WO2026003323A1 - Pesticidal mixtures - Google Patents

Abstract

The invention relates to a pesticidal mixture comprising components (A) and (B) as active ingredients, wherein component (A) is cyclobutrifluram, and component (B) is metconazole.

Description

PESTICIDAL MIXTURES

The present invention relates to novel pesticidal mixtures and compositions, and to methods for controlling or preventing infestation of plants by various phytopathogenic microorganisms using these mixtures and compositions. In particular, pesticidal mixtures of the invention comprise component (A), which is cyclobutrifluram, and component (B), which is metconazole.

Certain active ingredients and combinations of active ingredients for controlling pest attack are described in the literature.

An object of the present invention is to provide pesticidal mixtures having superior biological properties for use in controlling or preventing infestation of plants by phytopathogenic microorganisms. For example, mixtures possessing a greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, and/or increased biodegradability.

Accordingly, in an aspect, the present invention provides a pesticidal mixture comprising as component (A), a compound of formula A-1 :

(A-1 ; cyclobutrifluram) and, as component (B), a compound of formula B-1 :

(B-1 ; metconazole).

A reference to cyclobutrifluram and metconazole also includes agrochemically acceptable ionic forms, salts, solvates, isomers, including geometric and stereochemical isomers, tautomers, N-oxides, esters, prodrugs, isotopes and protected forms thereof. Preferably, a reference to cyclobutrifluram and metconazole also includes the salts or tautomers or isomers or N-oxides or solvates thereof; and more preferably, the salts or tautomers or N-oxides or solvates thereof, even more preferably the salts or tautomers or solvates thereof.

Cyclobutrifluram and metconazole as well as their pesticidal action are generally known. WO2019096860 describes a process for making cyclobutrifluram and US4938792 discloses a process for making metconazole.

Cyclobutrifluram comprises 80-100% N-[(1 S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2- (trifluoromethyl)pyridine-3-carboxamide as illustrated below as compound of formula A-1 a (hereinafter “the (1 S,2S) enantiomer”), and 20-0% of the corresponding (1 R,2R)-enantiomer as illustrated below as compound of formula A-1 b. These enantiomers arise because the phenyl ring on the left-hand side and the pyridyl-C(=O)-NH group on the right-hand side are cis to each other on the cyclobutyl ring.

In preferred embodiments, the mixtures and compositions of the invention comprise cyclobutrifluram in enantiomerically pure or substantially enantiomerically pure form. For the purposes of the present invention, “substantially enantiomerically pure cyclobutrifluram” is understood to be in an enantiomeric purity of at least 90% ee, more preferably at least 95% ee, at least 96% ee, even more preferably at least 97% ee, and especially at least 98% ee, e.g. at least 99% or 99.9% ee, wherein the fraction of the (1 S,2S) enantiomer is larger.

It has been found that, surprisingly, certain weight ratios of cyclobutrifluram and metconazole give rise to synergistic activity. Therefore, according to an aspect of the invention, there is provided a mixture, wherein cyclobutrifluram and metconazole are present in the mixture in amounts producing a synergistic effect. This synergistic activity is apparent from the fact that the activity of the mixture comprising cyclobutrifluram and metconazole is greater than the sum of the corresponding activities of cyclobutrifluram and metconazole alone. This synergistic activity extends the range of action of cyclobutrifluram and metconazole in two ways. Firstly, the rates of application of cyclobutrifluram and metconazole are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of pest control even where the two individual components have become totally ineffective in such a low application rate range. Secondly, there is a substantial broadening of the spectrum of pests that can be controlled.

A synergistic effect occurs whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture

X = % action by active ingredient A) using p ppm of active ingredient

Y = % action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is:

If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the difference of (O-E). In the case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.

Alternatively, the synergistic action may also be determined from the dose response curves according to the so-called WADLEY method. With this method the efficacy of the a.i. is determined by comparing the degree of fungal attack on treated plants with that on untreated, similarly inoculated and incubated check plants. Each a.i. is tested at 4 to 5 concentrations. The dose response curves are used to establish the EC50 (i.e. concentration of a.i. providing 50% disease control) of the single compounds as well as of the combinations (EC50_Observed). The thus experimentally found values of the mixtures at a given weight ratio are compared with the values that would have been found were only a complementary efficacy of the components was present (EC50 (A+ B)expected) . The EC50 (A+B)expected is calculated according to Wadley (NY/T 1156.6-2006 and Levi et al., EPPO- Bulletin 16, 1986, 651 -657): wherein a and b are the weight ratios of the compounds A and B in the mixture and the indexes (A), (B), (A+B) refer to the observed EC50 values of the compounds A, B or the given combination A+B thereof. The ratio EC50 (A+B)expected / EC50 (A+B)_Observed expresses the ratio of interaction, the synergy ratio (SR). In case of synergism, SR is >1.5.

