Bactericidal composition

Abstract

(i) florylpicoxamide as a fungicidal active ingredient; and (ii) a compound of formula (I) (wherein X=bond, -CH2-, -CH2CH2-, -CH=CH- (cis or trans); n=0, 1, 2 or 3; R 1 = -OH or -OCH3, or n = 1; R 1 5. A disinfectant composition comprising an organic acid selected from the group consisting of compounds of the formula: =-C(O)OH. [Formula 1] TIFF2024547121000008.tif24160

Description

[Technical field]

[0001] The present invention relates to compositions comprising the fungicidal active ingredient florylpicoxamide. Such compositions may be useful in agriculture to combat, prevent or control the spread of phytopathogenic diseases in crops. [Background technology]

[0002] WO 2016 / 122802 and WO 2016 / 109257 disclose certain picolinamide compounds, such as (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-{[3-(acetyloxy)-4-methoxy-2-pyridyl]carbonyl}-L-alaninate, i.e., florylpicoxamide (CAS number 1961312-55-9), and their use as fungicides. Florylpicoxamide is known to be particularly effective in controlling wheat leaf blight caused by Mycosphaerella graminicola (Septoria tritici), as well as other fungal pathogens. WO 2018 / 204435, WO 2018 / 204436, WO 2018 / 204437, WO 2019 / 042800 and WO 2019 / 101580 disclose certain fungicidal compositions comprising florylpicoxamide in combination with another fungicidal active ingredient. Summary of the Invention [Means for solving the problem]

[0003] It has been found that in certain florylpicoxamide-containing compositions, particularly those that are emulsion concentrates, the florylpicoxamide can undergo chemical decomposition that can adversely affect the viability of pesticide formulations that contain this active ingredient.Therefore, means have been sought to limit or prevent such chemical decomposition of florylpicoxamide.

[0004] According to the present invention, (i) florylpicoxamide as a fungicidal active ingredient; and (ii) Formula (I): [ka] (In the formula: X=bond, -CH2-, -CH2CH2-, -CH=CH- (cis or trans); where n=0, 1, 2 or 3; R 1 = -OH or -OCH3; or n=1; R 1 =-C(O)OH) An organic acid selected from the compounds A fungicidal composition is provided comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] The fungicidal compositions according to the invention have in fact a very advantageous level of biological activity for protecting plants against diseases caused by fungi, in particular for preventing or controlling the infestation of useful plants by plant pathogens selected from Mycosphaerella graminicola (Septoria tritici), Puccinia recondita or Puccinia striiformis, in particular of cereal plants, in particular of wheat.

[0006] Surprisingly, it has now been found that the addition of an organic acid selected from the compounds of formula (I) to certain compositions containing florylpicoxamide significantly improves the chemical stability (i.e., eliminates or limits decomposition) of the florylpicoxamide active ingredient component, thus improving the useful shelf life and viability of the fungicidal composition for crop protection applications that contains this active ingredient.Although not fully understood at present, it is believed that such chemical decomposition of florylpicoxamide may be initiated by certain emulsifying chemicals (emulsifiers) or by other ingredients present in such compositions, such as formulation inerts, other biocidal active ingredients, or even chemical impurities present in small amounts in these ingredients, possibly with batch variations in the supply of raw materials for pesticide formulation purposes.

[0007] The present invention further provides an aqueous composition comprising a germicidal composition according to the present invention, optionally further comprising one or more adjuvants or carriers.

[0008] Still further, according to the present invention there is provided a method for controlling or preventing the infestation of crops of useful plants by phytopathogenic microorganisms, in which a fungicidally effective amount of a composition according to the present invention is applied to a part or to the locus of the plant.

[0009] Still further, according to the present invention there is provided the use of an organic acid selected from the compounds of formula (I) as a chemical stabilizer for florylpicoxamide in a germicidal composition (such as an emulsifiable concentrate), wherein the organic acid is present in an amount of 0.02 to 1.5% by weight of the composition.

[0010] Preferably, the composition according to the invention is an emulsifiable concentrate (EC).

[0011] In another embodiment of the invention, the composition is an oil dispersion (OD).

[0012] Preferably, the composition according to the present invention comprises a florylpicoxamide component of 1-10% by weight of florylpicoxamide, more preferably 3-6% by weight of florylpicoxamide.

[0013] Preferably, the composition according to the invention comprises an organic acid present at from 0.02 to 1.5% by weight of the composition, more preferably from 0.02 to 0.2% by weight of the composition, even more preferably from 0.02 to 0.1% by weight of the composition.

[0014] For compounds of formula (I), preferably, n is 0 or 1.

[0015] For compounds of formula (I), preferably R 1 is hydroxy.

[0016] For compounds of formula (I), preferably X is a bond or -CH=CH- (trans).

