides, and / or nematicides, and / or molluscicides, and / or biological preparations, and / or plant growth regulators. These mixtures, and the use of these mixtures to control the growth of weeds and / or undesirable plants, form other aspects of the present invention.

[0065] The following mixtures of compounds of formula I with active ingredients (compounds II) are preferred:

[0066] An auxiliary agent selected from the group consisting of: petroleum (alias) (628);

[0067] Insect control active substances selected from abamectin, acetamiprid, acetophenone, acralthrin, acynonapyr, bicyclam, afoxolaner, cotton boll carb, allethrin, cis-cypermethrin, beta-cypermethrin, sulfamethoxazole, cypermethrin, triazotin, sulfamethoxazole, benzyl methacrylate, benzpyrimoxan, β-cypermethrin, β-cypermethrin, bifenazate, bifenthrin, binacarb, bioallethrin, S-bioallethrin, bioresmethrin, bistrifluan, bromofenapyr, bromofluthrin, bromothrin-ethyl, buprofezin, butanone, cadusafosfos, carbaryl, butansulfuron, and badan, CAS No. : 1632218-00-8, CAS No.: 1808115-49-2, CAS No.: 2032403-97-5, CAS No.: 2044701-44-0, CAS No.: 2128706-05-6, CAS No.: 2095470-94-1, CAS No.: 2377084-09-6, CAS No.: 1445683-71-5, CAS No.: 2408220-94-8, CAS No.: 2408220-91-5, CAS No.: 1365070-72-9, CAS No.: 2171099-09-3, CAS No.: 2396747-83-2, CAS No.: 2133042-31-4, C AS No.: 2133042-44-9, CAS No.: 1445684-82-1, CAS No.: 1922957-45-6, CAS No.: 1922957-46-7, CAS No.: 1922957-47-8, CAS No.: 1922957-48-9, CAS No.: 2415706-16-8, CAS No.: 1594624-87-9, CAS No.: 1594637-65-6, CAS No.: 1594626-19-3, CAS No.: 1990457-52-7, CAS No.: 1990457-55-0, CAS No.: 1990457-57-2, CAS No.: 1990457-77- 6. CAS No.: 1990457-66-3, CAS No.: 1990457-85-6, CAS No.: 2220132-55-6, CAS No.: 1255091-74-7, CAS No.: RNA (potato beetle-specific recombinant double-stranded interference GS2), CAS No.: 2719848-60-7, CAS No.: 1956329-03-5, chlorantraniliprole, chlordane, chlorfenapyr, chlorpromazine, clonpyrifos, cloethocarb, clothianidin, 2-chlorophenyl N-methylcarbamate (CPMC), benzonitrile, cyantraniliprole, cyclobromofenapyr, cyclobutrifluram,Pyrethroids, cycloheximide, cytoxan, cyetpyrafen (or etpyrafen), cyfluthrin, cyhalodiamide, cyhalothrin, cypermethrin, cypermethrin, cyproflanilide, cyromazine, deltamethrin, cyproconazole, chlorpyrifos, dibrom, diclorof, dichlorothiazine, fluazifop, diflubenzuron, dimpropyridaz, diclofenac, dimethoate, dimethomorph, emamectin (or emamectin benzoate), d-pyrethrin , epsilon-momfluorothrin, epsilon-methofluthrin, cypermethrin, ethion, ethiprole, ethoprolin, etoxazole, fenamiphos, fenazaquin, pentothrin, fenitrothion, fenmezoditiaz, fenitrothion, fenbutyl, fenthiocarb, fenoxycarb, cypermethrin, fenpyroximate, fenthiophos, fenthiocarb, fenoxycarb, cypermethrin, fenpyroximate, fenthiophos, fenthiophos, fenvalerate, fipronil, flometoquin, flonicamid, pyrimidine, fluazaindolizine, flufenoxam, flubendiamide, flumetyl, fluchl ordiniliprole), flucitrinate, flufenacet, flucythrinate, fluthiazide, flutolan ... tafluthrin), hexythiazox, hydrazone, imicyafos, imidacloprid, imiprodinil, indazapyroxamet, indoxacarb, iodomethane, isoprodinil, isocycloseram, isothiocarb, ivermectin, kappa-bifenthrin, kappa-tefluthrin, lambda-cyhalothrin, ledprona, lepidomectin, lotilaner, chlorfenuron, metaflumizone, metaldehyde, methomyl, methomyl, methoxyfenozide, methoxyfluthrin, cypermethrin, cypermethrin, cypermethrin,nicofluprole; nitenpyram, nithiazine, omethoate, oxamyl, oxazolidinone ... pyrafluprole), pyrafluprole, pyridalyl, pyrifluquinazon, pyrimidine, pyrafluprole ... imiphos), tefluthrin, bispyribac, tetrachlorvinphos, tetrachlorvinphos, tetrachlorvinphos, tetrachlorvinphos, tetrachlorvinphos, flucythrinate, cypermethrin, thiamethoxam, thiocarb, thiodicarb, long-acting carb, methyl thiophos, thiophanate-methyl, tigolaner, tiorantraniliprole, tioxazafen, tolfenpyrad, toxaphene, tralomethrin, trafluthrin, triazophos, trichlorfon, trifluenfurona te, chlorpyrifos, trichlorfon, triflumezopyrim, tyclopyrazoflor, ζ-cypermethrin, seaweed extracts and fermentation products derived from sugar acyl, seaweed extracts and fermentation products derived from sugar acyl (containing urea, amino acids, potassium and molybdenum, and EDTA-chelated manganese), seaweed extracts and fermented plant products, seaweed extracts and fermented plant products (containing plant hormones, vitamins, EDTA-chelated copper, zinc, and iron), azadirachtin, Bacillus ayuzawa (Bacillus aizawai), Bacillus chitinosporus AQ746 (NRRL Accession No. B-21 618), Bacillus firmus, Bacillus kurstaki, Bacillus mycoides AQ726 (NRRL Accession No. B-21664), Bacillus pumilus (NRRL Accession No. B-30087), Bacillus pumilus AQ717 (NRRL Accession No. B-21662), Bacillus species AQ178 (ATCC Accession No. 53522), Bacillus species AQ175 (ATCC Accession No. 55608),Bacillus species AQ177 (ATCC Accession No. 55609), unspecified Bacillus subtilis, Bacillus subtilis AQ153 (ATCC Accession No. 55614), Bacillus subtilis AQ30002 (NRRL Accession No. B-50421), Bacillus subtilis AQ30004 (NRRL Accession No. B-50455), Bacillus subtilis AQ713 (NRRL Accession No. B-21661), Bacillus subtilis AQ743 (NRRL Accession No. B-21665), Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619), Bacillus thuringiensis BD#32 (NRRL Accession No. B-21530), Bacillus thuringiensis subspec. kurstaki BMP 123, Beauveria bassiana, D-limonene, Granulovirus, Harpin, Helicoverpa armigera nuclear polyhedrosis virus, Heliothis cornella nuclear polyhedrosis virus, Heliothis virescens nuclear polyhedrosis virus, Helicoverpa armigera nuclear polyhedrosis virus, Metarhizium species, Muscodor albus 620 (NRRL Accession No. 30547), Muscodor roseus A3-5 (NRRL Accession No. 30548), neem-based products, Paecilomyces fumosorum, Paecilomyces lilacinus, Pasteuria szabalensis, Pasteuria penetrantis, Pasteuria mycorrhiza, Pasteuria thornei, Pasteuria thornei, p-cymene, Plutella xylostella granulovirus, Plutella xylostella nuclear polyhedrosis virus, polyhedrosis virus, Pyrethrum, QRD 420 (terpenoid blend), QRD 452 (terpenoid blend), QRD 460 (terpenoid blend), Quillaja saponaria, Rhodococcus sphaeroides AQ719 (NRRL Accession No. B-21663), Spodoptera frugiperda nuclear polyhedrosis virus, Streptomyces flavos (NRRL Accession No. 30232), Streptomyces species (NRRL Accession No. B-30145), terpenoid blend, and Verticillium species;

[0068] an algaecide selected from the group consisting of bethoxazin [CCN], copper dioctanoate (IUPAC name) (170), copper sulfate (172), cybutryne [CCN], dichlone (1052), dichlorophen (232), endoxan (295), fentin (347), slaked lime [CCN], nabam (566), quinoclamine (714), quinonamid (1379), simazine (730), triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347);

[0069] Anthelmintics selected from the group consisting of: avermectin (1), clefonate (1011), doramectin (alias) [CCN], emamectin (291), emamectin benzoate (291), eprinomectin (alias) [CCN], ivermectin (alias) [CCN], milbemycin oxime (alias) [CCN], moxidectin (alias) [CCN], piperazine [CCN], selamectin (alias) [CCN], spinosad (737) and thiophanate (1435);

[0070] Avicides selected from the group consisting of chloralose (127), endrin (1122), fenthion (346), pyridin-4-amine (IUPAC name) (23) and strychnine (745);

[0071] Bactericide selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222), 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748), 8-hydroxyquinoline sulfate (446), bronopol (97), copper dioctanoate (IUPAC name) (170), copper hydroxide (IUPAC name) (169), cresol [CCN], dichlorophen (232), disopyridine (1105), dodecine (1112), fenaminosulf (1144), formaldehyde (404), mercury Gafen (alias) [CCN], kasugamycin (483), kasugamycin hydrochloride hydrate (483), nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308), nitrapyrin (580), octhilinone (590), oxolinic acid (606), oxytetracycline (611), potassium hydroxyquinoline sulfate (446), probenazole (658), streptomycin (744), streptomycin sesquisulfate (744), chlorpheniramine (766), and thimerosal (alias) [CCN];

[0072] A biological agent selected from the group consisting of: GV of cotton brown banded moth (alias) (12), Agrobacterium radiobacterium (alias) (13), Amblyseius spp. (alias) (19), Spodoptera exigua NPV (alias) (28), Anagrus atomus (alias) (29), Aphelinus abdominalis (alias) (33), Aphidius colemani (alias) (34), Aphidoletes aphidimyza (alias) (35), Spodoptera exigua NPV (alias) (38), Bacillus firmus (alias) (48), Bacillus sphaericus Neide (scientific name) (49), Bacillus thuringiensis Berliner (scientific name) (51), Bacillus thuringiensis subsp. aizawai (scientific name) (51), Bacillus thuringiensis subsp. israelensis (scientific name) (51), Bacillus thuringiensis subsp. japonensis (scientific name) (51), Bacillus thuringiensis subsp. kurstaki (scientific name) (51), Bacillus thuringiensis subsp.tenebrionis (scientific name) (51), Beauveria bassiana (scientific name) (53), Beauveria brongniartii (scientific name) (54), Chrysoperla carnea (scientific name) (151), Cryptolaemus montrouzieri (scientific name) (178), GV (scientific name) (191), Dacnusa sibirica (scientific name) (212), Diglyphus isaea (scientific name) (254), Eretmocerus eremicus (scientific name) (293), Eretmocerus eremicus (scientific name) (300), NPV (scientific name) (431), Heterorhabditis bacteriophora and H. megidis (alias) (433), Hippodamia convergens (alias) (442), Leptomastix dactylopii (alias) (488), Macrolophus caliginosus (alias) (491), Spodoptera exigua NPV (alias) (494), Metaphycus helvolus (alias) (522), Metarhizium anisopliae var. acridum (scientific name) (523), Metarhizium anisopliae var. anisopliae (scientific name) (523), Neodiprion sertifer NPV and Neodiprion rubrum NPV.lecontei NPV (alias) (575), Paecilomyces species (alias) (596), Paecilomyces fumosoroseus (alias) (613), Phytoseiulus persimilis (alias) (644), Spodoptera exigua multicapsid nuclearpolyhedrosis virus (scientific name) (741), Steinernema bibionis (alias) (742), Steinernema carpocapsae (alias) (742), Steinernema glaseri (alias) (742), Steinernema riobrave (alias) (742), Steinernema leoboris (scientific name) (742), riobravis) (alias) (742), Steinernema scapterisci (alias) (742), Steinernema spp. (alias) (742), Trichogramma spp. (alias) (826), Typhlodromus occidentalis (alias) (844), and Verticillium lecanii (alias) (848);

[0073] A soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537);

[0074] A chemical sterilant selected from the group consisting of apholanate [CCN], bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN], busulfan (alias) [CCN], diflubenzuron (250), dimatif (alias) [CCN], hemel [CCN], hempa [CCN], metepa [CCN], methiotepa [CCN], methyl apholanate [CCN], methyl thiote ... apholate)[CCN], morzid[CCN], penfluron(alias)[CCN], tepa[CCN], thiohempa(alias)[CCN], thiohempa(alias)[CCN], trothamide(alias)[CCN] and ureaimide(alias)[CCN];

