Fungicidal composition

Abstract

A fungicidal composition comprising: (i) picolinamide as a fungicidal active ingredient; and (ii) an organic acid selected from aliphatic C2 to C8 hydroxymonocarboxylic acids or aliphatic C2 to C8 di or tricarboxylic acids or citric acids.

Description

[0001] The present invention relates to a composition comprising the fungicide active ingredient pyridobactamide. Such a composition can be used to combat, prevent or control the infection of plant pathogenic diseases on crop plants in agriculture.

[0002] WO 2016 / 122802 and WO 2016 / 109257 disclose certain pyridine amide compounds and their use as fungicides, including (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-{[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl}-L-alaninate, ie, pyridine amide (CAS No. 1961312-55-9). Pyridine amide has been shown to be particularly effective in controlling wheat leaf spot caused by Mycosphaerella graminicola (Septoria tritici) and other fungal pathogens. WO 2018 / 204435, WO 2018 / 204436, WO 2018 / 204437, WO 2019 / 042800 and WO 2019 / 101580 disclose certain fungicidal compositions comprising a combination of pyridobactamide and another fungicidally active ingredient.

[0003] It has been found that in certain pyridobactamide-containing compositions, in particular those which are emulsion concentrates, pyridobactamide can undergo chemical degradation, which can have a negative impact on the activity of agrochemical formulations containing the active ingredient. Methods of limiting or preventing this chemical degradation of pyridobactamide have therefore been sought.

[0004] According to the present invention, there is provided a fungicidal composition comprising:

[0005] (i) pyridobactamide as a fungicidal active ingredient; and

[0006] (ii) an organic acid selected from aliphatic C2 to C8 hydroxymonocarboxylic acids or aliphatic C2 to C8 di- or tricarboxylic acids.

[0007] For practical purposes, the fungicidal compositions according to the invention have a very advantageous level of biological activity for protecting plants from diseases caused by fungi. In particular, they are used to prevent or control infection of useful plants (cereal plants, in particular wheat) by plant pathogens selected from (i) Mycosphaeria graminicola (Septoria tritici), Puccinia recondita or Puccinia striiformis.

[0008] Surprisingly, it has now been found that the addition of an organic acid selected from aliphatic C3 to C8 hydroxymonocarboxylic acids or aliphatic C2 to C8 di- or tricarboxylic acids (e.g. lactic acid) to certain compositions comprising pyridobactamide significantly improves the chemical stability (i.e. eliminates or limits degradation) of the pyridobactamide active ingredient component and thus improves the effective storage life and activity of fungicidal compositions for crop protection applications containing the active ingredient. Although not fully understood at present, it is believed that this chemical degradation of pyridobactamide may be triggered by certain emulsifying agents (emulsifiers), or by other ingredients present in such compositions (e.g. formulation inerts, other biocidally active ingredients, or indeed small amounts of chemical impurities present in these ingredients), which may be due to batch variability in the supply of raw materials for agrochemical formulation purposes.

[0009] According further to the present invention, there is provided an aqueous composition comprising the fungicidal composition according to the present invention, optionally further comprising one or more adjuvants or carriers.

[0010] Still further according to the present invention, there is provided a method of controlling or preventing infestation of crops of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a composition according to the invention is applied to the plants, parts thereof or the locus thereof.

[0011] Even further according to the present invention, there is provided the use of an organic acid selected from an aliphatic C2 to C8 hydroxymonocarboxylic acid or an aliphatic C2 to C8 di- or tricarboxylic acid as a chemical stabilizer for pyridobactamide in a fungicidal 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.

[0012] As used herein, the term "aliphatic C2 to C8 hydroxymonocarboxylic acid" refers to a straight or branched hydrocarbon chain consisting only of carbon atoms and hydrogen atoms having two to eight carbon atoms and containing one carboxylic acid group and one or more hydroxyl substituents (and preferably one hydroxyl group). Examples include, but are not limited to, glycolic acid (C2), lactic acid (C3), 2-hydroxyoctanoic acid (C8).

[0013] As used herein, the term "aliphatic C2 to C8 di- or tri-carboxylic acids" refers to straight or branched hydrocarbon chains consisting only of carbon and hydrogen atoms having two to eight carbon atoms, which may contain one double bond and contain two or three carboxylic acid groups. Examples include, but are not limited to, oxalic acid (C2), malonic acid (C3), adipic acid (C6), suberic acid (C8), maleic acid (C4).

[0014] Preferably, the composition according to the invention is an emulsifiable concentrate (EC).

[0015] In other embodiments of the invention, the composition may be an oil dispersion (OD).

[0016] Preferably, the composition according to the invention comprises the pyridobactamide component at 1 to 10% by weight of pyridobactamide, and more preferably at 3 to 6% by weight of pyridobactamide.

[0017] Preferably, the composition according to the invention comprises an organic acid present at 0.02% to 1.5% by weight of the composition, more preferably at 0.02% to 0.2% by weight of the composition and still more preferably at 0.02% to 0.1% by weight of the composition.