[0017] In a particularly preferred embodiment, for compounds of formula (I), n is 0 or 1 and R 1 is hydroxy and X is a bond or -CH=CH- (trans).

[0018] Preferably, the organic acid is selected from benzoic acid, p-coumaric acid, o-coumaric acid, m-coumaric acid, salicylic acid (2-hydroxybenzoic acid), cinnamic acid, gallic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, caffeic acid, (E)-3-(4-hydroxy-3-methoxy-phenyl)prop-2-enoic acid (ferulic acid), (Z)-3-(4-hydroxy-3-methoxy-phenylprop-2-enoic acid, vanillic acid, syringic acid, phthalic acid, isophthalic acid, terephthalic acid.

[0019] Preferably, the composition according to the present invention is an emulsifiable concentrate (EC) formulation that can be diluted (e.g., in a tank with water) before spray application to crops.An emulsifiable concentrate is a liquid formulation that contains one or more fungicidal active ingredients, one or more solvents and one or more emulsifiers (such as ionic or nonionic surfactants).In the emulsifiable concentrate according to the present invention, preferably, at least one of the one or more emulsifiers is an alkoxylated emulsifier, more preferably an ethoxylated emulsifier.

[0020] In compositions according to the invention (including emulsifiable concentrates), the solvent is a fatty acid dimethylamide (e.g., C6-C 12 The esters may be selected from aliphatic chains, or aromatic esters, such as methyl benzoate or benzyl acetate.

[0021] The composition according to the invention may further comprise one or more additional ingredients selected from antifreeze agents, antifoam agents, thickeners, biocides (preservatives), stabilizers, pigments, water-miscible solvents, water-immiscible solvents and / or one or more additional non-ionic or ionic emulsifiers.

[0022] Organic solvents that may be used according to the present invention include, but are not limited to, benzyl acetate (e.g., Jeffsol® AG 1705, Huntsman Corporation Australia Pty Ltd), methyl benzoate (Polynt SpA, Italy) or N,N-dimethyldecanamide (e.g., HALLCOMID® M-10, Stepan Company, USA).

[0023] Emulsifiers that may be used according to the present invention include, but are not limited to, linear dodecylbenzenesulfonic acid, Ca salt (e.g., RHODACAL® 60 / BE, Rhodia Chimie SA, France), castor oil ethoxylates (e.g., ALKAMULS® EL-620, Solvay USA Inc, USA; SERVIROX OEG 59 E, KLK Kolb Specialties BV, Netherlands) and polyoxyethylene sorbitan monolaurate (Tween® 20, Croda).

[0024] Oil dispersion (OD) formulations contain solid active ingredients dispersed in an oil medium, typically where the active ingredient is uniformly suspended in the oil phase. The oil can vary from paraffinic oils to aromatic solvents, vegetable oils or methylated seed oils. The oil can also contain adjuvants, such as alkyl ester phosphate adjuvants or 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH).

[0025] An insecticide adjuvant may be defined as a substance present in an insecticide composition (e.g., a concentrated active ingredient formulation diluted in water in a tank for foliar application to crops) that improves the fungicidal active ingredient performance, for example by promoting the diffusion of the active ingredient on the leaf surface or the penetration into the leaves of the crop. Preferably, in the composition according to the invention (e.g., such as an emulsifiable concentrate or a tank-mix preparation prepared from an emulsifiable concentrate), the adjuvant is selected from mineral oil, vegetable oil, esterified vegetable oil, methylated vegetable oil or alkyl ester phosphate-based adjuvant. Alternatively, the adjuvant may be selected from 1,2-cyclohexanedicarboxylic acid di-isononyl ester (e.g., Agnique® AE 829, BASF Corp, USA).

[0026] Other commercially available adjuvant products that can be tank mixed with the compositions of the present invention to provide a spray formulation include HASTEN™ (Victorian Chemical Co. Pty. Ltd. - a blend of esterified vegetable oils and non-ionic surfactants), OCHIMA® (Syngenta - alkyl esters of phosphoric acid (EC formulation)), LEDNA™ (Polaquimia - an EC formulation containing methyl esters of soybean oil), Atplus® 463 (CRODA Europe Limited - a 60% paraffin oil blend with surfactants), Actirob® B (Bayer AG - rapeseed oil methyl ester (esterified vegetable oil)), Destiny® HC (Winfield Solutions LLC - methylated soybean oil), DYNE-AMIC® (HELENA - a blend of (methylated) vegetable oils and organosilicone-based non-ionic surfactants), FS Optique™ (GROWMARK, Inc. - methyl ester of canola oil) and tris(2-ethylhexyl) phosphate (TEHP, CAS number 78-42-2, Synergen™ TEHP (Clariant GmbH), Disflamoll® TOF (Lanxess)).

