Synergistic mixtures for fungal control in cereals

Abstract

To provide synergistic compositions comprising fungicidal compounds.SOLUTION: A fungicidal mixture is provided containing a fungicidally effective amount of the compound of Formula I, (S)-1,1-bis(4-fluorophenyl)propan-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-alaninate, and at least one fungicide selected from the group consisting of boscalid, metconazole, ipflufenoquin, isoflucypram and metyltetraprole.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 62 / 500199, filed May 2, 2017. No. 60 / 699,999, filed on Oct. 1, 2007, which provisional patent application is expressly incorporated herein by reference.

[0002] The present disclosure provides a compound comprising: (a) a compound of Formula I; and (b) a sterol biosynthesis inhibitor (e.g., prothiol). Conazole, epoxiconazole, cyproconazole, myclobutanil, metconazole , difenoconazole, tebuconazole, tetraconazole, fenbuconazole, pro piconazole, fluquinconazole, flusilazole, and flutriafol), strobilol Birurin (e.g., pyraclostrobin, fluoxastrobin, azoxystrobin, trifloxystrobin, picoxystrobin, and kresoximmethyl), succinic acid Dehydrogenase inhibitors (e.g., fluxapyroxad, benzovindiflupir, pentaerythroxad) Opirad, isopyrazam, bixafen, boscalid, penflufen, and fluopy ram), and multi-site inhibitors (e.g., chlorothalonil), At least one fungicide or other commercially available fungicides can be used to treat any plant Synergistic fungicidal mixtures that provide control of fungal pathogens.

[0003] Background and Summary of the Invention Fungicides act to protect plants against damage caused by fungi , compounds of natural or synthetic origin. Current agricultural practices rely heavily on the use of fungicides. In fact, some crops cannot be grown without the use of fungicides. By using chemicals, growers can increase the yield and quality of their crops, thereby increasing the value of their crops. In most cases, the increase in crop value outweighs the cost of fungicide application. This is at least three times the amount of

[0004] However, no single fungicide is useful in all situations, and no single fungicide is suitable for all conditions. Repeated use of fungicides frequently leads to the development of resistance to that and related fungicides. As a result, it is safer, has better performance, and requires lower doses. and fungicides and fungicide combinations that are easier to use and less expensive. Research is being carried out to produce

[0005] Synergy occurs when the activity of two or more compounds exceeds the activity of the compounds when used alone. occurs in.

[0006] It is an object of the present disclosure to provide synergistic compositions containing fungicidal compounds. A further object is to provide processes that use these synergistic compositions. The synergistic composition is from the classes Ascomycetes and Basidiomycetes It is possible to prevent or treat, or both, diseases caused by the fungi. Additionally, the synergistic composition is effective against Ascomycete and Basal molluscs, including barley scald. According to the present disclosure, the present invention provides a method for the preparation of a medicament for the treatment of idiomycete pathogens. Synergistic compositions are provided along with methods for their use. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present disclosure provides a fungicidally effective amount of (a) a compound of formula I; and (b) a compound of groups A.1, B.1, and and compounds of formula C.1, A.1 Sterol biosynthesis inhibitors selected from the following groups a), b), and c) ( SBI fungicide), a) C14 demethylase inhibitors (DMI fungicides), e.g., prothioconazole, Poxiconazole, cyproconazole, myclobutanil, metconazole, difenoconazole azole, tebuconazole, tetraconazole, fenbuconazole, propiconazole, fluquinconazole, flusilazole, flutriafol, and prochloraz, b) Delta 14-reductase inhibitors, such as fenpropimorph and aldimol centre, c) inhibitors of 3-ketoreductases, such as fenhexamid; B.1 Respiratory inhibitors selected from the following groups a) and b): a) inhibitors of complex II (SDHI fungicides, e.g., carboxamides), e.g., Ruxapyroxad, benzovindiflupyr, penthiopyrad, isopyrazam, bixafe fluopyram, boscalid, penflufen, and fluopyram, b) Q o Inhibitors of complex III at the site (e.g., strobilurins), e.g., Laclostrobin, fluoxastrobin, azoxystrobin, trifloxystrobin , picoxystrobin, and kresoxim-methyl, C.1 Inhibitors with multi-site action selected from the following groups a) and b): a) thiocarbamates and dithiocarbamates such as mancozeb; b) Organochlorine compounds such as chlorothalonil (e.g., phthalimide, sulfamide, chlorine) nitronitrile), or other commercially available fungicides. and a synergistic fungicidal mixture that provides control of any plant fungal pathogen. [ka]

[0008] As used herein, the compound of formula I refers to (S)-1,1-bis(4-fluorophenyl)-2-(4-fluorophenyl)-2-(2-methylphenyl)-1,1-bis ... (phenyl)propan-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-ara The compounds of formula I are effective against Rhynchosporin, the causative agent of barley scald. of economic importance, including but not limited to, ium secalis (RHYNSE) Provides control of a variety of pathogens in crops.

