Fungicidal and fungicidal compositions containing fludioxonil

Abstract

The present invention relates to a novel fungicidal composition, its use in agriculture or horticulture for controlling diseases caused by plant pathogens, in particular by phytopathogenic fungi, and to a method for controlling diseases in useful plants.

Description

[Technical field]

[0001] The present invention relates to novel fungicidal compositions, their use in agriculture or horticulture for controlling diseases caused by plant pathogens, in particular phytopathogenic fungi, and to a method for controlling diseases in useful plants. [Background technology]

[0002] Although many fungicidal compounds and compositions belonging to various different chemical classes have been developed / are in development for use as fungicides in useful plant crops, the crop resistance and activity against specific plant pathogens do not always meet the needs of agricultural practice in many respects. Therefore, there is a continuing need to find new compounds and compositions with superior biological properties for use in controlling or preventing plant infection by plant pathogens, such as compounds with greater biological activity, favorable spectrum of activity, increased stability profile, improved physicochemical properties, increased biodegradability, or other compositions with broader activity spectrum, improved crop resistance, synergistic interactions or enhancing properties, or compositions that show a more rapid onset of action or have a longer lasting residual activity, or that allow for reduced application times and / or reduced application rates of compounds and compositions required for effective control of plant pathogens, thereby allowing for beneficial resistance management practices, reduced environmental impact, and reduced worker exposure.

[0003] Compositions containing mixtures of different fungicidal compounds with different mechanisms of action can be used to meet some of these demands (eg, by combining fungicides with different spectra of activity). Summary of the Invention [Means for solving the problem]

[0004] According to the present invention, there is provided a bactericidal / fungicidal composition comprising as active ingredients a mixture of components (A) and (B), wherein component (A) is:

[0005] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5]

[0006] and component (B) is fludioxonil; Here, the weight ratio of component (A) to component (B) is 100:1 to 1:90.

[0007] In a preferred embodiment, component (A) is a compound selected from the following:

[0008] [Table 2]

[0009] In a preferred embodiment, component (A) is N-[(1,2 cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (the ISO name for this compound is cylcobutrifluram).

[0010] The possible presence of one or more asymmetric carbon atoms in a compound means that the compound can occur in optically isomeric forms, i.e., enantiomeric or diastereomeric forms. Atropisomers can also result from restricted rotation about a single bond. The present invention includes all of these possible isomeric forms (e.g., geometric isomers) of the compound, and mixtures thereof. The present invention also includes all of the possible tautomeric forms of the compound, and racemates, i.e., mixtures of at least two enantiomers in a substantially 50:50 ratio.

[0011] In a preferred embodiment, component (A) comprises the (1S,2S) and (1R,2R) enantiomers of the compound, and the ratio of the (1S,2S) enantiomer to the (1R,2R) enantiomer is greater than 4:1.

[0012] In preferred embodiments, the ratio of the (1S,2S) enantiomer to the (1R,2R) enantiomer is greater than 1.5:1, greater than 2.5:1, greater than 4:1, greater than 9:1, greater than 20:1, or greater than 35:1.

[0013] In a preferred embodiment, the ratio of the (1S,2S) enantiomer to the (1R,2R) enantiomer is about 9:1.

[0014] In a preferred embodiment, component (A) is the pure (1S,2S) enantiomer.

[0015] If necessary, enantiomerically pure final compounds may be obtained from appropriate racemic starting materials via standard physical separation techniques such as reverse phase chiral chromatography, or by stereoselective synthesis techniques, for example by using chiral starting materials.

[0016] The compounds of component (A) are commercially available and / or can be prepared using techniques known in the art and / or reported in the literature (e.g., WO2013143811 or WO2015003951, which are incorporated by reference in their entireties).

[0017] In each case, the compounds according to the invention are in free form, in oxidized form as N-oxides, or in salt form, for example agriculturally usable salt forms.

[0018] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds, as described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0019] Component (B) (fludioxonil) has the IUPAC name 4-(2,2-difluoro-benzo[1,3]dioxol-4-yl)pyrrole-3-carbonitrile and has the following structure: [ka]

[0020] Fludioxonil can be in the free form, in the oxidized form as the N-oxide, or in the salt form, and is known and commercially available and / or can be prepared using techniques known in the art and / or reported in the literature.

[0021] In a preferred embodiment, the weight ratio of component (A) to component (B) is from 50:1 to 1:90.

[0022] In a preferred embodiment, the weight ratio of component (A) to component (B) is from 20:1 to 1:50.

[0023] In a preferred embodiment, the weight ratio of component (A) to component (B) is from 10:1 to 1:50.

[0024] In preferred embodiments, the weight ratio of component (A) to component (B) is about 10:1 or about 1:50.

[0025] In a preferred embodiment, component (A) is N-[(1,2 cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide or a salt, enantiomer or N-oxide thereof and component (B) is fludioxonil in free form, in oxidized form as the N-oxide or in salt form, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:50 (in particular about 10:1 or about 1:50).

[0026] The present invention further provides a method for controlling or preventing phytopathogenic diseases, in particular phytopathogenic fungi, of a useful plant or its propagation material, which comprises applying a fungicidal composition according to the present invention to the useful plant, its locus, or its propagation material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The benefits provided by certain fungicidal mixture compositions according to the invention may include, in particular, advantageous levels of biological activity for protecting plants from diseases caused by fungi, or superior properties for use as an active ingredient in pesticides (e.g. high biological activity, advantageous activity spectrum, increased safety profile, improved physicochemical properties, or increased biodegradability).

[0028] The term "fungicide" as used herein means a compound that controls, modifies, or prevents fungal growth. The term "fungicidally effective amount" means an amount of such a compound or combination of such compounds that is capable of producing an effect on fungal growth. A controlling or modifier effect includes any deviation from natural development, such as killing, retardation, etc., and prevention includes the formation of a barrier or other defense in the plant to prevent infection by the fungus.