Alternatively, the synergistic action may also be determined evaluated by the Co-Toxicity Coefficient (CTC) according to the Sun-YP method (Yun-Pei, Sun. "Toxicity Index-An Improved Method of Comparing the Relative Toxicity of Insecticides." Journal of Economic Entomology 1 (1950):45-53.). A CTC value of less than 80 indicates an antagonistic effect, a CTC value of 80-120 indicates an additive effect, and a CTC value of greater than or equal to 120 indicates a synergistic effect.

CTC = (ATI / TTI) * 100

Component A represents standard Al, and component B represents the component to be mixed with the standard Al.

ATI (Measured toxicity index of a mixture) = (Standard Al’s ECso/Mixture’s EC50) * 100

TTI (Theoretical toxicity index of a mixture) = (TIA*PA+TIB*PB) * 100

TIA (Toxicity index of component A) = the EC50 of component A / the EC50 of component A

PA: Percentage of component A in the mixture

TIB (Toxicity index of component B) = the EC50 of component A / the EC50 of component B

PB: Percentage of component B in the mixture.

Besides any synergistic action, mixtures or compositions according to the invention also have further surprising advantageous properties. Examples of such advantageous properties include: more advantageous degradability, improved toxicological and/or ecotoxicological behaviour, or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigour, and early germination.

The mixtures or compositions of the present invention may comprise cyclobutrifluram and metconazole in a suitable ratio by weight, for example 1000:1 to 1 :1000, 500:1 to 1 :500, 250:1 to 1 :250, 125:1 to 1 :125, 100:1 to 1 :100, 50:1 to 1 :50, 40:1 to 1 :40, 30:1 to 1 :30, 25:1 to 1 :25, 20:1 to 1 :20, or 15:1 to 1 :15, or preferably 10:1 to 1 :10, 8:1 to 1 :8, 6:1 to 1 :6, or 5:1 to 1 :5; more preferably between 4:1 to 1 :4, between 10:3 to 3:10, between 3:1 to 1 :3, between 2.5:1 to 1 :2.5, between 2:1 to 1 :2, between 5:3 to 3:5, between 8:5 to 5:8, between 1 .5:1 to 1 :1 .5, between 4:3 to 3:4, between 5:4 to 4:5, or about 1 :1 by weight.

In preferred embodiments, the ratio by weight of cyclobutrifluram and metconazole is between 20:1 to 1 :20. In more preferred embodiments, the ratio by weight of cyclobutrifluram and metconazole is between 15:1 to 1 :10. In most preferred embodiments, the ratio by weight of cyclobutrifluram and metconazole is between 10:1 to 1 :3, 5:1 to 1 :3, or 2:1 to 1 :3. In some embodiments, the ratio by weight of cyclobutrifluram and metconazole is 10:1 , 5:1 , 3: 1 , 2: 1 , 1 :1 , 1 :2, and/or 1 :3.

Mixtures and compositions of this invention, including all of the above disclosed embodiments and preferred examples thereof, can be mixed with one or more additional pesticides including further fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.

Examples of such additional pesticides which the mixtures of this invention may further comprise are:

Fungicides such as etridiazole, fluazinam, benalaxyl, benalaxyl-M (kiralaxyl), furalaxyl, metalaxyl, metalaxyl-M (mefenoxam), dodicin, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine, N'-[4-(4,5-dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, N'-[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl- formamidine, ethirimol, 3'-chloro-2-methoxy-N-[(3RS)-tetrahydro-2-oxofuran-3-yl]acet-2',6'-xylidide (clozylacon), cyprodinil, mepanipyrim, pyrimethanil, dithianon, aureofungin, blasticidin-S, biphenyl, chloroneb, dicloran, benzovindiflupyr, pydiflumetofen, hexachlorobenzene, quintozene, tecnazene, (TCNB), tolclofos-methyl, metrafenone, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, fluopicolide (flupicolide), tioxymid, flusulfamide, benomyl, carbendazim, carbendazim chlorhydrate, chlorfenazole, fuberidazole, thiabendazole, thiophanate-methyl, benthiavalicarb, chlobenthiazone, probenazole, acibenzolar, bethoxazin, pyriofenone (IKF-309), acibenzolar-S-methyl, pyribencarb (KIF- 7767), butylamine, 3-iodo-2-propinyl n-butylcarbamate (IPBC), iodocarb (isopropanyl butylcarbamate), isopropanyl butylcarbamate (iodocarb), picarbutrazox, polycarbamate, propamocarb, tolprocarb, 3- (difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide diclocymet, N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1- methyl-pyrazole-4-carboxamide N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2- isopropylphenyl)methyl]-1-methyl-pyrazole-4-carboxamide carpropamid, chlorothalonil, flumorph, oxine-copper, cymoxanil, phenamacril, cyazofamid, flutianil, thicyofen, chlozolinate, iprodione, procymidone, vinclozolin, bupirimate, dinocton, dinopenton, dinobuton, dinocap, meptyldinocap, diphenylamine, phosdiphen, 2,6-dimethyl-[1 ,4]dithiino[2,3-c:5,6-c']dipy rrole-1 ,3,5,7(2H,6H)-tetraone, azithiram, etem, ferbam, mancozeb, maneb, metam, metiram (polyram), metiram-zinc, nabam, propineb, thiram, vapam (metam sodium), zineb, ziram, dithioether, isoprothiolane, ethaboxam, fosetyl, phosetyl-AI (fosetyl-al), methyl bromide, methyl iodide, methyl isothiocyanate, cyclafuramid, fenfuram, validamycin, streptomycin, (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonil), dodine, doguadine, guazatine, iminoctadine, iminoctadine triacetate, 2,4-D, 2,4-DB, kasugamycin, dimethirimol, fenhexamid, hymexazole, hydroxyisoxazole imazalil, imazalil sulphate, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenamidone, Bordeaux mixture, calcium polysulfide, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, cuprous oxide, sulphur, carbaryl, phthalide (fthalide), dingjunezuo (Jun Si Qi), oxathiapiprolin, fluoroimide, mandipropamid, KSF-1002, benzamorf, dimethomorph, fenpropimorph, tridemorph, dodemorph, diethofencarb, fentin acetate, fentin hydroxide, carboxin, oxycarboxin, drazoxolon, famoxadone, m-phenylphenol, p-phenylphenol, tribromophenol (TBP), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol 2-[2- fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol cyflufenamid, ofurace, oxadixyl, flutolanil, mepronil, isofetamid, fenpiclonil, fludioxonil, pencycuron, edifenphos, iprobenfos, pyrazophos, phosphorus acids, tecloftalam, captafol, captan, ditalimfos, triforine, fenpropidin, piperalin, osthol, 1- methylcyclopropene, 4-CPA, chlormequat, clofencet, dichlorprop, dimethipin, endothal, ethephon, flumetralin, forchlorfenuron, gibberellic acid, gibberellins, hymexazol, maleic hydrazide, mepiquat, naphthalene acetamide, paclobutrazol, prohexadione, prohexadione-calcium, thidiazuron, tribufos (tributyl phosphorotrithioate), trinexapac, uniconazole, a-naphthalene acetic acid, polyoxin D (polyoxrim), BLAD, chitosan, fenoxanil, folpet, 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2- (2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, fenpyrazamine, diclomezine, pyrifenox, boscalid, fluopyram, diflumetorim, fenarimol, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine ferimzone, dimetachlone (dimethaclone), pyroquilon, proquinazid, ethoxyquin, quinoxyfen, 4,4,5-trifluoro-3,3-dimethyl-1-(3- quinolyl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline 5-fluoro-3,3,4,4-tetramethyl- 1-(3-quinolyl)isoquinoline 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4-benzoxazepine, tebufloquin, oxolinic acid, chinomethionate (oxythioquinox, quinoxymethionate), spiroxamine, (E)-N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, (mandestrobin), azoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin, fenamistrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metaminostrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, triclopyricarb, trifloxystrobin, amisulbrom, dichlofluanid, tolylfluanid, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, dazomet, isotianil, tiadinil, thifluzamide, benthiazole (TCMTB), silthiofam, zoxamide, anilazine, tricyclazole, (.+-.)-cis-1-(4-chlorophenyl)-2-(1 H-1 ,2,4-triazol- 1-yl)-cycloheptanol (huanjunzuo), 1-(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1 , 1 -difluoro-3-(1 ,2,4- triazol-1 -yl)propan-2-ol 2-(1 -tert-buty l)-1 -(2-chlorophenyl)-3-(1 , 2 ,4-triazo I- 1 -yl)-propan-2-ol (TCDP), azaconazole, bitertanol (biloxazol), bromuconazole, climbazole, cyproconazole, difenoconazole, dimetconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triazoxide, triticonazole, mefentrifluconazole, 2-[[(1 R,5S)-5-[(4- fluorophenyl)methyl]-1 -hydroxy-2, 2-dimethyl-cyclopentyl]methyl]-4H-1 ,2,4-triazole-3-thione, 2-[[3-(2- chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1 ,2,4-triazole-3-thione, ametoctradin (imidium), iprovalicarb, valifenalate, 2-benzyl-4-chlorophenol (Chlorophene), allyl alcohol, azafenidin, benzalkonium chloride, chloropicrin, cresol, daracide, dichlorophen (dichlorophene), difenzoquat, dipyrithione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, NNF-0721 , octhilinone, oxasulfuron, propamidine and propionic acid.

Insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetra mat, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, trichlorfon and triflumuron;

Bactericides such as streptomycin and SAR products e.g. acybenzolar-S-methyl;

Acaricides such as amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and

Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

In preferred embodiments, the additional pesticide is selected from the group consisting of Fludioxonil, Difenoconazole, sedaxane, Tebuconazole, Ipconazole, Prothioconazole, pyraclostrobin, Metalaxyl-M, Picarbutrazox, Thiamethoxam, and Clothianidin.

The mixtures and compositions according to the invention are generally formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water- dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, micro- emulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydro-furfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances. A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surfaceactive substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate soaps, such as sodium stearate salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate sorbitol esters, such as sorbitol oleate quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate block copolymers of ethylene oxide and propylene oxide and salts of mono and dialkylphosphate esters and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredients and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.