[0009] As used herein, epoxiconazole refers to (2RS,3SR)-1-[3- (2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl] -1H-1,2,4-triazole is the generic name for triazole, which has the following structure: [ka]

[0010] Its fungicidal activity is described in The Pesticide Manual, Fifteenth Edition. Edition, 2009. Epoxiconazole is used for both prophylaxis and treatment. As has been shown to have therapeutic effects in bananas, cereals, coffee, rice, and sugar beets. comycete, Basidiomycete, and Deuteromycete provides broad spectrum control of diseases caused by

[0011] As used herein, prothioconazole refers to 2-[(2)RS)-2-(1- Chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2 It is the generic name for H-1,2,4-triazole-3(4H)-thione, which has the following structure: . [ka]

[0012] Its fungicidal activity is described in The Pesticide Manual, Fifteenth Edition. Edition, 2009. Prothioconazole is effective against rhododendrons by foliar application. and Pseudocercospoides gracilis in wheat, barley, and other crops. rella herpotrichoides), Fusarium head blight (Fusarium spp ., Microdochium nivale), leaf blight (Zymoseptoria tritici, Parastagonospora nodorum, Pyrenop hora spp., Rhynchosporium secalis, etc.), rust ( Puccinia spp.), and powdery mildew (Blumeria gramini s) and other disease control.

[0013] As used herein, azoxystrobin refers to (E)-2-{2-[6-(2- Cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate It is the common name for the compound and has the following structure: [ka]

[0014] Its fungicidal activity is as described in The e-Pesticide Manual, Version 5.2, 2011. Exemplary uses of azoxystrobin include the treatment of the following diseases: Protozoa, temperate cereals Erysiphe graminis, Puccinia spp. , Parastagonospora nodorum, Zymoseptoria t ritici, and Pyrenophora teres; Pyricular in rice oryzae and Rhizoctonia solani; vines Plas mopara viticola and Uncinula necator; Cucurbitaceae S phaerotheca fuliginea and Pseudoperonospor a cubensis; Phytophthora infestation of potatoes and tomatoes stans and Alternaria solani; Mycosphagia on peanuts erella arachidis, Rhizoctonia solani, and S clerotium rolfsii; Monilinia spp. on peaches and Cl adosporium carpophilum; Pythium spp. in lawns and and Rhizoctonia solani; Mycosphaerella spp. on bananas pp.; Cladosporium caryigenum on pecan; Elsi on citrus noe fawcettii, Colletotrichum spp., and Gui gnardia citricarpa; coffee Colletotrichum s pp. and Hemileia vastatrix control, including but not limited to It will not be done.

[0015] As used herein, pyraclostrobin refers to a methyl N-[2-[[[1-(4 -chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]phenyl]-N- It is the common name for methoxycarbamamate and has the following structure: [ka]

[0016] Its fungicidal activity is described in the BCPC Online Pesticide Manual ( Exemplary uses of pyraclostrobin include the use of Zymose in cereals. ptoria tritici, Puccinia spp., Drechslera tritici-repentis, Pyrenophora teres, Rhync hosporium secalis, and Septoria nodorum; Mycosphaerella spp. in nuts; Septoria gly in soybeans cines, Cercospora kikuchii, and Phakopsora pachyrhizi; Plasmopara viticola and Ery in grapes siphe necator; Phytophthora i on potatoes and tomatoes nfestans and Alternaria solani; Sphaer on cucumber otheca fuliginea and Pseudoperonospora cub ensis; Mycosphaerella fijiensis in bananas; E in citrus fruits lsinoe fawcettii and Guignardia citricarpa and Rhizoctonia solani and Pythium aphthora in lawns. This includes broad-spectrum disease control of major plant pathogens, including P. anidermatum. Not limited to these.

[0017] As used herein, fluxapyroxad refers to 3-(difluoromethyl)-1- Methyl N-(3',4',5'-trifluorobiphenyl-2-yl)pyrazole-4- It is the generic name for carboxamide, which has the following structure: [ka]

[0018] Its fungicidal activity is confirmed by Agrow Intelligence (https: / / www .agra-net.net / agra / agrow / databases / agrow -intelligence / ). Potential uses include Helmint on various crops such as barley, corn, and soybeans. hosporium teres, Rhynchosporium seca lis (brown leaf blight), Puccinia hordei (red rust), and Erys Plant pathogens such as Iphe graminis f.sp. hordei (powdery mildew) These include, but are not limited to, the control of

[0019] As used herein, benzovindiflupyr refers to N-[(1RS,4SR)-9 -(Dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalene- 5-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide It is a common name and has the following structure: [ka]

[0020] Its fungicidal activity is confirmed by Agrow Intelligence (https: / / www .agra-net.net / agra / agrow / databases / agrow -intelligence / ) is exemplified. Potential uses include the cultivation of a variety of crops, including vines, cereals, soybeans, cotton, and fruit and vegetable crops. In various crops, Botrytis spp., Erysiphe spp., Rhiz Octonia spp., Septoria spp., Phytophthora spp., Pythium spp., Phakopsora pachyrhizi, and Puccinia recondita, but Not limited to these.