[0029] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0030] The term "plant propagation material" means all reproductive parts of a plant, for example seeds or growing parts of a plant such as cuttings or tubers, including not only seeds in the strict sense, but also roots, fruits, tubers, bulbs, rhizomes and plant parts.

[0031] As used herein, the term "habitat" refers to the field in which the plant is growing or in which the seeds of the cultivated plant are sown or in which the seeds will be planted in the soil, including the soil, the seeds and seedlings, and established vegetation.

[0032] Throughout this specification, the expression "composition" refers to various mixtures or combinations of components (A) and (B) (including the embodiments defined above), such as single "premixed" forms, multiple spray mixtures such as "tank mixes" made up of individual combinations of single active ingredient components, and combinations of single active ingredients when applied sequentially (i.e., one after the other within a reasonably short time, such as hours or days). The order in which components (A) and (B) are applied is not critical to the working of the invention.

[0033] The compositions of the present invention are effective against harmful microorganisms, such as those causing phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

[0034] The compositions of the present invention can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the classes Basidiomycete, Ascomycete, Oomycete and / or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and / or Mucoromycete.

[0035] The compositions are effective in controlling a broad spectrum of plant diseases, including foliar pathogens of ornamental crops, turf, vegetables, field crops, cereals and fruit crops.

[0036] These pathogens may include: The class Oomycete includes: Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium aphanidermatum, Pythium aerenomanes, Pythium Pythium diseases such as those caused by P. arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida, Sclerophthora macrospora and Bremia lactucae;and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and Sclerospora graminicola; Ascomycetes, such as Stemphylium solani, Stagonospora tainanensis, Spirocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres), Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicolaPleosporales such as Alternaria solani and Alternaria tomatophila; Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Capnodiales, such as Cercosporella capsellae and Cercosporella herpotrichoides; Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella coepkeii, Magnaporthales, such as Pseudocercospora koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Gaeumannomyces graminis, Magnaporthe grisea, and Pyricularia oryzae; Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, and others. platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fruticolaDiaporthales, such as: Diaporthales fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma; as well as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophytonspp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans, and others; crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostomanovo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp. spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivoraomnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium spp, Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; e.g. Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera powdery mildew diseases, such as those caused by Erysiphales, such as Podospaera macularis, Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis;For example, Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta fungi, such as those caused by the Botryosphaeriales, for example Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata and Colletotrichum graminicola; anthracnose, for example those caused by the Glommerelales, for example Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata and Colletotrichum graminicola;As well as, for example, Acremonium strictum, Claviceps purpurea, Fusarium asiaticum, Fusarium pseudograminearum, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp.cubense, Gerlachia nivale, Gibberella Wilt or blight diseases such as those caused by Hypocreales such as F. fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum and Verticillium theobromae; Basidiomycete including smut fungi such as those caused by the Ustilaginales, e.g. Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, e.g. Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis ... graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.Hordei, Puccinia striiformis f.sp.the Pucciniales, such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Transchelia discolor and Uromyces visciae-fabiei; Rust fungi, such as those caused by the Uredinales, such as Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea cyrsinata, and others. Other rots and diseases such as those caused by Bacillus circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries. Blastocladiomycetes, such as Physoderma maydis. Mucoromycetes, such as Choanephora cucurbitarum, Mucor spp., and Rhizopus arrhizus. and diseases caused by other species and genera closely related to those listed above.

[0037] In addition to its fungicidal activity, the composition may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species, as well as certain protozoa.

[0038] The compositions of the present invention may be used in the classes of fungi, such as Ascomycetes (e.g., Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g., the genera Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (e.g., the fungi Mycosphaera, Mycosphaerella, Uncinula); imperfecti (also known as Deuteromycetes; e.g., Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia, and Pseudocercosporella) cosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).

[0039] In a preferred embodiment, the composition according to the present invention is particularly effective against wheat Fusarium blight caused by Fusarium graminearum or Fusarium asiaticum, wheat Fusarium stem rot caused by Fusarium pseudograminearum, and rice seedling disease caused by Gibberella fujikuroi.

[0040] Useful plant crops in which the compositions of the present invention can be used are typically berry plants, such as blackberries, blueberries, cranberries, raspberries, and strawberries; cereals, such as barley, corn (corn), millet, oats, rice, rye, sorghum, triticale, and wheat; fiber plants, such as cotton, flax, hemp, jute, and sisal; crops, such as sugar and fodder beets, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea, and tobacco; fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears, and plums; and grasses, such as bermudagrass, berry bush, bentgrass, centipedegrass, fescue, ryegrass, lawn grass, and lawn grass. grasses; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as vines, for example grapes.

[0041] Crops are understood to be those occurring naturally, obtained by traditional breeding methods, or obtained by genetic engineering, including crops that contain so-called output traits, such as increased storage stability, higher nutritional value, and improved flavor.

[0042] Crops are also understood to include crops that have been made tolerant to herbicides such as bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD-, and PPO-inhibitors. An example of a crop that has been made tolerant to imidazolinones, such as imazamox, by traditional breeding methods is Clearfield® summer canola. Examples of crops that have been made tolerant to herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant corn varieties, such as those available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0043] Crops should also be understood as those that are naturally occurring or that have been rendered resistant to harmful insects. This includes plants that have been transformed, for example by using recombinant DNA techniques, to have the ability to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria. Examples of toxins that can be expressed include delta-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of nematode symbiotic bacteria, and toxins produced by scorpions, arachnids, wasps and fungi.