[0075] An insect pheromone selected from the group consisting of (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222), (E)-tridec-4-en-1-yl acetate (IUPAC name) (829), (E)-6-methylhept-2-en-4-ol (IUPAC name) (541), (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779), (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285), (Z)-hexadec-11-enal (IUPAC name) (436), (Z)-hexadec-11-enal (IUPAC name) (437). 1-enyl acetate (IUPAC name) (437), (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438), (Z)-eicos-13-en-10-one (IUPAC name) (448), (Z)-tetradec-7-en-1-al (IUPAC name) (782), (Z)-tetradec-9-en-1-ol (IUPAC name) (783), (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784), (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283), (9Z,11E)-tetradec-9 ,11-dien-1-yl acetate (IUPAC name) (780), (9Z,12E)-tetradec-9,12-dien-1-yl acetate (IUPAC name) (781), 14-methyloctadec-1-ene (IUPAC name) (545), 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544), alpha-multistriatin (alias) [CCN], western pine beetle aggregation pheromone (brevicomin) (alias) [CCN], codlelure (alias) [CCN], codlemone (alias) (167), cuelure (alias) (179), disparlure (277), dodec-8-en-1-yl acetate (IUPAC name) (286), dodec-9-en-1-yl acetate (IUPAC name) (287), dodec-8, 10-dien-1-yl acetate (IUPAC name) (284), dominicalure (alias) [CCN], 4-methyloctanoic acid ethyl ester (IUPAC name) (317), eugenol (alias) [CCN], southern pine beetle aggregation pheromone (frontalin) (alias) [CCN], (alias; hexadeca-7,11-dien-1-yl acetate) a 1:1 mixture of (Z,E) and (Z,Z) isomers (420), grandlure (421), grandlure I (alias) (421), grandlure II (alias) (421), grandlure III (alias) (421), grandlure IV (alias) (421), hexalure [CCN], ipsdienol (alias) [ CCN], ipsenol (alias) [CCN], japonilure (alias) (481), lineatin (alias) [CCN], litlure (alias) [CCN], looplure (alias) [CCN], medlure (CCN], (3E,5Z)-tetradecene-3,5-dienoic acid (megatomoic acid) (alias) [CCN], methyl eugenol) (alias) (540), muscalure (563), octadecane-2,13-diene-1-yl acetate (IUPAC name) (588), octadecane-3,13-diene-1-yl acetate (IUPAC name) (589), orfralure (alias) [CCN], oryctalure (alias) (317), ostramone (alias) [CCN], siglure [CC N], banana bulb weevil attractant (sordidin) (Synonym) (736), sulcatol (Synonym) [CCN], tetradec-11-en-1-yl acetate (IUPAC name) (785), Mediterranean fruit fly attractant (839), Mediterranean fruit fly attractant A (Synonym) (839), Mediterranean fruit fly attractant B1 (Synonym) (839), Mediterranean fruit fly attractant B2 (Synonym) (839), Mediterranean fruit fly attractant C (Synonym) (839) and trunc-call (Synonym) [CCN];

[0076] Insect repellents selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591), butopyronoxyl (933), butoxy(polypropylene glycol) (936), dibutyl adipate (IUPAC name) (1046), dibutyl phthalate (1047), dibutyl succinate (IUPAC name) (1048), DEET [CCN], dimethyl carbate [CCN], dimethyl phthalate [CCN], ethyl hexanediol (1137), hexylurea [CCN], methoquin-butyl (1276), methyl neodecylamide [CCN], oxamate [CCN] and picaridin [CCN];

[0077] Molluscicide selected from the group consisting of: di(tributyltin) oxide (IUPAC name) (913), bromoacetamide [CCN], calcium arsenate [CCN], chloranil (999), copper acetyl arsenite [CCN], copper sulfate (172), triphenyltin (347), iron phosphate (IUPAC name) (352), metaldehyde (518), methiocarb (530), niclosamide (576), niclosamide-ethanolamine (576), pentachlorophenol (623) , sodium pentachlorophenoxide (623), tazimcarb (1412), thiodicarb (799), tributyltin oxide (913), trifenmorph (1454), trimethacarb (840), triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) and pyriprole [394730-71-3];

[0078] Nematicides selected from the group consisting of: AKD-3088 (compound code), 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045), 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062), 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063), 1,3-dichloropropene (233), 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) (1065), 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980), 5-methyl-6-thio-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286), 6-isopentenylaminopurine (alias) (210), avermectin (1), acetofenamide [CCN], cotton boll carb (15), aldicarb (16), aldicarb (863), AZ 60541 (compound code), benclothiaz [CCN], benomyl (62), butylpyridaben (alias), carbofuran (109), carbofuran (118), carbon disulfide (945), carbofuran butylsulfide (119), chloropicrin (141), chlorpyrifos (145), chlorpyrifos (999), cytokinin (alias) (210), dazomethane (216), DBCP (1045), DCIP (218), diamidafos (1044), chlorpyrifos (1051), dicliphos (alias), dimethoate (262), doramectin (alias) [CCN], emamectin (291), emamectin benzoate (291), eprinomectin (alias) [CCN], ethoprophos (312 ), ethylene dibromide (316), fenamiphos (326), fenpyrad (alias), fenthiophos (1158), thiamethoxam (408), butyric acid (1196), furfural (alias) [CCN], GY-81 (research code) (423), thiophos [CCN], methyl iodide (IUPAC name) (542), isamidophos (1230), chlorfenapyr (1231), ivermectin (alias) [CCN], kinetin (alias) (210), methyl aphid (1258), metamectin (519), metamectin potassium (alias) (519), metamectin sodium (519), methyl bromide (537), methyl isothiocyanate (543), milbemycin oxime (alias) [CCN], moxidectin (alias) [CCN], Myrothecium verrucaria) combination (alias) (565), NC-184 (compound code), oxamyl (602), phorate (636), phosphamidon (639), phosphamidon [CCN], chloranil (alias), selamectin (alias) [CCN], spinosad (737), terbufos (alias), terbufos (773), tetrachlorothiophene (IUPAC / CAS name) (1422), thiafenox (alias), chloranil (1434), triazophos (820), triazuron (alias), xylenol [CCN], YI-5302 (compound code) and zeatin (alias) (210), fluensulfone [318290-98-1] and fluopyram;

[0079] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580);

[0080] A plant activator selected from the group consisting of acibenzolar (6), acibenzolar-S-methyl (6), probenazole (658) and Reynoutria sachalinensis extract (alias) (720);

[0081] Rodenticides selected from the group consisting of: 2-isovaleryl indan-1,3-dione (IUPAC name) (1246), 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748), α-chlorohydrin [CCN], aluminum phosphide (640), anto (880), arsenic trioxide (882), barium carbonate (891), bifenthrin (912), brodifacoum (89), bromadiolone (or α-bromadiolone), bromodifacoum (92), calcium cyanide (444), chloralose (127), chlorfenapyrone (140), cholecalciferol (alias) (850), chlorfenapyr (1004), chlorfenapyr (1005), chlorfenapyr (175), chlorfenapyr (1009), chlorfenapyr (246), thiazolin (249), chlorfenapyr (273), calciferol (30 1), fludioxaline (357), fluoroacetamide (379), fludioxaline (1183), fludioxaline hydrochloride (1183), γ-HCH (430), HCH (430), hydrogen cyanide (444), methyl iodide (IUPAC name) (542), lindane (430), magnesium phosphide (IUPAC name) (640), methyl bromide (537), fosfomycin (1318), fosfomycin (1336), phosphine (IUPAC name) (640), phosphorus [CCN], fosfomycin (1341), potassium arsenite [CCN], fosfomycin (1371), scilla glycoside (1390), sodium arsenite [CCN], sodium cyanide (444), sodium fluoroacetate (735), strychnine (745), thallium sulfate [CCN], fosfomycin (851) and zinc phosphide (640);

[0082] Synergists selected from the group consisting of 2-(2-butoxyethoxy)ethyl piperate (IUPAC name) (934), 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903), farnesol with nerolidol (alias) (324), MB-599 (research code) (498), MGK 264 (research code) (296), piperonyl butoxide (649), pipertal (1343), propyl isomer (1358), S421 (research code) (724), sesamex (1393), sesasmolin (1394) and sulfoxide (1406),

[0083] Animal repellents selected from the group consisting of anthraquinone (32), chloralose (127), copper cyclopentane [CCN], copper oxychloride (171), diazinon (227), dicyclopentadiene (chemical name) (1069), guazatine (422), guazatine acetate (422), methiocarb (530), pyridin-4-amine (IUPAC name) (23), salamine (804), trimethacarb (840), zinc cyclopentane [CCN] and ziram (856);

[0084] A virucidal agent selected from the group consisting of: imipenem (alias) [CCN] and ribavirin (alias) [CCN];

[0085] A wound protection agent selected from the group consisting of mercuric oxide (512), octhilinone (590) and thiophanate-methyl (802);