[0021] As used herein, chlorothalonil refers to tetrachloroisophthalonitrile. is the common name for, and has the following structure: [ka]

[0022] Its fungicidal activity is described in The Pesticide Manual, Fifteenth Edition. Edition, 2009. Chlorothalonil is used in pome fruits, stone fruits, and apples. Peach, citrus fruits, shrub and woody stem fruits, cranberries, strawberries, pawpaws, Bananas, mangoes, coconuts, oil palms, rubber, pepper, vines, hops, vegetables, Cucurbits, tobacco, coffee, tea, rice, soybeans, peanuts, potatoes, sugar in a variety of crops, including icon, cotton, corn, ornamental flowers, mushrooms, and grasses , providing control of many fungal diseases.

[0023] In the compositions described herein, in protective applications, the fungicidal effect is achieved by Rhynchos Barley scald caused by porium secalis (RHYNSE) The concentration ratio of the mixture of compounds of formula I to the other fungicide that is synergistic with respect to It is within a range of approximately 1:64.

[0024] In the compositions described herein, in protective applications, the fungicidal effect is comparable to that of RHYNSE. The concentration ratio of the mixture of compounds of Formula I to the sterol biosynthesis inhibitor that is synergistic in terms of the amount of the compound is about 16 In one embodiment, in protective applications, the fungicidal effect is in the range of R Concentration ratios of the mixture of compounds of formula I to epoxiconazole that are synergistic against HYNSE In another embodiment, in a protective application, the fungicidal effect is The concentration ratio of the mixture of compounds of formula I to prothioconazole that is synergistic against SE is about It's 1:1.

[0025] In the compositions described herein, in protective applications, the fungicidal effect is comparable to that of RHYNSE. The concentration ratio of the mixture of compounds of formula I to the strobilurin fungicide that is synergistic is about 26 In one embodiment, in protective applications, the fungicidal effect is in the range of 1:1 to about 1:16. Mixtures of Compounds of Formula I Versus Azoxystrobin Concentrations That Are Synergistic Against RHYNSE The ratio is in the range of about 1:1 to about 1:16. In another embodiment, in protective applications: The fungicidal effect of the mixture of compounds of formula I is synergistic with RHYNSE vs. Pyraclost The concentration ratio of Robin is in the range of about 26:1 to about 1.6:1.

[0026] In the compositions described herein, in protective applications, the fungicidal effect is comparable to that of RHYNSE. The mixture of compounds of formula I and succinate dehydrogenase inhibitors (SDH1) is synergistic in ) is in the range of about 26:1 to about 1:1.3. In the present invention, the fungicidal effect of the mixture of compounds of formula I is synergistic with that of RHYNSE. The concentration ratio of ruxapyroxad is in the range of about 26:1 to about 6.5:1. In protective applications, the compound of formula I is synergistic in fungicidal effect to RHYNSE. The concentration ratio of the compound mixture to benzovindiflupyr is about 1:1.3.

[0027] In the compositions described herein, in protective applications, the fungicidal effect is comparable to that of RHYNSE. The concentration ratio of the mixture of compounds of Formula I to chlorothalonil fungicide that is synergistic is about 1: The range is 8 to approximately 1:64.

[0028] The rate at which the synergistic composition is applied will depend on the particular type of fungus being controlled, the amount of control required, and the amount of fungus being applied. The extent to which the effect of the ozone layer is reduced will depend on the timing and method of application. The composition of the present invention is applied at a rate of approximately 35 grams ( It can be applied at a rate of 1000g / ha to about 2600g / ha.

[0029] A composition comprising a compound of Formula I and a sterol biosynthesis inhibitor may be prepared by administering to a subject a therapeutically effective amount of the active ingredients in the composition. Based on the amount, it can be sprayed at a rate of about 60 g / ha to about 350 g / ha. The compound of formula I is applied at a rate of about 1.5 g / ha to about 250 g / ha. It is sprayed at a rate of 0g / ha to approximately 100g / ha. Prothioconazole is sprayed at a rate of approximately 50g / h. and the compound of formula I is applied at a rate of from about 10 g / ha to about 100 g / ha. It is sprayed at a rate of hectares.

[0030] Compositions containing a compound of formula I and a strobilurin fungicide may be prepared by adding a strobilurin fungicide to a composition containing the active ingredients in a proportion of 0.1 to 0.2% of the total active ingredients in the composition. Based on the amount, it can be sprayed at a rate of about 60 g / ha to about 475 g / ha. Trobin is applied at a rate of about 100 g / ha to about 375 g / ha, and the compound of formula I is applied at a rate of about It is sprayed at a rate of 10g / ha to 100g / ha. Pyraclostrobin is sprayed at a rate of about 50g / ha. The compound of formula I is applied at a rate of about 10 g / ha to about 100 g / ha. It is sprayed at a rate of / ha.