[0044] An example of a crop modified to express Bacillus thuringiensis toxins is Bt corn KnockOut® (Syngenta Seeds). An example of a crop containing more than one gene encoding insecticide resistance and therefore expressing more than one toxin is VipCot® (Syngenta Seeds). Crops or their seed material can also be resistant to multiple pests (so-called overlapping transgenic events when formed by genetic modification). For example, plants can be herbicide resistant and at the same time capable of expressing insecticidal proteins, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0045] In a preferred embodiment, the composition according to the invention is used to control or prevent phytopathogenic diseases in cereals, preferably wheat or rice.

[0046] The compositions of the present invention, including all of the embodiments and preferred examples thereof disclosed above, may also be mixed with one or more additional pesticides, such as further fungicides, insecticides, nematicides, bactericides, acaricides, plant growth regulators, sterilizers, semiochemicals, repellents, attractants, pheromones, feeding stimulants, or other bioactive compounds to form multi-component pesticides that provide even broader spectrum agricultural protection.

[0047] Examples of such agricultural protectants with which the compositions of the present invention may be formulated are: Petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-cinnamaldehyde, 4-chlorophenyl phenylsulfone, acetoprole, aldoxicarb, amidithione, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenic trioxide, azobenzene, azotoate, benomyl, benoxafos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprolol phezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfate, camphechlor, carbanolate, carbophenothione, cymiazole, quinomethionate, chlorbencide, chlordimeform, chlordimeform hydrochloride, chlorphenetole, chlorfenson, chlorophenesulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerin, closantel, coumaphos, crotamiton, crotoxyphos, kuffraeb, cinerin Anthate, DCPM, DDT, Demefion, Demefion-O, Demefion-S, Demeton-methyl, Demeton-O, Demeton-O-methyl, Demeton-S, Demeton-S-methyl, Demeton-S-methyl sulfone, Dichlofluanid, Dichlorvos, Dicrifos, Dienochlor, Dimefox, Zinex, Zinex-diclexin, Dinocap-4, Dinocap-6, Dinocton, Dinopenton, Dinosulfone, Dinotervon, Dioxathion, Diphenylsulfone, Disulfiram, DNOC, Dofenapine, Doramectin, Endothion, Epi Linomectin, ethoeate methyl, etrimphos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenethyl, fluorbenside, FMC1137, formetanate, formetanate hydrochloride, formoparanate, gamma-HCH, gliodin, halfenprox, hexadecylcyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolin II, jodofenphos, lindane,Malonoben, Mecarbam, Mefosfolan, Mesulfen, Methacrifos, Methyl bromide, Metolcarb, Mexacarbate, Milbemycin oxime, Mipafox, Monocrotophos, Morphothion, Moxidectin, Naled, 4-Chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, Nifluridide, Nikkomycin, Nitrilacarb, Nitrilacarb 1:1 zinc chloride complex, Omethoate, Oxydeprophos, Oxydisulfoton, pp'-DDT, Parathion, Permethrin, Fencapton, Phosalone, Phosphorane, Phosphamidon, Polychloroterpenes, Polynactin, Proclonol , Promacyl, Propoxur, Prothidathion, Prothoate, Pyrethrin I, Pyrethrin II, Pyrethrin, Pyridafenthion, Pirimitate, Quinalphos, Quintiophos, R-1492, Phosglycine, Rotenone, Shladan, Cebufos, Selamectin, Sofamid, SSI-121, Sulfiram, Sulfuramide, Sulfotep, Sulfur, Diflovidazin, Tau-Fulvalinate, TEPP, Terbam, Tetradifon, Tetrasulf, Thiafenox, Thiocarboxim, Thiofanox, Thiometon, Thioquinox , thuringiensin, triamiphos, triatene, triazophos, triazuron, triphenofos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, sibutrin, dichloron, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinoneamide, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy thi-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, doditin, phenaminosulf, formaldehyde, hydralgafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, probenazole, streptomycin,Streptomycin sesquisulfate, techloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae,Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii lecanii), apholate, bisadil, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, molzide, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en-1-yl acetate + (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)-icos-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)-dodeca-7,9-dien-1-yl acetate,(9Z,11E)-Tetradeca-9,11-dien-1-yl acetate, (9Z,12E)-Tetradeca-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol + 4-methylnonan-5-one, α-multistriatin, brevicomin, codrel, codremon, querle, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, fumaric acid Rontalin, Grandolure, Grandolure I, Grandolure II, Grandolure III, Grandolure IV, Hexalure, Ipsdienol, Ipsenol, Japonilure, Lineatin, Littleua, Louplure, Medulure, Megatomoic acid, Methyleugenol, Muscalure, Octadeca-2,13-dien-1-yl acetate, Octadeca-3,13-dien-1-yl acetate, Olfular, Orictalure, Ostramon, Siglua, Soldidin, Sulcatol, Tetradec-11-en-1-yl acetate, Trimedulure, Trimedulure A, Trimedulure Rimedlure B1, Trimedlure B2, Trimedlure C, trunc-call, 2-(octylthio)ethanol, butapyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyl toluamide, dimethylcarbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methyl neodecaneamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1, 2-Dichloropropane + 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate,2-Imidazolidone, 2-Isovalerylindan-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-xylylmethyl carbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate, acetione, acrylonitrile, aldrin, allosamidin, alixycarb, α-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis thuringiensis) delta endotoxin, barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl)ether, sodium borate, bromfenvinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, sebazine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlor Prazophos, cis-resmethrin, cismethrin, clocithrin, copper acetoarsenite, copper arsenate, copper oleate, cumitoate, cryolite, CS708, cyanofenphos, cyanophos, ciclethrin, cithioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dicapton, dichlorophenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilol, dimefluthrin, dimethane, dimethrin, dimethylvinphos, dimethylan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI 1642, EMPC, EPBP, ethaphos, ethiofencarb, ethyl formate, ethylene dibromide, dichloroethane, ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fensulfothion, fenthion-ethyl, flucofuron, fosmetiran, fospirate, fostietan, furathiocarb, fretrin, guazatine, guazatine acetate, sodium tetrathiocarboxylate, halfenprox,HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hikincarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kereban, kinoprene, lead arsenate, leptophos, lilimphos, ritidathion, m-cumenylmethylcarbamate, magnesium phosphide, magidox, mecarfone, menazone, mercurous