MXPA00002346A - Synergistic compositions comprising imazalil and epoxiconazole - Google Patents

Abstract

Synergistic antifungal compositions comprising imazalil, a salt, a stereoisomer or stereoisomeric mixture thereof, and epoxiconazole, a salt, stereoisomer or stereoisomeric mixture thereof, for protecting plants, fruits or seeds. Use of said compositions to protect plants or fruits against fungi.

Description

SYNERGIC COMPOSITIONS COMPRISING IMAZALIL AND EPOXYCONAZOLE Synergistic antifungal compositions comprising imazalil, a salt, a stereoisomer or a stereoisomeric mixture thereof, and epoxycinonazole, a salt, a stereoisomer or a stereoisomeric mixture thereof, to protect fruits or seeds plants. The use of said compositions to protect plants or fruits against fungi. Various classes of compounds are known as antimicrobial compounds and in particular anti-fungal. Among these classes, the group of imidazole and triazole derivatives is particularly interesting and several such compounds are currently widely used as antimicrobials and in particular as anti-fungal. In addition, fungicidal combinations comprising two or more of said fungicidally active compounds are known. DE-A-2916853 describes a combination of fenfuran, thiabendazole and imazalil to treat cereal grains. DE-A-2922292 describes combinations of a furan-3-carboxamide, imazalil and / or thiabendazole. DE-A-2823818 describes mixtures of 2,4,5-trimethyl-N-phenyl-3-furancarboxamide with imazalil and / or thiabendazole. And EP-0,336,489 (corresponding to Argentine Patent No. 246,161), describes synergistic compositions of mazalil and propiconazole. It has now been discovered that the compounds imazalil and epoxiconazole act synergistically.

The present invention relates to mixtures or compositions comprising imazalil (I), a salt, a stereoisomer or a stereoisomeric mixture thereof, and epoxiconazole (II), a salt, a stereoisomer or a stereoisomeric mixture thereof, in amounts which produce a mutual synergistic antifungal effect, and a carrier. The imazalil mentioned above is the generic name of the compound (±) -1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole, which compound may be represented by the formula Imazalil This compound, its synthesis, as well as its antifungal properties are described in the North American patent No. 3,658,813. Epoxiconazole, also known as BAS 489F, is the generic name of the compound cis- (±) -1 - [[3- (2- (4-fluorophenyloxyranyl] methyl] -1H-1, 2,4-triazole, whose compound can be represented by the formula epoxiconazole This compound, its synthesis, as well as its antifungal properties are described in European patent EP-A-0, 196, 038. The active ingredients (I) and (II) used in the mixtures or compositions according to the present invention can be used as stereochemical mixtures or as pure stereoisomers. The active ingredients (I) and (II) can be present in base form or in salt form, the latter being obtained by reaction of the base form with an appropriate acid. Suitable acids include, for example, inorganic acids such as hydrohalic and hydroiodic acids, sulfuric acid, nitric acid, phosphoric acid, phosphinic acid and the like; or organic acids such as for example, acetic, propanoic, hydroxyacetic, 2-hydroxypropanocic, 2-oxopropanoic, ethanedioic, propanedioic, butanedioic, (Z) -2-butanedioic, (E) -2-butenedioic, 2-hydroxybutanedioic acid, , 3-dihydroxybutanedioic acid, 2-hydroxy-1, 2,3-propanetricarboxylic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, 4-methylbenzenesulfonic acid, cyclohexanesulfamic acid, 2-hydroxybenzoic acid, 4-amino-2-hydroxybenzoic acid and similar acids.

