Synergistic fungicidial mixtures for fungal control in cereals

Description of the invention

Field of the Invention

The present invention relates to a synergistic fungicidal composition comprising (a) a compound of formula I, II, III, IV or V and (b) at least one fungicide selected from the group consisting of azoxystrobin and pyraclostrobin.

Background of the invention

[0002] Fungicides are compounds of natural or synthetic origin which serve to protect plants against damage caused by fungi. Current agricultural methods rely heavily on the use of fungicides. In fact, some plants cannot benefit from being cultivated without the use of fungicides. The use of fungicides allows the grower to increase the yield and quality of the crop, and thus increase the value of the crop. In most cases, the increase in yield value is worth at least three times the cost of applying a fungicide.

[0003] However, no fungicide is useful in all situations and the repeated use of one fungicide often leads to the development of resistance to this and related fungicides. Consequently, research is underway to produce fungicides and combinations of fungicides that are safer, have better results, require lower dosages, are easier to handle and cost less.

[0004] Synergism occurs when the activity of two or more compounds exceeds that of the compounds when used alone. Synergistic mixtures of picolinamides and a second compound selected from, inter alia, epoxiconazole, are described in an anonymous article titled Synergistic Fungicidal Compositions of Heterocyclic Aromatic Amides and Triazoles, published on IP.COM on July 20, 2004.

[0005] Fungicidal mixtures of picolinamides with an additional compound selected, inter alia, from azoxystrobin, are described in an anonymous publication entitled Fungicidal Mixtures, published on IP.COM on July 5, 2005.

Summary of the invention

[0006] It is an object of the present invention to provide a synergistic composition containing fungicidal compounds. It is a further object of the present invention to provide methods in which these synergistic compositions are used. The synergistic compositions are capable of preventing or treating either or both diseases caused by fungi of the Ascomycetes and Basidiomycetes classes. In addition, the synergistic compositions have improved efficacy against Ascomycete and Basidiomycete pathogens, including leaf blotch and wheat brown rust. In accordance with the present invention, synergistic compositions are provided together with methods for using them.

Detailed description of the invention

[0007] The present invention relates to a synergistic fungicidal mixture comprising a fungicidally effective amount of (a) a compound of formula I, II, III, IV or V, and (b) at least one fungicide selected from the group consisting of zazoxystrobin and pyraclostrobin.

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[0008] Azoxystrobin is the common name for methyl (aE) -2 - [[6-phenoxyocarboxamid- (2-cyanophenoxy) -4-pyrimidinyl] oxy] - (methoxymethylene) benzeneacetate. Its fungicidal activity is described in The Pesticide Manual, 14th edition, 2006. Azoxystrobin provides control of a wide range of pathogens at application rates ranging between 100 and 375 grams / hectare (g / ha).

[0009] Pyraclostrobin is the common name of methyl [2 - [[[1- (4-chlorophenyl) -oxy-1 / - / - pyrazol-3-yl] oxy] methyl] phenyl] methoxycarbamate. Its fungicidal activity is described in The Pesticide Manual, 14th edition, 2006. Piraclostrobin provides control of most cereal pathogens such as Septoria tritici, Puccinia spp., Drechslera tritici-repentis and Pyrenophora teres.

[0010] In the composition of the present invention, the weight ratio of compounds of Formula IV to azoxystrobin at which the fungicidal effect is synergistic ranges between about 1:10 to about 10: 1. The weight ratio of compounds of Formula IV to pyraclostrobin, with wherein the fungicidal effect is synergistic, ranges between about 1:10 to about 10: 1.

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[0011] The rate at which the synergistic composition is applied will depend on the particular type of fungus to be controlled, the degree of control required and the time and method of application. In general, the composition of the invention can be applied at an application rate in the range of about 65 grams per hectare (g / ha) and about 2300 g / ha based on the total amount of active ingredients in the composition. Azoxystrobin is applied in an amount in the range of about 50 g / ha and about 250 g / ha and the compound of formula IV is applied in an amount in the range of about 35 g / ha and about 300 g / ha. Pyraclostrobin is used in the range of about 50 g / ha and about 250 g / ha and the compound of formula IV is used in an amount in the range of about 35 g / ha and about 300 g / ha.