[0031] Compositions comprising a compound of Formula I and a carboxamide SDHI fungicide may be prepared by adding an active ingredient to the composition. Based on the total amount of ingredients, it can be sprayed at a rate of about 35 g / ha to about 400 g / ha. Ruxapyroxad is applied at a rate of about 45 g / ha to about 200 g / ha, and the compound of formula I is sprayed at a rate of about 10g / ha to about 100g / ha. The compound of formula I is applied at a rate of about 10 g / ha to about 300 g / ha. It is applied at a rate of 100g / ha.

[0032] A composition comprising a compound of Formula I and chlorothalonil may be used in an amount of about 100 mg / kg based on the total amount of active ingredients in the composition. It can be applied at a rate of about 1010g / ha to about 2600g / ha. The compound of formula I is applied at a rate of about 1000 g / ha to about 2500 g / ha. It is applied at a rate of 0g / ha to approximately 100g / ha.

[0033] The components of the synergistic mixtures described herein may be applied separately or together to form a multi-component fungicidal system. It may be dispersed as part of

[0034] The synergistic mixtures of the present disclosure may be applied in combination with one or more other fungicides to provide greater In combination with other fungicide(s), it can control undesirable diseases such as When used, the currently claimed compounds are formulated with other fungicide(s). Whether mixed with other fungicide(s), tank-mixed with other fungicide(s), or continuously mixed with other fungicide(s). Other such fungicides include 2-(thiocyanomethylthio)- Benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, Methoctrazine, Amisulbrom, Antimycin, Ampelomyces quis qualis, azaconazole, Bacillus subtilis, Bacillus S subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb- Isopropyl, benzylaminobenzene-sulfonic acid (BABS) salt, bicarbonate, biphenyl phenyl, bismerthiazole, bitertanol, bixafen, blasticidin-S, Borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide Captafol, Captan, Carbendazim, Carboxin, Carpropamid, Rubon, Clazafenone, Chloroneb, Chlozolinate, Coniothyrium m initans, copper hydroxide, copper octanoate, basic copper chloride, copper sulfate, copper sulfate (tribasic) , cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, Cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate) mate), dichlofluanid, dichlorophen, diclocymet, diclomedine, diclo Ran, Diethofencarb, Difenoconazole, Difenzoquat ion, Diflume Trim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, di Nobuton, Dinocap, Diphenylamine, Dipimetitron, Dithianon, Dodemorph , dodemorph acetate, dodine, dodine free base, edefenofos, enestrobin, Enestrobulin, ethaboxam, ethoxyquin, etridiazole, famoxadone, Fenamidon, fenarimol, fenbuconazole, fenfuram, fenhexamid , fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fen Pyrazamine, Fentin, Fentin Acetate, Fentin Hydroxide, Ferbam , Ferimzone, Fluazinam, Fludioxonil, Fluindapyr, Flumorph, Flu opicolide, Fluopyram, Fluorimide, Fluoxastrobin, Fluquinconazole, Flusila fluthiazole, flusulfamide, flutianil, flutolanil, flutriafol, folpet Formaldehyde, fosetyl, fosetyl-aluminum, fuberidazole, furalaki Sil, furametpyr, guazatine, guazatine acetate, GY-81, hexachlorobe Benzene, hexaconazole, hymexazole, imazalil, imazalil sulfate, Mibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine Lis (albesilate), iodocarb, ipconazole, ipfenpyrazolone, ip Robenfos, iprodione, iprovalicarb, isofetamide e), isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin Mancozeb hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mancozeb Dipropamide, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinoca Mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metalaxyl metham, metam-ammonium, metam-potassium, metam-sodium, metconazole, Metasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostro Bin, Metrafenone, Mildiomycin, Myclobutanil, Nabam, Nitrotar Isopropyl, Nuarimol, Octilinone, Ofrace, Oleic acid (fatty acid), Orisa Strobin, oxadixyl, oxathiapiprolin, oxine-copper, oxpoconazo Fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, Penflufen, pentachlorophenol, pentachlorophenyl laurate, penthio Pyrado, phenylmercuric acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, Polyoxin, Polyoxorim, Potassium Bicarbonate, Potassium Hydroxyquinoline Propylene glycol, Probenazole, Prochlorazide, Procymidone, Propamocarb, Propamo Carbene hydrochloride, propiconazole, propineb, proquinazid, pydiflumetofen, Lametostribin, pyraoxystrobin, pyraziflumide, pyrazophos, pyribencal p, pyributicarb, pyrifenox, pyrimethanil, pyriophenone, pyroquilon, Quinoclamine, quinoxyfen, quintozene, Reynoutria sachalin ensis extract, sedaxane, fenaminosulf, simeconazole, sodium 2-fluoride Phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spin Loxamine, sulfur, SYP-Z048, tar oil, tebuconazole, tebufloquine, tech Nazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl , thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, Riadimenol, triazoxide, tricyclazole, tridemorph, trifloxyst Robin, Triflumizole, Triforine, Triticonazole, Validamycin, Valife Nalate, Valifenal, Vinclozolin, Zineb, Ziram, Zoxamide, Candi da oleophila, Fusarium oxysporum, Glioclad ium spp., Phlebiopsis gigantea, Streptomyc es griseoviridis, Trichoderma spp., (RS)-N -(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2- Dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate , 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-( 2-Heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5- Phenyl-1,4-dithi-in 1,1,4,4-tetraoxide, 2-methoxyethyl ester Silver acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate , 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-ene Nyl)phenylthiocyanate, aminopyrifen, ampropylphos, anilazine, Dithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, ben Talon, Benzamacryl; Benzamacryl-isobutyl, Benzamorph, Binapacryl , Bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, Domium Calcium Copper Zinc Chromate Sulfate, Carbamorph, CECA, Clobene Thiazone, chloraniformethane, chlorphenazole, chlorquinox, and clinbazo Copper bis(3-phenylsalicylate), copper zinc chromate, chlorine, copper hydride Razinium sulfate, cuprobam, cyclafuramide, cypendazole, ciproflam , Decafentin, Diclobenthiazox, Dicloron, Diclozolin, Diclobutrazo Dimethirimol, Dinoctone, Dinosulfone, Dinotervone, Dipyrithione, Dithalithion Muhos, Dodisin, Drazoxolone, EBP, ESBP, Etaconazole, Etem, Ethi Rim, Fenaminosulf, Fenapanil, Fenitropan, Fluindapir, Fluopimo mido, fluotrimazole, flucarbanil, fluconazole, fluconazole-cis, Flumecyclox, Furofanate, Gliodin, Griseofulvin, Halacrinate , Hercules3944, Hexylthiophos, ICIA0858, Inpirfluxa Ipfentrifluconazole, Ipflufenoquin, Isoflucipram, Isopam Phos, isovaleion, mandestrobin, mebenil, mecarbinzide, mefentrif Luconazole, metazoxolone, metofloxam, methylmercuric dicyandiamide, Metos Lufobax, Methyltetraprole, Milneb, Mucochloric Acid Anhydride, Microzol N-3,5-dichlorophenyl succinimide, N-3-nitrophenyl itacone Imide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel Rubis (dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate nitrate, phenylmercury nitrate, phosdifen, prothiocarb; prothiocarb hydrochloride Salt, Picarburazox, Pydiflumetofen, Pyracarbollide, Pyrapropoin, Pi Lidaclomethyl, pyridinnitrile, pyroxchlor, pyroxyflur, quinacetol; cinchona Cetol sulfate, quinazamide, quinconazole, quinofumelin, rabenzazole, Salicylanilide, SSF-109, Sultropene, Tecoram, Thiazifluor, Thiothio Fen, thiochlorfenfim, thiophanate, tinoquinox, tiooximide, thiamine Riamifos, triarimol, triazbutyl, trichlamide, urvacid, zaliramide, and any combination thereof.

