fungicidal mixture

Abstract

Compositions comprising streptimidon and malonomycin, pesticide compositions comprising the mixtures, and methods and uses of the compositions in controlling or preventing fungal infestation of plants or other substrates.

Description

[Technical Field]

[0001] The present invention relates to a mixture comprising two known compounds, streptimidon and malonomycin, and its use, in particular for controlling fungi in agriculture or horticulture. The present invention also relates to a fungicidal composition, in particular an agrochemical fungicidal composition, comprising this mixture, and to a process for preparing this composition. [Background technology]

[0002] Streptomidone is a compound of formula (I) [ka] is a known compound.

[0003] Strepimidone has been described in Kondo, H., Oritani, T., and Kiyota, H. Synthesis and antifungal activity of the four stereoisomers of streptimidone, a glutarimide antibiotic from Streptomyces rimosus forma paromomycinus. Eur. J. Org. Chem. (20), 3459-3462 (2000). Many Streptomyces strains express streptimidone. Strepimidone is also commercially available.

[0004] Malonomicin (sometimes spelled "malonomycin") has the formula (II): [ka] {[(2S)-2-amino-3-hydroxypropanoyl]amino}{2-[(5S)-5-(aminomethyl)-4-hydroxy-2-oxo-2,5-dihydro-1H-pyrrol-3-yl]-2-oxoethyl}malonic acid.

[0005] Maronomycin is a natural compound prepared by fermentation. U.S. Patent No. 3,536,811 discloses maronomycin for use as an antibiotic and protozoan growth inhibitor. European Patent No. 1,860,939 describes maronomycin as an agricultural fungicide.

[0006] Surprisingly, it has now been found that mixtures comprising streptimidon and malonomycin can exhibit an unexpected synergistic fungicidal effect. Summary of the Invention [Means for solving the problem]

[0007] According to a first aspect of the present invention there is provided a mixture comprising streptimidon and malonomycin.

[0008] According to a second aspect of the present invention there is provided an agrochemical composition comprising a mixture comprising a fungicidally effective amount of streptimidon and malonomycin, and such agrochemical composition may further comprise an agrochemically acceptable diluent or carrier.

[0009] Reference herein to an agrochemical composition includes chemical compositions and biological compositions, preferably non-naturally occurring biological compositions, e.g., biologically produced compositions, e.g., microbiologically produced compositions, or non-naturally occurring compositions.

[0010] The composition according to the present invention is an isolated composition. An isolated composition refers to a non-naturally occurring composition.

[0011] According to a third aspect of the present invention there is provided a method for controlling or preventing fungal infestation of plants, comprising applying to a plant, part thereof or its habitat a fungicidally effective amount of an agrochemical composition comprising a mixture comprising streptimidon and malonomycin.

[0012] According to a fourth aspect of the present invention there is provided the use of a mixture comprising streptimidon and malonomycin as a fungicide. According to this particular aspect of the present invention, the use may not include methods involving the treatment of the human or animal body by surgery or therapy.

[0013] Many Streptomyces strains express streptimidon, which is also commercially available.

[0014] Maronomycin can be prepared according to the method disclosed in Examples IA and B of EP 1860939 or according to Law et al, 2018 (Nature Catalysis | VOL 1 | DECEMBER 2018 | 977-984). DETAILED DESCRIPTION OF THE INVENTION

[0015] Mixtures containing streptimidon and malonomycin can be used as active ingredients in agricultural and related fields of use, for example, to control fungal plant pests or in non-living materials to control decay fungi or fungi potentially harmful to humans. Mixtures containing streptimidon and malonomycin have surprising efficacy at low application rates and are well tolerated by plants. They have highly useful curative and preventative properties and can be used to protect a wide variety of cultivated plants. Mixtures containing streptimidon and malonomycin also have surprising synergistic effects. They can be used to suppress or eradicate fungi that appear on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while simultaneously protecting those parts of the plant that grow later.