Particular forms of imazalil salt (I) are salts of sulfate, phosphate, acetate, nitrate or phosphite. The term salt form comprises metal complexes which can form the basic components (I) or (II). One of the components can be produced in the form of one complex and the other can not; or both components can be produced as complex. The metal complexes mentioned above consist of a complex formed between one or more molecules of the active ingredient and one or more organic or inorganic salts. Examples of said organic or inorganic salts comprise the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, for example methylsulfonates, 4-methylphenylsulfonates, salicylates, benzoates and the like of the metals of the second main group of the periodic system, for example magnesium salts or of calcium, of the third or fourth main group, for example aluminum, tin, lead as well as also of the first to the eighth transition groups of the periodic system such as for example chromium, manganese, iron, cobalt, nickel, copper, zinc and the like. The metals that belong to the transition elements of the fourth period are preferred. Metals can be present in each of their possible valences. The metal ions may be present in any of their possible valences, the most preferred copper metal being advantageously used in its divalent form Cu (II). Suitable copper compounds are sulfate, acetate, hydroxide, oxide, borate, copper fluoride and in particular copper hydroxide carbonate Cu (OH) 2CuCO 3. The complexes can be mono- or polynuclear, they can contain one or more parts of the organic molecule as ligands. The term "salt" as used in the foregoing also encompasses solvates which are capable of forming the active ingredients of formula (I) or (II). Examples of said solvates are for example, hydrates, alcoholates and the like. The ratio between the active ingredients of formula (I) or (II) can vary within relatively wide ranges and will depend on the proposed application, but nevertheless, said relationship will be such that both active ingredients will act synergistically. Particularly, it has been contemplated that the compositions of the present invention comprise at least 750 mg / l of (I), and at least 187.5 mg / l (II) in a concentration of between 187.5 mg / l and 750 mg / l. Said concentrations of (I) or (II) are taken as their equivalent base. The amount of each of the active ingredients in the compositions according to the present invention will be such that a synergistic antifungal effect will be obtained. In particular, it is contemplated that in the compositions that are used directly in the plants or in the places where they are located, the concentration of imazalil, taken as the base equivalent, will be from 750 mg / l to 1500 mg / l: the concentration of Epoxiconazole taken as base equivalent has been contemplated within the range of 187.5 mg / L to 759 mg / L. The active ingredients can be formulated in waxes which will be used as a coating or coating of for example fruits, in particular citrus fruits. Said active ingredients can also be used in all kinds of aqueous treatment systems. Said compositions can be obtained from concentrates, such as for example emulsifiable concentrates, suspension concentrates or soluble concentrates, by dilution with aqueous or organic media, said concentrates intended to be covered by the term composition being used in the definitions of the present invention. An emulsifiable concentrate is a liquid, homogeneous formulation of the active ingredients of formula (I) and (II) which is applied as an emulsion after dilution in water. A suspension concentrate is a stable suspension of the active ingredients in a fluid intended for dilution with water before use. A soluble concentrate is a homogeneous, liquid formulation that is applied as a true solution of the active ingredients after being diluted in water. The synergistic mixtures of the present invention are active against a wide range of fungi. Examples of such fungi are Ascomycetes (for example Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula, Aureobasidium, Sclerophoma); Basidiomycetes (for example Hemileia, Rhizoctonia, Puccinia, Coniophora, Serpula, Poria, Uromyces, Gloeophyllum, Lentinus, Coriolus, Irpex); Fungi imperfecti (for example Botrytis, Helminthosporium, Rhinchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia, Penicillium Geotrichum). The synergistic mixtures according to the present invention possess an advantageous curative, preventive and systemic fungal activity to protect the plants in particular the crop plants. The present mixtures can be used to protect plants or parts of plants, for example fruits, buds, flowers, foliage, stems, roots, tubers of plants or cultivated plants infected, damaged or destroyed by microorganisms, whereby the latter plants of culture are protected against said microorganisms. The mixtures according to the present invention exhibit systemic activity. They can also be used for the disinfection of seeds (fruits, tubers, grains of cereals) and to treat cuttings of plants as well as to fight the phytopathogenic fungi that develop in the soil. The mixtures of the present invention are particularly attractive because they are well tolerated by plants and lack of environmental problems (at low application rates). As an example of the wide variety of crop plants in which combinations of active ingredients according to the present invention may be used, there may be mentioned, for example, cereals, for example wheat, barley, rye, oats, rice, sorghum and the like; beets, for example sugar beet and beet for fodder; pome fruits and pip fruits and berries such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, and blackberries; leguminous plants, for example, kidney beans, lentils, peas, soybeans; oleaginous plants, for example, rapeseed, mustard, poppy, olive, sunflower, coconut, castor oil plants, cocoa, hazelnuts; cucurbits, for example pumpkins, gherkins, melons, cucumbers, zucchini; fibrous plants, for example cotton, flax, hemp, jute, citrus fruits, for example orange, lemon, grapefruit, tangerine; vegetables, for example spinach, lettuce, asparagus, cruciferous vegetables such as cabbages and turnips, carrots, onions, tomatoes, potatoes, hot peppers and sweets; plants of the laurel type, for example avocado, cinnamon, camphor