[0086] The biologically active substance is selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenyl sulfone, acetothionil, aldicarb, sagofos, fomanphos, fenamiphos, fenamiphos hydrogen oxalate, amitraz, cypermethrin, arsenic trioxide, azobenzene, azophos, benomyl, benoxafos, benzyl benzoate, bixafen, bromomethrin, Bromophenazone, bromothion, bromopyralid, buprofezin, butanone carbendazim, butanone sulfone carbendazim, butyl pyridaben, calcium polysulfide, octachlorocamphene, chlormethoxam, trithion, cypermethrin, cypermethrin, cypermethrin, chlordimeform, chlordimeform hydrochloride, chlorfenapyr, chlorfenapyr, chlorfenapyr, ethyl chlorfenapyr, chlorfenapyr (chloromebuform), chlorfenapyr, propyl chlorfenapyr, chlorfenapyr, cypermethrin I, cypermethrin II, cypermethrin, closantel, coumaphos, crotamiton, chlorfenapyr, sulfur demeton-S, demeton-S-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl ... 6. Orthodimethoate, nitropentyl ester, nitrooctyl ester acaricide, nitrobutyl ester, dimethoate, sulfodiphenyl, disulfiram, DNOC, dofenapyn, doramectin, indophos, eprinomectin, thiophos, ethidium, anti-mite azole, fenbutatin, fenthiocarb, fenpyrad, fenpyrad, fenpyraclostrobin, fentrifanil, fluazifop, flufenamide, diflubenzuron, fluazifop, FMC 1137, fenthion, fenthion hydrochloride, formparanate, γ-HCH, chloranil, benzyl chloranil, hexadecyl cyclopropane carboxylate, isothiocarb, jasmonate I, jasmonate II, iodine, lindane, propanil, cypermethrin, dithiophos, methylthiophene, cypermethrin, methyl bromide, cypermethrin, chloranil, milbemid, propylamine, monocrotophos, malathion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3 -pyridyl)methoxy]pyridazine-3-one, fluazifop, nikkomycin, pentocyanamide, pentocyanamide 1:1 zinc chloride complex, omethoate, isothiocarb, sulfone, pp'-DDT, parathion, permethrin, fenthion, phosalone, thiocyanate, phosphamidon, polychloroterpenes, polynactins, chloranil, cypermethrin, propoxur, ethidium, thiophos, pyrethrin I, pyrethrin II, pyrethrin, pyridazithion, pyrimithiophos,Quinalphos, quintiofos, R-1492, glyphosate, rotenone, octamethrin, clomar, selamectin, thiothion, SSI-121, sulfluramid, sulfotep, sulfur, flumethoxine, τ-fluvalinate, TEPP, tert-butylcarb, tetrachlorothiazide, thiafenox, thiafenox, long-acting carb, methyl thiocarb, thiafenox, thiafenox, thiafenox, thiafenox, thiafenox, triazophos, triazuron, trichloropropene, triacylglycerol, triazophos, triazophos, triacylglycerol ... Endoic acid, triphenyltin, slaked lime, sodium mancozeb, algaquinone, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, fosfos, piperazine, thiophanate, chloralose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxaline-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, disipirthion, dodesine, sodium sulfone, formaldehyde, mercurygafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel di(dimethyldithiocarbamate), trichloromethylpyridine, octhiothionone, oxolinic acid, oxytetracycline, hydroxyquinoline potassium sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, chloranthol, thimerosal, cotton brown banded moth GV, Agrobacterium radiobacterium, species of the genus Amblyseius, NPV of the celery armyworm, the original cherry-winged tassel wasp, the short-spurred aphid wasp, the cotton aphid parasitoid wasp, the aphid-eating gall midge, the lucerne armyworm NPV, spherical Bacillus, Beauveria bassiana, common lacewings, Cryptolipidae, GV of the apple moth, Siberian jawed braconid, pea leafminer wasp, beautiful aphid wasp, paddle-horned aphid wasp, bacteriophagic Heterorhabditis elegans and Heterorhabditis elegans, spotted long-legged ladybird, parasitic wasp of citrus mealybug, blind bug, NPV of the cabbage armyworm, yellow-stalked jumping wasp, yellow-green Metarhizium anisopliae, Metarhizium anisopliae microspore variant, European new pine sawfly NPV and red-headed new pine sawfly NPV, species of the genus Apocynum, Penicillium fumosorum, Chilean small phytoseiid mite, hairy mosquito nematode, small-rolled moth nematode, noctuid Steinernema, and Grizzlie's nematode worms, Steinernema rapiensis, Steinernema leoborissa, Steinernema leoborissa, Steinernema spp., Trichogramma spp., western blind mite, Verticillium lecanii, oxazolidinone, bis(aziridine)methylaminophosphonium sulfide, busulfan, dimethivin, hexamethylmelamine, hexamethylphosphine, methyl tibacterium, methyl thiotibacterium, methyloxazolidinone, infertile chloranil, tibacterium, hexamethylphosphine thioate, thiotibacterium, trothamide, urethaneimide, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-trideca-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradec-4,10-dien-1-yl acetate,(Z)-Dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-eicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5- Alcohol and 4-methylnon-5-one, α-polymorph, western pine beetle gathering pheromone, dodecadienol, kodemon, fly attractant, epoxy nonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8, 10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, southern pine beetle gathering pheromone, trap-killing ene mixture, trap-killing ene mixture I, trap-killing ene mixture II, trap-killing ene mixture III, trap-killing ene mixture IV, hexane attractant, tooth beetle dienol, small stupid enol, scarab sex attractant, trimethyl dioxytricyclononane, litlure, cabbage looper sex attractant, trap ester, megatomoicacid, insect attractant Ether, entomophagen, octadecyl-2,13-dien-1-yl acetate, octadecyl-3,13-dien-1-yl acetate, Hecon, coconut rhinoceros beetle aggregation pheromone, filcon, insect trap, sordidin, fungi-eating acetoin, tetradecyl-11-en-1-yl acetate, Mediterranean fruit fly attractant, Mediterranean fruit fly attractant A, Mediterranean fruit fly attractant B1, Mediterranean fruit fly attractant B2, Mediterranean fruit fly attractant C, trunc-call, 2-(octylthio)-ethanol, dimethoate, butoxy (polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, DEET, mosquito repellent, dimethyl phthalate, ethyl hexanediol, hexylurea, mequindine, methyl neodecanoyl Amine, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-di(4-ethylphenyl)-ethane, 1,2-dichloropropane and 1,3-dichloropropylene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidinone,2-Isovaleryl indan-1,3-dione, 2-methyl (prop-2-ynyl) aminophenyl methyl carbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methyl carbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate, acethion, acrylonitrile, aldrin, alloamicin, cypermethrin, α-decandrin, aluminum phosphide, cypermethrin, neonicotinoid, ethyl methidathion, methyl pyrifos, Bacillus thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, cypermethrin, Bayer 22 / 190, Bayer 22408, β-cyfluthrin, β-chloro Cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromophenone, bromo-DDT, synthate, butanthiofos, butanthiofos, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, badan hydrochloride, cevadine, borneol, chlordane, chlordecone, chloroform, chloropicrin, chloraniloxime, chlorprazophos, cis-resmethrin, cismethrin, clocythrin (alias), copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, benzonitrile, cypermethrin, cypermethrin, d-methanthrin, DAEP, dazomethane, decarbofuran, diamidafos, isochlorophos, dimethoate, dicresyl, cypermethrin, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilor, tetrafluthrin, demicarb, pyrethrin, methyl chlorpyrifos, difenocarb, propanol, pentotropol, dinofuranoside, fenthion, vegetable phosphorus, thiopyrafos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiobencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenoxacrim, fenthion, fenoxacrim, cypermethrin, fenthion, ethyl fenthion, flucofuron, butylfenthion, phosphodiesteril, butylfenthion, furathiocarb, pyrethroid, biguanide salt, biguanide acetate, sodium tetrathiocarbonate, benzyl chlorpyrifos, HCH, HEOD, heptachlor, cypermethrin, HHDN, hydrogen cyanide, quinolincarb, IPSP, chlorfenapyr, carbofuran, isothrin, isoflavone, transplanting agent, rice blast, oxathiophos, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorpentyl, methoprene, lead arsenate,Bromophenphos, acetamiprid, thiamethoxam, m-isopropyl methyl carbamate, magnesium phosphide, phosphorus azide, methyl aphid, chlorpyrifos, mercurous chloride, methyl sulfoxide, metamifop, metamifop potassium, metamifop sodium, methyl sulfonyl fluoride, butylene phosphonate, methoprene, methyl ether thiocyanate, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, oxadiazine, anticide, naphthiophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, orthonicotine, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-ylphosphonothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate, O,O,O' ,O'-Tetrapropyl dithiodipyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH60-38, fenthion, parachlorothion, phosphine, methyl phoxim, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious element I, precocious element II, precocious element III, amidopyrimidine phosphorus, profluthrin, fenthion, prothiophos, pyraclostrobin, anti-pyrethroid, quassia extract, quinalphos-methyl, fenthion, iodophos, resmethrin, rotenone, thiamethoxam, ryanodine, sabadilla, octamethoxam, clostridium, SI-0009, thiamethoxam nitrile, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate , sodium pentachlorophenol, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, thiopromide, tar, thiabendazole, TDE, butylpyrimidinphos, dimethoate, cyclopentylthrin, tetrachloroethane, thiochlorvos, cyclohexane, cyclohexane oxalate, cypermethrin, cypermethrin sodium, tralomethrin, trans-permethrin, trichlormetaphos-3, trichlormetaphos-3, chlorpyrifos, tolprocarb, chlorpyrifos-butyl, methoprene, veratridine, veratridine, XMC, zetamethrin, zinc phosphide, tolfenphos, chlorpyrifos Ester, tetrafluthrin, bis(tributyltin) oxide, bromoacetamide, iron phosphate, niclosamide-ethanolamine, tributyltin oxide, pyromorph, snail killer, 1,2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thio-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine, anisiflupurin, phenylchlorothiol, cytokinin, DCIP, furfural, isoamidophos, kinetin, verrucospore mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Polygonum cuspidatum extract,α-Chlorohydrin, Antu, barium carbonate, bifenthion, brodifacoum, brodifacoum, brofenthion, chlorfenthion, cholecalciferol, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, calciferol, flufenthion, fluoroacetamide, flufenthion, flufenthion hydrochloride, flufenthion, chlorfenthion, phosphorus, chlorfenthion, chlorfenthion, chlorfenthion, sciline glycoside, sodium fluoroacetate, thallium sulfate, chlorfenthion, 2-(2-butoxyethoxy)ethyl piperate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic acetylene ether, MGK 264, piperonyl butoxide, synergistic aldehyde, propyl isomer, S421, synergistic powder, sesame, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, serene, zinc cyclohexane, zinc ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bifenthrin, fuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, nitrobenzene, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, imipenem, cyproconazole, metconazole, myclobutrazol, paclobutrazol, rice blast, penconazole, propyl Thioconazole, pyrifenox, prochloraz, propiconazole, pyraconazole, simeconazole, tebuconazole, fluconazole, triadimefon, triadimenol, triflumizole, trimethimazole, pyrimidine, chlorfenapyr, flufenapyr, bupirimate, dimethirimol, ethirimol, dodecacyclic morpholine, fenpropidin, fenpropimorph, spiroxamorph, tridecamorph, cyprodinil, pyrimidine, pyrimethanil anil), fenpyroxil, fludioxonil, benalaxyl, furaxyl, metalaxyl, R-metalaxyl, furamide, oxadixyl, carbendazim, debacarb, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid id), carboxin, flutolanil, flutolanil, oxacarb, penthiopyrad, thiofuran, dodine, biguanide, azoxystrobin, ethersstrobin, enestroburin, enestroburin, flutolanil, fluoxastrobin, ethersstrobin, fenoxystrobin, trifloxystrobin, trifloxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, ferram, mancozeb, maneb, manam, methyl propineb, maneb, captan, captan, pyraclostrobin, folpet, tolylfluanid,Bordeaux mixture, copper oxide, mancozeb, quinoline copper, phthalocyanine, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil ketone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, flusulfamide, flupyrosinamide, fenhexamid, fosetyl-aluminium, hymexazol, propineb, cyazofamid, methasulfocarb, mefentrazone, amikacin pencycuron, phthalide, polyoxins, propamocarb, pyraclostrobin, proquinazid, pyroquilon, pyriofenone, quinoxyfen, pentachloronitrobenzene, triazoxide, tricyclazole, triazine, validamycin, valeramide, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovintriazole, flutolanil Pyraclostrobin, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflurane, isothiopyram, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithia[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide,4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, jiaxiangjunzhi, lvbenmixianan, dichlobentiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl -3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiprolin, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, clofoconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)- 1-[(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester, 3-Chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, pyrifen, indazolesulfamide, fluopyraclostrobin,(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine, florylpicoxamid, fenpicoxamid, metaylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid, 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (which can be prepared by the method described in WO 2020 / 056090), 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (which can be prepared by the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012), methyl 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzathiostrobin, cyanobacterium methyl, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, fluthiazolin, flutoxamid, pyrapropoyne, picarbutrazox,2-(Difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(Difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3- [pyridyl]oxy]benzonitrile, metyltetraprole, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol, fluoxapyridine iprolin), enoxastrobin, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoic acid methyl ester (these compounds can be prepared by WO 2020 / 079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the method described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile )propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thio-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac acid, syringoxystrobin, zhongshengmycin, thiophanate-copper, thiazole zinc, amectotractin, iprodione,seboctylamine; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, -methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared from WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1- Benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide,8-Fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared from WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared by WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea,3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[ 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared from WO 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by WO 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone (this compound can be prepared by the method described in WO 2011 / 138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenethiocarboxamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in WO 2-(Difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO 2017 / 220485); 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-C-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428);