chloride, mesulfenphos, metam, metam-potassium, metam-sodium, methanesulfonyl fluoride , methoclotophos, methoprene, methothrin, methoxychlor, methyl isothiocyanate, methyl chloroform, methylene chloride, methoxadiazone, mirex, naphthalophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O, O',O'-Tetrapropyldithiopyrophosphate, Oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH60-38, fencapton, phosnichlor, phosphine, phoxim-methyl, pyrimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, pyrimidophos, profluthrin, promecarb, prothiophos, pyrazophos, pyresmethrin, cassia, quinalphos-methyl, quinocin On, rafoxanide, resmethrin, rotenone, cadethrin, ryania, ryanodine, sabadira), shradan, cebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide salt, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar oil, thionazine, TDE, tebupirimfos, temephos, telallethrin, tetrachloroethane, cyclophos, thiocyclam,Thiocyclam hydrogen oxalate, thionazine, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormethaphos-3, trichloronat, trimethacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprophos, and meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, nicotinamide-olamine oxide ... Tributyltin, pyrimorph, triphenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene, 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anicifluprine, benclothiaz, cytokinin, DCIP, rufural, isamidophos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis) extract, α-chlorohydrin, anth, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropazine, flupropazine hydrochloride, norbormide, fosacetim, phosphorus, pindone, pyrinuron, sciriloside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol + nerolidol, berubutin, MGK 264, piperonyl butoxide, piperotal, propyl isomer, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate,Ziram, Imanin, Ribavirin, Chlorinconazide, Mercuric oxide, Thiophanate-methyl, Azaconazole, Bitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Epoxiconazole, Fenbuconazole, Fluquinconazole, Flusilazole, Flutriafol, Furametpyr, Hexaconazole, Imazalil, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Paclobutrazol, Pefurazoate, Penco nazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, benalaxyl, furalaxyl, metalaxyl Sil, R-metalaxyl, Ofrace, Oxadixyl, Carbendazim, Debacarb, Fuberidazole, Thiabendazole, Chlozolinate, Diclozolin, Mycrozolin, Procymidone, Vinclozolin, Boscalid, Carboxin, Fenfuram, Flutolanil, Mepronil, Oxycarboxin, Penthiopyrad, Thifluzamide, Dodine, Iminoctadine, Azoxystrobin, Dimoxystrobin, Enestrobulin, Phenaminestrobin, Flufenoxystrobin, Fluoxastrobin, Kresoxim-methyl, Meth. Minostrobin, trifloxystrobin, oryzastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanid, Bordeaux mixture, copper oxide, mancopper, oxine copper, nitrothal-isopropyl, edifenphos, iprobenfos, phosdifen, turcophos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, Chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomedine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxythioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetyl-aluminum, hymexazole, iprovalicarb, ciazo Famid, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxin, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriophenone, quinoxyfen, quintozene, thiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamid, fluventeram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl) (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-3-carbonitrile, ... 4-Carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, methoxystrobin (jiaxiangjunzhi), lvbenmixianan, diclobenziazox, 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, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, impirfluxam, tulorprocarb, mefentrifluconazole, 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-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro -phenyl]methanesulfonic acid, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridaclomethyl, 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, amethoctrazine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-Dimethyl-pent-3-enamide, florylpicoxamide, fenpicoxamide, methallylpicoxamide, tebufloquine, ipurfenoquine, quinofumelin, isofetamide, 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, benzothiostrobin, phena Macril, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoin, 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, methyltetraprole, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol, fluoxapiproline, enoxastrobin, 4-[[6-[2-(2,4-di fluorophenyl)-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-pyridyl]oxy]benzonitrile, trinexapac, cumoxystrobin, zhongshengmycin, copper thiodiazole, zinc thiazole, amethotractin, iprodione, seboctylamin, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl] -N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1 -methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the methods described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (these compounds can be prepared by the methods 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)oxetan-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 may be prepared by the methods described in 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, 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 N-((1S)-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 by the methods described in 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 may be prepared by the method described in 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 may be prepared according to the methods 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, 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl) 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]urea, N,N-dimethyl-1-[[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, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, -yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds may be prepared by the methods 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 may be prepared by the methods 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 / 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 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (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']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared by the method described in WO 201 No. 1 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide; 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 may 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 may 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 may be prepared by the methods described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared by the methods described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound may be prepared by the methods described in WO 2018 / 065414). A compound selected from the group of substances consisting of 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-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the methods described in WO 2018 / 202428).