[0012] The components of the synergistic mixture according to the invention can be used alone or as part of a multipart fungicidal system.

[0013] The synergistic mixture of the present disclosure can also be used in conjunction with other fungicides to control a wider range of undesirable diseases. When used in combination with other fungicide (s), the compounds currently claimed may be formulated with other fungicide (s), tank mixed with another (s) fungicide (s), or be applied sequentially with other fungicide (s). Such other fungicides may include 2- (thiocyanatomethylthio) -benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus Qtus subtilis, benalarbal-bibalST713, strain-benbalbillus, isopropyl, benzylaminobenzene sulfonate (BABS) salt, bicarbonates, biphenyl, bismertiazole, bitertanol, bixaphene, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamide, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyfljaufenofamide , cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, ethylenebis- (dithiocarbamate) diammonium, dichlofluanid, dichlorophen, diclocymet, diclomezin, dichlorane, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenfos, enestrobin, epoxyconazole, etridiazole, etridiazole, etaboxadiazole fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluchinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-guinea, fuberidazole, furalachlorexyl, hexazenatine, Hexacetin, Hetazenatine Hexasolate , hymexazole, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris (albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isothianil, kasugamycin, kasugamycin hydrochloride hydrate, cresoxim-methyl, laminarin, mancoper, mancozeb, mandipropamide, maneb, mefenoxam, mepanipyrim, mepronil, meptyl dinocap, mercuric chloride, mercuric chloride, mercuric chloride, metal oxide , metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, metasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrotal-isopropyl, nuarimol octylinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, Cu-oxin, oxopo fumarate

EP-2904901B1PL of conazole, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercuric acetate, phosphonic acid, phthalide, picoxystrobin, polyoxychlorimoxin Bachoxin, polyoxychlorinate, polyoxychlorimine procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazide, prothioconazole, pyraclostrobin, pyrazostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyribenicarb, pyrifenox, pyrimethanil, pyriophenone, pyroquilone, quinoclamine, quinoxifene, chintozen, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium sulfurophenolate, pentachlorophenolate, pentachlorophenolate, pentachlorophenolate. tebuconazole, tebufloquine, tecnazene, tetraconazole, thiabendazole, tifluzamide, thiophanatmethyl, thiram, tiadinil, tolclophos-methyl, tolylfluanid, triadimhephon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforina, triticonazole, validamycin, valiphenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsisida-gigesa. 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-dithiin, 1,1,4,4-tetroxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercuric chloride, 2-methoxyethylmercury silicate, 3- (4-chlorophenyl) -5-methyl rhodanine , 4- (2-nitroprop-1-enyl) phenylthiocyanate, ampropylphos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benchinox, bentaluron, benzamacryl; benzamacryl-isobutyl, benzamorph, binapacryl, bis (methylmercury) sulfate, bis (tributyltin) oxide, butiobate, cadmium, calcium, copper, zinc chromate sulfate, carbamorph, CECA, chlobentiazone, chloraniformethane, chlorphenazole, chlorquinox, climbazole, -phenylsalicylate) copper, zinc copper chromate, kufraneb, copper hydrazinium sulphate, cuprobam, cyclafuramide, cypendazole, ciprofuram, decafentin, dichlone, dichlozoline, diclobutrazole, dimethirimol, dinoctone, dinosulfon, dinoterbon, dipyrion, ditalimfos, dodicin, drazoxolone, EBP, ESBP, etaconazole, etem, etirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furofanate, glyodine, Herthexyofulvin, griseopryofulvin, griseopryofulvin, griseofulvin , isovaledione, mebenil, mecarbinside, metazoxolone, metfuroxam, methyl copper dicyandiamide, metsulfovax, milneb, mucochloric acid anhydride, myclozoline, N-3,5-dichlorophenyl succinimide, Ν-3-nitrophenyl itaconimide, natamycin, N-ethylmercury-4-toluenesulfonanilide, nickel bis (dimethyldithiocarbamate), OCH, phenylmercuric dimethyldithiocarbamate, phenylmercuric nitrate, phosdiphene, prothiocarb; prothiocarb hydrochloride, piracarbolide, pyridinitrile, pyroxychlor, pyroxifur, quinacetol; quinacetol sulfate, quinazamide, quinkonazole, rabenzazole, salicylanilide, SSF-109, sultropene, tekoram, thiadifluor, thicofen, thiochlorphenphim, thiophanate, thiquinox, thioximide, triamphos, triarimol, trlamidilate, triamidil, or any of the ichthybutil.