[0027] Antifoaming agents are chemical additives that reduce and prevent the formation of foam in compositions, such as insecticide formulations. Antifoaming agents that may be used according to the present invention include, but are not limited to, polydimethylsiloxanes (e.g., XIAMETER ACP-1500, Dow, Inc; Antifoam MSA, Univar; Xiameter ACP-0001, Dow Brasil; Xiameter ACP-0100, Dow Chemical) or silicone antifoam emulsions (e.g., SAG 1572, Momentive Performance Materials Inc., USA).

[0028] The term "water-soluble emulsifying surfactant system" that can be used according to the present invention means any emulsifying surfactant system that allows the formation of an oil-in-water emulsion when an emulsifiable concentrate is diluted with an aqueous solution. Such an emulsifying surfactant system can include one or more surfactants. The surfactant can be nonionic, anionic, cationic or zwitterionic. Examples of specific suitable surfactants include, but are not limited to, alkyl polyglycosides, polyalkylene oxide block copolymers and polyaryl-phenyl ether phosphates. Alkyl polyglycosides include Agnique PG ("APG") 8107 (Cognis Corporation, Cincinnati, Ohio, USA) (an alkyl polyglycoside in which the alkyl group contains 8-10 carbon atoms and has an average degree of polymerization of 1.7), Agnique PG 9116 (Cognis Corporation, Cincinnati, Ohio, USA) (a 20 alkyl polyglycoside in which the alkyl group contains 9-11 carbon atoms and has an average degree of polymerization of 1.6) and Agnique PG 8105 (Cognis Corporation, Cincinnati, Ohio, USA) (an alkyl polyglycoside in which the alkyl group contains 8-10 carbon atoms and has an average degree of polymerization of 1.5). The polyalkylene oxide block copolymers can be di- and triblock copolymers, such as ABA or BAB block copolymers or BA block copolymers. Examples include the Genapol PF series (Clariant), the Pluronic series (BASF), the Synperonic PE series (Uniqema), and the Toximul series (Stepan Chemical Co.). A group of ethylene oxide / propylene oxide block copolymers that may be used in the compositions of the present invention are butyl-based poly(oxypropylene) / poly(oxyethylene) block copolymers having average molecular weights ranging from 2400 to 3500, e.g., Toximul 8320, Stepan Chemical Co.).Suitable examples include Pluronic L10, Pluronic L44, Pluronic L63, Pluronic L64, Pluronic L84, Pluronic P104, Pluronic P105, Step-Flow 26, Toximul 8323 and Toximul 8320. Polyaryl-phenyl ether phosphates include ethoxylated tristyrylphenol phosphates such as Soprophor 35 3D33 (Rhodia), Soprophor 3D33 LN (Rhodia), Emulsogen 57 (Clariant), Agnique PE TSP-16A (BASF), Agrhospec 7822 (Rhodia), Dispersogen TP 160 (Clariant), Stepfac TP 160 (Stepan), Stepfac TSP-PE (Stepan). The degree of ethoxylation of the polyaryl-phenyl ether phosphates for this purpose is preferably 8-20, more preferably 14-18.

[0029] Examples of suitable solvents that may be used according to the present invention include, but are not limited to, mixtures of aromatic hydrocarbons such as Aromatic / Solvesso 100, 150, 150ND, 200 and 200ULN (Exxon Mobil Chemical), C4-C12 aliphatic methyl or ethyl esters (e.g., Steposol 1C-25, Steposol C-40, Steposol C-42, Steposol C-48 and Steposol C-65 (Stepan), Agnique ME 610 and Aqnique ME810 (BASF)), methylated soybean oil, methyl oleate / methyl linoleate, palmitic acid esters, carboxylic acids (C4-C10), ethyl esters (C4-C10), aliphatic mineral oils, and mixtures thereof.

[0030] Examples of suitable non-aqueous polar solvents (Hansen Solubility Parameter (HSP) values ​​greater than 2, particularly greater than 5, more particularly 5 to 15) include acetone, amyl acetate, butanol, benzyl alcohol, cetyl alcohol, dimethyl ether, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, octanol, Halcomid M-8-10, hexylene glycol, cyclohexanol, ethyl lactate, ethyl alcohol, 2-ethylhexanol, glycerol monoacetate, glycerol diacetate, glycerol triacetate, 3-hexanol, n-hexyl alcohol, isopropyl myristate, 2-ethylhexyl lactic acid ester, n-propyl lactic acid ester, methyl alcohol, methyl n-amyl ketone, methyl isobutyl ketone, oleyl alcohol, propanol, tetrahydrofurfuryl alcohol, butyrolactone, chlorobenzene, diacetone alcohol. dimethyl lactamide, n-decyl alcohol, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether, isobornyl acetate, isobutyl alcohol, mesityl oxide, methyl ethyl ketone, 2-methyl-2,4-pentanediol, N-octylpyrrolidone, N-methylpyrrolidone, n-octyl alcohol, oxo-decyl acetate, oxo-heptyl acetate, oxo-hexyl acetate, oxo-nonyl acetate, oxo-octyl acetate, oxo-tridecyl acetate, propylene glycol monomethyl ether, triethylene glycol, triethyl phosphate, n-butyl lactic acid ester, ethyl lactic acid ester, dodecylpyrrolidone, N,N-dimethylacetamide, propylene carbonate and mixtures thereof. In particular, the non-aqueous polar solvent is selected from propylene glycol, dipropylene glycol, dipropylene monotyl glycol ether, and mixtures thereof.