[0018] In some embodiments of the invention, aliphatic C2 to C8 hydroxy monocarboxylic acid or aliphatic C3 to C8 di- or tricarboxylic acid has a straight (unbranched) carbon chain and / or has a single hydroxyl substituent. In some embodiments of the invention, the organic acid is an aliphatic C2 to C4 hydroxy monocarboxylic acid, an aliphatic C2 to C6 dicarboxylic acid, or citric acid.

[0019] Preferably, the organic acid is selected from glycolic acid, oxalic acid, malonic acid, adipic acid, maleic acid, lactic acid, suberic acid, 2-hydroxyoctanoic acid, citric acid, succinic acid, fumaric acid, glutaric acid, pimelic acid, 2-hydroxycaproic acid, more preferably lactic acid or citric acid, and most preferably lactic acid (2-hydroxypropionic acid). Other organic acids that can be utilized include malic acid or tartaric acid.

[0020] Preferably, the composition according to the present invention is an emulsifiable concentrate (EC) formulation, which can be diluted (e.g., in a tank with water) before spraying on crops. The emulsifiable concentrate is a liquid formulation containing one or more fungicidal active ingredients, one or more solvents and one or more emulsifiers (e.g., 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, and more preferably an ethoxylated emulsifier.

[0021] In the compositions according to the invention (including emulsifiable concentrates), the solvent may be selected from fatty acid dimethyl amides (e.g., C6 to C 12 aliphatic chains) such as N,N-dimethyldecylamide, or aromatic esters such as methyl benzoate or benzyl acetate.

[0022] The composition according to the invention may further comprise one or more additional ingredients selected from antifreeze agents, defoamers, thickeners, biocides (preservatives), stabilizers, pigments, water-miscible solvents, water-immiscible solvents and / or one or more additional nonionic or ionic emulsifiers.

[0023] Organic solvents that can be used according to the present invention include, but are not limited to, benzyl acetate (e.g., AG1705, Huntsman Corporation Australia Pty Ltd), methyl benzoate (Polynt SpA, Italy) or N,N-dimethyldecylamide (e.g. M-10, Stepan Company, USA).

[0024] Emulsifiers that can be used according to the present invention include, but are not limited to, linear dodecylbenzenesulfonic acid, Ca-salts (e.g., 60 / BE, Rhodia Chimie SA, France), castor oil ethoxylates (e.g., EL-620, Solvay USA Inc, USA; SERVIROX OEG 59E, KLK Kolb Specialties BV, The Netherlands) and polyoxyethylene sorbitan monolaurate ( 20, Croda).

[0025] Oil dispersion (OD) formulations contain solid active ingredients dispersed in an oil medium, typically wherein the active ingredient is uniformly suspended in the oil phase. The oil can vary among paraffin oils, aromatic solvents, vegetable oils, or methylated seed oils. The oil can also contain adjuvants, such as adjuvants based on alkyl phosphates or diisononyl 1,2-cyclohexanedicarboxylate (DINCH).

[0026] Pesticide adjuvants can be defined as substances present in pesticidal compositions (e.g., concentrated active ingredient formulations diluted in water in a tank for foliar spray application to crops) which improve the performance of fungicidal active ingredients, for example, by promoting the spreading of the active ingredient on the leaf surface or penetration into the leaves of crop plants. Preferably, in the composition according to the invention (e.g., as an emulsifiable concentrate or a tank mix prepared from an emulsifiable concentrate), the adjuvant is selected from mineral oils, vegetable oils, esterified vegetable oils, methylated vegetable oils or adjuvants based on alkyl phosphates. In addition, the adjuvant can be selected from diisononyl 1,2-cyclohexanedicarboxylate (e.g., AE 829, BASF Corp, USA).

[0027] Other commercially available adjuvant products that can be tank mixed with the compositions of the present invention to produce spray formulations include HASTEN TM(Victorian Chemical Co. Pty. Ltd. - blend of esterified vegetable oil and nonionic surfactant), (Syngenta - Alkyl Phosphate (EC Formulation)), LEDNA TM (Polaquimia - EC formulation containing soybean oil methyl ester), 463 (CRODA Europe Limited - 60% paraffin oil and surfactant blend), B (Bayer AG - rapeseed oil methyl ester (esterified vegetable oil)), HC(Winfield Solutions-methylated soybean oil), DYNE- (HELENA - blend of (methylated) vegetable oil and silicone-based nonionic surfactant), FS Optique TM (GROWMARK Company - canola oil methyl esters) and tri (2-ethylhexyl) phosphate (TEHP, CAS No. 78-42-2. Synergen TM TEHP (Clariant GmbH), TOF (Lanxess).

[0028] Antifoaming agents are chemical additives that reduce and hinder the formation of foam in compositions such as pesticidal formulations. Antifoaming agents that can be used according to the present invention include, but are not limited to, polydimethylsiloxanes (e.g., XIAMETER TM ACP-1500, Dow, Inc; Antifoam MSA, Univar; Xiameter ACP-0001, Dow Brasil; Xiameter ACP-0100, Dow Chemical or silicone antifoam emulsion (e.g., SAG 1572, Momentive Performance Materials Inc., USA)).