[0048] In the above specification, most of the above active ingredients are referred to by using in individual cases the so-called "common name", the relevant "ISO common name" or other "common name". In the absence of a "common name" designation, the nature of the designation used instead is stated in parentheses for the particular compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "customary name", "compound name" or "development code" is used, or, if none of these designations or "common name" is used, an "alternative name" is adopted. "CAS Registry Number" means Chemical Abstracts Registry Number.

[0049] Mixtures containing the compound of component (A) (above), fludioxonil and one or more of the active ingredients described above can be applied, for example, in a single "premixed" form, in multiple spray mixtures such as "tank mixes" composed of individual combinations of single active ingredient components, and in combination with the single active ingredients when applied sequentially (i.e., one after the other within a reasonably short time such as a few hours or days). The order in which the compound of component (A) (above), fludioxonil and the active ingredients described above are applied is not critical to the operation of the invention.

[0050] The compositions of the present invention can also be used in crop enhancement, where "crop enhancement" in the present invention means improved plant vigor, improved plant quality, improved resistance to stress factors, and / or improved input use efficiency.

[0051] In the present invention, "improved plant vigor" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. Such traits include, but are not limited to, early and / or improved germination, improved emergence, ability to use fewer seeds, increased root growth, more developed root system, increased nodulation, increased shoot growth, increased tillers, stronger tillers, more productive tillers, increased or improved plant standing, less plant verse (lodging), increased and / or improved plant height, increased plant weight (fresh or dry), larger leaf blades, greener leaf color, increased pigment content, increased photosynthetic activity, earlier flowering, longer ears, earlier grains, increased seed, fruit, or pod size, increased number of pods or ears, increased number of seeds per pod or ear, increased seed mass, enhanced seed filling, fewer basal leaves, delayed senescence, improved plant vigor, increased amino acid levels in storage tissues, and / or less required inputs (e.g. less fertilizer, water, and / or labor required). A plant with improved vigor may have an increase in any of the aforementioned traits, or any combination or two or more of the aforementioned traits.

[0052] In the present invention, "improved plant quality" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. Such traits include, but are not limited to, improved plant appearance, reduced ethylene (reduced production and / or suppressed susceptibility), improved quality of the harvested product, such as seeds, fruits, leaves, vegetables, etc. (such improved quality may be manifested as improved visual appearance of the harvested product), improved carbohydrate content (e.g., increased sugar and / or starch amounts, improved sugar acid ratios, reduced reducing sugars, increased rate of sugar production), improved protein content, improved oil content and composition, improved nutritional value, reduced anti-nutritional compounds, improved organoleptic properties (e.g., improved taste), and / or improved consumer health benefits (e.g., increased levels of vitamins and antioxidants), improved post-harvest properties (e.g., enhanced shelf life and / or storage stability, easier processability, easier compound extraction), more uniform crop development (e.g., synchronized germination, flowering, and / or fruit set of plants), and / or improved seed quality (e.g., for use in the next growing season). Plants with improved quality may have an increase in any of the aforementioned traits, or any combination or two or more of the aforementioned traits.

[0053] In the present invention, "improved tolerance to stress factors" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. Such traits include, but are not limited to, increased tolerance and / or resistance to abiotic stress factors (e.g., any stress that causes a lack of moisture in the plant, a lack of water uptake capacity, or a reduced supply of water to the plant) that cause suboptimal growth conditions such as drought, cold exposure, high temperature exposure, osmotic stress, UV stress, flooding, increased salinity (e.g., in the soil), increased exposure to minerals, ozone exposure, high light exposure, and / or limited availability of nutrients (e.g., nitrogen and / or phosphorus nutrients). A plant with improved tolerance to stress factors may have an increase in any of the aforementioned traits, or any combination or two or more of the aforementioned traits. In the case of drought and nutritional stress, such improved tolerance may be due to, for example, more efficient uptake, use, or retention of water and nutrients.

[0054] In the present invention, "improved input use efficiency" means that a plant can grow more efficiently using a given input level compared to the growth of a control plant grown under the same conditions in the absence of the method of the present invention. Specifically, the inputs include, but are not limited to, fertilizers (such as nitrogen, phosphorus, potassium, micronutrients, etc.), light, and water. A plant with improved input use efficiency may have improved use of any of the aforementioned inputs, or any combination of two or more of the aforementioned inputs.

[0055] Other crop enhancements of the present invention include reduced plant height, or reduced tillering, which are beneficial traits in crops or conditions where it is desirable to have less biomass and fewer tillers.

[0056] Any or all of the above crop enhancements may result in improved yields, for example, by improving plant physiology, plant growth and development, and / or plant architecture. In the context of the present invention, "yield" includes, but is not limited to, (i) increased biomass production, grain yield, starch content, oil content, and / or protein content, which may result from (a) an increase in the amount produced by the plant itself, or (b) an improved ability to harvest the plant body, (ii) improved crop composition (e.g. improved sugar acid ratio, improved oil composition, increased nutritional value, reduced anti-nutritional compounds, increased consumer health benefits), and / or (iii) increased / promoted ability to harvest the crop, improved crop processability, and / or better storage stability / shelf life. Increased yield of an agricultural plant means that, when a quantitative measurement can be made, the yield of the product of the respective plant is increased by a measurable amount over the yield of the same product of a plant produced under the same conditions but without the application of the present invention. According to the present invention it is preferred that yield is increased by at least 0.5%, more preferably at least 1%, even more preferably at least 2%, and even more preferably at least 4%, preferably 5% or more.

[0057] Any or all of the above crop intensification may result in improved utilization of land, i.e. land that was previously unavailable or suboptimal for cultivation may become available, for example plants that exhibit an increased ability to survive drought conditions may become cultivated in areas with suboptimal rainfall, such as perhaps on the fringes of deserts or even in the desert itself.

[0058] In one aspect of the invention, crop enhancement is achieved in the substantial absence of pressure from pests and / or diseases and / or abiotic stress. According to a further aspect of the invention, the improvement of plant vigor, stress resistance, quality and / or yield is achieved in the substantial absence of pressure from pests and / or diseases. For example, pests and / or diseases may be controlled by an insecticidal treatment applied prior to or simultaneously with the method of the invention. In yet another aspect of the invention, the improvement of plant vigor, stress resistance, quality and / or yield is achieved in the substantial absence of pressure from pests and / or diseases. In a further embodiment, the improvement of plant vigor, quality and / or yield is achieved in the substantial absence of abiotic stress.