[0035] The compositions of the present disclosure preferably comprise: (a) a compound of formula I; and (b) epoxiconazole. Prothioconazole, azoxystrobin, pyraclostrobin, fluxapyroxad, at least one selected from the group consisting of benzovindiflupyr, and chlorothalonil; The composition of the fungicide and the fungicide is prepared by adding the fungicide to a phytologically acceptable carrier. It is sprayed in the form of a formulation containing the substance.

[0036] The concentrated formulation may be dispersed in water or another liquid for application, and the formulation may be further The formulation may be dust-like or granular, which can be spread without further treatment. Although conventional in the art, the presence of synergistic compositions therein makes them novel and important. It is prepared according to the essential procedures.

[0037] The most frequently applied formulations are aqueous suspensions or emulsions. Water-suspendable or emulsifiable formulations are solid or emulsifiable concentrates commonly known as wettable powders. The liquid is commonly known as a concentrate, aqueous suspension, or aqueous concentrate. Any vehicle in which the synergistic composition may be formulated for delivery and use as a fungicide. The plan is to:

[0038] As will be readily appreciated, any material to which these synergistic compositions may be added may be used. provided that they are in agreement with the activity of these synergistic compositions as antifungals. Provided that it provides the desired utility without significantly interfering.

[0039] The wettable powder may be compressed to form water dispersible granules, and the synergistic composition and the carrier and an agriculturally acceptable surfactant. The concentration is typically about 10% to about 90% by weight, more preferably about 10% to about 90% by weight, based on the total weight of the formulation. In preparing wettable powder formulations, the synergistic composition is , prophyllite, talc, chalk, gypsum, fuller's earth, tonite, attapulgite, starch, casein, gluten, montmorillonite clay The cellulose may be combined with either finely divided solids such as silicate, diatomaceous earth, or purified silicates. In a typical procedure, the finely divided carrier is milled or mixed with the synergistic composition in a volatile organic solvent. The effective surfactants, which make up about 0.5% to about 10% by weight of the wettable powder, include: Sulfonated lignin, naphthalene sulfonate, alkylbenzene sulfonate, alkyl sulfuric acid, and nonionic surfactants (ethylene oxide of alkylphenols) Additions, etc.