[0014] The compositions of the present invention are preferably used in the form of a formulation comprising a composition (a) of a compound of formula I (b) at least one fungicide selected from the group consisting of azoxystrobin and pyraclostrobin together with a phytologically acceptable carrier.

[0015] The concentrated application formulation may be dispersed in water or other liquid, or the formulation may be dust-like or granulated, and such formulations may be applied without further processing. The formulation is prepared according to procedures which are conventional in the field of agricultural chemistry but which are new and important due to the synergistic composition present therein.

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[0016] The formulations most frequently used are aqueous suspensions or emulsions. The water-soluble, water-suspendable or emulsifiable formulations are solids, usually known as wettable powders, or liquids, usually known as emulsifiable concentrates, aqueous suspensions or suspension concentrates. The present invention includes all carriers with which synergistic compositions can be formulated for delivery and use as a fungicide.

[0017] As can be readily appreciated, any substance to which the synergistic compositions are added may be used as long as they give the desired utility without significantly interfering with the activity of these synergistic compositions as antifungal agents.

[0018] Wettable powders that can be compressed to produce water-dispersible granules include the intimate mixture of the synergistic composition, carrier, and agriculturally acceptable surfactants. The concentration of the synergistic composition in the wettable powder is typically from about 10% to about 90% by weight, more preferably from about 25% to about 75% by weight, based on the total weight of the formulation. In preparing wettable powder formulations, the synergistic composition can be mixed with any of the finely divided solids such as profylite, talc, chalk, gypsum, Fuller earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier is ground or mixed with the synergistic composition in a volatile organic solvent. Effective surfactants from about 0.5% to about 10% by weight of the wettable powder include sulfonated lignins, naphthalenesulfonates, alkylbenzene sulfonates, alkyl sulfates, and nonionic surfactants such as ethylene oxide and alkyl phenol adducts.

[0019] The emulsifiable concentrates of the synergistic composition contain a suitable concentration of the compounds, such as from about 10% to about 50% by weight, in a suitable liquid, based on the total weight of the emulsifiable concentrate formulation. The ingredients of the synergistic composition, together or separately, are dissolved in an inert carrier which is a water-miscible solvent or a mixture of water-immiscible organic solvents and emulsifiers. The concentrates may be diluted with water and oil to prepare spray mixtures as oil-in-water emulsions. Useful organic solvents include aromatic solvents, especially high boiling naphthalene and olefinic petroleum stocks such as naphtha. Other organic solvents, such as, for example, terpene solvents, including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol, can also be used.

[0020] The emulsifiers which can advantageously be used in the present invention can be readily determined by one skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers or mixtures of two or more emulsifiers. Examples of nonionic emulsifiers useful in the preparation of emulsifiable concentrates include polyalkylene glycol polyethers and condensation products of alkyl aryl phenols, aliphatic alcohols, aliphatic amines, or fatty acids with ethylene oxide, propylene oxides such as ethoxylated alkyl phenols and polyol or polyoxyalkylene solubilized carboxyl esters. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts (e.g., calcium) of alkylarylsulfonic acids, oil-soluble salts or sulfated polyglycol ethers, and the corresponding phosphated polyglycol ether salts.