tree; or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapes, hops, bananas, rubber plants as well as ornamental plants such as flowers, shrubs, deciduous trees, and evergreen trees such as conifers . That enumeration of crop plants is provided for the purpose of illustrating the invention and not to delimit it. The active ingredient combinations of formulas (I) and (II) are preferably applied as compositions. The active ingredients of formula (I) and those of formula (II) can be applied to the plants or to the places where they grow, simultaneously, or they can also be administered consecutively in a selected period of time so that both active ingredients can act synergistically, for example within 24 hours. In such applications, the active ingredients are optionally used in conjunction with adjuvants conventionally employed in the art of formulation such as carriers, surfactants or other useful additives. Therefore, the present invention also relates to products comprising a compound of formula (I) a salt, a stereoisomer or a stereoisomeric mixture thereof, and a compound of formula (II), a salt, a stereoisomer or a stereoisomeric mixture thereof, in the form of a combination for simultaneous, separate or sequential use in antifungal applications. Such products may consist of appropriate packages comprising containers with both active ingredients, preferably in formulated form. Said formulations have in general the same composition described for the formulations containing both active ingredients. Suitable carriers and adjuvants for use in the compositions of the present invention may be solid or liquid and correspond to appropriate substances known in the art of the formulation, such as, for example, regenerated natural or mineral substances, solvents, dispersants, surface-active agents. , wetting agents, adhesives, thickeners, binders, fertilizers or antifreeze agents. A particular mode of administration of an active composition comprising at least one of the active ingredients of formula (I) or (II) is the administration to the parts of the plants protruding from the soil, in particular to the leaves of the plants. same (application to the sheets). The number of applications and the doses administered are chosen according to the biological and climatic conditions of life of the causative agent. The active ingredients can, however, be applied to the soil and enter the plants through the root system (systemic activity), in the case where the plants are sprayed with a liquid composition or if the compounds are added. to the ground in a solid formulation for example in the form of a granulate (application to the soil). The compounds of formulas (I) or (II) can also be applied as a coating on the seeds, in case the seeds in grains are irrigated consecutively with a liquid composition of the active ingredients or if they are coated with a previously combined composition. The compositions of the present invention are particularly useful in the post-harvest treatment of fruits, especially citrus fruits. In this last case, the fruits will be sprinkled or submerged or watered with liquid formulations or the fruits will be coated with a waxy composition. This final waxy composition is conveniently prepared by carefully mixing a suspension concentrate with an appropriate wax. The formulations for spraying, dipping or pouring, can be prepared by diluting a concentrate such as for example an emulsifiable concentrate, a suspension concentrate or a soluble liquid, with an aqueous medium. Said concentrate consists in the majority of cases in the active ingredients, in a dispersing or suspending agent (surfactant), a thickening agent, a small amount of organic solvent, a wetting agent, optionally some anti-freezing agent, and water. The active ingredient combinations of formulas (I) or (II) may be applied in general as compositions. The active ingredients of the formula (I) and those of the formula (II) can generally be applied simultaneously or consecutively to the plants, or to the place where they grow, optionally in admixture with adjuvants conventionally used in the art of formulations such as, for example, carriers, surfactants and other additives that can improve the application. Apart from the two aforementioned active ingredients of formulas (I) or (II) the compositions according to the present invention can additionally comprise other active ingredients for example other microbiocides, in particular fungicides and also acaricidal insecticides, nematicides, herbicides, regulators of the development of plants and fertilizers. The aforementioned active ingredients of formulas (I) and (II) are used unmodified, or are preferably used in conjunction with adjuvants conventionally employed in the art of formulation. They are therefore formulated following procedures well known in the art of emulsifiable concentrates, in directly sprayable or dilutable solutions, in dilute emulsions, wettable powders, soluble powders, powders, granulates, and also encapsulations in for example polymeric substances. As with the nature of the compositions, the methods of application, such as sprays, sprays, dusting, scattering or watering, are chosen in accordance with the proposed objectives and the prevailing circumstances. The formulations, ie the compositions, preparations or mixtures comprising the active ingredients and, where appropriate, a solid or liquid adjuvant, are prepared in a known manner, for example by homogenously mixing and / or grinding the active ingredients with extenders, for example solvents, solid carriers and when appropriate, surfactant compounds (surfactants). Suitable solvents are aromatic hydrocarbons, preferably fractions containing 8 to 11 carbon atoms, for example mixtures of dimethylbenzene or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic or alicyclic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide as well as vegetable oils or epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water. The solid carriers used, for example for dispersible powders and powders, normally consist of natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granular absorbent carriers are porous type, for example pumice, brick powder, sepiolite or bentonite; and the appropriate non-absorbent carriers are materials such as calcite or sand.