[0040] The emulsifiable concentrate of the synergistic composition may be prepared by mixing the following: Constituents of synergistic compositions include those having convenient concentrations such as about 10% to about 50% by weight in total. are dissolved together or separately in a carrier, which may be a water-miscible or water-immiscible solvent. The concentrate is diluted with water and oil to form a mixture of water-soluble organic solvents and emulsifiers. The spray mixture may be formed in the form of an oil emulsion. Useful organic solvents include aromatic, especially petroleum, It includes the high-boiling naphthalenic and olefinic portions of the oil (such as heavy aromatic naphtha). For example, terpene solvents (including rosin derivatives), aliphatic ketones (cyclohexanone, etc.) Other organic solvents, such as ethanol, ethanol, and complex alcohols (e.g., 2-ethoxyethanol), can also be used. It can be used.

[0041] Emulsifiers that may be advantageously used herein can be readily determined by one skilled in the art, They include a variety of nonionic, anionic, cationic, and amphoteric emulsifiers, or Blends of two or more emulsifiers are included. Nonionic emulsifiers useful in preparing emulsifiable concentrates Examples of emulsifiers include polyalkylene glycol ethers, and alkyl and aryl Phenol, fatty alcohol, fatty amine, or fatty acid with ethylene oxide, propanediol, Propylene oxide (such as ethoxylated alkylphenols), and polyols or poly Condensation products of carboxylic acid esters solubilized with oxyalkylenes are included. Anionic emulsifiers include quaternary ammonium compounds and fatty amine salts. Emulsifiers include oil-soluble salts of alkylaryl sulfonic acids (e.g., calcium), phosphate Oil-soluble salts of polyglycol ethers or sulfated polyglycol ethers and suitable salts Includes:

[0042] Representative organic liquids that may be used in preparing the emulsifiable concentrates of the present disclosure include aromatic liquids ( xylene, propylbenzene fraction, or mixed naphthalene fraction), mineral oil, substituted aromatics Aromatic organic liquids (such as dioctyl phthalate), kerosene, dialkylamides of various fatty acids, especially Dimethylamides of aliphatic glycols and glycol derivatives (diethylene glycol -butyl ether, ethyl ether, or methyl ether, and triethylene glycol Mixtures of two or more organic liquids are also often Suitable for use in preparing emulsifiable concentrates. Preferred organic liquids are xylene and propane. The most preferred are the pyrobenzene fraction and xylene. In the composition, it is used in an amount of 0.1 to 20 weight percent of the total weight of the dispersant and the synergistic composition. The formulation may also contain other compatible additives, such as plant growth regulators and agricultural It may also contain other biologically active compounds that are used.

[0043] The aqueous suspension may be present in an amount ranging from about 5% to about 70% by weight based on the total weight of the aqueous suspension formulation. The present invention includes a suspension of one or more water-insoluble compounds dispersed in an aqueous vehicle at a concentration within the range of 1000 ppm. The suspension is prepared by finely grinding the components of the synergistic combination either together or separately. and a binder composed of water and a surfactant selected from the same types discussed above. It is prepared by vigorously mixing the ground material into the vehicle. or by adding other ingredients such as natural gums to increase the density and viscosity of the aqueous vehicle. In many cases, an aqueous mixture is prepared and then milled in a sand mill, ball mill, or pit mill. Simultaneous grinding and mixing can be achieved by homogenizing in a device such as a ton homogenizer. It is most effective to combine

[0044] The synergistic composition can also be applied as a granular formulation, which can be applied to the soil. Granular formulations are typically composed entirely or predominantly of coarsely ground attapulgite, Granules dispersed in a carrier of bentonite, diatomaceous earth, clay, or similar inexpensive material The compound is contained in an amount of about 0.5% by weight to about 10% by weight based on the total weight of the granule formulation. Such formulations are typically prepared by dissolving the synergistic composition in a suitable solvent and dissolving it in a solvent containing from about 0.5 to about 100% water. Spread onto a granular carrier preformed to a suitable particle size within the 3 millimeter (mm) range Such formulations may also be prepared by mixing the carrier and the synergistic composition. Also prepared by making a paste, milling to obtain the desired granule size, and drying. It is possible.

[0045] The dust containing the synergistic composition may be applied by dissolving the synergistic composition in powder form in a suitable dust-like agricultural Prepared by homogeneously mixing with a carrier (e.g., kaolin clay and crushed volcanic rock) The dust preferably contains from about 1% to about 10% by weight of the synergistic composition / carrier combination. It can be contained in.