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[0021] Representative organic liquids that can be used to prepare the emulsifiable concentrates of the present invention are aromatic liquids such as xylene, propylbenzene fractions or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerozsn; dialkylamides of various fatty acids, in particular dimethylamides of fatty glycols and glycol derivatives, such as n-butyl ether, diethyl ether or diethylene glycol methyl ether and triethylene glycol methyl ether. Mixtures of two or more organic liquids are often suitably also used to prepare emulsifiable concentrates. The preferred organic liquids are xylene and propylbenzene fractions, with xylene being most preferred. In liquid formulations, surface-active dispersants are typically used in an amount of from 0.1 to 20 percent by weight of the total weight of the dispersant with the synergistic compositions. The formulations may also contain other compatible additives, for example plant growth regulators and other biologically active compounds used in agriculture.

[0022] Aqueous suspensions include suspensions of one or more water-insoluble compounds dispersed in an aqueous carrier at a concentration ranging from about 5% to about 70% by weight based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding the ingredients of the synergistic combination together or separately and vigorously mixing the ground material in a vehicle consisting of water and surfactants selected from the same types as discussed above. Other ingredients, such as inorganic salts and synthetic or natural gums, can also be added to increase the density and viscosity of the aqueous carrier. Often times, it is most effective to grind and mix at the same time by preparing the aqueous mixture and homogenizing it in an apparatus such as a sand mill, ball mill, or piston type homogenizer.

[0023] The synergistic composition can also be used as a granular formulation which is particularly useful for application to soil. Granular formulations typically contain from about 0.5% to about 10% by weight of the compounds based on the total weight of the granular formulation dispersed in a carrier which consists entirely or largely of coarsely divided attapulgite, bentonite, diatomite, clay or similar inexpensive substance . Such formulations are typically prepared by dissolving the synergistic composition in a suitable solvent and applying it to a granular carrier that has been preformulated to a suitable particle size in the range of about 0.5 to about 3 mm. Such formulations can also be prepared by preparing a dough or paste from the carrier and synergistic composition, and grinding and drying to obtain the desired granular particles.

[0024] Dusts containing the synergistic composition can be simply prepared by intimately mixing the synergistic composition in powdered form with a suitable dusty agricultural carrier such as, for example, kaolin clay, crushed volcanic rock, and the like. Dusts may suitably contain from about 1% to about 10% by weight of the synergistic composition / carrier combination.

[0025] The formulations may contain agriculturally acceptable adjuvant surfactants to enhance deposition, wetting, and penetration of the synergistic composition in the target crop or organism. Such adjuvant surfactants can optionally be used as a formulation ingredient or as a tank mixture. The amount of adjuvant surfactant will be in the range of

In the range of 0.01 to 1.0 percent volume / volume (v / v) based on the volume of water sprayed, preferably 0.05 to 0.5 percent. Suitable adjuvant surfactants include, but are not limited to, ethoxylated nonylphenols, ethoxylated synthetic or natural alcohols, salts of esters or sulfosuccinic acids, ethoxylated organosilicon compounds, ethoxylated fatty amines, and blends of surfactants with mineral or vegetable oils.

[0026] The formulations can optionally be combinations that comprise at least 1% by weight of one or more synergistic compositions with another pesticidal compound. Such additional pesticide compounds may be fungicides, insecticides, acaricides, nematicides, bactericides, arthropodicides, or combinations thereof, which are compatible with the synergistic compositions of the present invention in the medium selected for use and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments of the invention, another pesticidal compound is used as a complementary toxic substance for the same or a different pesticidal application. The pesticidal compound and the synergistic composition can generally be mixed together in a weight ratio of from 1: 100 to 100: 1.

[0027] The present invention includes within its scope methods of combating or preventing attack of fungi. These methods include applying to the site of the fungus or to the site where it is intended to prevent infestation of the fungus (e.g., application to wheat or barley plants) a fungicidally effective amount of the synergistic composition. The synergistic composition is suitable for treating various plants in fungicidal amounts and at the same time has low phytotoxicity. The synergistic composition may be useful in either a protective or a debilitating mode. The synergistic composition is applied by any of a variety of known techniques, either as a synergistic composition or as a formulation including a synergistic composition. For example, the synergistic composition can be applied to the roots, seeds, or foliage of plants to control various fungi without destroying the commercial value of the plants. The synergistic composition is applied in the form of any of the generally used formulation types, for example solutions, dusts, wettable powders, liquid concentrates or emulsifiable concentrates. These substances are preferably used in a variety of known ways.