Formulation Examples

Wettable powders a) b) c) active ingredients [components (A) and (B)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

Powders for dry seed treatment a) b) c) active ingredients [components (A) and (B)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %

Kaolin 65 % 40 %

Talcum 20 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable concentrate active ingredients [components (A) and (B)] 10 % octylphenol polyethylene glycol ether 3 %

(4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %

Cyclohexanone 30 % xylene mixture 50 %

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Dusts a) b) c) active ingredients [components (A) and (B)] 5 % 6 % 4 % talcum 95 %

Kaolin 94 % mineral filler 96 % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruder granules active ingredients [components (A) and (B)] 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %

Kaolin 82 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.

The mixture is extruded and then dried in a stream of air.

Coated granules active ingredients [components (A) and (B)] 8 % polyethylene glycol (mol. wt. 200) 3 %

Kaolin 89 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate active ingredients [components (A) and (B)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %

Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 %

Water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredients [components (A) and (B)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %

1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %

Silicone oil (in the form of a 75 % emulsion in water) 0.2 %

Water 45.3 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the active ingredients [components (A) and (B)] is mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

In some embodiments, the pesticidal composition of the present invention may be a seed treatment composition.

As used herein, the term "seed" denotes any resting stage of a plant that is physically detached from the vegetative stage of a plant and/or may be stored for prolonged periods of time and/or can be used to re-grow another plant individual of the same species. Here, the term "resting" refers to a state wherein the plant retains viability, within reasonable limits, in spite of the absence of light, water and/or nutrients essential for the vegetative (i.e. non-seed) state. In particular, the term refers to true seeds but does not embrace plant propagules such as suckers, corms, bulbs, fruit, tubers, grains, cuttings and cut shoots.

The term "seed treatment" generally refers to application of a material to a seed prior to or during the time it is planted in soil to improve the handling characteristics of the seed, protect the seed prior to germination, support the germination and/or support the growth of the resulting plant. Some seed treatments are employed solely for the purpose of improving the handling characteristics or other physical characteristics of seeds, and include no agricultural active ingredients. Other seed treatments bind one or more active ingredients to seeds for various beneficial purposes. For example, seed treatments that include one or more active ingredients are commonly used to ensure uniform stand establishment by protecting against soilborne diseases and insects. Typical examples include the application of pesticides such as fungicides, insecticides and plant growth regulators. Systemic seed treatments may eliminate, or at least reduce the need for, traditional broadcast sprays of foliar fungicides or insecticides for certain early season airborne diseases and insects.

The seed treatment composition can be applied to a seed in a variety of manners conventional in the seed treating art, including but not limited to mixing in a container (e.g., a bottle, bag or tumbler), mechanical application, tumbling, spraying, and immersion, followed by drying. Examples of seed coating techniques and machines that can be employed include fluidized bed techniques, the roller mill method, rotary seed treaters, drum coaters, side vended pan, tumble mixers and spouted beds. The seeds may be pre-sized before coating. In one embodiment, the seed treatment mixture is applied to seeds in a Hege seed treater, which rotates as the formulation is being added to the seeds. Mixing is preferably continued until the seed treatment mixture is distributed uniformly on the seed (i.e. , uniform coatings over all of the seeds to be treated and an even coating on each individual seed). The seed treatment mixture can be applied to seeds in a batch treatment process or in a continuous treatment process. In one representative batch treatment process, the seeds to be treated are introduced to a batch treatment tank and the seed treatment mixture is then added and mixed with the seeds. Alternatively, a continuous treatment process can be used to apply the seed treatment mixture to seeds in which a stream of seeds is introduced into a receptacle containing the seed treatment slurry and, after contacting the formulation, recovered from the receptacle for drying. A stream of seed treatment mixture can continuously flow into the receptacle as well to replenish quantities of the mixture that are removed with treated seeds.

When the composition according to the invention is used for treating seed, rates of 0.001 to 50 g of a compound of component (A) per 100kg of seed, preferably from 1 to 50g per 100kg of seed, and 0.001 to 50 g of a compound of component (B), per 100kg of seed, preferably from 1 to 30 g per 100kg of seed, are generally sufficient.

Preferably, the seed treatment composition comprises between 1 and 50 g ai of component (A) and between 1 and 30 g ai of component (B) per 100kg of seed.

In a further aspect, the present application also relates to a plant propagation material coated with the pesticidal composition of the present invention.

The term "plant propagation material” denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.

In another aspect, the present invention provides a method of controlling or preventing infestation of a plant by phytopathogenic microorganisms which comprises applying on the pest, their habitat, breeding grounds, their locus or the plant, the locus thereof, the soil or plant propagation material, an effective amount of the pesticidal mixture comprising, as component (A), cyclobutrifluram and, as component (B), metconazole.

The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation. The mixtures and compositions of the invention may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.