[0016] The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and / or harvested food crops that are susceptible to fungal attack by treating the plants or plant propagation material and / or harvested food crops, wherein a mixture comprising a fungicidally effective amount of streptimidon and malonomycin is applied to the plants, their parts or their habitat.

[0017] A mixture containing streptimidon and malonomycin can also be used more broadly as a fungicide. As used herein, the term "fungicide" refers to a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount," when used, refers to the amount of such a compound or combination of such compounds that is capable of producing an effect on fungal growth. A controlling or modifying effect includes any deviation from natural occurrence, such as killing, delaying, etc., and prevention includes the formation of a barrier or other defense in plants to prevent fungal infection.

[0018] For protection against fungal infections and phytopathogenic fungi occurring in the soil, a mixture containing streptimidon and malonomycin may also be used as a dressing for treating plant propagation material, such as seeds, such as fruits, tubers, or grains, or plant cuttings. The propagation material may be treated with a composition containing streptimidon and malonomycin before planting: for example, seeds may be dressed before sowing. Streptomycin and malonomycin may also be applied to seeds (coatings) by impregnating the seeds in a liquid formulation or by coating the seeds with a solid formulation. The composition may also be applied to the planting site, for example, in the sowing furrow during sowing, when the propagation material is to be planted. The present invention also relates to a method for treating such plant propagation material, and to plant propagation material treated in this way.

[0019] Furthermore, mixtures comprising streptimidon and malonomycin can be used to control fungi, for example in the protection of technical materials and wood-related technical products, food preservation, pharmaceutical applications, veterinary applications and related fields of hygiene.

[0020] Additionally, the present invention can be used to protect non-living materials such as timber, wallboard, wallpaper and paint from fungal attack.

[0021] Examples of important fungi that need to be controlled in agriculture and other sectors are: Botrytis cinerea, Cercospora kikuchii, Cercospora sojina, Cochliobolus sativus, Colletotrichum lindemuthianum, Colletotrichum orbiculare, Corynespora cassiicola, Fusarium avenaceum, Fusarium culmorum, Fusarium langsethiae, Fusarium poae, Fusarium sporotrichioides sporotrichioides, Fusarium tricinctum, Fusarium virguliforme, Gibberella avenacea, Gibberella fujikuroi, Gibberella zeae, Microdochium majus, Monographella nivalis, Mycosphaerella arachidis, Phakopsora pachyrhizi, Puccinia triticinae triticina (=P. recondita), wheat yellow spot fungus (Pyrenophora tritici-repentis), Ramularia collo-cygni, Rhynchosporium secalis, Septoria glycines, Tilletia tritici, Ustilago segetum var.Tritici (Ustilago segetum var. Tritici), apple scab fungus (Venturia inaequalis), and Zymoseptoria tritici.

[0022] Preferred examples of fungi are Gibberella species, including Gibberella zeae (also known as Fusarium graminearum), Fusarium species, including Fusarium virguliforme (also known as Fusarium solani f.sp. glycines, or soybean sudden death syndrome), Microdochium species, such as Monographella nivalis (also known as Microdichium nivale or cereal head blight), and Zymoseptoria tritici (Septoria tritici, wheat leaf blight (also known as Mycosphaerella graminicola or Septoria leaf blight), in particular Zymoseptoria tritici, Microdichium nivale (=Monographella nivalis) and Gibberella zeae (=Fusarium graminearum).

[0023] Fusarium avenaceum, Fusarium culmorum, Fusarium langsethiae, Fusarium poae, Fusarium sporotrichioides, Fusarium tricinctum, Fusarium virguliforme, Fusarium verticillioides, Fusarium subglutinans, Zymoseptoria tritici, Puccinia triticina Particularly preferred are P. triticina (= P. recondita), Mycosphaerella fijiensis, Puccinia striiformis, Magnaporthe grisea and Rhizoctonia solani.

[0024] Target crops and / or useful plants to be protected are typically berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; field crops, such as sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus fruit, nectarine, peach, pear and plum; pasture grasses, such as bermudagrass, bluegrass, bentgrass, centipedegrass, fescue, rye, lawn grass and wild grass; Includes herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, radish, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as vines.