[0029] The term "water-soluble emulsifying surfactant system" that can be used according to the present invention means any emulsifying surfactant system that is capable of forming an oil-in-water emulsion when the emulsifiable concentrate is diluted with an aqueous solution. Such an emulsifying surfactant system may comprise one or more surfactants. The surfactant may be nonionic, anionic, cationic or zwitterionic. Examples of particularly 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) (alkyl polyglycosides wherein the alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.7), Agnique PG 9116 (Cognis Corporation, Cincinnati, Ohio, USA) (20 alkyl polyglycosides wherein the alkyl group contains 9 to 11 carbon atoms and has an average degree of polymerization of 1.6), and Agnique PG 8105 (Cognis Corporation, Cincinnati, Ohio, USA) (alkyl polyglycosides wherein the alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.5). The polyalkylene oxide block copolymers may be diblock 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 useful in the compositions of the present invention are butyl-based poly(propylene oxide) / poly(ethylene oxide) block copolymers having an average molecular weight in the range of 2400 to 3500, such as 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 3D33LN (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 used for this purpose is preferably between 8 and 20, more preferably between 14 and 18.

[0030] Examples of suitable solvents that can 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 C-25, Steposol C-40, Steposol C-42, Steposol C-48 and Steposol C-65 (Stepan), Agnique ME 610 and Aqnique ME 810 (BASF)), methylated seed oil blends such as methylated soybean oil, methyl oleate / linoleate, palmitate, carboxylic acids (C4-C10), ethyl esters (C4-C10), aliphatic mineral oils, and mixtures thereof.

[0031] Examples of suitable non-aqueous polar solvents (Hansen Solubility Parameter (HSP) values ​​greater than 2, particularly greater than 5 and more particularly between 5 and 15) include acetone, amyl acetate, butanol, benzyl alcohol, cetyl alcohol, dimethyl ether, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, octanol, hallcomid M-8-10, hexylene glycol, cyclohexanol, ethyl lactate, ethanol, 2-ethylhexanol, glyceryl monoacetate, glyceryl diacetate, glyceryl triacetate, 3-hexanol, n-hexanol, isopropyl myristate, 2-ethylhexyl lactate, n-propyl lactate, methanol, methyl n-amyl ketone, methyl isobutyl ketone, oleyl alcohol, propanol, tetrahydrofurfuryl alcohol, butyrolactone, chlorobenzene, diacetone alcohol, n-decanol, N,N-dimethyldecylamide, N,N-dimethyloctanamide, dimethyl lactamide, n-decanol, dipropylene glycol monomethyl ether, ethylene glycol monobutyl The non-aqueous polar solvent is selected from propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and mixtures thereof.

[0032] As used herein, the term "Hansen Solubility Parameters" (HSP) refers to a system for describing the solubility of a solute in a solvent based on a nonpolar parameter, a polar parameter, a hydrogen bonding parameter, and an overall solubility parameter, as disclosed in "Hansen Solubility Parameters" by Charles M. Hansen, ISBN 0-8493-7248-8. For the definition of Hh = hydrogen bonding solubility parameter, see page 17 of the aforementioned book. For the definition of Hp = polar solubility parameter, see pages 16-17 of the aforementioned book.

[0033] Other suitable solvents may include saturated and unsaturated C6-C14 dimethylamines (e.g. 4166, M8-10, M-10, 1025, M12-14, AMD810, AMD10, AMD12).

[0034] Crops of useful plants to which the compositions according to the invention can be applied include:

[0035] perennial and annual crops, such as berry plants, such as blackberries, blueberries, cranberries, raspberries, and strawberries;

[0036] Cereals, for example, barley, maize (corn), millet, oats, rice, rye, sorghum, triticale, and wheat;

[0037] fiber plants, such as cotton, flax, jute, and sisal;

[0038] Field crops, for example, sugar and fodder beets, coffee beans, hops, mustard, rapeseed (canola), sugar cane, sunflower, tea, and tobacco;

[0039] Fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears, and plums;

[0040] grasses, such as bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass, and zoysia grass;

[0041] Herbs such as basil, borage, chives, cilantro, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme;

[0042] Legumes, such as beans, lentils, peas, and soybeans;

[0043] Nuts, such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios, and walnuts;

[0044] Palm plants, e.g., oil palm;

[0045] ornamental plants, such as flowers, shrubs, and trees;

[0046] other trees, such as cocoa, coconut, olive, and rubber trees;

[0047] vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, watermelon, okra, onions, leeks, peppers, potatoes, pumpkin, squash, rhubarb, spinach, and tomatoes; and

[0048] A vine, such as grapes.

[0049] In a preferred embodiment, in the method of the present invention, the plant pathogen may be selected from the causative agent of wheat leaf spot Mycosphaeria graminearum (Septoria graminearum), Puccinia graminearum or Puccinia spp., and the plant is a cereal, in particular wheat.