[0028] The synergistic composition has been found to have significant fungicidal activity, in particular in agricultural applications. The synergistic composition is particularly useful for use in agricultural and horticultural crops or for wood, paint, leather or carpet backing.

[0029] In particular, the synergistic composition is effective in controlling various undesirable fungi that infect crops of useful plants. The synergistic composition can be applied to a wide variety of Ascomyceteand Basidiomycete fungi, including, for example, the following representative fungal species: wheat brown rust (Puccinia recondita · Bayer code PUCCRT); wheat yellow rust (Puccinia striiformis ·, Bayer code PUCCST); wheat leaf spot (Mycosphaerella graminicola ·, anamorph: Septoria tritici; Bayer code SEPTTR); wheat chaff blotch (Leptosphaeria nodorunr, Bayer code LEPTNO; anamoda. Stagonospora nodorurriy, barley blotch (Cochliobolus sativum; Bayer code COCHSA; anamorph: Helminthosporium sativumy sugar beet blotch (Cercospora beticola, Bayer code CERCBE); brown peanut blotch (codla Bayer7A arachosphaerel)

EP-2,904,901B1PL morph: Cercospora arachidicola); cucumber anthracnose (Glomerella lagenarium; anamorph: Colletotrichum lagenarium ·, Bayer code COLLLA) and banana leaf black spot (Mycosphaerella fijiensis ·, Bayer code MYCOFI).

It will be understood by those skilled in the art that the efficacy of the synergistic composition against one or more of the above-mentioned fungi demonstrates the general utility of the synergistic compositions as fungicides.

[0030] The synergistic composition has a wide range of efficacy as a fungicide. The exact amount of the synergistic composition to be used depends not only on the relative amounts of the ingredients, but also on the particular action desired, the species of fungi to be controlled and their stage of development, as well as the parts of the plant or other product to be brought into contact with the composition. synergistic. Thus, formulations containing the synergistic composition may not be as effective at similar concentrations or against the same species of fungi.

[0031] The synergistic composition is effective when used with plants in a disease-inhibiting and phytologically acceptable amount. The term disease-inhibiting and phytologically acceptable amount refers to that amount of a compound that kills or inhibits a plant disease for which control is desired, but is not significantly toxic to the plant. The exact concentration of the synergistic composition required will vary depending on the fungal disease to be controlled, the type of formulation used, the mode of application, the particular plant species, climatic conditions, and the like.

[0032] The present compositions can be applied to the fungi or their locus by the use of conventional earth sprays, pellet applicators, and other conventional means known to those skilled in the art.

[0033] The following examples are provided to further illustrate the invention.

Examples

Evaluation of the therapeutic and protective activity of fungicidal mixtures against wheat leaf blotch (Mycosphaerella graminicola; anamorph: Septoria tritici; Bayer code: SEPTTR)

[0034] Wheat plants (cv. Yuma) were grown from seed in a greenhouse in 27.5 square centimeters plastic pots containing 50% mineral soil / 50% Metro mix with 8-12 seedlings per pot. Plants used for the test when the first leaf has fully developed, usually lasting 7 to 8 days after planting. The test plants were inoculated with an aqueous suspension of Septoria critici spores 3 days before (3-day treatment test) or after 1 day of fungicidal treatment (1-day protective test). After inoculation, the plants were kept at 100% relative humidity (one day in a dark retracted chamber followed by two to three days in a lighted retracted chamber) to allow the spores to germinate and infect the leaf. The plants were then transferred to a greenhouse for disease development.

Evaluation of the therapeutic activity of fungicidal mixtures vs. wheat brown rust (Puccinia recondita; Bayer code: PUCCRT)

[0035] Yuma wheat seedlings grown as described above were inoculated with an aqueous spore suspension of Puccinia recondita 3 days before or 1 day after the fungicidal treatment. After inoculation, the plants were kept at 100% relative humidity for 24 hours in a dark retracted chamber to allow the spores to germinate and infect the leaf. The plants were then transferred to a greenhouse for disease development.