[0059] The composition of the invention may be used in the field of protecting stored goods from fungal attack. In the present invention, the term "storage goods" is understood to mean natural substances of plant and / or animal origin and their processed forms, for which long-term protection from the natural life cycle is desired. Stored goods of plant origin, such as plants or parts thereof (such as stems, leaves, tubers, seeds, fruits or grains), can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, crushed, ground, pressed or roasted. The definition of stored goods also includes wood in the form of raw wood (such as building timber, electricity transmission towers and fences) and wood in the form of finished products (such as furniture or wooden products). Stored goods of animal origin are leather, leather products, furs and hairs. The composition of the invention can prevent adverse effects, such as decay, discolouration or the development of mould. Preferably, "storage products" is understood to mean natural substances of plant origin and / or their processed forms, more preferably fruits and their processed forms, such as pome fruits, drupe fruits, soft fruits and citrus fruits and their processed forms. In another preferred embodiment of the invention, "storage products" is understood to mean trees.

[0060] Therefore, a further aspect of the present invention is a method for protecting a stored item which comprises applying to the stored item a composition of the present invention.

[0061] The composition of the present invention can also be used in the field of protecting industrial raw materials from fungal attack.In the present invention, the term "industrial raw materials" includes paper; carpets; buildings; cooling and heating systems; wallboards; ventilation and air conditioning systems, etc.; preferably, "industrial raw materials" is understood to mean wallboards.The composition of the present invention can prevent adverse effects such as rotting, discoloration, or mold growth.

[0062] The compositions of the present invention are usually formulated in various ways using formulation aids such as carriers, solvents and surfactants. The formulations may be in various physical forms, such as dusts, gels, wettable powders, wettable granules, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oil-based dispersions, suspoemulsion formulations, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films, or other forms known, such as from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations may be used directly or may be diluted before use. Dilution may be performed, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0063] The formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain a composition in the form of a finely divided solid, granules, liquid, dispersion, or emulsion. The active ingredient can also be formulated with other auxiliaries, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants, or combinations thereof.

[0064] The active ingredient can also be contained in microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released in controlled amounts into the environment (e.g., sustained release). Microcapsules usually have a diameter of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient can be in the form of a large solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane can, for example, comprise natural or synthetic rubber, cellulose, styrene / butadiene + copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers and starch xanthate, or other polymers known to those skilled in the art. Alternatively, fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the base, but the microcapsules themselves are not encapsulated.

[0065] The formulation auxiliaries suitable for the preparation of the formulations of the present invention are known per se. The following can be used as liquid carriers: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, 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, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid carboxylic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols (amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc.), ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.,

[0066] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.

[0067] A large number of surface-active substances can be used advantageously in both solid and liquid formulations, especially in those which may be diluted with a carrier before use. The surface-active substances may be anionic, cationic, nonionic, or polymeric and they can be used as emulsifying agents, wetting agents or suspending agents, or for other purposes. Typical surface-active materials include, for example, alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylaryl sulfonates, such as calcium dodecylbenzene sulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; alkylnaphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl) sulfoccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium 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 di-alkyl phosphate esters; and further materials, such as those described in, for example, McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0068] Further adjuvants that may be used in the agrochemical formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides, and liquid and solid fertilizers.

[0069] The formulations of the present invention may contain additives including oils of vegetable or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils, and mixtures with oil derivatives. The amount of oil additive in the formulations of the present invention is usually 0.01-10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank at the desired concentration after the spray mixture is prepared. Preferred oil additives include mineral oils or oils of vegetable origin, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of oils of vegetable origin, such as methyl derivatives, or oils of animal origin, such as fish oil or beef tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids are included, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are described in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0070] The formulations usually contain 0.1-99% by weight, in particular 0.1-95% by weight, of the compounds of components (A) and (B), and 1-99.9% by weight of formulation auxiliaries, which preferably include 0-25% by weight of surface-active substances. Commercially available products may preferably be formulated as concentrates, but end users will usually use dilute formulations.

[0071] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing climatic conditions, as well as other factors which depend on the method of application, the time of application and the target crop. As a general guideline, the compounds can be applied at a rate of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0072] Certain mixture compositions according to the present invention may exhibit synergistic effects. This occurs whenever the effect of the combination of active ingredients exceeds the sum of the effects of the individual ingredients. The toxicity of two combined drugs can be evaluated by the Co-Toxicity Coefficient (CTC) according to the Sun-YP method (Yun-Pei, Sun. "Toxicity Index-An Improved Method of Comparing the Relative Toxicity of Insecticides." Journal of Economic Entomology 1 (1950): 45-53.). A CTC value of less than 80 indicates an antagonistic effect, a CTC value of 80-120 indicates an additive effect, and a CTC value of 120 or more indicates a synergistic effect.

[0073] CTC = (ATI / TTI) x 100 Component A represents a standard AI and component B represents the component that is mixed with the standard AI. ATI (Accurate Toxicity Index of Mixtures) = (EC of standard AI 50 / Mixture of EC 50 ) x 100 TTI (Theoretical Toxicity Index of Mixtures) = (TI A ×P A +TI B ×P B ) x 100 T.I. A (Toxicity index of ingredient A) = EC of ingredient A 50 / EC of component A 50 P A Component A in the mixture T.I. B (Toxicity index of component B) = EC of component A 50 / EC of component B 50 P B Component B in the mixture

[0074] The combined effect of two drugs can also be evaluated by the COLBY method. In particular, the expected activity E for a given combination of active ingredients can be calculated according to the so-called COLBY formula as follows (COLBY, SR “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (=ai) per litre of spray mixture X=% effect of active ingredient A) using p ppm of active ingredient Y=% effect of active ingredient B) using q ppm of active ingredient.

[0075] According to COLBY, the expected (active) effect of active ingredients A)+B) using p+q ppm of active ingredients is:

number

[0076] When the actual observed effect (O) is greater than the expected effect (E), the effect of the combination is superadditive, i.e. synergism exists. In mathematical terms, synergy corresponds to a positive value of the difference (OE). In the case of a pure complementary addition of activities (expected activity), said difference (OE) is zero. A negative value of said difference (OE) indicates a loss of activity compared to the expected activity.