[0050] The application rate of the composition of the present invention depends on the specific type of plant pathogens to be controlled, the degree of control required, and the application schedule and method, which can be easily determined by those skilled in the art. Generally, the composition of the present invention can be applied at an application rate between 0.005 kilograms per hectare (kg / ha) and about 5.0 kg / ha, based on the total amount of active ingredients in the composition. Application rates between about 0.1 kg / ha and about 1.5 kg / ha are preferred, with application rates between about 0.1 kg / ha and 0.5 kg / ha being particularly preferred.

[0051] In an aqueous composition (eg, a tank-mix composition) comprising the fungicidal composition according to the present invention, one or more additional fungicidal active ingredients may be added separately prior to crop application.

[0052] The composition according to the present invention may comprise one or more additional fungicidal active ingredients selected from, but not limited to, sterol demethylase inhibitors (DMIs), quinone exogenous inhibitors (QoIs) and succinate dehydrogenase inhibitors (SDHIs).

[0053] In particular, the composition may comprise one or more of the following as one or more additional active ingredients, e.g. in a weight ratio of 1:1 to pyrithione: benzovinflumazole, isopyrazam, fluopyrazol, azoxystrobin, difenoconazole, prothioconazole, thiophanate-methyl, fenpropidin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, fluthiazol-pyridone, paclobutrazol, sulfur, thiabendazole, Aspergillus Flavus NRRL 21882 (Afla- ) or Bacillus subtilis var. amyloliquefaciens Strain FZB24 folpet, chlorfluanid, boscalid, oxaconazole, flutolanil, epoxiconazole, fluindapyr, fluopyram, fluoxytioconazole, fluquinconazole, fluoxazolidinone, indopyram, cyproconazole, isoflurane, isoflurane, kresoxim-methyl, mancozeb, chlorfluanid, metconazole, metrafenone, metyltetraprole, penthiopyrad, picoxystrobin, prochloraz, iodoquinol, pyraclostrobin, spiroxabiocin, tebuconazole, tetrafluconazole, trifloxystrobin, trichlorfonazole, fluoxapiprolin, Ipfentrifluconazole, sedaxane, cyclobutrifluram, flufenoxadiazam, quinofumelin, isothiopyrad, mandestrobin, imipenem, ipflufenoquin, isobutylethoxyquin, tolprocarb, dichlobentiazox, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate (known from WO 2019 / 093522).

[0054] More preferably, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from benzovindiflupyr and trifloxystrobin, wherein the additional fungicidal active ingredient is present in a weight ratio of 10:1 to 1:10, and preferably in a weight ratio of 5:1 to 1:5 relative to pyrithione.

[0055] The fungicidal composition according to the invention (e.g., a ready-to-use concentrate of a tank-mix composition for spraying) may comprise, for example, an additional pesticidal active ingredient component selected from one of the following in a weight ratio of 1:1 to pyridobactamide:

[0056] A compound selected from the group consisting of petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenyl sulfone, acetothionil, aldicarb, sirox, fomanphos, fenthion, fenthion hydrogen oxalate, amitraz, cypermethrin, arsenic trioxide, azobenzene, azophos, benomyl, benoxafos, benzyl benzoate, chloranil Amine, bromethrin, bromothion, bromothion, bromothion, buprofezin, butanone carbendazim, butanone sulfone carbendazim, butyl pyridaben, calcium polysulfide, octachlorocamphene, chlormethoxam, trithion, cypermethrin, cypermethrin, cypermethrin hydrochloride, cypermethrin, cypermethrin, cypermethrin hydrochloride, cypermethrin, cypermethrin, chlorfenapyr, ethyl cypermethrin, cypermethrin (chloromebuform), cypermethrin, propyl cypermethrin, cypermethrin, cypermethrin I, cypermethrin II, cypermethrin, closantel, coumaphos, crotamiton, baclofos 、thiophanate-methyl, chlorpyrifos, DCPM, DDT, dinex, dinex-O, dinex-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl, demeton-S-methyl, demeton-S-methyl, bacteriostatic, dichlorvos, dicliphos, dimethoate, chlorpyrifos, dinex, dinex-diclexine, dimethoate Pu-4, dimethoate-6, ortho-dimethoate, nitropentyl, nitrooctyl, nitrobutyl, dimethoate, sulfodiphenyl, disulfiram, DNOC, dofenapyn, doramectin, indophos, eprinomectin, phosphothioate, ethidium bromide, anti-mite azole, fenbutatin, fenthiocarb, fenpyrad, fenpyrad, fenpyraclostrobin, fentrifanil, fluazifop-butyl, flufenoxuron, fluazifop-butyl, flufenoxuron, fluazifop-butyl, FMC 1137, fenthion, fenthion hydrochloride, formparanate, γ-HCH, chloranil, benzyl chloranil, hexadecyl cyclopropane carboxylate, isothiocarb, jasmonate I, jasmonate II, iodine, lindane, propanil, cypermethrin, dithiophos, methylthiophene, cypermethrin, methyl bromide, cypermethrin, chloranil, milbemid, propylamine, monocrotophos, malathion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5- [(6-iodo-3-pyridyl)methoxy]pyridazine-3-one, fluazifop, nikkomycin, pentocarb, pentocarb 1:1 zinc chloride complex, omethoate, isothiocarb, sulfone, pp'-DDT, parathion, permethrin, fenthion, phosalone, thiocyanate, phosphamidon, polychloroterpenes, polynactins, chloranil, cypermethrin, propoxur, ethidium, pyrethrin I, pyrethrin II,Pyrethrins, pyridazinon, pyrimithiophos, quinalphos, quintiofos, R-1492, glyphosate, rotenone, octamidine, clomiphene, selamectin, thion, SSI-121, sulfluramid, sulfotep, sulfur, flumethoxine, τ-fluvalinate, TEPP, tert-butylcarb, tetrachlorothiazide, thiafenox, thiafenox, long-acting thiocarb, methyl thiosulfate, thiafenox ... Naphthoquinone, dichlorophen, endosin, triphenyltin, slaked lime, sodium mancozeb, quinone, quinone, simazine, triphenyltin acetate, triphenyltin hydroxide, fufufos, piperazine, thiophanate, chloralose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, disipirthion, dodesin, sodium fensulfonate, formaldehyde, mercurygafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel di(dimethyldithiocarbamate), trichloromethylpyridine, octhiothion, oxolinic acid, oxytetracycline, hydroxyquinoline potassium sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, chloranthate, thimerosal, cotton brown banded tormentor GV, Agrobacterium radiobacterium, Amblyseius species (Amblyseius spp.), celery armyworm NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletesaphidimyza, Spodoptera exigua NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Codling moth GV, Dacnusa sibirica, Diglyphus isaea, Eretmocerus eremicus, Heterorhabditis bacteriophora) and Heterorhabditis megidis, Hippodamia convergens,Leptomastix dactylopii, Macrolophus caliginosus, Cabbage armyworm NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, species of the genus Pseudomonas, Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema carpocapsae, Steinernema carpocapsae, Steinernema carpocapsae glaseri), Steinernema riobrave, Steinernema riobravis, Steinernemascapterisci, Steinernema spp., Trichogramma species, Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate apholate), morzid, penfluron, tepa, thiohempa, thiohempa, trothamide, urethaneimide, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z )-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-eicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol,(Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, α-polystyrene, western pine beetle aggregation pheromone, codlelure, codlemone, cuelure, epoxynonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8, 10-dien-1-yl acetate ethyl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, southern pine beetle aggregation pheromone (frontalin), grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acid acid), methyleugenol, muscalure, octadecane-2,13-diene-1-yl acetate, octadecane-3,13-diene-1-yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol, tetradecane-11-ene-1-yl acetate, trimedlure, trimedlure A, trimedlure B1, trimedlure B2, trimedlure C, trunc-call, 2-(octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, DEET, dimethyl carbate), dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methylneodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane,1,2-Dichloropropane and 1,3-dichloropropylene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chloro Vinyl diethyl phosphate, 2-imidazolidinone, 2-isovaleryl indan-1,3-dione, 2-methyl (prop-2-ynyl) aminophenyl methyl carbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethyl carbamate, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methyl carbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate, acethion, acrylonitrile, chloromethyl bridged naphthalene, alloamicin, Aluminum phosphide, α-decadin, chloranthrin ... os), butyl phosphate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, badan hydrochloride, cevadine, borneol, chlordane, chlordecone, chloroform, chloropicrin, chloraniloxime, chlorprazophos, cis-resmethrin, cismethrin, clocythrin, copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, benzonitrile, cypermethrin, cypermethrin, d-methrin, DAEP, dazomethane, decarbofuran, diamidafos, isochlorophos, cypermethrin, dicresyl, cypermethrin, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilor, tetrafluthrin, demicarb, pyrethrin, methyl chlorpyrifos, difenocarb, propanol, pentotropol, dinoseb, fenpyroxil, vegetable phosphorus, thiopyraphos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, ethiofencarb, ethiofencarb, fenpyroxil,Fenoxacrim, cypermethrin, fenthion, ethyl fenthion, flucofuron, butyl fenthion, phosphoarsenic acid ester, butyl cyclothion, furathiocarb, pyrethroid, biguanide salt, biguanide acetate, sodium tetrathiocarbonate, benzyl chlorpyrifos, HCH, HEOD, heptachlor, cypermethrin, HHDN, hydrogen cyanide, quinoline carbendazim, IPSP, chlorfenapyr, carbochlorin, isodrin, isofenphos, transplanting spirit, rice blast spirit, oxazophos, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorpentyl, methoprene, lead arsenate, bromophenylphos, acetamiprid, thiamethoxam, m-isopropyl methyl carbamate, magnesium phosphide, phosphorus azide, methyl aphidron, aphidron, mercurous chloride, methyl Sulfoxide, metamex, metamex potassium salt, metamex sodium salt, methyl sulfonyl