[0025] The term "crop" or "useful plant" should also be understood to include plants that have been rendered tolerant to herbicides such as bromoxynil or to classes of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional methods of breeding (mutagenesis). Crops that have been rendered tolerant to imidazolinones, such as imazamox, by conventional methods of breeding (mutagenesis) include, for example, Clearfield® summer rape (canola). Crops that have been genetically engineered to be tolerant to herbicides or classes of herbicides include, for example, glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0026] It should be understood that the term "crop" or "useful plant" also includes plants that have been transformed using recombinant DNA techniques so as to be able to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly Bacillus bacteria.

[0027] Mixtures containing streptimidon and malonomycin may also be used, for example, on turf, ornamental plants such as flowers, shrubs, broadleaf trees, or evergreen trees such as conifers, as well as for trunk injections, pest control, and the like.

[0028] Preferred crops on which mixtures comprising streptimidon and malonomycin can be used include bananas, cereals and pulses such as peanuts or soybeans, and grains such as wheat, barley, rice or corn.

[0029] As used herein, the term "habitat" means the field in which the plant is growing or in which the seeds of the plant to be cultivated have been sown or will be sown in the soil. It includes the soil, seeds and seedlings, and established vegetation.

[0030] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0031] The term "plant propagation material" is understood to refer to reproductive parts, such as seeds, of plants and vegetative parts, such as cuttings or tubers, which can be used for their propagation, for example potatoes. Examples include seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Mention may also be made of germinated plants and seedlings that are to be transplanted after germination or emergence from the soil. These seedlings can be protected by a complete or partial immersion treatment before transplanting. Preferably, "plant propagation material" is understood to refer to seeds.

[0032] The mixtures containing streptimidon and malonomycin can be used in their original form or, preferably, with adjuvants conventionally used in the formulation art. For this purpose, they can be formulated in a known manner into emulsifiable concentrates, coatable pastes, ready-to-spray or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, or even encapsulated in polymeric materials. The application method, such as spraying, atomizing, dusting, scattering, coating, or pouring, as well as the type of composition, are selected depending on the intended purpose and the circumstances. The compositions can also contain further adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, sources of trace elements, or other ingredients for special effects.

[0033] When streptimidon is produced by a microorganism, it can be isolated from the microorganism. Alternatively, significant amounts of streptimidon may be present in the medium in which the microorganism is grown, in which case the medium or liquid medium can be used together with malonomycin to formulate the fungicidal composition. As a further alternative, the microorganism may produce both streptimidon and malonomycin, in which case the microorganism itself can be used to formulate the composition. Thus, a process for producing streptimidon and malonomycin is disclosed, which comprises fermenting the microorganism in a suitable fermentation medium under conditions conducive to the production of streptimidon and malonomycin. In such cases, the microorganism can be formulated as viable cells actively producing streptimidon and malonomycin, or can be inactivated, for example, by heat treatment. The microorganism can be concentrated, if desired, by centrifugation or other conventional techniques.

[0034] Suitable carriers and adjuvants, for example for agricultural applications, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0035] Suspension concentrates are formulations in which finely divided solid particles of the active compound are suspended in a liquid. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents, as well as anti-foaming and crystal growth inhibitors to enhance activity. When used, these concentrates are diluted in water and typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0036] Wettable powders are in the form of finely divided particles that disperse readily in water or other liquid carriers. The particles contain the active ingredient held in a solid matrix. Typical solid matrices include fuller's earth, kaolin clay, silica, and other readily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents, or emulsifying agents.

[0037] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, high-boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquid and typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0038] Granular formulations include both extrudates and relatively coarse particles, and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cobs, ground peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredient, which may include surfactants or vegetable oils such as high-boiling aromatic naphtha, kerosene, and other petroleum fractions; and / or adhesives such as dextrin, glue, or synthetic resins.