[0077] However, apart from the actual synergistic action with respect to the fungicidal activity, the compositions of the invention may also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageous degradability; improved toxicological and / or biotoxicological behavior; or improved properties of useful plants (germination, crop yield, more developed root system, increased tillers, increased plant height, larger leaf blades, less basal leaves, stronger tillers, greener leaf color, less fertilizer required, less seed required, more productive tillers, earlier flowering, earlier grain, less plant verse (lodging), increased shoot growth, improved plant vigor, and earlier germination, etc.).

[0078] The compositions of the invention can be applied to phytopathogenic microorganisms, useful plants, their habitats, their seedlings, stocks or industrial origins threatened by microbial attack.

[0079] The compositions of the invention may be applied before or after the useful plants, their seeds, stocks, or industrial raw materials are infected with microorganisms.

[0080] The amount of the composition of the present invention applied will depend on various factors, such as the composition used; the target of treatment (e.g., plants, soil, or seedlings); the type of treatment (e.g., spraying, dusting, or seed dressing); the purpose of the treatment (e.g., preventive or curative); the type of fungus to be controlled; or the time of application.

[0081] When applied to useful plants, component (A) is typically applied in an amount of 5 to 2000 g ai / ha, especially 10 to 1000 g ai / ha, for example 50, 75, 100 or 200 g ai / ha, in conjunction with 1 to 5000 g ai / ha, especially 2 to 2000 g ai / ha, for example 100, 250, 500, 800, 1000, 1500 g ai / ha of component (B).

[0082] In agricultural practice, the application rates of the compositions of the invention depend on the type of effect desired and typically range from 20 to 4000 g of total composition per hectare.

[0083] When the compositions of the invention are used to treat seeds, an amount of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g per kg of seed of the compound of component (A), and 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g per kg of seed of the compound of component (B) will generally be sufficient.

[0084] It is noted that wherever a reference, patent application, or patent is cited within the text of this application, the entire text of said cited text is incorporated herein by reference. EXAMPLES

[0085] The following examples serve to illustrate the invention. The compositions of the present invention may be distinguished from known compositions by their high efficacy at low application rates, which can be verified by one skilled in the art using the experimental procedures outlined in the examples and using low application rates, such as, for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm or 0.2 ppm of active ingredient, as appropriate.

[0086] Formulation example

[0087] [Table 3]

[0088] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to give wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0089] [Table 4]

[0090] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0091] emulsifiable concentrate Active ingredient [component (A) and (B)] 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0092] Emulsions of any required dilution which can be used for plant protection are available from this concentrate by dilution with water.

[0093] [Table 5]

[0094] Ready-to-use dusts are obtained by mixing the complex with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0095] Extrusion Granules Active ingredient [component (A) and (B)] 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0096] The active ingredient is mixed with the auxiliaries and ground, the mixture is moistened with water, the mixture is extruded and then dried in a current of air.

[0097] Coated Granules Active ingredient [component (A) and (B)] 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0098] In a mixer, the finely ground composite is applied uniformly to the kaolin moistened with polyethylene glycol, thus obtaining non-dusty coated granules.

[0099] Suspension concentrate Active ingredient [component (A) and (B)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0100] Finely divided active ingredients are thoroughly mixed with auxiliaries to obtain suspension concentrates, which can be diluted with water to obtain suspensions of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or immersion.

[0101] Seed treatment flowable concentrate Active ingredient [component (A) and (B)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 10-20 moles of EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0102] Finely ground active ingredient can be thoroughly mixed with adjuvants to obtain a suspension concentrate which can then be diluted with water to obtain a suspension of any desired dilution. Such dilutions can be used to treat and protect living plants and plant propagation material against infestation by microorganisms by spraying, pouring, or immersion.

[0103] Sustained-release capsule suspension 28 parts of a combination of active ingredients [components (A) and (B)] are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size is obtained. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium-sized capsules is 8 to 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for that purpose.

[0104] Biological Example 1 The fungicidal activity of circobutrifluram (ISO name for N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide), fludioxonil (FDL), and mixtures of these with circobutrifluram and FDL at various weight ratios (e.g., 20:1, 10:1, 1:50, and 1:100) was tested against Gibberella fujikuroi and Fusarium graminearum.

[0105] The test was carried out according to Pesticides guidelines for laboratory bioactivity tests, Part 2: Petri plate test for determining fungicides inhibition of mycelial growth (NY / T 1156.2-2006). In particular, the best concentration ranges for determining the susceptibility of pathogens to silcobtriflurum, FDL and their mixtures were determined according to the results of preliminary experiments, and a 5-7 concentration gradient was set up so that the inhibition rate at the lowest concentration was close to 10% and the inhibition rate at the highest concentration was close to 90%. The same volume of solutions of silcobtriflurum, FDL and their mixtures in DMSO with the desired concentrations were added to dissolved PDA medium to prepare test plates, and the PDA plates with the same volume of DMSO were used as controls.

[0106] Mycelial plugs were prepared from the edge of the colonies using a 5 mm diameter punch. With the mycelium facing up, the mycelial plugs were transferred to the center of the PDA medium plates containing Circobutriflurum, FDL and their mixtures and the control plate. After 3 days of dark incubation at 25°C in an incubator, the diameters of all mycelial colonies on the PDA plate were measured twice at right angles and then averaged. Inhibition rate (%) = (average diameter of mycelial colonies on the control plate - average diameter of mycelial colonies on the test plate) / (average diameter of mycelial colonies on the control plate) x 100%.

[0107] EC of each of the tested drugs and mixtures 50 The values ​​were calculated by linear regression analysis between the probability values ​​of the inhibition rate and the logarithmic values ​​of the series of concentrations. The co-toxicity coefficients (CTC) of the mixtures were calculated and evaluated according to the Sun-YP method. The results are shown in Tables 1 and 2 below, respectively.