fluoride, butenamidophos, methoprene, methyl ether thiocyanate, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, oxadiazine, ant killer, naphthiophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, orthonicotine, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate, O,O,O',O'-tetrapropyl dithiodipyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenthion, parachlorothion, phosphine, methyl phoxim, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious phosphine I, precocious phosphine II, precocious phosphine III, amidophos, profluthrin, fenthion, prothiophos, pyraclostrobin, anti-pyrethroid, quassia, quinalphos-methyl, fenthion, iodophos, resmethrin, rotenone, thiamethoxam, ryanodine, sabadilla, octamidine, clostridium, SI-0009, thiamethoxam, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron sodium salt ron-sodium), sulfuryl fluoride, thiopromide, tar, thiabendazole, TDE, butylpyrimidinphos, dimethoate, cyclopentyl thiocarb, tetrachloroethane, thiochlorvos, cyclohexane, cyclohexane oxalate, cypermethrin, cypermethrin monosodium, tralomethrin, trans-permethrin, trichlormetaphos-3, chlorpyrifos, tolprocarb, chlorpyrifos-butyl, methoprene, veratridine, veratridine, XMC, zetamethrin, zinc phosphide, tolfenphos, chlorfluanid, tetrafluanid, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-ethanolamine, tributyltin oxide, pyroximate, snail killer,1,2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine, anisin, benclothiaz, cytokinin, DCIP, furfural, isamidophos, kinetin, verrucosporium mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis) extract, α-chloroalcohol, antu, barium carbonate, bifenthion, brodifacoum, brodifacoum, brofenthion, chlorfenthion, cholecalciferol, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, calciferol, flufenthion, fluoroacetamide, flufenthion, flufenthion hydrochloride, flufenthion, chlorfenthion, phosphorus, flufenthion, chlorfenthion, chlorfenthion, sciline glycoside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy) ethyl piperate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic acetylenic ether, MGK 264, synergistic ether, synergistic aldehyde, synergistic ester (propyl isomer), S421, enhanced powder, sesasmolin, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, serene, zinc cyclohexane, zinc thiam, imanin, ribavirin, chloroindole hydrazide, mercuric oxide, methyl thiophanate, azaconazole, bifenthionol, cyproconazole, difenoconazole, diniconazole, fluepiconazole, nitrobenzazole, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, amide azole, cyproconazole, metconazole, myclobutrazol, paclobutrazol, rice blast ester, penconazole, prothioconazole, pyrimidine oxime, prochloraz, propiconazole, pyrimidine oxazole, silylate, tebuconazole, tetrafluconazole, triadimefon, triadimenol, triflumizole, trichlorfonazole, pyrimidine alcohol, chlorfenapyr, flurimidine alcohol, bupirima te), dimethirimol, ethirimol, dodecacyclic morpholine, fenpropidin, fenpropimorph, spiroxaplanol, tridecacyclic morpholine, cyprodinil, pyraclostrobin, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furaxyl, metalaxyl, R-metalaxyl, furamide, oxadixyl, carbendazim, debacarb, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone,Vinclozoline, boscalid, carboxin, flutolanil, flutolanil, oxacarb, penthiopyrad, thiofuran, dodine, oxazolidinone, azoxystrobin, oxazolidinone, oxazolidinone, oxazolidinone, flutolanil, fluoxastrobin, oxazolidinone, oxazolidinone, oxazolidinone, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, ferram, mancozeb, maneb, metiram, propineb, maneb, captafol, captan, fluoroimide, folpet, tolylfluanid, bordeaux mixture, copper oxide oxide), mancopper, oxine-copper, nitrothal-isopropyl, kefansan, iprobenphos, phosdiphen, tolclofos-methyl, dithiocarb, benzathiapiprolin, blasticidin-S, chloroneb, chlorothalonil, cyfluanid, cymoxanil, diclocymet, diclomezine, dicloran, diethofencarb, oxadiazine, flumorph, dithianon, ethaboxam, etridiazole, fenamidone, fenamidone, fenoxanil, ferrimazole imzone), fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, flusulfamide, fluoxazolidinone, fenhexamid, fosetylaluminium, hymexazol, propineb, cyazofamid, methasulfocarb, mefenoxam, pencycuron, phthalide, polyoxins, propamocarb, pyraclostrobin, proquinazid, pyroquilon, pyriofenone, quinoxyfen, pentachloronitrobenzene, thiazide, triazoxide, tricyclazole, triazine, validamycin, valeramide, zoxamide,mandipropamid, fluphenazine, isopyrazam, sedaxane, benzovinflumizone, fluopyrazol, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucyclamide, isothiocyanate, dipymetitrone, 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-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluinoxam, jiaxiangjunzhi, ribonucleic acid, dichlorobenzyl, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3- dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiprolin, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, chlorfenapyr, 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-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester,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, pyridachlometyl chloride, 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]benzene [4-(2-(4-chlorophenyl)-1-(4-chlorophenyl)-1-(4-(trifluoromethyl)-phenoxy)]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, thiopyraclostrobin, cyanamide, thiopyraclostrobin, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb, oxathiocarb Ester, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenamid, fluthiazolin, fluopyram, pyriproxyfen, 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, methyl tetraproline, 2-(difluoromethyl)-N- ((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol, fluoroxaprolin, 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-ethyl, syringoxystrobin, zhongshengmycin, thiophanate-copper, thiophanate-zinc, amitolin, iprodione, cinclorac, 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 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-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 from WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-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 [(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 by WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared by WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide,1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5- [(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared from WO 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 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); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (this compound can be prepared by the method described in WO 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (this compound can be prepared by the method described in WO 2011 / 138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenethiocarboxamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in WO 2-(Difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared by the method described in WO 2014 / 095675); 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-C-methyl-carbonimide]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428). 、