[0031] As used herein, the term "Hansen Solubility Parameters" (HSP) refers to a system that indicates the solubility of a solute in a solvent based on the non-polar parameters, polar parameters, hydrogen bond parameters, and total solubility parameters as disclosed in "Hansen Solubility Parameters" by Charles M. Hansen, ISBN 0-8493-7248-8. For the definition of Hh=hydrogen bond solubility parameter, see page 17 of the above book. For the definition of Hp=polar solubility parameter, see pages 16-17 of the above book.

[0032] Other suitable solvents may include saturated and unsaturated C6-C14 dimethylamines (e.g., Genagen® 4166, Hallcomid® M8-10, Hallcomid® M-10, Hallcomid® 1025, Hallcomid® M12-14, Agnique® AMD810, Agnique® AMD10, Agnique® AMD12).

[0033] Useful plant crops to which the compositions according to the invention can be applied include: Perennial and annual crops, such as berry plants, for example blackberries, blueberries, cranberries, rasberries and strawberries; Cereals such as barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; Fibre plants, such as cotton, flax, hemp, jute and sisal; Agricultural crops, such as sugar and fodder beet, coffee, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; Fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears and plums; Grasses such as corngrass, strawberry grass, bentgrass, centipedegrass, fescue, ryegrass, St. Augustine grass and zoysia grass; 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, ground nuts, hazelnuts, peanuts, pecans, pistachios and walnuts; Palms, e.g., oil palms; 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, cucumbers, garlic, lettuce, marrow, melon, watermelon, okra, onions, leeks, peppers, potatoes, pumpkins, squash, rhubarb, spinach and tomatoes; and Vines, such as grapes Includes:

[0034] In a preferred embodiment, in the method of the invention, the plant pathogen may be selected from Mycosphaerella graminicola (Septoria tritici), the causative agent of wheat leaf blight, Puccinia recondita or Puccinia striiformis, and the plant is a cereal, in particular wheat.

[0035] The rate at which the compositions of the present invention are applied will depend on the degree of control required, such as the particular type of plant pathogen to be controlled, and the timing and method of application, which can be readily determined by one skilled in the art. In general, the compositions of the present invention can be applied at an application rate of 0.005 kilograms per hectare (kg / ha) to about 5.0 kg / ha, based on the total amount of active ingredient in the composition. An application rate of about 0.1 kg / ha to about 1.5 kg / ha is preferred, with an application rate of about 0.1 kg / ha to 0.5 kg / ha being especially preferred.

[0036] In aqueous compositions (eg tank-mix compositions) comprising a fungicidal composition according to the invention, one or more additional fungicidal active ingredients may be added separately prior to crop application.

[0037] The compositions according to the invention may comprise one or more additional fungicidal active ingredients selected from, but not limited to, sterol demethylation inhibitors (DMIs), quinone exogenous inhibitors (QoIs) and succinate dehydrogenase inhibitors (SDHIs).

[0038] In particular, the composition may contain the additional active ingredient benzovindiflupyr, isopyrazam, pydiflumetofen, azoxystrobin, difenoconazole, prothioconazole, chlorothalonil, fenpropizin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiproline, paclobutrazol, sulfur, thiabendazole, Aspergillus Flavus NRRL 21882 (Afla-Guard®) or Bacillus subtilis var. amyloliquefaciens Strain®. FZB24 (Taegro®), Folpet, Bixafen, Boscalid, Bromuconazole, Cyflufenamid, Epoxiconazole, Fluindapyr, Fluopyram, Fluoxythioconazole, Fluquinconazole, Fluxapyroxad, Impilfluxam, Ipconazole, Isoflucipram, Kresoxim-methyl, Mancozeb, Mefentrifluconazole, Metconazole, Metrafenone, Methyltetraprole, Penthiopyra , picoxystrobin, prochlorazide, proquinazid, pyraclostrobin, spiroxamine, tebuconazole, tetraconazole, trifloxystrobin, triticonazole, fluoxapiproline, ipfentrifluconazole, sedaxane, cyclobutrifluram, flufenoxadiazam, quinofumelin, isotianil, mandestrobin, fenpyrazamine, ipflufenoquin, tebufloquin, tolprocarb, diclobenzizox, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate (known from WO 2019 / 093522), for example in a weight ratio of 1:1 to the florylpicoxamide.