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[0036] The treatments consisted of a fungicidal compound I, II, III, IV, V, azoxystrobin and pyraclostrobin, applied singly or as two-component mixtures with compounds IV. Technical grades of material purity were dissolved in acetone to prepare stock solutions which were then used to make acetone dilutions for each individual fungicide component or binary mixture. The desired fungicide ratio was obtained by mixing the dilutions with 9 volumes of water containing 110 parts per million (ppm) of Triton®-100. Twenty milliliter (ml) solutions of the fungicide were applied to 12 pots of plants using an automated spray booth which used two 6218-1 / 4 JAUPM spray nozzles operating at 20 pounds per square inch (psi) positioned at opposite angles to cover both leaf surfaces. All sprayed plants were allowed to dry before proceeding further. Control plants were sprayed in the same manner in a solvent blank.

[0037] Once the disease had fully developed on the control plants, the levels of infection were scored visually on the treated plants and scored on a 0 to 100 percent scale. The percentage of disease control was then calculated using the ratio of the disease on the treated plants compared to the control plants.

[0038] The Colby equation was used to determine the fungicidal effects expected from the mixtures. (See Colby, SR Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967, 15, 20-22).

[0039] The following equation was used to calculate the expected activity of mixtures containing the two active ingredients, A and B:

Expected = A + B - (A χ 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.

[0040] Representative synergistic interactions are shown in the following Tables 1-12.

Obs. % DC = Observed Disease Control Percentage Mesh. % DC = Percent Disease Control Expected Synergy Factor = Obs. % DC / Wait. % DC

Table 1: Synergistic Interactions of Compound I and Other Fungicides in Septoria tritici (SEPTTR) 3-Day Treatment Trials (3DC)

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound I + azoxystrobin</td><td> 6,25+0,4</td><td> 100</td><td> 89</td><td> 1,12</td>

<td>Compound I + prothioconazole</td><td> 1,35+2,25</td><td> 99</td><td> 83</td><td> 1,19</td>

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<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound 1 + azoxystrobin</td><td> 0,45+0,75</td><td> 72</td><td> 15</td><td> 4,78</td>

<td>Compound 1 + azoxystrobin</td><td> 0,1+0,4</td><td> 92</td><td> 80</td><td> 1,15</td>

Table 2: Synergistic Interactions of Compound I and Other Fungicides in the SEPTTR 1-Day Protective Test (1DP)

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound 1 + azoxystrobin</td><td> 0,1 + 1,56</td><td> 91</td><td> 66</td><td> 1,38</td>

<td>Compound 1 + azoxystrobin</td><td> 0,1+0,4</td><td> 72</td><td> 43</td><td> 1,66</td>

<td>Compound 1 + azoxystrobin</td><td>ο, ι + ο, ι</td><td> 80</td><td> 61</td><td> 1,31</td>

<td>Compound 1 + pyraclostrobin</td><td>ο, ι + ο, ι</td><td> 99</td><td> 92</td><td> 1,08</td>

<td>Compound 1 + pyraclostrobin</td><td> 0,05+0,08</td><td> 68</td><td> 30</td><td> 2,27</td>

Table 3: Synergistic Interactions of Compound I and Other Fungicides in the 3DC Puccinia recondita (PUCCRT) tests

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound 1 + azoxystrobin</td><td> 0,4+0,4</td><td> 90</td><td> 84</td><td> 1,07</td>

<td>Compound 1 + azoxystrobin</td><td> 0,15+0,25</td><td> 43</td><td> 14</td><td> 3,14</td>

<td>Compound 1 + pyraclostrobin</td><td> 0,4+0,1</td><td> 74</td><td> 55</td><td> 1,34</td>

<td>Compound 1 + pyraclostrobin</td><td> 0,1+0,4</td><td> 74</td><td> 64</td><td> 1,15</td>

Table 5: Synergistic Interactions of Compound II and Other Fungicides in the 1DP SEPTTR Assay

<td></td><td>PPm indicator</td><td>Obs. DC</td><td> %</td><td>Wait. DC</td><td> %</td><td>Gism factor</td><td>son er-</td>