[0039] Dusts are free-flowing mixtures of the active ingredient and finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

[0040] Microcapsules are typically droplets or granules of an active ingredient enclosed in an inert, porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's weight and may contain solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule, retaining the active species in liquid form within the pores of the granule. Granules typically range in diameter from 1 millimeter to 1 centimeter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or are naturally occurring. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthates.

[0041] Other useful formulations for pesticide applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene, and other organic solvents. Pressurized sprayers can also be used, in which the active ingredient is dispersed in finely divided form as a result of evaporation of the low-boiling dispersant solvent carrier.

[0042] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0043] Liquid carriers that can be used include, for example, water, vegetable oil, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, 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, alkylpyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octyl Examples of suitable carriers include methylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for dilution of concentrates.

[0044] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, walnut hulls, and lignin.

[0045] A wide variety of surfactants are advantageously employed in both the liquid and solid compositions, especially those designed to be diluted with a carrier before application. These agents, when used, typically comprise 0.01% to 15% (by weight) of the formulation. They may be anionic, cationic, nonionic, or polymeric in nature and may be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surfactants include Tween 20, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide adducts, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide adducts, such as tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, 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.

[0046] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizers, defoamers, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and adhesives.

[0047] In addition, other agrochemically active ingredients or compositions can be combined with the compositions of the present invention and used in the methods of the present invention, and applied simultaneously or sequentially with the compositions of the present invention. When applied sequentially, the compositions of the present invention can be applied to plants during a different growth phase than the other agrochemically active ingredients. When applied simultaneously, these additional active ingredients can be formulated together with the compositions of the present invention or mixed, for example, in a spray tank. These additional agrochemically active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, growth stimulants, and / or plant growth regulators.

[0048] Pesticides are referred to herein using their common names and are known, for example, from "The Pesticide Manual", 19th Ed., British Crop Protection Council 2021.

[0049] The mixtures according to the invention can be mixed with one or more pesticides known in the art.

[0050] The mixtures according to the present invention may be mixed with one or more fungicides, including biofungicides known in the art.

[0051] The mixture comprising streptimidon and malonomycin can be used in the form of agrochemical compositions, and can be applied simultaneously or sequentially to crop areas or treated plants with additional compounds.These additional compounds can be, for example, fertilizers or trace element sources or other preparations that affect plant growth.They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, and if necessary, also contain additional carriers, surfactants, or application-promoting adjuvants commonly used in the technical field of formulation.

[0052] The mixture containing streptimidon and malonomycin can be used in the form of a (fungicidal) composition for the control or protection against phytopathogenic microorganisms, which contains as active ingredients streptimidon and malonomycin, and at least one of the above-mentioned adjuvants.

[0053] Thus, the present invention provides a composition, preferably a fungicidal composition, comprising streptimidon, malonomycin, an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may contain, in addition to streptimidon and malonomycin, at least one or more pesticidal active compounds, such as additional fungicidal active ingredients.

[0054] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized palm oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0055] The compositions according to the invention are prepared in a manner known per se in the absence of auxiliaries, for example by grinding, sieving and / or compressing the solid active ingredient, and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliaries and / or grinding. These methods for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0056] Another aspect of the present invention relates to the use of a composition comprising streptimidon and malonomycin, or a fungicidal or insecticidal mixture comprising streptimidon and malonomycin, in admixture with other fungicides or insecticides as mentioned above, for the control or prevention of infestation by insects or by phytopathogenic microorganisms, preferably fungal organisms, on plants, such as useful plants, e.g. crop plants, their propagation material, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material.

[0057] A further aspect of the present invention relates to a method for controlling or preventing infestation by insects, or by plant pathogenic or spoilage microorganisms, or by organisms potentially harmful to humans, in particular fungal organisms, on plants, such as useful plants, e.g. crop plants, their propagation material, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material, which method comprises applying a mixture comprising streptimidon and malonomycin as active ingredients to the plant, plant parts or their habitat, their propagation material, or any part of the non-living material.

[0058] Control or prevention means the reduction of infestation by plant pathogenic or spoilage microorganisms or by organisms potentially harmful to humans, especially fungal organisms, to the extent that an improvement can be demonstrated.