In addition, a large amount of pregranulated materials of organic or inorganic nature can be used, for example, in particular, dolomite or pulverized plant residues. Suitable surfactant compounds which are used in the compositions of the present invention are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" also comprises mixtures of surfactants. Suitable carriers and coadjuvants for use in the compositions of the present invention may be solid or liquid and correspond to appropriate substances known in the art for the preparation of formulations for treating plants or the places where they grow, or for treating plant products, in particular for treating wood, such as for example natural or regenerated mineral substances, solvents, dispersants, surfactants, wetting agents, adhesives, binding thickeners, fertilizers, anti-freezing agents. repellents, color additives, corrosion inhibitors, water repellent agents, drying agents, UV stabilizers and other active ingredients. Suitable anionic surfactants can be water-soluble soaps and can be water-soluble synthetic surfactant compounds. Appropriate soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C.0-C22), for example the sodium or potassium salts of oleic or stearic acid, or mixtures of natural fatty acid which can be obtained, for example, from coconut oil or tallow oil. In addition, methyl taurine salts of fatty acid may be mentioned. More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, benzimidazole sulfonate derivatives or alkylarylsulfonates. The sulphonates or fatty sulfates usually have the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and may contain an alkyl radical having from 8 to 22 carbon atoms also comprising said radicals derived from radicals acyl, for example the sodium or calcium salts of lignosulfonic acid of dodecyl sulfate or of a mixture of fatty alcohol sulfates, obtained from natural acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol / ethylene oxide adducts. The suifonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylaryl sulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or the condensation product of naphthalenesulfonic acid / formaldehyde. Also suitable are the corresponding phosphates, for example the salts of the phosphoric acid ester of a p-nonylphenol adduct with 4 to 14 moles of ethylene oxide, or phospholipids. The nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing from 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon portion ( aliphatics) or 6 to 18 carbon atoms in the alkyl portion of the alkylphenols. Other suitable nonionic surfactants are the adducts of polyethylene oxide with water-soluble polypropylene glycol, ethylene diamine propylene glycol containing 1 to 10 carbon atoms in the alkyl chain, the adducts of which contain 20 to 250 ethylene glycol ether groups and 10 to 100 carbon atoms. propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of nonionic surfactants are nonylphenol polyethoxy ethanols, castor oil polyglycol ethers, polypropylene / polyethylene adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. The polyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants. The cationic surfactants are preferably quaternary ammonium salts containing, as N substituent, at least one C 8 -C 22 alkyl radical and, as additional substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts preferably have the form of halides, methylsulphates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide. Surfactants commonly employed in the art of formulation have been described, for example, in the following publications "McCutcheon's Detergents and Emulsifiers Annual," MC Publishing Corp. Ridgewood, New Jersey 1981; H. Schache, "Tensid-Taschenbuch", 2nd Edition, C. Hanser Verlag, Munich & Vienna, 1981, M and J. Ash, "Encyclopedia of Surfactants", Vol. I-III Chemical Publishing Co., New York, 1980-81. Particularly advantageous additives useful for improving the application and for reducing the dose of active ingredients, are natural (animal or plant) or synthetic phospholipids of the cephalin or lecithin type such as, for example, phosphatidylethanolamine, phosphatidylglycerin, lysolecite, or cardiolipin. Said phospholipids can be obtained, for example, from animal or plant cells, in particular from brain, heart or liver tissues, from egg yolks or soybeans. Such lipids are suitable, for example, as mixtures of phosphatidylchlorin. Synthetic phospholipids are, for example, dioctanilphosphatidylcholine and dipalmitoylphosphatidylcholine. In the case of liquid formulations, and particularly of aqueous or alcoholic formulations, it is advisable to add an appropriate surfactant agent of either anionic, cationic or neutral type. In particular said surfactants will be of cationic type and more particularly said surfactants will consist of quaternary ammonium salts or a mixture of quaternary ammonium salts. Said quaternary ammonium salt surfactants comprise, for example, ammonium salts having four hydrocarbon radicals which may be optionally substituted with halo, phenyl, substituted phenyl or hydroxy; said hydrocarbon radicals are in particular alkyl or alkenyl radicals; they may also be derived from alcohols or fatty acids, for example cetyl, lauryl, palmityl, myristyl, oleyl and the like or from hydroxylates of coconut oil, tallow oil, soybean oil, or the hydrogenated forms thereof, and the like . Examples of said quaternary ammonium salts are of the trimethylalkylammonium halide type, for example trimethyldecylammonium chloride, trimethyldodecylammonium chloride, trimethylseboammonium