<td>Compound II + pyraclostrobin</td><td> 0,45+0,1</td><td colspan="2"> 80</td><td colspan="2"> 61</td><td colspan="2"> 1,32</td>

Table 6: Synergistic Interactions of Compound II and Other Fungicides in 3DC SEPTTR Assays

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound II + azoxystrobin</td><td> 1,35+2,25</td><td> 98</td><td> 72</td><td> 1,36</td>

<td>Compound II + azoxystrobin</td><td> 0,45+0,75</td><td> 71</td><td> 52</td><td> 1,36</td>

<td>Compound II + pyraclostrobin</td><td> 0,15+0,25</td><td> 95</td><td> 50</td><td> 1,89</td>

<td>Compound II + pyraclostrobin</td><td> 0,05+0,08</td><td> 29</td><td> 16</td><td> 1,78</td>

Table 7: Synergistic Interactions of Compound III and Other Fungicides in the 1DP SEPTTR Assay

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<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound III + azoxystrobin</td><td> 0,15+0,25</td><td> 38</td><td> 27</td><td> 1,42</td>

<td>Compound III + pyraclostrobin</td><td> 0,3+0,1</td><td> 76</td><td> 63</td><td> 1,21</td>

Table 8: Synergistic Interactions of Compound III and Other Fungicides in 3DC SEPTTR Assays

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound III + azoxystrobin</td><td> 0,45+0,75</td><td> 95</td><td> 63</td><td> 1,51</td>

<td>Compound III + azoxystrobin</td><td> 0,15+0,25</td><td> 63</td><td> 43</td><td> 1,44</td>

<td>Compound III + pyraclostrobin</td><td> 0,5+0,15</td><td> 75</td><td> 56</td><td> 1,33</td>

Table 10: Synergistic Interactions of Compound IV and Other Fungicides in 3DC SEPTTR Assays

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound IV + azoxystrobin</td><td> 4,2+7</td><td> 96</td><td> 84</td><td> 1,14</td>

<td>Compound IV + azoxystrobin</td><td> 1,35+2,25</td><td> 70</td><td> 57</td><td> 1,23</td>

<td>Compound IV + pyraclostrobin</td><td> 6+0,15</td><td> 97</td><td> 62</td><td> 1,56</td>

<td>Compound IV + pyraclostrobin</td><td> 0,05+0,08</td><td> 30</td><td> 22</td><td> 1,40</td>

Table 11: Synergistic Interactions of Compound V and Other Fungicides in the 1DP SEPTTR Assay

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound V + azoxystrobin</td><td> 0,45+0,75</td><td> 38</td><td> 12</td><td> 3,09</td>

<td>Compound V + pyraclostrobin</td><td> 2+0,1</td><td> 99</td><td> 93</td><td> 1,07</td>

<td>Compound V + pyraclostrobin</td><td> 0,05+0,08</td><td> 50</td><td> 17</td><td> 3,00</td>

Table 12: Synergistic Interactions of Compound V and Other Fungicides in 3DC SEPTTR Assays

<td></td><td>PPm indicator</td><td>Obs. % DC</td><td>Wait. % DC</td><td>The synergism factor</td>

<td>Compound V + pyraclostrobin</td><td> 2+0,15</td><td> 86</td><td> 38</td><td> 2,30</td>

<td colspan="5">For all Tables,% DC =% Disease Control</td>

Aspects of the present invention

[0041]

1. A synergistic fungicidal mixture comprising a fungicidally effective amount of a compound of Formula IV and at least one fungicide selected from the group consisting of azoxystrobin and pyraclostrobin.

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<img file="PL2904901T3_D0005.tif" />

2. A mixture according to Aspect 1 wherein the weight ratio of Compound of formula IV to azoxystrobin is in the range 1:10 to 10: 1.

3. A mixture according to Aspect 1 wherein the weight ratio of Compound of formula IV to pyraclostrobin is in the range 1:10 to 10: 1.

4. A fungicidal composition comprising a fungicidally effective amount of a mixture according to Aspect 1 and an agriculturally acceptable adjuvant or carrier