The mixtures and compositions are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Bremia lactucae' and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and Sclerospora graminicola'

Ascomycetes, including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phom a destructiva, Phaeosphaeria herpotrichoides , Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis , Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis , Alternaria alternata, Alternaria brassicicola, Alternaria solani and Altemaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew diseases for example those caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis; molds for example those caused by Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta cucurbitacearum; anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and wilts or blights for example those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae;

Basidiomycetes, including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis, Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis , Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries;

Blastocladiomycetes, such as Physoderma maydis; Mucoromycetes, such as Choanephora cucurbitarum.', Mucor spp.; Rhizopus arrhizus', as well as diseases caused by other species and genera closely related to those listed above.

In addition to their fungicidal activity, the mixtures and compositions of the present invention may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa. Furthermore, the mixtures and compositions may have activity against nematodes such as Meloidogyne spp., Heterodera spp., Rotylenchus spp. and Pratylenchus spp.

The mixtures, compositions, methods and uses according to the present invention are preferably for controlling or preventing infestation of the crop by phytopathogenic microorganisms of the genera Alternaria, Ascochyta, Bipolaris, Blumeria, Botrytis, Cercospora, Cladosporium, Colletotrichum, Corynespora, Curvularia, Diaporthe, Exserohilum, Fusarium, Macrophoma, Macrophomina, Marssonina, Microdochium, Mycosphaerella, Phialophora, Phoma, Plasmodiophora, Puccinia, Pyricularia, Rhizoctonia, Sclerotina, Sclerotium, Septoria, Sphaceloma, Sphaerotheca, Spongospora, Stemphylium, Streptomyces, Ustilaginoidea, Venturia, and/or Verticillium.

The mixtures, compositions, methods and uses according to the present invention are more preferably for controlling or preventing infestation of the crop by phytopathogenic microorganisms of Fusarium graminearum, Fusarium virguliforme, Fusarium psendograminearum , Fusarium fujikuroi, Fusarium proliferatum, Fusarium verticillioides, Fusarium solani, Fusarium pallidoroseum, Fusarium Poea, Fusarium semitectum, Fusarium sulphureum, Fusarium subglutinans, Fusarium Tricinctum, Microdochium nivale, Blumeria graminis, Puccinia recondite, Puccinia striiformis, Rhizoctonia cereadis, Exserohilum turcicum, Bipolaris maydis, Cercospora zeae-maydis, Curvularia lunata, Puccinia polysora, Rhizoctonia solani, Pyricularia oryzae, Ustilaginoidea virens, Septoria glycines, Cercospora sojina, Cercospora arachidicola, Cercospora personata, Cercospora kikuchii, Phoma arachidicola, Sclerotium rolfsii, Alternaria solani, Spongospora subterranean, Streptomyces spp., Sclerotina sclerotiorum, Alternaria alternate, Corynespora cassiicola, Ascochyta citrulline, Sphaerotheca cucurbitae, Stemphylium solani, Cladosporium fulvum, Diaporthe citri, Diaporthe longicolla, Diaporthe sojae, Sphaceloma fawcetti, Alternaria mall, Macrophoma Kawatsukai, Macrophomina phaseoli, Venturia inaequalis, Marssonina mall, Mycosphaerella fijiensis, Mycosphaerella musicola, Plasmodiophora brasicae, Phialophora gregata, Colletotrichum spp., Botrytis cinereal, Verticillium dahlia, Verticillium spp., Fusarium oxysporum, or Fusarium spp., including phytopathogenic fungi or oomycetes that are resistant to other fungicides or oomyceticides. Fungi or oomycetes that are "resistant" to particular fungicides or oomyceticides refer e.g. to strains that are less sensitive to that fungicide or oomyceticide compared to the expected sensitivity of the same species. The expected sensitivity can be measured using e.g. a strain that has not previously been exposed to the fungicide or oomyceticide.

The mixtures, compositions, methods and uses of the invention are suitable for control of the genera Alternaria, Bipolaris, Blumeria, Cercospora, Curvularia, Exserohilum, Fusarium, Phoma, Septoria, and Ustilaginoidea. The mixtures, compositions, methods and uses of the invention are particularly suitable for control of Fusarium graminearum, Fusarium virguliforme, Fusarium psendograminearum , Fusarium fujikuroi, Fusarium proliferatum, Fusarium verticillioides, Fusarium solani, Blumeria graminis, Exserohilum turcicum, Bipolaris maydis, Cercospora zeae-maydis, Curvularia lunata, Ustilaginoidea virens, Septoria glycines, Cercospora sojina, Alternaria solani, Cercospora arachidicola, Cercospora personata, or Phoma arachidicola.

In an embodiment, the mixtures, compositions, methods and uses according to the present invention are for controlling or preventing infestation of the crop by phytopathogenic microorganisms of the Fusarium genus, including phytopathogenic fungi or oomycetes that are resistant to other fungicides or oomyceticides.