chloride, trimethylolethylammonium chloride; or of the dimethylalkylbenzylammonium type, for example dimethyldecylbenzylammonium chloride, dimethyldodecylbenzylammonium chloride, dimethylhexadecylbenzylammonium chloride (commonly referred to as "ketalkonium chloride"), dimethyloctadecylbenzyl ammonium chloride, dimethylcocobenzylammonium chloride, dimethylsilobenzylammonium chloride; and particularly the mixture of dimethylalkyl chloride C-8-.8-benzylammonium which is commonly known as "benzalkonium chloride", dimethyldialkyl ammonium halides, for example dimethyldioctylammonium chloride, dimethyldidylammonium chloride, dimethyldidodecylammonium chloride, dimethyldiocoammonium chloride, dimethyldiseboammonium, dimethyloctylcylammonium chloride, dimethyldodecyloctylammonium chloride, dimethylsebodihydrogenadoammonium chloride. As used in the above enumeration of quaternary ammonium salts, the terms "coco", "tallow" and "hydrogenated tallow" designate the hydrocarbon radicals derived from the hydroxylates of coconut oil, tallow oil or hydrogenated tallow oil. . Apart from the two aforementioned active ingredients of formulas (I) and (II), the compositions according to the present invention may further comprise other active ingredients, for example other microbicides, in particular fungicides, and also insecticides, acaricides, nematicides, herbicides, regulators of the development of plants and fertilizers. As antimicrobial agents, which can be used in combination with the active substances can be considered products of the following classes: phenolic derivatives such as 3,5-dichlorophenol, 2,5-dichlorophenol, 3,5-dibromophenol, 2,5-dibromophenol, 2.5- (resp. 3.5) -dichloro-4-bromophenol, 3,4,5-trichlorophenol, chlorinated hydrodiphenyl ethers such as, for example, 2-hydroxy-3,2,4'-trichlorodiphenylether, phenylphenol, 4- chloro-2-phenylphenol, 4-chloro-2-benzylphenol, dichlorophene, hexachlorophene; aldehydes such as formaldehyde, glutaraldehyde, salicylaldehyde; alcohols such as phenoxyethanol; antimicrobial active carboxylic acids and their derivatives; organometallic compounds such as tributyltin compounds; iodine compounds such as iodophors, iodonium compounds; mono-, di- and polyamines such as dodecylamine or 1,10-di (n-heptyl) -1,10-diaminodecane; sulfonium- and phosphonium compounds; mercapto compounds as well as their alkali metal salts, alkaline earth and heavy metals such as 2-mercaptopyridine-N-oxide and its sodium and zinc salt, 3-mercaptopiridacin-2-oxide, 2-mercaptoquinoxalina-1 -oxide, 2 -mercaptoquínoxalina-di-N-oxido, as well as the symmetrical disulfides of said mercapto compounds; ureas such as tribromo- or trichlorocarbanilide, dichlorotrifluoromethyl-diphenylurea; tribromosalicylanilide; 2-bromo-2-nitro-1,3-dihydroxypropane; dichlorbenzoxazolone; chlorhexidine; isothia- and benzisothiazolone derivatives. As insecticidal agents that can be used in the compositions according to the present invention, the following classes of products can be considered: insecticides having natural origin, for example nicotine, rotenone, pyrethrum and the like; chlorinated hydrocarbons, for example lindane, chlordane, endosulfan and the like; organophosphorus compounds such azinfosetilo, azinphos-methyl, 1- (4-chlorophenyl) -4 (O-ethyl, S-propyl) phosphoryl-oxipirazol, chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoate , ethoprophos, etrimfos fenitrothion, fenthion, heptenophos, parathion, parathion, phosalone, phoxim, pirimfos-ethyl, profenofos, prothiofos, sulfoprofos, triazophos, trichlorfon, carbamates, for example aldicarb, beniocarb, carbaryl, carbofuran, carbosulfan, cloethocarb, 2- (1-methylpropyl) phenylmethylcarbamate, butocarboxim, butoxicarboxime, phenoxycarb, isoprocarb, methomyl. methiocarb, oxamyl, pirimicarb, promecarb, propuxur and thiodicarb; biological insecticides, for example products originating from Bacillus thuringiensis; synthetic pyrethroids, for example allethrin, alphamethrin, bioresmethrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, decamethrin, deltamethrin, fenpropathrin, fenfluthrin, fenvalerate, flucitrinate, flumethrin, fluvalinate, halothrin, permethrin, resmethrin and tralometrine, alpha-cyano-3 phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoromethyl-vinyl) -cyclopropanecarboxylate; organosilicon compounds such as dimethylphenylsilyl-methyl-3-phenoxybenzyl ethers for example dimethyl () 4-ethoxyphenyl) -silylylmethyl-3-phenoxybenzylether; or dimetilfenilsililmetill-2-phenoxy-6-piridilmetiléteres for example dimethyl (9-ethoxyphenyl) silylmethyl-2-phenoxy-6-piridilmetiléter or [(phenyl) -3- (3-phenoxyphenyl) propyl] dimethylsilane, silafluofen; nitroimines and nitromethylethenes, for example 1- (6-chloro-3-pyridinylmethyl) -4,5-dihydro-N-nitro-1 H-imidazol-2-amine (imidacloprid); benzoylureas, for example lufenuron, hexaflumuron, flufenoxuron. In a further aspect of the present invention a method of combating fungi comprising treating plants or places where subsequently plants or simultaneously with a fungicidally effective amount of imazalil, a salt, a stereoisomer or stereoisomeric mixture develop it is provided same, and with epoxiconazole, a salt or a stereoisomer or stereoisomeric mixture thereof. The synergistic activity of imizalil and epoxiconazole can be demonstrated in vitro for example oranges inoculated with, Geotrichum candidum such and then dipped into a suitable liquid formulation containing both active ingredients. The following examples are intended to illustrate and not limit the scope of the present invention in all its aspects.