[0087] Microorganisms, including: Acinetobacter lwoffii, Acremonium alternatum, Acremonium cephalosporium, Acremonium diospyri, Acremonium obclavatum, Adoxophyes orana granulovirus (AdoxGV) Agrobacterium radiobacter strain K84 (Galltrol- ), Alternariaalternate, Alternaria cassia, Alternaria destruens Ampelomyces quisqualis Aspergillus flavus AF36 Aspergillus flavus NRRL 21882 Aspergillus species, Aureobasidium pullulans, Azospirillum, TAZO ), Azotobacter , Azotobacter chroocuccum Bionatural Blooming ), Bacillus amyloliquefaciens, Bacillus cereus, Bacillus chitinosporus strain CM-1, Bacillus strain AQ746, Bacillus licheniformis strain HB-2 (Biostart TM before ), Bacillus licheniformis strain 3086 ( Green ), Bacillus circulans, Bacillus firmus ( BioNem- ), Bacillus firmus strain I-1582, Bacillus macerans, Bacillus marismortui, Bacillus megaterium, Bacillus mycoides strain AQ726, Bacillus papillae (Milky Spore ), Bacillus pumilus spp., Bacillus pumilus strain GB34 (Yield ), Bacillus pumilus strain AQ717, Bacillus pumilus strain QST 2808 ( Ballad ), Bacillus sphaericus Bacillus spp., Bacillus strain AQ175, Bacillus strain AQ177, Bacillus strain AQ178, Bacillus subtilis strain QST 713 Bacillus subtilis strain QST 714 Bacillus subtilis strain AQ153, Bacillus subtilis strain AQ743, Bacillus subtilis strain QST3002, Bacillus subtilis strain QST3004, Bacillus subtilis variant Bacillus amyloliquefaciens strain FZB24 Bacillus thuringiensis Cry 2Ae, Bacillus thuringiensis Cry1Ab, Bacillus thuringiensis aizawai GC 91 Bacillus thuringiensis israelensis Bacillus thuringiensis kurstaki ( Scutella Turilav Dipel ), Bacillus thuringiensis kurstaki BMP 123 Bacillus thuringiensis subsp. Kurstaki HD-1 (Bioprotec- ), Bacillus thuringiensis strain BD#32, Bacillus thuringiensis strain AQ52, Bacillus thuringiensis var.aizawai Bacterial species G Bacteriophage of Clavipacter michiganensis Beauveria bassiana Beauveria bassiana GHA (Mycotrol Mycotrol )、Beauveria brongniartii ( Schweizer ), Beauveria spp., Botrytis cineria, Bradyrhizobium japonicum Brevibacillus brevis, Bacillus thuringiensis tenebrionis BtBooster, Burkholderia cepacia ( Blue ), Burkholderia gladii, Burkholderia gladioli, Burkholderia spp., Canadian thistle fungus (CBHCanadian ), Candida butyri, Candida famata, Candida fructus, Candida glabrata, Candida guilliermondii, Candida melibiosica, Candida oleophila strain O, Candida parapsilosis, Candida pelliculosa, Candida pulcherrima, Candida reukaufii, Candida saitoana (Bio- ), Candida sake, Candida spp., Candida tenius, Cedecea dravisae, Cellulomonas flavigena, Chaetomium cochliodes (Nova- ), Chaetomium globosum (Nova- ), Chromobacterium subtsugae strain PRAA4-1T Cladosporium cladosporioides, Cladosporium oxysporum, Cladosporium chlorocephalum, Cladosporium spp., Cladosporium tenuissimum, Clonostachys rosea Colletotrichum acutatum, Coniothyrium minitans (Cotans ), Coniothyrium spp., Cryptococcus albidus Cryptococcus humicola, Cryptococcus infirmo-miniatus, Cryptococcus laurentii, Cryptophlebia leucotreta granulovirus Cupriavidus campinensis, Cydia pomonella granulovirus (CYD- ), Cydia pomatia granulosis virus ( Plus, Madex Max, )、Cylindrobasidium laeve Cylindrocladium, Debaryomyces hansenii, Drechslera hawaiinensis, Enterobacter cloacae, Enterobacteriaceae, Entomophtora virulenta Epicoccum nigrum, Epicoccum purpurascens, Epicoccum species, Filobasidium floriforme, Fusarium acuminate, Fusarium chlamysporum, Fusarium oxysporum Biofox ), Fusarium, Fusarium species, Galactomyces geotrichum, Gliocladium catenulatum Gliocladium roseum, Gliocladium species Gliocladium virens Granulovirus Halobacillus halophilus, Halobacillus litoralis, Halobacillus trueperi, Halomonas species, Halomonas subglaciescola, Halovibrio variabilis, Hansenula vinifera, Helicoverpa armigera nuclear polyhedrosis virus Spodoptera exigua nuclear polyhedrosis virus Isoflavone-Formononetin Kloeckner's yeast, Kloeckner's yeast species, Lagenidium giganteum Lecanicillium longisporum Lecanicillium muscarium Gypsy moth nuclear polyhedrosis virus Halococcus, Meira geulakonigii, Metarhizium anisopliae Destruxin ), Metschnikowia fruticola Metschnikowia pulcherrima, Microdochium dimerum Micromonospora coerulea, Microsphaeropsisochracea, Muscodor albus 620 Muscodor roseus strain A3-5, Mycorrhizae spp. ( Root ), Verrucospora strain AARC-0255 BROS Ophiostoma piliferum strain D97 Paecilomyces farinosus, Paecilomyces fumosorum Paecilomyces lilacinus (Biostat ), Paecilomyces lilacinus strain 251 (MeloCon ), Bacillus polymyxa, Pantoea agglomerans (BlightBanC9- ), Pantoea species, Pasteurella species Pasteuria nishizawae, Penicillium chrysogenum, Penicillium billai Penicillium breviscompactum, Penicillium familiale, Penicillium griseo-yellowensis, Penicillium purpurogenum, Penicillium species, Phlebiopsis gigantean Phosphate-solubilizing bacteria Phytophthora cryptogenomica, Phytophthora palmi Pichia anomala, Pichia guilermondii, Pichia membranaceus, Pichia nails, Pichia stipitis, Pseudomonas aeruginosa, Pseudomonas aureofasciens (Spot-Less ), Pseudomonas cepacia, Pseudomonas chlororaphis Pseudomonas corrugate, Pseudomonas fluorescens strain A506 ), Pseudomonas putida, Pseudomonas reactans, Pseudomonas species, Pseudomonas syringae (Bio- ), Pseudomonas aureus, Pseudomonas fluorescens Pseudozyma flocculosa strain PF-A22 UL (Sporodex )、Puccinia canaliculata、Puccinia thlaspeos(Wood ), Pythium oligandrum, Pythium, Rhanella aquatilis, Rhanella spp., Rhizobia Rhizoctonia, Rhodococcusgloberulus strain AQ719, Rhodosporidium diobovatum, Rhodosporidium toruloides, Rhodotorula spp., Rhodotorula glutinis, Rhodotorula graminis, Rhodotorulamucilagnosa, Rhodotorula rubra, Saccharomyces cerevisiae, Salinococcus roseus, Sclerotinia minor, Sclerotinia minor Scytalidium spp., Scytalidium uredinicola, Spodoptera exigua nuclear polyhedrosisvirus (Spodoptera exigua nuclear polyhedrosisvirus) ), Serratia marcescens, Serratia plymuthica, Serratia spp., Sordaria fimicola, Spodoptera littoralis nuclear polyhedrovirus Sporobolomyces roseus, Stenotrophomonas maltophilia, Streptomyces ahygroscopicus, Streptomyces albaduncus, Streptomyces exfoliates, Streptomyces galbus, Streptomyces griseoplanus, Streptomyces griseoviridis Streptomyces lydicus Streptomyces lydicus WYEC-108 Streptomyces violaceus, Tilletiopsis minor, Tilletiopsis spp., Trichoderma asperellum (T34 ), Trichoderma gamsii Trichoderma atroviride Trichoderma hamatum TH 382, ​​Trichoderma harzianum rifai Trichoderma harzianum T-22 (Trianum- PlantShield Trianum- ), Trichoderma harzianum T-39 Trichoderma inhamatum, Trichoderma koningii, Trichoderma spp. LC 52 Trichoderma lignorum, Trichoderma longibrachiatum, Trichoderma polysporum (Binab ), Trichoderma taxi, Trichoderma virens, Trichoderma virens (formerly known as Gliocladium virens GL-21) Trichoderma viride, Trichoderma viride strain ICC 080 Trichosporon pullulans, Trichosporon spp., Trichothecium spp., Trichothecium roseum, Typhula phacorrhiza strain 94670, Typhula phacorrhiza strain 94671, Ulocladium atrum, Ulocladium oudemansii (Botry- ), Ustilago maydis, various bacteria and supplemental micronutrients (Natural ), various fungi (Millennium ), Verticillium chlamydosporium, Verticillium lecanii Vip3Aa20 Virgibaclillus marismortui, Xanthomonas campestris pv.Poae Xenorhabdus burnetii, and Xenorhabdus nematophila;

[0088] Plant extracts including: pine oil Azadirachtin (Plasma Neem Plant IGR Canola Oil (Lilly Miller ), Chenopodium ambrosioidesnear ambrosioides Chrysanthemum Extract Neem Oil Extract Labiatae essential oil Clove-rosemary-peppermint and thyme oil extract (Garden insect ), Betaine Garlic and lemongrass oil Neem Oil, Catnip (Nepeta cataria) (Catnip Oil), Nepeta catarina, Nicotine, Oregano Oil Pedaliaceae Oil Pyrethrum, Soapbark Tree (Quillaja saponaria) Giant knotweed (Reynoutria sachalinensis) Rotenone (Eco ), Rutaceae plant extracts Soybean oil (Ortho ), Melaleuca alternifolia extract (also known as tea tree oil) (Timorex ), thyme oil, MMF, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF ), clove-rosemary and peppermint extract blend (EF ), Clove-Peppermint-Garlic Oil and Mint Blend (Soil ), Kaolin Storage Glucans from Brown Algae

[0089] Pheromones, including: 3M Sprayable Blackheaded Fireworm ), codling moth pheromone (Paramount dispenser-(CM) / Isomate ), Grape Leaf Roller Pheromone (3M MEC-GBM Sprayable ), leaf roller pheromone (3M MEC-LR Sprayable )、Muscamone(Snip7Fly StarbarPremium Fly ), 3M oriental fruit moth sprayable ), Peachtree Borer pheromone (Isomate- )、Tomato Pinworm pheromone (3M Sprayable Entostat powder (Exosex )、(E,Z,Z)-3,8,11-tetradecatriene acetate, (Z,Z,E)-7,11,13-hexadecatrienal, (E,Z)-7,9-dodecadien-1-yl acetate, 2-methyl-1-butanol, calcium acetate, Lavandulylsenecioate;

[0090] Macrobial agents, including: Aphidius ervi, Aphelinus ervi ), Acerophagus papaya, Adalia- ), Coccinella bispotata Two-spotted ladybug Ageniaspiscitricola, Amblyseius andersoni ( Andersoni- ), Amblyseius californicus Amblyseius cucumeris Bugline ), Pseudoseiidae Bugline Swirskii- ), Amblyseius osborne Amitus hesperidum, Anagrusatomus, Anagyrus fusciventris, Anagyruskamali, Anagyrus loecki, Anagyrus pseudococci Red wax scale flat-horned jumping wasp (Anicetus benefices), golden wasp (Anisopteromalus calandrae), woodland flower stink bug (Anthocoris nemoralis) (Anthocoris- ), Aphididae Aphelinus asychis, Aphidius colemani Aphidida albicans Aphipar- ), Aphid midge Aphid midge Lingnan yellow aphid wasp, Indian yellow aphid wasp, Aprostocetus hagenowii, Atheta coriaria Bombus species, European bumblebee (Natupol ), European Bombus Cephalonomia stephanoderis, Chilocorus nigritus, Chrysoperla carnea Common lacewings Chrysoperla rufilabris, Cirrospilus ingenuus, Cirrospilus quadristriatus, Citrostichusphyllocnistoides, Closterocerus chamaeleon, species of Closterocerus, Coccidoxenoides perminutus Coccophagus cowperi, Coccophagus lycimnia, Coccophagus lycimnia, Coccophagus lycimnia, Coccophagus lycimnia, Coccophagus lycimnia Japanese square-headed beetle, Siberian ceratosaurus, Siberian ceratosaurus Pea leafminer Small black ladybug (Delphastuscatalinae) Delphastus pusillus, Diachasmimorpha krausii, Diaparsis jucunda, Diaphorencyrtus aligarhensis, Diaphorencyrtus sphaeroides, Diaphorencyrtus sphaeroides Ceratognathus sibirica Species of the genus Encarsia, Encarsia spp. En- ), Eretmocerus eremicus Encarsia guadeloupae, Encarsia haitiensis, Encarsia guadeloupae Eretmoceris siphonini, Eretmocerus californicus, Eretmocerus eremicus ( Eretline ), Eretmocerus eremicus Henri's aphid wasp, Monsonia's aphid wasp Eretmocerus siphonini, Exochomus quadripustulatus, Feltiella acarisuga Gall midge Alishan flyminer, Fopius ceratitivorus, Wirless ), Slender-waisted Thrips Galendromus occidentalis, Goniozus legneri, Galendromus occidentalis, Harmonia axyridis Heterorhabditis spp. (Lawn ), Heterorhabditis elegans (NemaShield Terranem- B- ), Heterorhabditis megidis (Nemasys BioNem Exhibitline Larvanem- ), Hippodamiaconvergens, Hypoaspis aculeifer (Aculeifer- Entomite- ), Hypoaspis miles Entomite- ), Lbalia leucospoides, Lecanoideus floccissimus, Lemophagus errabundus, Leptomastidea abnormis, Leptomastix dactylopii Leptomastix epona, Lindorus lophanthae, Lipolexis oregmae, Lucilia caesar Lysiphlebus testaceipes, Macrolophus caliginosus (Mirical- Macroline ), Mesoseiulus longipes, Metaphycus flavus, Metaphycus lounsburyi, Micromus angulatus Microterysflavus, Muscidifurax raptorellus and Spalangia cameroni Neodryinustyphlocybae, Neoseiulus californicus, Neoseiuluscucumeris Neoseiulus fallacis, Nesideocoristenuis Bronze blackfly (Ophyra aenescens) Orius insidiosus (Thripor- ), Orius laevigatus (Thripor- Oriline ), Orius majusculus (Oriline ), Orius strigicollis (Thripor- ), Pauesiajuniperorum, Pediobius foveolatus, Phasmarhabditishermaphrodita Phymastichus coffea, Phytoseiulus macropilus, Phytoseiulus persimilis ( Phytoline ), Podisus maculiventris Pseudacteon curvatus, Pseudacteon obtusus, Pseudacteon tricuspis, Pseudaphycus maculipennis, Pseudleptomastix mexicana, Psyllaephagus pilosus, Psyttalia concolor (complex), Quadratichus spp., Rhyzobius lophanthae, Rodolia cardinalis, Rumina decollate, Semielacher petiolatus, Sitobion avenae Steinernema carpocapsae (Nematac BioNem Steinernema carinata Nemasys BioNem Steinernema- Exhibitline Scia- ), Saw Wasp Nematode (Steinernema kraussei) (Nemasys BioNem ), Steinernema riobrave Steinernema scapterisci (Nematac ), Steinernema spp., Steinernematid spp., Guardian ), Stethorus punctillum Tamarixia radiate, Tetrastichus setifer, Thripobius semiluteus, Torymussinensis, Trichogramma brassicae (Tricholine ), Trichogramma brassicae (Tricho- ), Trichogramma evanescens, Trichogramma minutum, Trichogrammaostriniae, Trichogramma platneri, Trichogramma retiosum, Xanthopimpla stemmator;

[0091] Other biological agents, including: abscisic acid, Chondrostereum purpureum (Chontrol ), Discosporium Copper Octanoate Delta trap ), Erwinia amylovora (Harpin) ( Ni-HIBIT Gold ), fatty acids derived from natural by-products of extra virgin olive oil Ferric Phosphate Funnel trap ), Grower's Homo-brassonolide, ferric phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )、MCP hail trap ), parasitic insects such as the southern food braconid wasp (Microctonus hyperodae), Mycoleptodiscus terrestris (Des- ), Pheromone Net (Thripline ), Potassium bicarbonate Potassium salts of fatty acids Potassium silicate solution (Sil- ), potassium iodide + potassium thiocyanate SuffOil- Spider venom, locust microsporidia (Semaspore Organic Grasshopper ), Trapline Rebell ) and capture (Takitrapline y+ );

[0092] (1) An antibacterial agent selected from the group consisting of:

[0093] (1.1) Bacteria, examples of which are Bacillus mojavensis strain R3B (accession number NCAIM (P) B001389) (WO 2013 / 034938), from Certis USA LLC; Bacillus pumilus, in particular strain BU F-33, with NRRL accession number 50185 (accession number NCAIM (P) B001389) (WO 2013 / 034938), from Certis USA LLC; EPA registration number 71840-19); Bacillus subtilis, in particular strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP in the United States, with NRRL registration number B21661, U.S. Pat. No. 6,060,051); Bacillus subtilis strain BU1814, (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP in the United States, with NRRL registration number B21661, U.S. Pat. No. 6,060,051); Bacillus subtilis strain BU1814, (available as SERENADE OPTI from BASF SE PLUS, FLEX and Bacillus subtilis var. amyloliquefaciens strain FZB24, with registration number DSM 10271 (available as or ECO (EPA Reg. No. 70127-5) from Novozymes); Bacillus subtilis CX-9060 from Certis USA LLC; Bacillus species, particularly strain D747 (available as DOUBLE obtained from Kumiai Chemical Industry Co., Ltd.), with registration number FERM BP-8234, U.S. Patent No. 7,094,592; Paenibacillus sp. strains, with registration number NRRL B-50972 or registration number NRRL B-67129, WO 2016 / 154297; Paenibacillus polymyxa, in particular strain AC-1 (e.g., from Green Biotech Company Ltd.) ); Pantoea agglomerans, in particular strain E325 (registration number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL TM FD BIOPESTICIDE from Northwest Agri Products); Pseudomonas proradix (e.g., from Sourcon Padena); );and

[0094] (1.2) Fungi, examples of which are budding Aglaonema, in particular blastospores of strain DSM 14940, blastospores of strain DSM 14941 or a mixture of blastospores of strains DSM 14940 and DSM 14941 (e.g., blastospores from bio-ferm, Switzerland). and BLOSSOM ); Pseudozyma aphidis (as disclosed in WO 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem); Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 from Lesaffre et Compagnie of France (WO 2010 / 086790);

[0095] (2) A biofungicide selected from the group consisting of:

[0096] (2.1) Bacteria, an example of which is Agrobacterium radiobacterium strain K84 (e.g. GALLTROL- ); Radiation-forming Agrobacterium strain K1026 (e.g. NOGALL from BASF TM ); Bacillus subtilis var. amyloliquefaciens strain FZB24, with registration number DSM 10271 (available as ECO (EPA registration number 70127-5) obtained from Novozymes); Bacillus amyloliquefaciens, particularly strain D747 (available as Double Nickel TM obtained from Kumihiko Chemical Industries, Ltd., with accession number FERM BP-8234, U.S. Patent No. 7,094,592); Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) (obtained from Marrone Bio Innovations, Inc., with accession number FERM BP-8234, U.S. Patent No. 7,094,592); Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) ); Bacillus amyloliquefaciens strain FZB42, registration number DSM23117 (can be used as from ABiTEP, Germany); Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN from the University of Pretoria); TM ); Bacillus licheniformis, in particular strain SB3086, having registration number ATCC 55406, WO 2003 / 000051 (available as BIOFUNGICIDES AND GREEN RELEAFTM Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (from FMC (WG) and (WP)); Bacillus methylotrophicus strain BAC-9912 (from the Institute of Applied Ecology, Chinese Academy of Sciences); Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) (WO 2013 / 034938), from Certis USA LLC; Bacillus mycoides isolate with accession number B-30890 (available as BMJ or WG and LifeGard TM Bacillus pumilus, particularly strain QST2808 (available as obtained from Bayer CropScience, USA, with registration number NRRL B-30087 and described in U.S. Pat. No. 6,245,551); Bacillus pumilus, in particular strain GB34 (available as Yield Bacillus pumilus, particularly strain BU F-33, having NRRL accession number 50185 (available as part of the CARTISSA product from BASF, EPA accession number 71840-19); Bacillus subtilis, particularly strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP in the United States, having NRRL accession number B21661, and described in U.S. Pat. No. 6,060,051); Bacillus subtilis Y1336 (available as WP was obtained from Bion-Tech, Taiwan, China, and registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277); Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF, with registration number NRRL B-50595, U.S. Patent No. 5,061,495); Bacillus subtilis strain GB03 (available as obtained from Bayer AG, Germany); Bacillus subtilis strain BU1814, (available as PLUS, FLEX and EXTRA from BASF); Bacillus subtilis CX-9060 from Certis USA LLC; Bacillus subtilis KTSB strain (from Donaghys ); Bacillus subtilis IAB / BS03 (AVIV from STKBio-Ag Technologies TM , from Idai Nature ); Bacillus subtilis strain Y1336 (can be used as WP was obtained from Biotech, Taiwan, China, and is registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096 and 5277); Paenibacillus epiphyticus (WO 2016 / 020371) from BASF SE; Paenibacillus plantarum species (WO 2016 / 020371) from BASF SE; Paenibacillus species strains with registration number NRRL B-50972 or registration number NRRL B-67129, WO 2016 / 154297; Pseudomonas chlororaphis strain AFS009 with registration number NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER from AgBiome Innovations, USA) TM and chlororaphis strains, in particular strain MA342 (eg, from Bioagri and Koppert) and ); Pseudomonas fluorescens strain A506 (e.g., from NuFarm A506); Pseudomonas proradix (e.g., from Sourcon Padena); ); Streptomyces griseoviridis strain K61 (also known as Streptomyces flavoviridis strain K61) (accession number DSM7206) (from Verdera From BioWorks

[0097] See Crop Protection 2006, 25, 468-475); Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO- and );and

[0098] (2.2) Fungi, an example of which is Pseudomonas sphaeroides, in particular strain AQ 10 (e.g. AQ ); Pseudomonas graminearum strain AQ10, with registration number CNCM 1-807 (e.g., AQ ); Aspergillus flavus strain NRRL 21882 (as AFLA- and known products); budding spores of Adenophora short-stalked, especially strain DSM 14940; budding spores of Adenophora short-stalked, especially strain DSM 14941; budding spores of Adenophora short-stalked, especially strains DSM 14940 and DSM 14941 budding spore mixture (e.g. from Bio-Philippines of Switzerland) ); Chaetomium cupreum (accession number CABI353812) (e.g., BIOKUPRUM TM ); Chaetomium globosum (can be used as from Rivale); Cladosporium cladosporioides, strain H39, with accession number CBS122244, US2010 / 0291039 (from Wageningen Research Foundation (Stichting Dienst Landbouwkundig Onderzoek)); Coniothyrium minitans, in particular strain CON / M / 91-8 (accession number DSM9660, e.g., from Bayer CropScience Biologics GmbH ); Cryptococcus flavescens, strain 3C (NRRL Y-50378), (B2.2.99); Dactylaria candida; Dilophosphora alopecuri (can be used as TWIST Fusarium oxysporum, strain Fo47 (available as from Natural Plant Protection); Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g., from Lallemand ); pink slime mold (Gliocladium roseum) (also known as pink slime mold (Clonostachys rosea)), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea [Pink slime mold strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea], Can Jour Plant Sci [Canadian Journal of Plant Science], 2003, 83 (3): 519-524), or strain IK726 (Jensen DF et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain 'IK726' [with particular emphasis on the development of a biocontrol agent for plant disease control using the near-commercial fungal antagonist Gliocladium roseum strain 'IK726'], Australasian Plant Pathol. 2007, 36(2):95-101); conidia of Lecanicillium lecanii (formerly Verticillium lecanii) strain KV01 (e.g., from Corbett / Arysta ); Metschnikowia fructicola, in particular strain NRRL Y-30752, (B2.2.3); Microsphaeropsis ochracea; Muscodor roseus, in particular strain A3-5 (accession number NRRL 30548); Penicillium steckii (DSM 27859, WO 2015 / 067800), from BASF; Penicillium vermiculatum; Phlebiopsis gigantea strain VRA 1992 (from Danstar Ferment) C); Pichia anomala, strain WRL-076 (NRRL Y-30842), U.S. Patent No. 7,579,183; Pseudozyma flocculosa, strain PF-A22 UL (can be used as L from Plant Products Co., California); Saccharomyces cerevisiae, in particular strain LASO2 (from Agro-Levures et Dérivés), strain LAS117 cell wall (from Lesaffre From BASF ), strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (WO 2010 / 086790) from Lesaffre, France; Simplicillium lanosoniveum; Talaromyces flavus, strain V117b; Trichoderma asperelloides JM41R (registration number NRRL B-50759) (TRICHO from BASF ); Trichoderma asperellum, in particular strain kd (e.g. T-Gro from Andermatt Biocontrol); Trichoderma asperellum, in particular strain SKT-1, with registration number FERM P-16510 (e.g. ECO- ), strain T34 (e.g., T34 from Biocontrol Technologies S.L., Spain) or strain ICC 012 from Isagro; Trichoderma atroviride, in particular strain SC1 (accession number CBS122089, WO 2009 / 116106 and U.S. Pat. No. 8,431,120 (from Bi-PA), strain 77B (T77 from Andermat Biocontrol) or strain LU132 (e.g., Sentinel from Agrimm Technologies Limited); Trichoderma atroviride, strain CNCM 1-1237 (e.g., Sentinel from Agrauxine, France) WP); Trichoderma atroviride, strain number V08 / 002387; Trichoderma atroviride, strain number NMI number V08 / 002388; Trichoderma atroviride, strain number NMI number V08 / 002389; Trichoderma atroviride, strain number NMI number V08 / 002390; Trichoderma atroviride, strain LC52 (e.g. Tenet from Agri-Med Technologies Ltd.); Trichoderma atroviride, strain ATCC20476 (IMI 206040); Trichoderma atroviride, strain T11 (IMI352941 / CECT20498); Trichoderma atroviride, strain number NMI number V08 / 002389; Trichoderma atroviride, strain number NMI number V08 / 002390; Trichoderma atroviride, strain LC52 (e.g. Tenet from Agri-Med Technologies Ltd.); Trichoderma atroviride, strain ATCC20476 (IMI 206040); Trichoderma atroviride, strain T11 (IMI352941 / CECT20498); atroviride), strain SKT-1 (FERM P-16510), Japanese Patent Publication (Kokai) 11-253151A; Trichoderma atroviride, strain SKT-2 (FERM P-16511), Japanese Patent Publication (Kokai) 11-253151A; Trichoderma atroviride, strain SKT-3 (FERM P-17021), Japanese Patent Publication (Kokai) 11-253151A; Trichoderma fertile (e.g., the product TrichoPlus from BASF); Trichoderma gamsii (original viride), strain ICC080 (IMI CC 392151CABI, for example, from AGROBIOSOL DE MEXICO, SADE CV) of BioDerma); Trichoderma gamsii (formerly viride), strain ICC 080 (IMI CC 392151 CABI) (can be used as from Agribarso Mexico); Trichoderma harmatum; Trichoderma harmatum, with accession number ATCC 28012; Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Kobert) or strain Cepa Simb T5 (from Simbiose Agro); Trichoderma harzianum; Trichoderma harzianum slant (rifai) T39 (e.g., from Makhteshim, USA); ); Trichoderma harzianum, strain ITEM 908 (e.g., Trianum-P from Cobbert); Trichoderma harzianum, strain TH35 (e.g., Root-Pro from Mycontrol); Trichoderma harzianum, strain DB 103 (available as T- 7456 from Dagutat Biolab); Trichoderma polysporum, strain IMI 206039 (e.g., from Binab TF WP of BINAB Bio-Innovation AB, Sweden); Trichoderma stromaticum, with accession number Ts3550 (e.g., from Tricovab of CEPLAC, Brazil); Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g., from SoilGard of Certis, USA); Trichoderma virens strain G-41, formerly known as Gliocladium virens (accession number ATCC 20906) (e.g., from Biovox, USA); PLUS WP and PLUS WP); Trichoderma viride, strain TV1 (e.g. Trianum-P from Kobert); Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie [Science of the Agricultural University of Szczecin] 161: 125-137); a mixture of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC 012) (with registration number CABI CC IMI 392716) and Trichoderma gamsii (formerly Trichoderma viride) strain ICC 080 (with registration number IMI 392151) (e.g. BIO-TAM from Eseg USA, Inc. TM and from Agriberso Mexico ); Ulocladium oudemansii strain U3, having accession number NM 99 / 06216 (e.g., BOTRY-Zen Ltd. from New Zealand); and from Byworth ); Verticillium albo-atrum (formerly V. dahliae), strain WCS850, having accession number WCS850, deposited with the Central Bureau for Fungi Cultures (e.g., by DUTCH of Tree Care Innovations) ); Verticilliumchlamydosporium;

[0099] (3) Biological control agents having the effect of improving plant growth and / or plant health selected from the following group:

[0100] (3.1) Bacteria, an example of which is Azospirillum brasilense (e.g., from KALO, Inc.) ); Azospirillum lipoferum (e.g., VERTEX-IF from TerraMax, Inc.); TM); Azorhizobiumcaulinodans, in particular strain ZB-SK-5; Azotobacter chroococcum, in particular strain H23; Azotobacter vinelandii, in particular strain ATCC 12837; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (which can be used as Bacillus amyloliquefaciens pm414 (LOLI- ); Bacillus amyloliquefaciens SB3281 (ATCC#PTA-7542, WO 2017 / 205258); Bacillus amyloliquefaciens TJ1000 (can be used as Bacillus amyloliquefaciens, in particular strain IN937a; Bacillus amyloliquefaciens, in particular strain FZB42 (e.g., from Ebitech, Germany ); Bacillus amyloliquefaciens BS27 (registration number NRRL B-5015); EE128, a member of the family Bacillaceae (NRRL number B-50917); EE349, a member of the family Bacillaceae (NRRL number B-50928); Bacillus cereus, in particular strain BP01 (ATCC 55675, e.g., from Arysta Lifescience, USA ); Bacillus firmus, in particular strain CNMC1-1582 (e.g., from BASF ); Bacillus mycoides BT155 (NRRL No. B-50921); Bacillus mycoides EE118 (NRRL No. B-50918); Bacillus mycoides EE141 (NRRL No. B-50916); Bacillus mycoides BT46-3 (NRRL No. B-50922); Bacillus pumilus, in particular strain QST2808 (accession number NRRL No. B-30087); Bacillus pumilus, in particular strain GB34 (e.g., YIELD from Bayer CropScience, Germany) ); Bacillus siamensis, particularly strain KCTC 13613T; Bacillus subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B-21661 and described in U.S. Pat. No. 6,060,051, which can be used as Opti or ASO was obtained from Bayer CropScience, Inc., USA); Bacillus subtilis, in particular strain AQ30002 (accession number NRRL No. B-50421 and described in U.S. Patent Application No. 13 / 330,576); Bacillus subtilis, in particular strain AQ30004 (and NRRL No. B-50455 and described in U.S. Patent Application No. 13 / 330,576); Bacillus subtilis strain BU1814 (available as from BASF), Bacillus subtilis rm303 (from Biofilm Crop Protection ); Bacillus thuringiensis BT013A (NRRL No. B-50924), also known as Bacillus thuringiensis 4Q7; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (can be used as (WG), (WP) from FMC Corporation); Bacillus subtilis, in particular strain MBI 600 (e.g. from BASF ); Bacillus tequilensis, in particular strain NII-0943; Bradyrhizobium japonicum (e.g. from Novozymes ); Delftia acidovorans, in particular strain RAY209 (e.g., from Brett Young Seeds ); Mesorhizobium cicer (e.g., NODULATOR from BASF); Lactobacillus species (e.g., ); Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF); Pseudomonas proradix (e.g., aeruginosa, in particular strain PN1; Rhizobium leguminosarum, in particular bv. viceae strain Z25 (accession number CECT 4585); Paenibacillus polymyxa, in particular strain AC-1 (e.g., from Green Biotech Company Ltd.) ); Serratia marcescens, in particular strain SRM (accession number MTCC8708); Sinorhizobium meliloti strain NRG-185-1 (from Bayer CropScience GOLD); Thiobacillus sp. (e.g., from Cropaid Ltd, UK); );and

[0101] (3.2) Fungi, examples of which are Purpureocillium lilacinum (formerly Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g. BioAct from Bayer CropScience Biotech); Penicillium bilaii, strain ATCC 22348 (e.g. BioAct from Acceleron BioAg); ), Talaromyces flavus, strain V117b; Trichoderma atroviride, strain CNCM 1-1237 (e.g. from Aglaocosin, France); WP), Trichoderma viride, for example strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie [Science Volume of Agricultural University of Szczecin] 161: 125-137); Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, for example Sentinel from Agrimm Technologies Limited); Trichoderma atroviride strain SC1 (described in WO2009 / 116106); Trichoderma asperellum strain kd (for example T-Gro from Andermatt Biocontrol); Trichoderma asperellum strains (Eco-T from Plant Health Products of New Zealand), Trichoderma harzianum (Trichoderma atroviride strain SC2 (described in WO2009 / 116106); harzianum) strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Coppert); Myrocyproterensis strain AARC-0255 (e.g., DiTera from Valent Biosciences); TM ); Penicillium bilaii strain ATCC ATCC20851; Pythium oligandrum strain M1 (ATCC 38472, for example, Polyversum from Bioprepraty, Czech Republic); Trichoderma virens strain GL-21 (for example, from Sertis, USA ); Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS276.92, for example Dutch Trig from Tree Care Innovations); Trichoderma atroviride, in particular strain No. V08 / 002387, strain No. NMI No. V08 / 002388, strain No. NMI No. V08 / 002389, strain No. NMI No. V08 / 002390; Trichoderma harzianum strain ITEM 908, Trichoderma harzianum strain TSTh20; Trichoderma harzianum strain 1295-22; Pythium oligandrum) strain DV74; Rhizopogon amylopogon (Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company); Rhizopogon fulvigleba (e.g., Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company); Trichoderma virens strain GI-3;

[0102] (4) Insecticidal biological control agents selected from the following

[0103] (4.1) Bacteria, examples of which are Bacillus radiobacter strain K84 (Galltrol from Egger Biochemicals); Bacillus amyloliquefaciens, in particular strain PTS-4838 (for example AVEO from Hualun Biosciences, USA); Bacillus firmus, in particular strain CNMC 1-1582 (for example, from BASF ); Bacillus mycoides, isolate J. (e.g., BmJ from Certis USA LLC); Bacillus sphaericus, in particular serotype H5a5b strain 2362 (strain ABTS-1743) (e.g., from Hualun Biosciences, Inc., USA ); Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. from Hualun Biosciences ); Bacillus thuringiensis subsp. aizawai, particularly serotype H-7 (e.g., from Hualun Biosciences, USA WG); Bacillus thuringiensis israelensis strain BMP 144 (e.g., from Becker Microbial Products, Inc., Illinois); ); Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (registration number ATCC 1276) (eg, from Hualun Biosciences, Inc., USA ); Bacillus thuringiensis subsp. aizawai strain GC-91; Bacillus thuringiensis var. Colmeri (e.g., TIANBAOBTC from Changzhou Jianghai Chemical Factory); Bacillus thuringiensis var. japonicum strain Buibui; Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, Illinois, BARITONE from Bayer CropScience); Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g., from Hualun Biosciences, USA); ES); Bacillus thuringiensis variant Kurstaki strain EVB-113-19 (e.g., from AEF Global ); Bacillus thuringiensis subsp. kurstaki strain ABTS 351; Bacillus thuringiensis subsp. kurstaki strain PB 54; Bacillus thuringiensis subsp. kurstaki strain SA11 (JAVELIN from Sertis, USA); Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Sertis, USA); Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Sertis, USA); Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Sertis, USA); Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, such as BioFa from Germany FC); Brevibacillus laterosporus (LATERAL from Ecolibrium Biologicals); Burkholderia spp., in particular Burkholderia rinojensis strain A396 (also known as Burkholderia strain MBI 305) (Accession No. NRRL B-50319; WO 2011 / 106491 and WO 2013 / 032693; for example MBI206 TGAI and MBI206 TGAI from Marrone BioInnovations); ); Chromobacterium subtsugae, in particular strain PRAA4-1T (e.g., MBI-203; e.g., from Maroni BioInnovations ); Lecanicillium muscarium Ve6 (MYCOTAL from Kobert); Paenibacillus popilliae (formerly Bacillus popilliae); MILKY SPORE POWDER from St. Gabriel Laboratories TM or MILKY SPORE GRANULAR TM); Pasteurella pseudoszavara strain Pn1 (CLARIVA from Syngenta / China National Chemical Corporation); Serratia entomophila (e.g., from Wrightson Seeds) ); Serratia marcescens, in particular strain SRM (accession number MTCC 8708); Trichoderma asperellum (TRICHODERMAX from Novozymes); Wolbachia pipientis ZAP strain (e.g., ZAP from MosquitoMate); );and

[0104] (4.2) Fungi, an example of which is Beauveria bassiana strain ATCC 74040 (e.g. from Intrachem Bio, Italy) ); Beauveria bassiana strain GHA (Accession No. ATCC 74250, e.g., from Laverlam International Corporation); ES and MYCONTROL- ); Beauveria bassiana strain ATP02 (accession number DSM 24665); Isaria fumosorosea (formerly known as Paecilomyces fumosoroseus strain) Apopka 97, (PREFERAL from SePRO); Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074, disclosed in WO 2017 / 066094; Pioneer Hi-Bred International); Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073); Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073); Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073); Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073); Metarhizium robertsii) 23013-3 (deposited under NRRL accession number 67075); Paecilomyces lilacinus strain 251 (MELOCON from Surtice, USA); Zoophtoraradicans;

[0105] (5) A virus selected from the group consisting of: summer fruit tortrix granulovirus (GV); Cydia pomonella (codling moth) granulovirus (GV); Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV); Spodoptera exigua (beet armyworm) mNPV; Spodoptera frugiperda (fall armyworm) mNPV; Spodoptera littoralis (African cotton leaf moth) NPV;

[0106] (6) Bacteria and fungi selected from the group consisting of Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Brachyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp. or Gigaspora monosporum, Glomus spp., Laccaria spp., LactoBacillus buchneri, Paraglomus spp., Pisolithus spp. tinctorus); Pseudomonas spp.; Rhizobium spp., in particular Rhizobium trifolii; Rhizopogon spp.; Scleroderma spp.; Suillus spp.; Streptomyces spp.;

[0107] (7) Plant extracts and products formed by microorganisms (including proteins and secondary metabolites) that can be used as biological control agents, selected from garlic (Allium sativum) (NEMGUARD from Eco-Spray; BRALIC from ADAMA); Armour-Zen; Artemisia absinthium; azadirachtin (e.g. AZATIN XL from Sertis, USA); Biokeeper WP; extracts from the Brassicaceae family, in particular rapeseed meal or mustard meal; Cassia nigricans; Celastrusangulatus; Chenopodium anthelminticum; Chitin; Dryopteris filix-mas; Equisetum arvense; Fortune Aza; Fungastop; Quinoa saponin extract from quinoa seeds (e.g. Heads Up Plant Protectants, Canada). (quinoa saponins); naturally occurring Blad peptides extracted from lupinus seeds (from Certis EU ); naturally occurring Blad polypeptide extracted from lupin seeds (from FMC ); Pyrethrum / pyrethrins; Quassia amara; Quercus; Quillaja extract (QL AGRI 35 from BASF); Knotweed extract (REGALLIA, REGALIA MAXX from Marrone Bio); "Requiem TMinsecticide”; rotenone; ryania / ryanodine; Symphytum officinale; Artemisia selengensis; Thymol; Thymol mixed with geraniol (CEDROZ from Eden Research); Thymol mixed with geraniol and eugenol (MEVALONE from Eden Research); Triact 70; TriCon; Tropaeulum majus; Melaleuca alternifolia (TIMOREX GOLD from Stockton & Co., Inc.); Urtica dioica; Veratrin; and Viscum album; and

[0108] Safeners such as fenthiocarb, cloquintocet (including cloquintocet-mexyl), cyproconazole, dichloropropene, fenthiocarb (including fenthiocarb-ethyl), fenthiocarb, fluazifop, fenthiocarb, isoxadiazole (including isoxadiazole-ethyl), mefenpyr (including fenthiocarb-diethyl), herbicide safeners (metcamifen) and fenthiocarb nitrile.

[0109] The weight ratio of the compound of formula I to compound II may preferably be from 100:1 to 1:100, from 50:1 to 1:50, from 20:1 to 1:40, from 15:1 to 1:30, from 12:1 to 1:25, from 10:1 to 1:20, from 5:1 and 1:15, from 3:1 to 1:10 or from 2:1 to 1:5.

[0110] In a preferred embodiment, the agrochemical composition may comprise at least one additional fungicide and optionally may further comprise at least one insecticide and / or at least one nematicide.