[0057] The compositions of the present invention may be prepared according to standard formulation methods known to those skilled in the art.

[0058] Examples :

[0059] The following examples serve to illustrate the invention, and in particular to illustrate how the addition of an organic acid according to the invention to a composition comprising pyridobactamide affects the chemical stability of the pyridobactamide active ingredient (i.e. eliminates or limits degradation) compared to a composition without the organic acid or an organic acid not according to the invention. See Tables 1 to 4 below.

[0060] Each composition of samples 1-1 to 1-11, 2-1 to 2-14, 3-1 to 3-8 and 4-1 to 4-3 was prepared by weighing an emulsifier (if present, refer to Tables 1 to 4) into a glass vial, adding a solvent (N,N-dimethyldecylamide, M10 or methyl benzoate), whereby the sample was then mixed on a roller until a homogenous emulsion was formed. Acid (if present) was added to the vial and the sample was placed back on the roller for at least 2 hours. Pyridine (technical grade AI) was then added to the vial and roller mixing was continued until complete dissolution. Each sample was then divided into two equal parts and stored at -18°C and 54°C for 14 days and then analyzed by standard HPLC techniques for the remaining pyridine content, a relative measure between storage at -18°C and 54°C, where 100% indicates an unchanged sample.

[0061] Emulsifiers used in these examples include 8320 (Stepan Company, USA), which is polyethylene glycol-polypropylene glycol monobutyl ether (CAS No. 9038-95-3); LF 300 (BASF, USA), which contains ethylene oxide-propylene oxide block copolymer monoisotridecyl ether; Marlox TM RT 64 (Sasol Chemicals, South Africa), which contains ethoxylated, propoxylated C16-18 alcohol (>=2.5 EO / PO, CAS No. 68002-96-0); or Emulsogen TM EL360 (Clariant Ltd.), which comprises a condensation product of castor oil and ethylene oxide.

[0062] The solvent used in these examples is M-10 (Stepan Company, USA), which is N,N-dimethyldecylamide or methyl benzoate (Bolin Chemical Co., Ltd., Italy).

[0063] Use lactic acid as a 90% solution such as PF 90 (PuracBiochem BV, The Netherlands). Other organic acids were used as pure compounds.

[0064] Pyridobactamide (structure below) was prepared according to the methods described in WO 2016 / 122802 and WO 2016 / 109257.

[0065]

[0066] The amounts of pyridobactamide active ingredient, emulsifier, solvent and organic acid in each sample are identified in Tables 1 to 4 based on % w / w in the corresponding samples.

[0067] Table 1 : Content of pyridobactamide active ingredient (AI) in compositions comprising pyridobactamide and lactic acid after storage (14 days at 54°C relative to -18°C) in the presence of different alkoxylated emulsifiers.

[0068]

[0069]

[0070] As can be seen from Table 1, for sample 1-1, the solution of pyridobactamide remained essentially unchanged. For samples 1-3, 1-5, 1-7, 1-9 and 1-11 according to the present invention (lactic acid was present), the degradation of pyridobactamide was significantly lower than that of samples 1-2, 1-4, 1-6 and 1-10 (these are direct controls without the presence of lactic acid).

[0071] Table 2: Content of pyridobactamide active ingredient (AI) in compositions comprising pyridobactamide and an organic acid according to the invention (Samples 2-6 to 2-14) and not according to the invention (Samples 2-1 to 2-5) after storage (14 days at 54°C relative to -18°C).

[0072]

[0073] As can also be seen from Table 2, for sample 2-1, the solution of pyrithione remained essentially unchanged in terms of the active ingredient content. For sample 2-2, pyrithione was significantly degraded in the presence of an alkoxylated emulsifier. For samples 2-3 to 2-5, pyrithione was also significantly degraded in the presence of an organic acid not according to the present invention. For samples 2-6 to 2-14 according to the present invention, the degradation of pyrithione was significantly lower (less than about 5% degradation) than samples 2-2 to 2-5 (these are direct controls without the presence of an organic acid or with an organic acid not according to the present invention).

[0074] Table 3: Content of pyridobactamide active ingredient (AI) in compositions comprising pyridobactamide and citric acid (according to the invention) in different amounts after storage (14 days at 54°C relative to -18°C).

[0075]

[0076] It can also be seen from Table 3 that for sample 3-1, the solution of pyridobactamide remained essentially unchanged. Compared with sample 3-2 without citric acid, all samples 3-3 to 3-8 showed significantly lower degradation or no degradation.