EXAMPLES A. BIOLOGICAL EXAMPLES EXAMPLE 1 Compounds: Imazalil was applied as mazalil sulfate containing 75% imazalil base. Epoxiconazole was applied as "Opus ™", a formulation containing 125 g of active ingredient per liter. Opus ™ is commercially available at BASF. Inoculation: An inoculum of Geotrichum candidum was prepared by a suspension of an aliquot of conidia and / or mycelial fragments in sterile distilled water. Oranges not subjected to any treatment were used, carefully washed as experimental subjects.

Each fruit was inoculated in 3 sites, distributed equidistantly around the perimeter by means of a corkscrew previously submerged in the inoculum.

Two fruits were used for each concentration of the treatment. Treatment: Four hours after the inoculation, two fruits were treated by immersing them in the test solution for one minute. Concentrations of the compound: each compound was applied in three concentrations: an average concentration, a concentration two times higher and a concentration two times lower. In a preliminary experiment, the average concentration for each compound was determined as a concentration at which the compound exhibited only partial efficacy. In this way, the probabilities of detecting possible synergy between the compounds were optimized. The following concentrations (in mg / liter) of imazalil and epoxiconazole were combined in all possible ways. epoxiconazole: 750/375 / 187.5 / 0 imazalil: 1500/750/375/0 After treatment they were kept in the dark in plastic bags at room temperature. Evaluation: After six and eight days, each inoculated site was inspected for decomposition and fungal development. The fungal attack was quantified by measuring the distance, in mm, between the perimeter of the 10 mm diameter inoculation ring and the perimeter of the damaged area. When no visible damage was seen outside the inoculation ring, the fungal extension was reported to be 0 mm, but the amount of damage inside the ring was noted as "observations". After each evaluation, the fungal extension was calculated in mm, for each treatment, as the average of six inoculations. The percentage of activity was calculated for the treatments, comparing it with the untreated controls. The possible synergy was investigated using the Limpel formula (Richter, D.L., Pestic.Sci. 1978, 19: 309-315): Er = X + Y- X.X c 100 where Ec is an expected additive response, X is the control percentage observed when compound A is applied alone, and Y is the control percentage observed when compound B is applied alone. It was considered that the synergy occurred when the effect of a combination of both compounds was higher than the corresponding value Ec.