[0039] More preferably, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from benzovindiflupyr and pydiflumetofen, which are present in a weight ratio to florylpicoxamide of from 10:1 to 1:10, preferably from 5:1 to 1:5.

[0040] The fungicidal composition according to the invention (e.g., as a premixed concentrate for a tank-mix composition for application) comprises: Petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenyl phenylsulfone, acetoprole, aldoxicarb, amidithione, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenic acid, azobenzene, azotoate, benomyl, benoxafos, benzyl benzoate, bixafen, brofenvalerate , Bromocyclen, Bromophos, Bromopropylate, Buprofezin, Butocarboxim, Butoxycarboxim, Butylpyridaben, Calcium polysulfide, Camphechlor, Carbanolate, Carbophenothione, Cymiazole, Quinomethionate, Chlorbeneside, Chlordimeform, Chlordimeform hydrochloride, Chlorphenetole, Chlorfenson, Chlorphenesulfide, Chlorbenzilate, Chlormebuform, Chlormethuron, Chloropropylate, Chlorthiophos, Cymiazole, Nerin I, Cinerin II, Cinerin complex, Closantel, Coumaphos, Crotamiton, Crotoxyphos, Kufuraneb, Cyanthoate, 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, Dimex, Dixinex, Dixinex-4, Dixinex-5, Dixinex-6, Dixinex-7, Dixinex-8, Dixinex-9, Dixinex-10, Dixinex-11, Dixinex-12, Dixinex-13, Dixinex-14, Dixinex-15, Dixinex-16, Dixinex-17, Dixinex-18, Dixinex-19, Dixinex-20, Dixinex-21, Dixinex-22, Dixinex-23, Dixinex-24, Dixinex-25, Dixinex-26, Dixinex-27, Dixinex-28, Dixinex-29, Dixinex-30, Dixinex-41, Dixinex-42, Dixinex-43, Dixinex-44, Dixinex-45, Dixinex-46, Dixinex-47, Dixinex-48, Dixinex-49 ... Nocap-6, Dinoctone, Dinopentone, Dinosulfone, Dinotervone, Dioxathion, Diphenylsulfone, Disulfiram, DNOC, Dofenapine, Doramectin, Endothion, Eprinomectin, Ethoate-methyl, Etrimphos, Fenazaflor, Fenbutatin oxide, Fenothiocarb, Fenpyrad, Fenpyroximate, Fenpyrazamine, Fenson, Fentrifanil, Flubenzimine, Flucycloxuron, Fluenethyl, Fluorobenside, FMC 1137, Formetanate, Formetanate hydrochloride, Formoparanate, Gamma-HCH, Gliodin, Halfenprox, Hexadecyl cyclopropanecarboxylate, Isocarbophos, Jasmolin I, Jasmolin II, Iodofenphos, Lindane,Malonoben, mecarbam, mesfolan, 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, Phenkaptone, phosalone, phospholane, phosphamidon, polychloroterpene, polynactin, proclonor, promacyl, propoxur, prothidathion, protoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quinthiophos, R-1492, phosglycine, rotenone, shradan, cebufos, selamectin, sofamid, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, diflovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasulfur , thiafenox, thiocarboxim, thiofanox, thiometon, thioquinox, thuringiensin, triamiphos, triatene, triazophos, triazuron, tripenophos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, sibutrin, dichloron, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinonamide, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridine- 4-Amine, stroquinine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodizin, phenaminosulf, formaldehyde, hydralgafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, probenazole, streptomycin,Streptomycin sesquisulfate, tecloftalam, 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 bronniathii 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 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 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 with (E)-dec-5-en-1-yl acetate, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E, (Z)-Tetradeca-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)-Tetradeca-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 with 4-methylnonan-5-one, alpha-multistriatin, brevi Comin, Codrel, Codremon, Querle, Disparlure, Dodec-8-en-1-yl acetate, Dodec-9-en-1-yl acetate, Dodec-8,10-dien-1-yl acetate, Dominicale, Ethyl 4-methyloctanoate, Eugenol, Frontalin, Grandrule, Grandrule I, Grandrule II, Grandrule III, Grandrule IV, Hexalule, Ipsdienol, Ipseno ru, japonirure, lineatin, litreure, lupurure, medulure, megatomoic acid, methyleugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfuralure, orictalure, ostramon, siglua, sordidin, sulcatol, tetradec-11-en-1-yl acetate, trimedulure, trimedulure A, trimedulure B1, trimethylol ... Rimedlure B2, Trimedlure C, Trunc-call, 2-(octylthio)-ethanol, Butopyronoxyl, Butoxy(polypropylene glycol), Dibutyl adipate, Dibutyl phthalate, Dibutyl succinate, Diethyl toluamide, Dimethylcarbamate, Dimethyl phthalate, Ethyl hexanediol, Hexamide, Methoxy-butyl, Methyl neodecane amide, Oxamate, Picaridin, 1-Dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane with 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate, 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-imidazolidone, 2-isovalerylindan-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acetione, acrylonitrile, aldrin, allosamidin, alixicarb, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, varsuline, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl)ether, borax, bromfenvinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, sebazine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxime, chlorprazophos, cis-resmethrin, cismethrin, clocitrin, copper acetoarsenite, copper arsenate, copper oleate, kumitoate, cryolite, CS708, cyanofenphos, cyanophos, ciclethrin, cithioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dikapton, diclofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilol, dimefluthrin, dimethane, dimethylvinphos, dimethyllan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI 1642, EMPC, EPBP, ethaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fensulfothion, fenthion-ethyl, flucofuron, fosmetiran, fospirate, fostietan, furathiocarb, fretrin, guazatine, guazatine acetate, sodium tetrethiocarbonate, halfenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hikincarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane, iso Xathion, 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 