Examples of the above-mentioned pests are from the genus Fusarium, for example Fusarium virguliforme, Fusarium fujikuroi, Fusarium solani, Fusarium oxysporum, Fusarium acuminatum, Fusarium chlamydosporum, Fusarium compactum, Fusarium culmorum, Fusarium equiseti, Fusarium graminearum, Fusarium merismoides, Fusarium proliferatum, Fusarium pseudograminearum, Fusarium semitectum, Fusarium subglutinans, Fusarium verticilliodes, Fusarium avenaceum, Fusarium moniliforme, and Fusarium tricinctum.

The mixtures and compositions of the invention are particularly suitable for control of Fusarium graminearum, Fusarium fujikuroi and Fusarium pseudograminearum.

Crops of useful plants in which the mixtures and compositions according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

Crops or plants are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Crops or plants are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

Crops or plants are also to be understood as being those which naturally are or have been rendered resistant to harmful microorganisms or insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include 6 -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

An example of a crop or plant that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut (Syngenta Seeds). An example of a crop or plant comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

In preferrable embodiments, the plant is selected from wheat, maize, rice, soybean, potato, peanuts, cotton, oil seed rape, sunflower, tobacco, cucurbits, melon, solanaceae, citrus, apple, banana, and all other fruits and/or vegetables.

In preferrable embodiments, the plant is selected from wheat, maize, rice, soybean, potato, and peanuts.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation by phytopathogenic microorganisms of wheat plants.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation by phytopathogenic microorganisms of rice plants.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation by phytopathogenic microorganisms of maize plants.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation by phytopathogenic microorganisms of soybean plants.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation by phytopathogenic microorganisms of potato plants.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation by phytopathogenic microorganisms of peanuts plants.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation of wheat plants, by Fusarium graminearum or Fusarium pseudograminearum. In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation of rice plants by Fusarium fujikuroi.

In an embodiment, the mixtures and compositions as disclosed herein are used for controlling or preventing infestation of maize plants by Fusarium pseudograminearum .

The pesticidal mixtures of the present invention are suitable for treating the below diseases: Fusarium head blight (FHB), crown rot, stalk rot and/or bakanae disease.

The pesticidal mixtures of the present invention are particularly suitable for treating the below diseases: wheat Fusarium head blight (FHB), wheat crown rot, maize stalk rot and/or rice bakanae disease.

Table 1 sets out certain preferred mixtures for controlling or preventing infestation of a plant. Table 1 lists example application ratios, Table 1 also lists key pests against which the mixtures are particularly effective and key crops for which the inventive mixtures are particularly advantageous.

Table 1A

Table 1B Table 1C

Optionally, the active ingredients in the mixtures of the present invention may be applied to a pest, plant, plant propagation material or plant growing locus either simultaneously, for example in a single “ready-mix” form or in a combined spray mixture composed from separate formulations of the single active ingredient components such as a “tank-mix”, or sequentially i.e. one after the other within a reasonably short period, such as a few hours or days. The order of applying the components (A) and (B) is not essential for working the present invention.

The mixtures and compositions of the present invention may be applied to a crop or plant with any suitable application method, such as foliar, drench, spraying, atomizing, dusting, scattering, coating or pouring, to be chosen in accordance with the intended objectives and the prevailing circumstances. In a preferred embodiment, the mixtures and compositions of the present invention are applied to the leaves of the plants. In another preferred embodiment, the mixtures and compositions of the present invention are applied to the soil in or on which useful plants are growing and/or will grow.

The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.

Generally, the mixtures and compositions of the present invention are applied at a rate of from 40 to 1000 g ai /ha, preferably from 75 to 500 g ai/ha, more preferably from 150 to 350 g ai/ha.

In certain embodiments, the rate of application of component (A) is 20 to 500 g ai /ha, preferably from 25 to 250 g ai/ha, more preferably from 50 to 250 g ai/ha, e.g. 50, 75, 100, 150, 200 or 250 g ai/ha.

In certain embodiments, the rate of application of component (B) is from 20 to 500 g ai /ha, preferably from 50 to 250 g ai/ha, more preferably from 50 to 200 g ai/ha, e.g. 50, 75, 100, 150, or 200 g ai/ha.

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

In yet a further aspect, the present application relates to use of the pesticidal mixture or composition as described above for controlling phytopathogenic microorganisms on a plant, wherein the plant is selected from wheat, maize, rice, soybean, potato, peanuts, cotton, oil seed rape, sunflower, tobacco, cucurbits, melon, solanaceae, citrus, apple, banana and all other vegetables and fruits. In preferred embodiments, the plant is selected from wheat, maize, rice, soybean, potato, and peanuts. Most preferably, the plant is selected from wheat, rice and maize.

Preferably, the phytopathogenic microorganisms are phytopathogenic harmful fungi, oomycetes, and/or nematodes.

Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.

The present invention provides a method of improving the tolerance of a plant to abiotic stress, wherein the method comprises applying to the plant, plant part, plant propagation material, or plant growing locus a composition as described herein.

Where a range of numbers is disclosed herein (for example, 1 to 10), this is intended to include all numbers and intervening values within that range (for example, 1 , 1 .1 , 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any sub-range of numbers and intervening values within that range (for example, 2 to 8, 1 .5 to 5.5 and 3.1 to 4.7). Additionally, it is intended that the both the upper and lower limits specified are included within the range.