[0059] Preferred methods for controlling or preventing infestation of crop plants by phytopathogenic microorganisms, particularly fungal organisms, or insects include those in which the application of a compound of formula (I) and a compound of formula (II), or an agrochemical composition containing at least one of the aforementioned compounds, is a foliar treatment. The frequency and amount of application will depend on the risk of infestation by the corresponding pathogen. However, the compositions of the present invention can also be applied to plants through the roots via the soil by drenching the plant habitat with a liquid formulation or by applying the compound in solid form, for example, in granular form, to the soil (soil application). In rice crops, such granules can be applied to flooded rice fields. The mixtures of the present invention can also be applied to seeds by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation (coating).

[0060] Formulations, e.g., compositions, containing the mixtures of the present invention and, if desired, solid or liquid adjuvants or monomers encapsulating the mixtures of the present invention, can typically be prepared in a known manner by intimately mixing and / or grinding the compounds together with extenders, e.g., solvents, solid carriers, and, optionally, surface-active compounds (surfactants).

[0061] The weight / molar ratio of streptimidon to malonomycin is preferably 10:1 to 1:500, more preferably 1:1 to 1:300, and most preferably 1:10 to 1:100.

[0062] The preferred application rate is generally 0.1 g to 6 kg of active ingredient (ai; total weight of streptimidon and malonomycin) per hectare (ha), preferably 0.1 g to 1 kg ai / ha, and most preferably 10 g to 800 g ai / ha.

[0063] When the combinations according to the invention are used for seed treatment, a rate of from 0.001 to 100 g of active ingredient per kg of seed, preferably from 0.01 to 10 g per kg of seed, is generally sufficient.

[0064] Preferably, the compositions comprising streptimidon and malonomycin according to the invention are applied either prophylactically, meaning before the onset of disease, or curatively, meaning after the onset of disease.

[0065] Certain mixtures of streptimidon and malonomycin may exhibit synergistic effects. This occurs whenever the effect of the combination of active ingredients is greater than the sum of the effects of the individual components. The expected effect E of a given combination of active ingredients can be calculated according to the so-called Colby formula as follows (COLBY, SR "Calculating synergistic and antagonistic responses of herbicide combinations". Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (=ai) per liter of spray mixture X = % effect of active ingredient A) using p ppm of active ingredient Y = % effect of active ingredient B) using q ppm of active ingredient.

[0066] According to COLBY, the expected (additive) effect of active ingredients A) + B) using p+q ppm of active ingredients is as follows:

number

[0067] If the actual observed effect (O) is greater than the expected effect (E), the effect of the combination is superadditive, i.e., a synergistic effect is present. In mathematical terms, synergy corresponds to a positive value for the difference (OE). If the activities are purely complementary and additive (expected activity), the difference (OE) is zero. A negative value for the difference (OE) indicates a loss of activity compared to the expected activity.

[0068] However, in addition to the actual synergistic action with respect to fungicidal activity, the composition according to the present invention may also have other unexpected advantageous properties.Examples of such advantageous properties that may be mentioned include: more advantageous decomposition; improved toxicological and / or ecotoxicological behavior; or improved useful plant properties, including emergence, crop yield, more developed root system, increased tillers, increased plant height, larger leaf blades, fewer dead basal leaves, stronger tillers, greener leaf color, less fertilizer required, less seed required, more productive tillers, earlier flowering, earlier grain maturation, less plant lodging (lodging), increased shoot growth, improved plant vigor, and earlier germination.