[0111] When the crystalline polymorph of the present invention is combined with at least one additional fungicide, the following mixtures of the polymorph of formula I with compound II are preferred: mixtures with a compound selected from the group consisting of petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenyl sulfone, acetothionil, aldicarb, sirox, fomanphos, fenthion, fenthion, oxalothion, amitraz, trioxyfon, chloranil ... Arsenic chloride, azobenzene, azophos, benomyl, benoxafos, benzyl benzoate, bixafen, bromothion, bromothion, bromopyralid, buprofezin, butanone, butanone sulfone, butylpyridaben, calcium polysulfide, octachlorocamphene, chlormethoxam, trithion, cypermethrin, cypermethrin, cypermethrin, cypermethrin hydrochloride, cypermethrin, cypermethrin, chlormebuform, chlormebuform hydrochloride, chlormebuform, chlormebuform, chlormebuform, chlormebuform ethyl, chlormebuform (chloromebuform), chlormebufen, propyl chlormebuform, chlormebuform, melon Pyrethrin I, cypermethrin II, cypermethrin, closantel, coumaphos, crotamiton, baclofos, thiophanate, fruit insect phosphorus, DCPM, DDT, dinex, dinex-O, dinex-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl, demeton-S-methyl, bacteriostatic, dichlorvos, dichlorvos, chlorpyrifos, chlorpyrifos, chlorpyrifos, dinex, dinex-dicl exine), dimethoate-4, dimethoate-6, ortho-dimethoate, nitropentyl, nitrooctyl ester acaricide, nitrobutyl ester, dimethoate, sulfodiphenyl, dithiocarb, DNOC, dofenapyn, doramectin, indophos, eprinomectin, thiophos, ethimphos, anti-mite azole, fenbutatin, fenthiocarb, fenpyrad, fenpyrad, fenpyrad, fenpyrad, fentrifanil, fluazifop-butyl, flufenoxuron, fluazifop-butyl, flufenoxuron, flufenoxuron, flufenoxuron, FMC 1137, fenthion, fenthion hydrochloride, formparanate, γ-HCH, chloranil, benzyl chloranil, hexadecyl cyclopropane carboxylate, isothiocarb, jasmonate I, jasmonate II, iodine, lindane, propanil, cypermethrin, dithiophos, methylthiophene, cypermethrin, methyl bromide, cypermethrin, chloranil, milbemid, oxime, propylamine, monocrotophos, malathion, moxidectin, nale d), 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, fluazifop, nikkomycin, pentocarb, pentocarb 1:1 zinc chloride complex, omethoate, isothiocarb, sulfone, pp'-DDT, parathion, permethrin, fenthion, phosalone, thiocyanate, phosphamidon, polychloroterpenes,Polynactins, chloranil, cypermethrin, propoxur, ethidium, thiamethoxam, pyrethrin I, pyrethrin II, pyrethrin, pyridazithion, pyrimithiophos, quinalphos, quintiofos, R-1492, glyphosate, rotenone, octamethoxam, clomar, selamectin, thiothion, SSI-121, sulfluramid, sulfotep, sulfur, flumethoxazine, τ-fluvalinate, TEPP, tert-butylcarb, tetrachlorothiazide, thiafenox, thiamethoxam, long-acting thiophanate, methyl thiophanate, chloranthate, Sulimycin, fenthion, benzyl thiocarb, triazophos, triazuron, triclofos, triactivin, aphidazole, vaniliprole, permethrin, copper dioctanoate, copper sulfate, cybutryne, dichloronaphthoquinone, dichlorophen, endoxan, triphenyltin, slaked lime, sodium mancozeb, quinonamid, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, fusulin, piperazine, thiophanate, chloralose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxaline) -2-amino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, disopyrtioxon, dodesine, sodium sulfone, formaldehyde, mercurygafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel di(dimethyldithiocarbamate), trichloromethylpyridine, octhiothione, oxolinic acid, oxytetracycline, hydroxyquinoline potassium sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, chlorothiazide, thimerosal, cotton brown banded moth GV, radiobacterium, blunt mite species, celery armyworm NPV, original cherry-winged tassel wasp, short-spur aphid wasp, cotton aphid parasitic wasp, aphid gall midge, clover silver-striped armyworm NPV, spherical Bacillus, cloth Beauveria bassiana, common lacewings, Cryptolabia monnieri, GV of apple moth, Siberian sibirica, pea leafminer, Aphididae, Aphididae, bacteriophagic Heterorhabditis and Heterorhabditis spp., long-legged ladybird, parasitic wasp of citrus mealybug, blind bug, cabbage armyworm NPV, yellow broad-stalked jumping wasp, Metarhizium anisopliae, Metarhizium anisopliae microspore variant, European new pine sawfly NPV and red-headed new pine sawfly NPV, species of the genus Microsei, Penicillium fumosorum, Chilean phytoseiid mite, mosquito nematode, small-rolled moth nematode, noctuid moth nematode, Gricea nematode, sharp-sided nematode, Steinernema leoboris riobravis), mole cricket Steinernema, Steinernema species, Trichogramma species, western blind mite, Verticillium lecanii, oxazolidinone, bis(aziridine)methylaminophosphine sulfide, busulfan, dimethivin, hexamethylmelamine, hexamethylphosphine, methyl tib, methylthiotib, methyloxazolidinone, infertility amine, fluoroquinolone, tib, hexamethylphosphine thioate, thiotib, trothamide, urethaneimide,(E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-eicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate 、(9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, α-polymorphin, western pine beetle aggregation pheromone, dodecadienol, kodemone, fly attractant, epoxy nonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8, 10-dien-1-yl acetate Acid ester, dominicalure, ethyl 4-methyloctanoate, eugenol, southern pine beetle gathering pheromone, trap-ene mixture, trap-ene mixture I, trap-ene mixture II, trap-ene mixture III, trap-ene mixture IV, hexane attractant, tooth beetle dienol, small beetle alcohol, scarab sex attractant, trimethyl dioxytricyclononane, litlure, cabbage looper sex attractant, trap-ene ester, megatomoic acid, entophore, entophore, octadecyl-2,13-diene-1-yl acetate, octadecyl-3,13-diene-1-yl acetate, Hecon, coconut rhinoceros beetle aggregation pheromone, philoxenia, entophore ring, sordidin, fungi-eating acetoin, tetradecyl-11-ene-1-yl acetate, Mediterranean fruit fly attractant, Mediterranean fruit fly attractant A, Mediterranean fruit fly attractant B1, Mediterranean fruit fly attractant B2, Mediterranean fruit fly attractant C, trunc-call, 2-(octylthio)-ethanol, pyrrolidone, butoxy (polypropylene glycol), dibutyl adipate, o- Dibutyl phthalate, dibutyl succinate, DEET, mosquito repellent, dimethyl phthalate, ethyl hexanediol, hexyl urea, mequindine, methyl neodecylamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-di(4-ethylphenyl)-ethane, 1,2-dichloropropane and 1,3-dichloropropylene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate,2-(2-Butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidinone, 2-isovaleryl indan-1,3-dione, 2-methyl (prop-2-ynyl) aminophenylmethylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-Methyl-1-phenylpyrazol-5-yl dimethyl-carbamate, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acethion, acrylonitrile, aldrin, alloamicin, cypermethrin, α-decimin, aluminum phosphide, cypermethrin, neonicotinoids, ethyl methidathion, methyl pyrifos, Bacillus thuringiensis delta- Endotoxin, barium hexafluorosilicate, barium polysulfide, fumonisin, Bayer 22 / 190, Bayer 22408, β-cyfluthrin, β-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromophenone, bromo-DDT, synthate, butathiofos, butathiofos, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, badan hydrochloride, cevadine, borneol, chlordane, chlordecone, chloroform, chloropicrin, chloraniloxime, chlorprazophos, cis-resmethrin, cismethrin, clocythrin (alias), copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, benzonitrile, cypermethrin, cypermethrin, d-methanthrin, DAEP, dazomethane, decarbofuran, diamidafos, isochlorophos, dimethoate, dicresyl, cypermethrin, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dior, tetrafluthrin, demicarb, pyrethrin, methyl chlorpyrifos, difenocarb, propanol, pentotropol, dinofuranoside, fenthion, vegetable phosphorus, thiopyrafos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiobencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenthion, ethylbencarb, fenitrothion, fenoxacrim, cypermethrin, fenthion, ethylfenthion, flucofuron, butylfenthion, phosphonium arsenate, butylfenthion, furathiocarb, pyrethroid, biguanide salt, biguanide acetate, sodium tetrathiocarbonate, benzyl chlorpyrifos, HCH,HEOD, heptachlor, cypermethrin, HHDN, hydrogen cyanide, quinoline, IPSP, chlorfenapyr, carbon chlorine, isoaldrin, isofenphos, transplanting spirit, rice blast, oxazophos, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorpentyl, methoprene, lead arsenate, bromophenylphos, acetamiprid, thiamethoxam, m-isopropyl methylcarbamate, magnesium phosphide, phosphorus azide, methyl aphid, aphid, mercurous chloride, methyl sulfoxide, metamifene, metamifene potassium salt, metamifene sodium salt, methylsulfonyl fluoride, butenyl phosphine, methoprene, methylthiocyanate, methoxychlor, isothiocyanate Methyl ester of acid, methyl chloroform, dichloromethane, anthracene, anthelminth, naphthion, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, orthonicotine, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate, O,O,O',O'-tetrapropyl dithiodipyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenthion, parachlorothion, phosphine, methyl phoxim, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious element I, precocious element II, precocious element III, amidophos, profluthrin, fenthion, pyraclostrobin, anti-pyrethroid, quassia extract, quinalphos-methyl, oxazolidinone, iodophos, resmethrin, rotenone, thiamethoxam, ryanodine, ryanodine, Sabadilla, octamethoxam, clostridium, SI-0009, thiamethoxam, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, thiopromide, tar, thiamethoxam, TDE, butylpyrimidinphos, dimethoate, cypermethrin, tetramethoxythion Ethyl chloride, thiochlorvos, cyclopentadione, cyclopentadione oxalate, cypermethrin, cypermethrin, cypermethrin sodium, tralomethrin, trans-permethrin, trichlormetaphos-3, chlorpyrifos, chlorfenapyr, tolprocarb, chlorpyrifos-butyl, methoprene, veratridine, veratridine, XMC, zetamethrin, zinc phosphide, tolfenphos, chlorpyrifos Fluorothrin, tetrafluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-ethanolamine, tributyltin oxide, pyroximate, snail killer, 1,2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thio-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine,Anisiflupurin, phenylchlorothiazide, cytokinin, DCIP, furfural, isoamidophos, kinetin, verrucospore mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin, potassium ethyl xanthate, acibenzolar, acibenzolar-S-methyl, Polygonum cuspidatum extract, α-chlorohydrin, antu, barium carbonate, bifenthrin, brodifacoum, bromodiolone, brofenamide, chlorfenapyrone, cholecalciferol, chlorfenapyr, rodenticide, Naphthalene, cypermethrin, cypermethrin, thiamethoxam, difacoum, calciferol, flufenacet, fluoroacetamide, flufenacet, flufenacet hydrochloride, cypermethrin, chloranthrin, phosphorus, chloranthone, chloranthide, scillarin, sodium fluoroacetate, thallium sulfate, cypermethrin, 2-(2-butoxyethoxy)ethyl piperate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic alkynyl ether, MGK 264, piperonyl butoxide, synergistic aldehyde, propyl isomer, S421, synergistic powder, sesame, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, serene, zinc cyclohexane, zinc ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bifenthrin, fuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, nitrobenzene, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, imipenem, Ipomoconazole, metconazole, myclobutrazol, paclobutrazol, pyrifenox, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyraclostrobin, simeconazole, tebuconazole, fluconazole, triadimefon, triadimenol, triflumizole, trimethimol, pyrimidine, chlorfenapyr, flufenapyr, bupirimate, dimethirimol, ethirimol, dodecacyclic morpholine, fenpropidin (fenpropidine), fenpropimorph, spiroxafil, tridemorph, cyprodinil, pyrimethanil, fenpropimorph, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, furamide, oxadixyl, carbendazim, debacarb, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin, furamide, flutolanil, oxadiazine, oxycarboxin, penthiopyrad, thiofuran, dodine, biguanide, azoxystrobin, etherstrychnine, enestroburin,Enoxabio, flutoxin ester, fluoxastrobin, kresoxim-methyl, fenoxystrobin, trifloxystrobin, trifloxystrobin, pyraclostrobin, pyraclostrobin, ferram, mancozeb, maneb, methanamide, methyl propineb, maneb, captol, captan, azoles, folpet, tolylfluanid, Bordeaux mixture, copper oxide, mancozeb, quinoline copper, phthalocyanine, kefansan, isoflavone, chlorpyrifos, methyl tolclofos, captol, methyl propionate, chlorpyrifos ... iclomezine), dicloran, diethofencarb, oxadiazine, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, sulfamethoxazole lusulfamide), flupyraclostrobin, fenacet, fosetyl-aluminium, hymexazol, propineb, cyazofamid, methasulfocarb, methaquinone, pencycuron, phthalide, polyoxins, propamocarb, pyraclostrobin, proquinazid, pyroquilon, pyriofenone, quinoxyfen, pentachloronitrobenzene, triazomethin, and oxazolidinone. xide), tricyclazole, trimethoprim, validamycin, valeramide, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovinflumizone, flutoxazone, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflurane, isothiopyram, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithia[1,2-c]isothiazole-3-carbonitrile,2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, jiaxian gjunzhi), lvbenmixianan, dichlobentiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]propan-2-ol, oxathiapiprolin, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, clofoconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-thiazol-2 ... -piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, flubenzylpyridazine (pyridachlometyl), 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide,1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazolyl-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazolyl-5-one, aminopyrifen, pyrifen, indazolesulfamide, fluopyrafen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pentane-3 -enamine, florylpicoxamid, fenpicoxamid, metaylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid, 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (can be made from WO 2020 / 056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylate (can be prepared by the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide,N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzathiostrobin, cyanothiostrobin, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, fluthiazolin, fluopyram, pyrapropoyne, picarbutrazox, 2-(difluoromethyl)-N-( 3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, metyltetraprole, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide 3-(trimethylindan-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol, fluoxapiprolin, enoxastrobin, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, 5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoic acid methyl ester (these compounds can be prepared from WO 2020 / 079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the method described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, trinexamic acid, syringoxystrobin, zhongshengmycin, thiophanate-methyl, thiophanate-zinc, amectotractin, isobacillus urea, seboctylamine; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl- 6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared from WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide,N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide,

[0112] N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1 -benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide -quinoline-3-carboxamide (these compounds can be prepared by the method described in WO2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4, 4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared from WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by the method described in WO 2016 / 156085);N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4 -oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared by WO 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (this compound can be prepared by the method described in WO 2014 / 006945);2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone (this compound can be prepared by the method described in WO 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenethiocarboxamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound can be prepared by the method described in WO 2011 / 138281), 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-C-methyl-carbonimide]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428). ;

[0113] In particular, the following fungicidal mixed pairs are preferred:

[0114] - strobilurin fungicides selected from the group consisting of azoxystrobin, orysastrobin, fluoxastrobin, orysastrobin, fenoxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin;

[0115] - an azole fungicide selected from the group consisting of azaconazole, oxadiazole, cyproconazole, difenoconazole, diniconazole, diniconazole M, oxadiazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imipenem, methiconazole, metconazole, myclobutanil, oxadiazole, pyraclostrobin, penconazole, prochloraz, propiconazole, prothioconazole, silyfenazole, tebuconazole, fluconazole, triadimefon, triadimenol, triflumizole, triclopyralid, benzimidazole, ethiconazole, furconazole, furofenazole and clofenac;

[0116] - a morpholine fungicide selected from the group consisting of 4-dodecyl-2,6-dimethylmorpholine, cyclohexanemorpholine, fenpropimorph, tridemorpholine, fenpropidin, spiroxafil and chloranil;

[0117] - an anilinopyrimidine fungicide selected from the group consisting of cyprodinil, mefenamic acid and pyrimethanil; and / or

[0118] - A fungicide selected from the group consisting of bensulfuron, bensulfuron-M, benomyl, bifenthrin, boscalid, captan, carboxin, cyproconazole, chlorothalonil, copper, cyazolin, cymoxanil, ethofluthrin, dithianon, famoxadone, fenamidone, fenhexamid, fenoxycarb, fenpiclonil, fluazinam, fludioxonil, flutolanil, folpet, biguanide, oxamoxadone, chlorfenapyr, chlorfenapyr, mancozeb, metalaxyl, Metalaxyl, mefenamic acid, fluazifop, paclobutrazol, pencuron, penthiopyrad, procymidone, propoxyquin, pyroquilon, quinoxyfen, silthiopyrad, sulfur, thiabendazole, thiram, imidazobactam, tricyclazole, pyraclostrobin, fluazifop, flupyrad, benzovinflumazole and 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide.