Where ranges or values used herein are preceded by the term “about”, this term is intended to provide support for both the exact number that it precedes, and also a number that is near to or approximately the number that it precedes. In determining whether a number is near to or approximately a specifically recited number, the near or approximating number may be a number, which would be rounded to or be substantially equivalent to the specifically recited number. For example, the term “about 5” includes 5.0, 4.5, 5.4, 4.92, 5.01 , and so on.

Biological Examples

Example 1: Fusarium qraminearum bioassay

The synergistic biological activity of mixtures of component (A) and component (B) as disclosed herein was assessed using a Fusarium graminearum bioassay.

The test was performed according to Pesticides guidelines for laboratory bioactivity tests, Part 2: Petri plate test for determining fungicides inhibition of mycelial growth (NY/T 1156.2-2006). Specifically, according to the results of pre-experiment, the best concentration ranges for determination of the sensitivity of pathogens to component (A), component (B) and mixtures thereof were respectively determined, and 5-7 concentration gradients were set to make the inhibition rate at the minimum concentration close to 10% and the inhibition rate at the highest concentration close to 90%. Same volumes of solutions of component (A), component (B) and mixtures thereof in DMSO with desired concentrations were respectively added to melted YBA culture medium to prepare the test plate, and a YBA plate having a same volume of DMSO was used as control.

Mycelial plugs in the edge of colony were prepared by hole puncher with a diameter of 5 mm. With mycelium upward, the mycelial plugs were shifted to the centre of YBA medium plates containing component (A), component (B) and mixtures thereof and the control plate. After cultured in an incubator at 25°C for four days in darkness, the diameters of every mycelial colony on YBA plates were measured twice perpendicularly and then averaged. The inhibition rate was calculated as follows: inhibition rate (%) = (the average diameter of mycelial colony on the control plate - the average diameter of mycelial colony on the test plate) / (the average diameter of mycelial colony on the control plate) * 100%.

The EC50 values of each tested agent and each mixture were calculated by the linear regression analysis between the probability value of the inhibition rate and the log value of the series of concentrations. The synergistic coefficient (SR value) of the mixture was calculated according to Wadley method in NY/T 1 156.6-2006. A SR>1.5 is considered to indicate a synergistic effect. The results are shown Table 2 below.

Table 2

Example 2 Fusarium fujikuroi bioassay

The synergistic biological activity of mixtures of component (A) and component (B) as disclosed herein was assessed using a Fusarium fujikuroi bioassay.

The test was performed according to Pesticides guidelines for laboratory bioactivity tests, Part 2: Petri plate test for determining fungicides inhibition of mycelial growth (NY/T 1156.2-2006). Specifically, according to the results of pre-experiment, the best concentration ranges for determination of the sensitivity of pathogens to component (A), component (B) and mixtures thereof were respectively determined, and 5-7 concentration gradients were set to make the inhibition rate at the minimum concentration close to 10% and the inhibition rate at the highest concentration close to 90%. Same volumes of solutions of component (A), component (B) and mixtures thereof in DMSO with desired concentrations were respectively added to melted PDA culture medium to prepare the test plate, and a PDA plate having a same volume of DMSO was used as control.

Mycelial plugs in the edge of colony were prepared by hole puncher with a diameter of 5 mm. With mycelium upward, the mycelial plugs were shifted to the centre of PDA medium plates containing component (A), component (B) and mixtures thereof and the control plate. After cultured in an incubator at 25°C for three days in darkness, the diameters of every mycelial colony on PDA plates were measured twice perpendicularly and then averaged. The inhibition rate was calculated as follows: inhibition rate (%) = (the average diameter of mycelial colony on the control plate - the average diameter of mycelial colony on the test plate) / (the average diameter of mycelial colony on the control plate) * 100%.

The EC50 values of each tested agent and each mixture were calculated by the linear regression analysis between the probability value of the inhibition rate and the log value of the series of concentrations. The co-toxicity coefficient (CTC) of the mixtures was calculated and evaluated according to the Sun-YP method. A CTC5: 120 is considered to indicate a synergistic effect. The results are shown Table 3 below.

Table 3

Example 3: Fusarium pseudograminearum bioassay

The synergistic biological activity of mixtures of component (A) and component (B) as disclosed herein was assessed using a Fusarium pseudograminearum bioassay, using the same methodology as described in Example 2.

The results are shown Table 4 below.

Table 4

Claims

1. A pesticidal mixture comprising components (A) and (B) as active ingredients, wherein component (A) is cyclobutrifluram, and component (B) is metconazole.

2. The pesticidal mixture according to claim 1 , wherein the ratio by weight of component (A) to component (B) is from 20:1 to 1 :20, preferably between 10:1 to 1 :3, more preferably between 5:1 to 1 :3.