salt, metam sodium salt, 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, PH 60-38, Phenkapton, Phosnichlor, Phosphine, Phoxim-methyl, Pyrimetaphos, Polychlorodicyclopentadiene isomers, Potassium arsenite, Potassium thiocyanate, Precocene I, Precocene II, Precocene III, Primidophos, Profluthrin, Promecarb, Prothiophos, Pyrazophos, Pyresmethrin, Cassia, Quinalphos-methyl, Quinothione, Lafoxanide, Resmethrin, Rotenone, Kadethrin, Riania, Ryanodine, Sabadila, Shradan, Cebufos, SI-0009, Thiapronil, Sodium arsenite, Sodium cyanide, Sodium fluoride, Sodium hexafluorosilicate, Sodium pentachlorophenoxide, Sodium selenate, Sodium thiocyanate, Sulcofuron, Sulcofuron-sodium, Sulfuryl fluoride, Sulprofos, Tall oil, thazimcarb, TDE, tebupirimfos, temephos, telallethrin, tetrachloroethane, cyclofos, thiocyclam, thiocyclam hydrogen oxalate, thionazine, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormethaphos-3, trichloronath, trimethacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprophos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, triphenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodamine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anicifluprine, benclothiaz, cytokinin, DCIP, furfural, isamidophos, kinetin, Myrotheciumverrucaria composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, diphenacon, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropazine, flupropazine hydrochloride, norbormide, fosacetim, phosphorus, pindone, pyrinuron, sciriloside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, berubutin, MGK264, piperonyl butoxide, piprotal, propyl isomer, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifeno oxal, prochloraz, propiconazole, polysoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofrace, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozolin, mycozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, Flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestrobulin, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, Fluorimide, folpet, tolylfluanid, Bordeaux mixture, copper oxide, mancopper, oxine copper, nitrothar-isopropyl, edifenphos, iprobenfos, phosdifen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomedine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenami Don, Fenoxanil, Ferimzone, Fluazinam, Flumethylsulfolim, Fluopicolide, Fluoxythioconazole, Flusulfamide, Fluxapyroxad, Fenhexamid, Fosetyl-aluminum, Hymexazole, Iprovalicarb, Cyazofamid, Methasulfocarb, Metrafenone, Pencycuron, Phthalide, Polyoxin, Propamocarb, Pyribencarb, Proquinazid, Pyroquilon, Pyriophenone, Quinoxyfen, Quintozene, Tiadinil, Triazoxide, Tricyclazole, Triforine, Valida mycin, valifenalate, zoxamide, mandipropamide, fluveneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucipram, isotianil, dipimethitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[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-fluoro-phenyl)-N-(2-chloro- 6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, qmethoxystrobin (jiaxiangjunzhi), lvbenmixianan, diclobenthiazox, 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, inpirfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy) 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]methanesulfonate, 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, fenpicoxamide, tebufloquine, ipflufenoquine, quinofumelin, isofetamide, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazo 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoin, picarbutorazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide ... -(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-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-pyridyl]oxy]benzonitrile, trinexapac, comoxystrobin, zhongshengmycin, copper thiodiazole, zinc thiazole, ametholact ... amectotractin, iprodione, seboctylamine, 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 are, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared from 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 from the methods 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-methylformamidine (these compounds can be prepared from 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-[(1 S)-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 the method 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 were prepared from 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 can be prepared from 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)-1,2,4-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, 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]-1,2,4-triazol-3-amine (these compounds can be prepared from 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 can be prepared from 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 from 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 from 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 from the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-Amino-6-methyl-pyridine-3-carboxylate (this compound can be prepared from 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 from the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound can be prepared from 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 from 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 from 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, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared from the methods described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (these compounds can be prepared from 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 can be prepared from 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-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared from the process described in WO 2018 / 202428); In one embodiment, the composition further comprises a further insecticidal active ingredient component, for example in a 1:1 weight ratio relative to the florylpicoxamide, selected from one of the following:

[0041] The compositions of the present invention may be prepared according to standard formulation methodologies known to those skilled in the art. EXAMPLES

[0042] The following examples are useful for illustrating the present invention, in particular to demonstrate how the addition of an organic acid (compound of formula (I)) according to the present invention to a composition containing florylpicoxamide affects the chemical stability (i.e., eliminates or limits decomposition) of the florylpicoxamide active ingredient, compared to a composition that does not contain an organic acid. See Tables 1 and 2 below.

[0043] Each composition of prepared samples 1-1 to 1-5 and 2-1 to 2-8 was prepared by weighing the emulsifier (if present, see Tables 1 and 2) into a glass vial and adding a solvent (N,N-dimethyldecaneamide, Hallcomid® M10), whereby the sample was then mixed on a roller until a homogenous emulsion was produced. The acid (if present) was added to the vial and the sample was placed back on the roller for a minimum of 2 hours. Florylpicoxamide (technical grade AI) was then added to the vial and roller mixing continued until completely dissolved. Each sample was then split into two equal portions and stored at -18°C and 54°C for 14 days, after which it was analyzed for residual Florylpicoxamide content by standard HPLC techniques, with a relative measurement between storage at -18°C and 54°C indicating a 100% unchanged sample.

[0044] The emulsifiers used in these examples were TOXIMUL® 8320 (Stepan Company, USA), which is a polyethylene-polypropylene glycol monobutyl ether (CAS number 9038-95-3); Plurafac® LF 300 (BASF, USA), which contains an ethylene oxide-propylene oxide block copolymer monoisotridecyl ether; Marlox™ RT 64 (Sasol Chemicals, South Africa), which contains an ethoxylated propoxylated alcohol, C16-18 (≧2.5 EO / PO, CAS number 68002-96-0); or Emulsogen™ EL360 (Clariant GmbH), which contains a condensation product of castor oil with ethylene oxide.

[0045] The solvent used in these examples was HALLCOMID® M-10 (Stepan Company, USA), N,N-dimethyldecanamide. Organic acids were used as pure compounds from commercial sources.

[0046] Florylpicoxamide (structure below) is prepared according to the methods described in WO 2016 / 122802 and WO 2016 / 109257. [ka]

[0047] The amounts of florylpicoxamide active ingredient, emulsifier, solvent and organic acid in each of the samples are specified in Tables 1 and 2 on a w / w % basis in each sample.

[0048] [Table 1]

[0049] From Table 1, it can be seen that for sample 1-1 the florylpicoxamide content remains essentially unchanged. For samples according to the invention, 1-3, 1-4, and 1-5 (organic acid present), the florylpicoxamide degrades significantly less than for sample 1-2, the direct comparison in which no acid is present.

[0050] [Table 2]

[0051] From Table 2, it can be seen that for samples 2-1 and 2-2, the florylpicoxamide content remains essentially unchanged. This is also true for samples 2-4, 2-6, and 2-8, which contain salicylic acid (in the presence of a chemically destabilized initiator) and in accordance with the present invention. For samples 2-3, 2-5, and 2-7, which are not in accordance with the present invention (i.e., no organic acid is present) and contain a chemically destabilized initiator, the florylpicoxamide decomposes significantly compared to the other samples.

[0052] The data in Tables 1 and 2 show a clear beneficial effect for the use of a variety of different organic acids according to formula (I) in the chemical stabilization of active ingredients in emulsion compositions containing florylpicoxamide.

Claims

1. (i) florylpicoxamide as a fungicidal active ingredient; and (ii) Formula (I): 【Chemistry 1】 (In the formula: X=bond, -CH 2 -, -CH 2 CH 2 -, -CH=CH- (cis or trans); n=0, 1, 2 or 3; R 1 =-OH or -OCH 3 Is it; or n=1; R 1 = -C(O)OH) an organic acid selected from the compounds A disinfectant composition comprising:

2. The composition of claim 1 which is an emulsifiable concentrate.

3. The composition of claim 2 , wherein the emulsifiable concentrate comprises an alkoxylated emulsifier.

4. The composition of claim 1, wherein florylpicoxamide is present at 1 to 10% by weight of the composition, preferably at 3 to 6% by weight of the composition.