[0119] Even more preferably, the polymorphs of the invention are combined with strobilurins or azoles.

[0120] Although compositions comprising a polymorph of the invention and another fungicide are explicitly disclosed above, one skilled in the art will appreciate that the invention extends to ternary, as well as additional combinations including binary mixtures thereof.

[0121] For the avoidance of doubt, although not explicitly stated above, these mixing partners may also be in the form of any suitable agrochemically acceptable ester or salt, as mentioned, for example, in The Pesticide Manual (19th Edition, British Crop Protection Council, 2021).

[0122] The invention will now be described by means of the following non-limiting examples and the accompanying drawings, in which:

[0123] Figure 1 The powder X-ray diffraction pattern of the crystalline polymorph according to the present invention (Form B) is shown.

[0124] Figure 2 The X-ray diffraction pattern calculated from the unit cell parameters according to Table 2 of the crystalline polymorph according to the present invention (Form B) is shown.

[0125] Figure 3 Shown is the DSC trace of the crystalline polymorph according to the invention (Form B).

[0126] Figure 4 Near infrared spectral traces of the crystalline polymorph according to the present invention (Form B) and the crystalline polymorph according to the prior art (Form A) are shown.

[0127] Figure 5 Shown are mid-infrared spectral traces of a crystalline polymorph according to the present invention (Form B) and a crystalline polymorph according to the prior art (Form A).

[0128] Figure 6 Shown is a powder X-ray diffraction pattern of a crystalline polymorph (Form A) according to the prior art.

[0129] Examples

[0130] 1. Preparation of polymorphs

[0131] The original drug compound of formula I used in the preparation of the polymorph according to the present invention is a racemic mixture of a compound of formula I (3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-bridged methylene-naphthalen-5-yl)-amide) prepared as described in Example P11 of WO 2012 / 101139 with a purity of 99.0%.

[0132] Xylene (580 g) was added to a 1000 mL jacketed crystallization vessel and heated to 40 ° C, with a stirring speed set at 100 rpm. The original drug compound (30 g) of Formula I was slowly added, and the mixture was stirred at 40 ° C for 30 min until only a small amount of solid remained (reaching the mark of saturation). The mixture was then heated to 45 ° C to ensure complete dissolution, and hot filtered (at 45 ° C) into 4 preheated glass bottles (each with a magnetic stirrer) through a preheating funnel equipped with a paper filter (type 1). The stirred solution was allowed to slowly cool to room temperature (20 ° C) under stirring, more particularly under gentle (magnetic) stirring, and the obtained suspension was kept at room temperature for 4 weeks under stirring, more particularly under gentle (magnetic) stirring. The suspension was filtered, and the solid was analyzed to confirm the formation of the desired polymorph (B form) according to the present invention.

[0133] 2. Analysis of polymorphs

[0134] After preparation by the methods detailed above, the samples were analyzed by powder X-ray diffraction, and / or single crystal X-ray diffraction, and / or differential scanning calorimetry (DSC), and / or near infrared spectroscopy, and / or mid infrared spectroscopy.

[0135] Powder X-ray diffraction analysis of solid materials was performed using a Bruker D2 phaser powder diffractometer at room temperature (20°C) and at a relative humidity above 40%. The sample was mounted in a standard PMMA sample holder and the sample was flattened. The sample holder was rotated and the range was from 3.5 to 44° 2θ with a step size of 0.02° and a The X-rays are collected by incident X-rays of a wavelength. The powder X-ray diffraction pattern of the crystalline polymorph (Form B) according to the present invention is shown in Figure 1 and the powder X-ray diffraction pattern of the crystalline polymorph (Form A) according to the prior art is shown in Figure 6 middle.

[0136] Using Cu Kα radiation on a Rigaku Supernova diffractometer Single crystal intensity data were collected with a graphite monochromator. The crystal was mounted in NVH oil at -173°C for data collection. The data were processed using the CRYSTALS software package and the results are collected in Table 2 (unit cell parameters). The X-ray diffraction pattern calculated from the unit cell parameters of the crystalline polymorph (Form B) is shown in Figure 2 middle.

[0137] DSC was performed using a Mettler Toledo DSC1, using a standard 40 μL aluminum sample holder with a perforated lid (to allow any gases formed during sample heating to escape), heating from 30°C to 200°C at a rate of 10°C / min. The DSC trace of the crystalline polymorph according to the invention (Form B) is shown at Figure 3 middle.

[0138] Near infrared spectroscopy was performed at room temperature (25°C) using a wavelength range of 3,500 to 12,500 cm -1 The integrating sphere of the crystalline polymorph according to the present invention (Form B) and the crystalline polymorph according to the prior art (Form A) are shown in Figure 1. Figure 4 middle.

[0139] Mid-infrared spectroscopy was performed on a Bruker Alpha II spectrometer in the range of 400 to 4,000 cm -1 The Alpha II (FTIR) has an anvil that presses the sample onto a diamond window for analysis. The mid-infrared spectra traces of the crystalline polymorph according to the present invention (Form B) and the crystalline polymorph according to the prior art (Form A) are shown in Figure 5 middle.

[0140] 3. Experiment

[0141] In order to demonstrate the advantages of the crystalline polymorph according to the present invention, the following experiments were performed.

[0142] 3.1. Formation of seed crystals

[0143] Solid seed crystals B are prepared according to the above-mentioned polymorph preparation of the present invention (see the item “1. Preparation of polymorph”).

[0144] Solid seed A was prepared according to WO 2012 / 101139 (Example P11), wherein the powder X-ray diffraction pattern is shown in Figure 6 In, and is related to the anhydrous form 1 described in WO 2015 / 128322. The solid seed crystal A (i.e., anhydrous form 1) can also be prepared according to WO 2011 / 131544 (step f of preparation example), WO 2011 / 131545 (step g of preparation example), WO2011 / 131546 (step d of preparation example), or US2012 / 136162 (Example P6 or Example P7).

[0145] 3.2. Seeding method

[0146] Xylene (774 g) and the technical compound of formula I (125 g) were added to a 1000 ml jacketed vessel equipped with an anchor stirrer (stirring speed: 150 rpm) and heated to 75° C. until all solids were dissolved.

[0147] After allowing the solution to cool to 50°C (seed temperature), solid seed B (2.0 g) or solid seed A (2.0 g) was added. The suspension was held at 50°C for 60 minutes and then cooled to 0°C over 20 hours (linear cooling slope from 50°C to 0°C for 20 hours). The suspension was discharged into a filtration unit for cake specific resistance measurement.

[0148] 3.3. Filtration experiment

[0149] In the first part, the suspension is loaded onto a filtration unit equipped with a 20 μm polytetrafluoroethylene filter with a diameter of 5 cm. The equipment is placed under pressure (+0.5 bar gauge (barg)) and filtration is started. Once the surface of the filter cake is exposed, the filtration is terminated and the filtrate is refilled into a container and cooled to 0° C. In the second part, the filtration is then repeated at a pressure of +0.5 barg. The final product is dried at 57° C. under vacuum (1-10 mbar) to obtain polymorph B or A.

[0150] In terms of filtration, the initial run builds a filter cake on the filter and allows the filter media (cloth) impedance to be evaluated. Subsequent runs allow the cake specific resistance to be calculated. The data required are pressure, filtrate liquid viscosity (which is 0.75 mPa·s), the amount of filtrate collected over time, and the final filter cake height after filtration.

[0151] The following Tables 3 and 4 summarize the results obtained from the second part of each experiment from which the filter cake specific resistance was calculated. More specifically, Table 3 (Example 1) is according to the invention (crystals of Form B), wherein the filter cake height is 0.100 m, and Table 4 (Example 2) is a comparative example (crystals of Form A), wherein the filter cake height is 0.199 m. All experiments were carried out in the same way, except for the solids used (B or A).

[0152]

[0153]

[0154] Table 3

[0155]

[0156]

[0157] Table 4

[0158] The filter cloth impedance of both Examples 1 and 2 is 1.14×10 10 m -1 .

[0159] Filter cake resistance 滤饼 This can be calculated using the following equation:

[0160]

[0161] Where: R 滤布 =[m -1 ] represents the filter cloth (filter) impedance; A = filter area [m 2 ]; Δp = pressure difference [Pa]; μ = dynamic viscosity [Pa·s]; r 滤饼 = Filter cake specific resistance [m -2 ];h c = filter cake height [m];

[0162] The compressibility data as described in the above equation is summarized in Table 5.

[0163]

[0164]

[0165] Table 5

[0166] According to the results of Table 5, the filter cake obtained by Example 1 according to the present invention has a filter cake specific resistance at least twenty times lower than that of the filter cake obtained by Example 2, so that the filtration of polymorph B is faster than the filtration of polymorph A. This advantage is a significant improvement during one or more filtration steps of the compound of Formula I according to the present invention, especially in reducing the filtration time.

[0167] Although the present invention has been described with reference to its preferred embodiments and examples, the scope of the present invention is not limited to only those described embodiments. As will be apparent to those skilled in the art, the above invention may be modified and rewritten without departing from the spirit and scope of the present invention, which is defined and limited by the appended claims. All publications cited herein are hereby incorporated by reference in their entirety for all purposes, to the same extent as if each individual publication was specifically and individually indicated to be so incorporated by reference.

Claims

1. A crystalline polymorph of a compound of formula I It has a powder X-ray diffraction pattern comprising at least three 2θ angle values ​​selected from the group consisting of 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 15.9±0.2°, 16.4±0.2°, 19.9±0.2°, 20.7±0.2°, 22.2±0.2°, 22.6±0.2°, 23.9±0.2°, 24.6±0.2°, 26.0±0.2°, 26.3±0.2°, 27.5±0.2°, 30.0±0.2°, 32.0±0.2°, and 32.7±0.2°.

2. The crystalline polymorph according to claim 1, characterized in that The powder X-ray diffraction pattern comprises at least six 2θ angle values ​​selected from the group consisting of 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 15.9±0.2°, 16.4±0.2°, 19.9±0.2°, 20.7±0.2°, 22.2±0.2°, 22.6±0.2°, 23.9±0.2°, 24.6±0.2°, 26.0±0.2°, 26.3±0.2°, 27.5±0.2°, 30.0±0.2°, 32.0±0.2°, and 32.7±0.2°.

3. The crystalline polymorph according to any one of the preceding claims, characterized in that The powder X-ray diffraction pattern comprises at least the following 2θ angle values: 7.2±0.2°, 10.8±0.2°, 13.8±0.2°, 14.4±0.2°, 14.8±0.2°, 16.4±0.2°, 20.7±0.2°, 22.2±0.2°, 24.6±0.2° and 26.0±0.2°.

4. The crystalline polymorph according to any one of the preceding claims, characterized in that The crystalline polymorph has the following lattice parameters: α=70.2±0.2°, β=84.1±0.2°, γ=74.4±0.2°, and 5. The crystalline polymorph according to any one of the preceding claims, characterized in that The crystalline polymorph has a melting point ranging from 153° C. to 156° C. (peak position), and preferably ranging from 154° C. to 155° C. (peak position).

6. An agrochemical composition comprising the crystalline polymorph as claimed in any one of the preceding claims and at least one agriculturally acceptable carrier or diluent.

7. The composition according to claim 6, characterized in that The composition comprises at least one additional fungicide.

8. The composition according to claim 6 or claim 7, characterized in that The additional fungicide is a strobilurin or an azole.

9. The composition according to any one of claims 6 to 8, characterized in that The composition further comprises at least one insecticide and / or at least one nematicide.

10. A method of preventing or controlling fungal infestation on plants or plant propagation material, which comprises treating the plants or plant propagation material with an agrochemical composition as claimed in any one of claims 6 to 9.

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