[0077] Table 4: Content of pyridobactamide active ingredient (AI) in compositions comprising pyridobactamide and lactic acid (according to the invention) after storage (14 days at 54°C relative to -18°C) with methyl benzoate as solvent.

[0078]

[0079] It can also be seen from Table 4 that for sample 4-1, the solution of pyridobactamide in methyl benzoate remained essentially unchanged in terms of AI content after storage. However, as shown in sample 4-2, the inclusion of an emulsifier resulted in significant degradation of pyridobactamide. Sample 4-3 illustrates that the degradation of pyridobactamide was significantly reduced with the additional inclusion of lactic acid.

[0080] The data in Tables 1 to 4 show the clear beneficial effect of using an aliphatic C2 to C8 hydroxymonocarboxylic acid or an aliphatic C2 to C8 di- or tricarboxylic acid in the chemical stabilization of active ingredients in emulsion compositions comprising pyridobactamide in a range of different formulation environments.

Claims

1. A fungicidal composition comprising: (i) pyridobactamide as a fungicidal active ingredient; and (ii) an organic acid selected from an aliphatic C2 to C8 hydroxymonocarboxylic acid or an aliphatic C2 to C8 di- or tricarboxylic acid or citric acid.

2. The composition according to claim 1, which is an emulsifiable concentrate.

3. The composition according to claim 2, wherein The emulsifiable concentrate comprises an alkoxylated emulsifier.

4. The composition according to any one of claims 1 to 3, wherein Pyridobactamide is present at 1% to 10% by weight of the composition, and preferably at 3% to 6% by weight of the composition.

5. The composition according to any one of claims 1 to 4, wherein The organic acid is present at 0.02% to 1.5% by weight of the composition, and preferably at 0.02% to 0.2% by weight of the composition.

6. The composition according to any one of claims 1 to 5, wherein The composition comprises a compound selected from C6 to C 12 Solvents of fatty acid dimethyl amides or aromatic esters.

7. The composition according to any one of claims 1 to 6, wherein The organic acid is selected from glycolic acid, oxalic acid, malonic acid, adipic acid, maleic acid, lactic acid, suberic acid, 2-hydroxyoctanoic acid or citric acid.

8. The composition according to any one of claims 1 to 7, wherein The organic acid is lactic acid or citric acid.

9. The composition according to any one of claims 1 to 8, wherein The composition comprises one or more additional fungicidal active ingredients selected from: Benzovinflumazole, pyraclostrobin, fluazifop-p-butyl, azoxystrobin, difenoconazole, prothioconazole, thiophanate-methyl, fenpropidin, arachnid-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyraclostrobin, fludioxonil, pyraquinone, tricyclazole, fluazinam, mandipropanil, metalaxyl, metalaxyl-M, oxadixyl, fluthiazide, paclobutrazol, sulfur, thiabendazole, aflatoxin NRRL 21882 Bacillus subtilis var. amyloliquefaciens strain FZB24 Foliumbol, chlorofluorochlorofluorobiphenylpyrazone, boscalid, oxaclostrobin, cyfluthrin, epoxiconazole, fluopyram, flutolanil, flutolanil, flutolanil, flutolanil, flutolanil, indoppyram, cyproconazole, isofloxacin, kresoxim-methyl, mancozeb, chlorofluoroacetobacillus, metconazole, mefenamic acid, tetrazobacyl, penthiopyrad, picoxystrobin, prochloraz, propoxyiodoquinoline, pyraclostrobin, spiroxam, tebuconazole, tetrafluoroacetobacillus, trifloxystrobin, trifloxystrobin, flutolanil ...

10. The composition according to claim 9, wherein The additional fungicidal active ingredient is selected from benzovinflumizone or trifloxystrobin, and wherein the additional fungicidal active ingredient is present in a weight ratio of 10:1 to 1:10, and preferably 5:1 to 1:5, relative to pyrithione.

11. The composition according to any one of claims 1 to 10, further comprising one or more additional ingredients selected from the group consisting of antifreeze agents, defoamers, thickeners, biocides (preservatives), stabilizers, pigments, water-miscible solvents, water-immiscible solvents and one or more non-ionic or ionic emulsifiers.

12. An aqueous composition comprising the composition according to any one of claims 1 to 11, optionally further comprising one or more adjuvants or carriers.

13. A method for controlling or preventing infestation of crops of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a composition according to any one of claims 1 to 12 is applied to the plants, parts thereof or the locus thereof.

14. The method according to claim 13, wherein: The phytopathogenic microorganism is selected from Mycosphaeria graminearum (Septoria tritici), Puccinia graminearum or Puccinia striiformis, and the plant is a cereal, in particular wheat.

15. Use of an organic acid selected from the following as a chemical stabilizer for pyridobactamide in a fungicidal composition: (i) an aliphatic C2 to C8 hydroxymonocarboxylic acid, or (ii) a C2 to C8 di- or tri-carboxylic acid, in, The organic acid is present at 0.02% to 1.5% by weight of the composition.

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