TABLE 1 Epoxiconazol-imazalil: There is an obvious synergy between the lowest dose of epoxiconazole (187.5 mg / l) and imazalil at 750 and 1500 mg / l. The same doses of mazalil are also, to a limited degree, synergistic with epoxiconazole at 375 mg / l. However, there is a pronounced antagonism between the lower dose of imazalil (375 mg / l) and the three doses of epoxiconazole applied.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. A composition comprising imazalil (I), a salt, a stereoisomer or a stereoisomeric mixture thereof, an epoxiconazole (II), a salt, an extereoisomer or a steroisomeric mixture thereof, in amounts that produce a synergistic antifungal effect mutual, and a carrier.

2. A composition according to claim 1, comprising at least 750 mg / l of imazalil and at least 187.5 mg / l of epoxiconazole.

3. A composition according to claim 1, comprising imazalil in a concentration comprised between 750 mg / l and 1500 mg / l and epoxiconazole in a concentration between 187.5 mg / l and 750 mg / l.

4. A composition according to claims 1 to 3, formulated as a concentrate.

5. A composition according to claim 4, wherein the concentrate is an emulsifiable concentrate, a suspension concentrate or a soluble concentrate.

6. A product containing imazalil (I), a salt, a stereoisomer or a stereoisomeric mixture thereof, and epoxiconazole (II), a salt, a stereoisomer or a stereoisomeric mixture thereof in combination for simultaneous, separate or sequential in antifungal applications.

7. Use of a composition as defined in any of claims 1 to 5, to protect plants or places where they grow, against fungi.

8. Use of a composition as defined in any of claims 1 to 5, to protect the fruits, against fungi.

9. Use of a composition as defined in any of claims 1 to 5, to protect the seeds, against fungi.

10. A process for preparing a synergistic composition according to any of claims 1 to 5, characterized in that the active ingredients are intimately mixed with the carrier.