[0108] [Table 6]

[0109] [Table 7]

[0110] Biological Example 2 The fungicidal activities of circobutriflurum, fludioxonil (FDL), and mixtures of circobutriflurum and FDL at various weight ratios (e.g., 10:1 and 1:50) were tested against Fusarium asiaticum and Fusarium pseudograminearum.

[0111] The test was carried out according to Pesticides guidelines for laboratory bioactivity tests, Part 2: Petri plate test for determining fungicides inhibition of mycelial growth (NY / T 1156.2-2006). In particular, the best concentration ranges for determining the susceptibility of pathogens to silcobtriflurum, FDL and their mixtures were determined according to the results of preliminary experiments, and a 5-7 concentration gradient was set up so that the inhibition rate at the lowest concentration was close to 10% and the inhibition rate at the highest concentration was close to 90%. The same volume of solutions of silcobtriflurum, FDL and their mixtures in DMSO with the desired concentrations were added to dissolved PDA medium to prepare test plates, and the PDA plates with the same volume of DMSO were used as controls.

[0112] Mycelial plugs were prepared from the edge of the colonies using a 5 mm diameter punch. With the mycelium facing up, the mycelial plugs were transferred to the center of the PDA medium plates containing Circobutriflurum, FDL and their mixtures and the control plate. After 3 days of dark incubation at 25°C in an incubator, the diameters of all mycelial colonies on the PDA plate were measured twice at right angles and then averaged. Inhibition rate (%) = (average diameter of mycelial colonies on the control plate - average diameter of mycelial colonies on the test plate) / (average diameter of mycelial colonies on the control plate) x 100%.

[0113] EC of each of the tested drugs and mixtures 50 The values ​​were calculated by linear regression analysis between the probability values ​​of the inhibition rate and the logarithmic values ​​of the series of concentrations. The co-toxicity coefficients (CTC) of the mixtures were calculated and evaluated according to the Sun-YP method. The results are shown in Tables 3 and 4 below, respectively.

[0114] [Table 8]

[0115] [Table 9]

[0116] Biological Example 3 The efficacy of cilcobtrifluram plus fludioxonil (FDL) against Fusarium graminearum is further evaluated by the COLBY method.

[0117] Methodology: Fungal strain: Gibberella zeae strain K-6102; Fungal colonies on PDA; Growth medium used for testing: PDB + 0.3% agar The experiments were carried out in 96-well plates used for microprofiling screens (MPS). Fungicides and fungicides: Cyclobutrifluram, FDL Treatments: single fungicides and all possible fungicide mixtures + Circobutriflurum; application rates: 0.1, 1, 10 mg ai / L; 5 replicates (wells) per treatment; For each treatment; check: uninfected, infected, infected + DMSO All substances were dissolved in DMSO and diluted in Tween 20 (0.025%). Conidia were added to each well at the same time as the fungicide treatment (3600 spores / well). Incubation: 4 days, 95% RH, 24°C, dark Assessment: The optical density was measured with a photometer (620 nm) and the observed efficacy (E obs, %) was calculated. The expected potency (E exp) of the mixture was calculated using Colby's formula (1) as follows: E exp=A+B-(A×B / 100), where A and B are the control levels by a single fungicide. For the calculation of synergy, the ratio of the observed experimental potency of the mixture (E obs) to the expected potency of the mixture (E exp) (SF, synergy coefficient) is calculated as follows: SF=E obs / E exp. If SF>1, this indicates synergy.

[0118] [Table 10]

[0119] [Table 11]

[0120] [Table 12]

[0121] The test results show that a synergistic effect is achieved by the combination of cyclobutriflurum and FDL (SF: 1.023-1.413) against Fusarium graminearum using in vitro bioassay.

Claims

1. A bactericidal / fungicidal composition or mixture containing components (A) and (B) as active ingredients, wherein component (A) is N-[(1,2cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide, and Component (B) is fludioxonil; A bactericidal / fungicidal composition or mixture, wherein the weight ratio of component (A) to component (B) is from 100:1 to 1:

90.

2. Component (A) comprises the (1S,2S) and (1R,2R) enantiomers of the compound, and the (1S,2S) enantiomer 2. The fungicidal composition or mixture of claim 1, wherein the ratio of isomer to the (1R,2R) enantiomer is greater than 4:

1.

3. 2. The fungicidal composition or mixture of claim 1, wherein component (A) is the pure (1S,2S) enantiomer.

4. 2. The fungicidal composition or mixture of claim 1, wherein the weight ratio of component (A) to component (B) is from 50:1 to 1:

90.

5. 2. The fungicidal composition or mixture of claim 1, wherein the weight ratio of component (A) to component (B) is from 20:1 to 1:

50.

6. 2. The fungicidal composition or mixture of claim 1, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:

50.

7. 10. The fungicidal composition or mixture of claim 1, wherein the weight ratio of component (A) to component (B) is about 10:1 or about 1:

50.

8. 10. The bactericidal composition or mixture of claim 1, wherein the composition or mixture comprises one or more additional pesticides.

9. 10. The bactericidal composition or mixture of claim 1, wherein the composition or mixture further comprises an agriculturally acceptable carrier and, optionally, a surfactant and / or formulation adjuvant.

10. A method for controlling or preventing phytopathogenic diseases, in particular phytopathogenic fungi, in useful plants or their propagation material, which comprises the step of applying to said useful plants, their habitat or their propagation material a bactericidal or fungicidal composition or mixture according to any one of claims 1 to 9.

11. 11. The method of claim 10, wherein the composition or mixture comprising components (A) and (B) is in the form of a single "ready mix" or a combined spray mixture, or wherein components (A) and (B) of the composition or mixture are applied sequentially.

12. 11. The method of claim 10, wherein the plant is a cereal, preferably wheat or rice.

13. 11. The method of claim 10, wherein the plant pathogenic disease is wheat Fusarium blight, wheat Fusarium stem rot, or rice seedling disease.

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