5. The composition of claim 1, wherein the organic acid is present at 0.02 to 1.5% by weight of the composition, preferably at 0.02 to 0.2% by weight of the composition.

6. C 6 ~C 12 10. The composition of claim 1, comprising a solvent selected from fatty acid dimethylamides or aromatic esters.

7. 2. The composition of claim 1, wherein the organic acid is selected from benzoic acid, p-coumaric acid, o-coumaric acid, m-coumaric acid, salicylic acid (2-hydroxybenzoic acid), cinnamic acid, gallic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, caffeic acid, (E)-3-(4-hydroxy-3-methoxy-phenyl)prop-2-enoic acid (ferulic acid), (Z)-3-(4-hydroxy-3-methoxy-phenyl)prop-2-enoic acid, vanillic acid, syringic acid, phthalic acid, isophthalic acid, and terephthalic acid.

8. 2. The composition of claim 1, wherein the organic acid is benzoic acid, p-coumaric acid, or salicylic acid.

9. Benzovindiflupyr, isopyrazam, pydiflumetofen, azoxystrobin, difenoconazole, prothioconazole, chlorothalonil, fenpropidin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiprolin, paclobutrazol, sulfur, thiabendazole, Aspergillus flavus NRRL 21882 (Afla-Guard®) or Bacillus subtilis var. amyloliquefaciens var. amyloliquefaciens) Strain FZB24 (Taegro®), folpet, bixafen, boscalid, bromuconazole, cyflufenamid, epoxiconazole, fluindapir, fluopyram, fluoxythioconazole, fluquinconazole, fluxapyroxad, inpirfluxam, ipconazole, isoflucipram, kresoxim-methyl, mancozeb, mefentrifluconazole, metconazole, metrafenone, methyltetraprole, penthiopyrad, picoxystrobin, prochlor 10. The composition of claim 1, further comprising one or more additional fungicidal active ingredients selected from the group consisting of benzophenone, benzophenone-3, benzophenone-4, benzophenone-5, benzophenone-6, benzophenone-7, benzophenone-8, benzophenone-9, benzophenone-10, benzophenone-11, benzophenone-12, benzophenone-13, benzophenone-14, benzophenone-15, benzophenone-16, benzophenone-17, benzophenone-18, benzophenone-19, benzophenone-20, benzophenone-21, benzophenone-22, benzophenone-23, benzophenone-24, benzophenone-25, benzophenone-26, benzophenone-27, benzophenone-28, benzophenone-29, benzophenone-30, benzophenone-31, benzophenone-32, benzophenone-33, benzophenone-34, benzophenone-35, benzophenone-36, benzophenone-37, benzophenone-38, benzophenone-39, benzophenone-40, benzophenone-41, benzophenone-42, benzophenone-43, benzophenone-44, benzophenone-45, benzophenone-46, benzophenone-47, benzophenone-48, benzophenone-49, benzophenone-51, benzophenone-52, benzophenone-53, benzophenone-54, benzophenone-55, benzophenone-55, benzophenone-55, benzophenone-56, benzophenone-57, benzophenone-58, benzophenone-59, benzophenone-60, benzophenone-61, benzophenone

10. 10. The composition of claim 9, wherein the additional fungicidal active ingredient is selected from benzovindiflupyr or pydiflumetofen, and the additional fungicidal active ingredient is present in a weight ratio to florylpicoxamide of from 10:1 to 1:10, preferably from 5:1 to 1:

5.

11. 10. The composition of claim 1, further comprising one or more additional ingredients selected from antifreeze agents, antifoaming agents, thickeners, biocides (preservatives), stabilizers, pigments, water-miscible solvents, water-immiscible solvents, and one or more non-ionic or ionic emulsifiers.

12. 10. An aqueous composition comprising the composition of claim 1, optionally further comprising one or more adjuvants or carriers.

13. 13. A method for controlling or preventing the infestation of crops of useful plants by phytopathogenic microorganisms, comprising applying a fungicidally effective amount of a composition according to any one of claims 1 to 12 to the plant, to a part thereof or to the location thereof.

14. 14. The method according to claim 13, wherein the plant pathogenic microorganism is selected from Mycosphaerella graminicola (Septoria tritici), Puccinia recondite or Puccinia striiformis and the plant is a cereal, in particular wheat.

15. Formula (I): 【Chemistry 2】 (In the formula: X=bond, -CH 2 -, -CH 2 CH 2 -, -CH=CH- (cis or trans); n=0, 1, 2 or 3; R 1 =-OH or -OCH 3 Is it; or n=1; R 1 = -C(O)OH) 1. Use of an organic acid selected from the compounds of formula (I) as a chemical stabilizer for florylpicoxamide in a fungicidal composition, wherein said organic acid is present in an amount of 0.02 to 1.5% by weight of said composition.

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