[0046] The formulation enhances deposition, wetting, and penetration of the synergistic composition into target crops and organisms. These adjuvants may also contain agriculturally acceptable surfactants for the purpose of The bunt surfactant may optionally be used as a component of the formulation or as a tank mix. The amount of adjuvant surfactant is less than 0.01 percent based on the spray volume of water. to 1.0 percent volume / volume (v / v), preferably 0.05 to 0.5 percent Suitable adjuvant surfactants include ethoxylated nonylphenol, ethoxylated nonylphenol, of ethoxylated synthetic alcohols or ethoxylated natural alcohols, esters or sulfosuccinic acids Salt, ethoxylated organosilicon, ethoxylated fatty amine, and surfactant with mineral oil or Including, but not limited to, blends with vegetable oils.

[0047] The formulation optionally contains at least 1% by weight of one or more of the synergistic compositions in combination with another antibacterial agent. Such additional insecticidal compounds may be included in combination with the insecticidal compounds. are compatible with the synergistic composition of the present disclosure in the medium selected for application and Does not antagonize the activity of the compound, fungicide, insecticide, nematicide, acaricide, arthropodicide, bactericide In such embodiments, other The insecticidal compound may be a complementary toxin for such an embodiment or for a different insecticidal application. Insecticidal compounds and synergistic compositions are generally used in a ratio of 1:100 to 100: They can be mixed together in a weight ratio of 1:1.

[0048] The present disclosure includes within its scope methods for controlling or preventing fungal attack. The method involves applying the fungus to the site or sites to be prevented from infestation (e.g., wheat or barley). The method comprises applying a fungicidally effective amount of the synergistic composition to the plant (spraying the plant). The composition is suitable for treating a variety of plants at fungicidal levels while exhibiting low phytotoxicity. The synergistic composition is useful in a protective or repellent manner. as a composition or as a formulation, including synergistic compositions, by any of a variety of known techniques. For example, the synergistic composition may be applied to the roots, seeds, or leaves of a plant. A variety of fungi can be controlled without damaging the commercial value of the plant. The composition may be in the form of any of the commonly used formulation types, for example, a solution, a dust, They are applied as wettable powders, flowable concentrates, or emulsifiable concentrates. It is conveniently dispersed in a known manner.

[0049] The synergistic composition has been found to have significant fungicidal efficacy, particularly for agricultural applications. The synergistic compositions are used with agricultural crops and horticultural plants, or in the treatment of wood, paints, leather, It is particularly useful for use with carpet backing.

[0050] Specifically, the synergistic composition combats a variety of undesirable fungi that infect useful plant crops. The synergistic compositions are effective in controlling, for example, the following representative fungal species: barley Rhynchosporium secalis; Barley Ramula ria spot disease (Ramularia collo-cygni); barley web spot disease (Py renophora teres); Barley powdery mildew (Blumeria gram inis f.sp.hordei); wheat powdery mildew (Blumeria gram inis f.sp.tritici); wheat leaf rust (Puccinia tritici) icina); wheat stripe rust (Puccinia striiformis); wheat Leaf blight (Zymoseptoria tritici); Wheat blight (Parasta) gonospora nodorum; sugar beet leaf spot (Cercospora beticola); Peanut spot disease (Mycosphaerella arachchii) idis); Cucumber anthracnose (Colletotrichum lagenarium) ; Cucumber powdery mildew (Erysiphe cichoracearum); Watermelon vine blight (Didymella bryoniae); apple scab (Venturia i naequalis); Apple powdery mildew (Podosphaera leucotri cha); Botrytis cinerea; Sclerotinia rot inia sclerotiorum); Grape powdery mildew (Erysiphe nec ator); Tomato summer blight (Alternaria solani); Rice blast (P yricularia oryzae); stone fruit brown rot (Monilinia fr ucticola) and banana black Sigatoka disease (Mycosphaerella fij Various Ascomycetes and Basidiomycetes, including Bacillus iensis It can be used against fungi. Synergistic compositions against one or more of the aforementioned fungi. The effectiveness of the compounds establishes the general usefulness of synergistic compositions as fungicides. will be understood by the traders.

[0051] The synergistic composition has broad-spectrum effectiveness as a fungicide. The exact amount will depend on the relative amounts of the components as well as the particular effect desired, the fungal species to be controlled, and the and their developmental stages, as well as plants or other products that are contacted with the synergistic composition. Therefore, formulations containing synergistic compositions may be may not be equally effective against different fungal species, or even against the same fungal species.

[0052] The synergistic compositions inhibit disease and are used in conjunction with plants in botanically acceptable amounts. The term "disease-inhibiting, botanically acceptable amount" refers to the amount of the plant for which control is desired. Synergistic compounds that kill or inhibit the disease of the target plant without significant toxicity to the plant. The exact concentration of the synergistic composition required will depend on the fungal disease being controlled. These vary with the type of plant damage, the type of formulation used, the method of application, the specific plant species, and the climatic conditions. Move.