3. The pesticidal mixture according to claim 1 or claim 2, further comprising at least one additional pesticide.

4. The pesticidal mixture according to claim 3, wherein the additional pesticide is selected from the group consisting of Fludioxonil, Difenoconazole, sedaxane, Tebuconazole, Ipconazole, Prothioconazole, pyraclostrobin, Metalaxyl-M, Picarbutrazox, Thiamethoxam, and Clothianidin.

5. A pesticidal composition, comprising a liquid or solid carrier and the pesticidal mixture as defined in any one of claims 1 to 4.

6. The pesticidal composition according to claim 5, wherein the pesticidal composition is a foliar or seed treatment composition.

7. The pesticidal composition according to claim 6, wherein the composition is a seed treatment composition, and comprises between 1 and 50 g ai of component (A) and between 1 and 30 g ai of component (B) per 100kg of seed.

8. A coated plant propagation material, wherein the coating comprises the pesticidal composition according to claim 5 or 6.

9. A method of controlling or preventing infestation of a plant by a phytopathogenic microorganism, which comprises applying on the pest, their habitat, breeding grounds, their locus or the plant, the locus thereof, the soil or plant propagation material, an effective amount of the pesticidal mixture as defined in any one of claims 1 to 4 or the pesticide composition as defined in any one of claims 5 to 7.

10. The method according to claim 9, wherein the phytopathogenic microorganism is selected from the genera Alternaria, Ascochyta, Bipolaris, Blumeria, Botrytis, Cercospora, Cladosporium, Colletotrichum, Corynespora, Curvularia, Diaporthe, Exserohilum, Fusarium, Macrophoma, Macrophomina, Marssonina, Microdochium, Mycosphaerella, Phialophora, Phoma, Plasmodiophora, Puccinia, Pyricularia, Rhizoctonia, Sclerotina, Sclerotium, Septoria, Sphaceloma, Sphaerotheca, Spongospora, Stemphylium, Streptomyces, Ustilaginoidea, Venturia, and Verticillium; preferably, the phytopathogenic microorganism is selected from Fusarium graminearum, Fusarium virguliforme, Fusarium psendograminearum , Fusarium fujikuroi, Fusarium proliferatum, Fusarium verticillioides, Fusarium solani, Fusarium pallidoroseum, Fusarium Poea, Fusarium semitectum, Fusarium sulphureum, Fusarium subglutinans, Fusarium Tricinctum, Microdochium nivale, Blumeria graminis, Puccinia recondite, Puccinia striiformis, Rhizoctonia cereadis, Exserohilum turcicum, Bipolaris maydis, Cercospora zeae-maydis, Curvularia lunata, Puccinia polysora, Rhizoctonia solani, Pyricularia oryzae, Ustilaginoidea virens, Septoria glycines, Cercospora sojina, Cercospora arachidicola, Cercospora personata, Cercospora kikuchii, Phoma arachidicola, Sclerotium rolfsii, Alternaria solani, Spongospora subterranean, Streptomyces spp., Sclerotina sclerotiorum, Alternaria alternate, Corynespora cassiicola, Ascochyta citrulline, Sphaerotheca cucurbitae, Stemphylium solani, Cladosporium fulvum, Diaporthe citri, Diaporthe longicolla, Diaporthe sojae, Sphaceloma fawcetti, Alternaria mall, Macrophoma Kawatsukai, Macrophomina phaseoli, Venturia inaequalis, Marssonina mall, Mycosphaerella fijiensis, Mycosphaerella musicola, Plasmodiophora brasicae, Phialophora gregata, Colletotrichum spp., Botrytis cinereal, Verticillium dahlia, Verticillium spp., Fusarium oxy s porum, or Fusarium spp.

11. The method according to claim 9, wherein the phytopathogenic microorganism is of the Fusarium genus, preferably is Fusarium graminearum, Fusarium fujikuroi or Fusarium pseudograminearum .

12. The method according to any one of claims 9 to 11 , wherein the plant is selected from wheat, maize, rice, soybean, potato, peanuts, cotton, oil seed rape, sunflower, tobacco, cucurbits, melon, solanaceae, citrus, apple, and banana, preferably is wheat, maize, rice, soybean, potato, or peanuts.

13. The method according to any one of claims 9 to 12, wherein the pesticidal mixture as defined in any one of claims 1 to 4 is applied in any desired sequence or simultaneously.

14. The method according to any one of claims 9 to 13, wherein the pesticidal mixture as defined in any one of claims 1 to 4 is applied to the leaves of the plants.

15. The method according to any one of claims 9 to 14, wherein the rate of application of component (A) is from 20 to 500 g ai /ha, preferably from 25 to 250 g ai/ha, more preferably from 50 to 250 g ai/ha; and the rate of application of component (B) is from 20 to 500 g ai /ha, preferably from 50 to 250 g ai/ha, more preferably from 50 to 200 g ai/ha.

16. Use of the pesticidal mixture as defined in any one of claims 1 to 4 or of the pesticidal composition as defined in any one of claims 5 to 7 for controlling phytopathogenic microorganisms on a plant, wherein the plant is selected from wheat, maize, rice, soybean, potato, and peanuts.