[0053] The compositions can be applied by using conventional surface sprayers, spreaders, and by any method known to those skilled in the art. The fungi or their loci can be sprayed with the agent by other conventional means, such as by spraying with water or by spraying with water.

[0054] The following examples are provided for illustrative purposes and should not be construed as limitations on the present disclosure. isn't it. [Example]

[0055] Fungicide mixtures versus barley scald (Rhynchosporium secalis; Evaluation of the protective activity of (Bayer code: RHYNSE):

[0056] Barley seedlings (Harrington variety) were grown in a soil-free Metro mix Each pot contained 8-12 plants, and the test was started when the first leaves fully emerged. The treatments used were the fungicidal compounds epoxiconazole and prothioconazole. , Azoxystrobin, Pyraclostrobin, Benzovindiflupyr, Fluxapyroxa and chlorothalonil, either individually or as a binary mixture with the compound of formula I. This began with the following:

[0057] The compounds were tested as technical grade materials formulated in acetone and the spray solution was 10% The fungicide solution contained acetone and 100 ppm Triton X-100. Plants are sprayed using an automated booth sprayer that is designed to cover both leaf surfaces. 6218 operating at 20 pounds per square inch (psi) with opposing angles set as shown. Two 1 / 4" JAUPM spray nozzles were used. All sprayed plants were screened for further handling. Control plants were sprayed in the same manner with a blank solvent.

[0058] One day after fungicide treatment (1-day protection test), the test plants were inoculated with Rhyncosporium After inoculation, the plants were kept at 100% relative humidity for 2 days. The plants were then kept for 1 day to allow the spores to germinate and infect the leaves. After that, the plants were moved to a greenhouse and the disease was investigated. When the disease was fully developed on the untreated plants, the disease severity on the first leaves of the seedlings was calculated as The results were assessed by the percentage of leaf area free of RHYNSE infection compared to untreated plants. The activity was expressed as follows.

[0059] The Colby equation was used to determine the expected fungicidal effect of the mixture. by,SRCalculation of the synergistic an d antagonistic response of herbicide com (See binations. Weeds 1967, 15, 20-22.)

[0060] Use the following equation to calculate the predicted activity of a mixture containing two active ingredients, A and B: Calculated. Predicted value = A + B - (A × B / 100) A = observed efficacy of active ingredient A at the same concentration as used in the mixture; B = observed efficacy of active ingredient B at the same concentration as used in the mixture.

[0061] Synergistic interactions between Compound I and other fungicides provide protection against RHYNSE (Table 1). was detected in the assay. [Table 1]

Claims

1. 1. A synergistic fungicidal mixture comprising: a fungicidally effective amount of a compound of formula I, (S)-1,1-bis(4-fluorophenyl)propanol; Ben-2-yl(3-acetoxy-4-methoxypicolinoyl)-L-alaninate: 【Chemical 1】 and a compound selected from the group consisting of a sterol biosynthesis inhibitor, a respiratory inhibitor, and a multi-site action inhibitor. and at least one additional fungicide.

2. The sterol biosynthesis inhibitor (SBI) is selected from the group consisting of epoxiconazole and prothioconazole.

2. The mixture of claim 1, wherein the mixture is selected from the group consisting of:

3. 3. The method of claim 2, wherein the concentration ratio of the compound of formula I to epoxiconazole is about 16:

1. The mixture is as follows.

4. 3. The method of claim 2, wherein the concentration ratio of the compound of formula I to prothioconazole is about 1:

1. A mixture of.

5. The respiratory inhibitor is selected from the group consisting of azoxystrobin and pyraclostrobin.

2. The mixture of claim 1 ,

6. wherein the concentration ratio of the compound of formula I to azoxystrobin is from about 1:1 to about 1:

16.

6. The mixture according to claim 5.

7. the concentration ratio of said compound of formula I to pyraclostrobin is from about 26:1 to about 1.6:1; 6. The mixture according to claim 5.

8. The respiratory inhibitor is selected from the group consisting of fluxapyroxad and benzovindiflupyr.

2. The mixture of claim 1, wherein

9. the concentration ratio of said compound of formula I to fluxapyroxad is from about 26:1 to about 6.5:1; 9. The mixture according to claim 8.

10. 9. The concentration ratio of the compound of formula I to benzovindiflupyr is about 1:1.

3. The mixture according to claim 1.

11. 2. The mixture of claim 1, wherein the multi-site inhibitor is chlorothalonil.

12. A concentration ratio of the compound of formula I to chlorothalonil is from about 1:8 to about 1:

64.

12. The mixture according to claim 11.

13. The mixture provides control of a fungal pathogen, the pathogen causing barley scald (R The mixture according to claims 1 to 12, wherein the plant is hynchosporium secalis. 。

14. A method comprising: applying a fungicidally effective amount of the mixture of claims 1 to 12 to a plant; and applying the mixture ... , a synergistic fungicidal composition.

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