[0069] The compositions of the present invention may be in any conventional form, such as, for example, two-part systems, dry seed treatment powders (DS), seed treatment emulsions (ES), seed treatment flowable concentrates (FS), seed treatment solutions (LS), seed treatment water dispersible powders (WS), seed treatment capsule suspensions (CF), seed treatment gels (GF), emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (WG), They may be employed in the form of granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0070] Such compositions can be prepared in a conventional manner, for example, by mixing the active ingredient with suitable formulation inerts (diluents, solvents, fillers, and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, spreading agents, thickeners, and compounds providing auxiliary effects). Conventional sustained-release formulations can also be employed when long-lasting effectiveness is intended. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, can contain surfactants, such as wetting agents and dispersants, as well as other compounds providing auxiliary effects, such as condensation products of formaldehyde with naphthalenesulfonates, alkylarylsulfonates, ligninsulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0071] The seed dressing formulation is applied to seeds in a manner known per se, using the combination of the present invention and a diluent in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form with good adhesion to the seeds. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as slow-release capsules or microcapsules.

[0072] Typically, the formulation contains 0.01 to 90% by weight of the active agent, 0 to 20% by weight of an agriculturally acceptable surfactant, and 10 to 99.99% by weight of a solid or liquid inert compounding agent and adjuvants, including streptimidon and malonomycin, optionally together with other active agents, particularly microbicides or preservatives. Concentrate forms of the composition generally contain about 2 to 80% by weight, preferably about 5 to 70% by weight, of the active agent. The application form of the formulation can contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of the active agent. Commercially available products are preferably formulated as concentrates, but end users typically use diluted formulations. [Example]

[0073] The following examples illustrate the invention. Temperatures are given in degrees Celsius (°C), rh means relative humidity, and ppm means parts per million by weight. Colby, supra, see COLBY, SR, "Calculating synergistic and antagonistic responses of herbicide combinations." Weeds, Vol. 15, pages 20-22; 1967.

[0074] Example 1. Fungicidal activity of mixtures with malonomycin in liquid culture assays method: Streptomycin (CAS: 738-72-7) was purchased from a commercial supplier. A stock solution of streptimidon was prepared in DMSO (up to 10 mg / ml). Maronomycin was prepared according to Law et al., 2018 (Nature Catalyses | VOL 1 | DECEMBER 2018 | 977-984). A stock solution of maronomycin was prepared in water with 0.025% Tween 20.

[0075] An assay to test the effectiveness of a mixture of streptimidon in combination with malonomycin for control of fungal pathogens in liquid culture assays was designed for 96-well plates.

[0076] Table 1: Overview of the 96-well test plate with compound concentrations per well. The upper number in the cell indicates the malonomycin concentration (ppm), and the lower number indicates the streptimidon concentration (ppm). Column (1) holds the dilution series of streptimidon, row (H) holds the dilution series of malonomycin, and column (12) holds cells representing the untreated test.

[0077] [Table 1]

[0078] The 96-well plate design allows for the comparison of the disease control of the mixture with that of each single compound at the same rate. By comparing the estimated efficacy from the mixture with the efficacy calculated from the same mixture according to Colby, it is possible to describe the mixture as either additive (efficacy is similar to the Colby calculation), synergistic (efficacy is better than the Colby calculation), or antagonistic (efficacy is worse than the Colby calculation).

[0079] The same 96-well plate design also allows for the evaluation of whether the two compounds can be mixed at different rates and mixing ratios. The plate design outlined in Table 1 provides the following mixing ratios, as shown in Table 2:

[0080] Table 2: Mixing ratios of two compounds in the 96-well plate assay design outlined in Table 1. The numbers represent the ratio of compound 1:compound 2. Compound 1 is malonomycin and compound 2 is streptimidon. The plate design spans a wide range, from 641:1 to 1:100.

[0081] [Table 2]

[0082] A master plate was prepared containing 10x concentrated solutions of compound stock solutions diluted in water with 0.025% Tween 20. The concentrations of DMSO (from streptimidon stock) and Tween 20 were kept constant in all cells of the master plate. 10 μl was transferred from the master plate to a 96-well test plate. Nutrient broth containing fungal spores / mycelium fragments was then added to the test plate to obtain a 1x final concentration for the test compound (as outlined in Table 1). The test plate was incubated in the dark at 24°C and 96% rh. Inhibition of fungal growth was determined photometrically after approximately 3 days, and the percentage of fungal growth reduction relative to untreated controls was calculated. The effectiveness of the mixtures was tested on various fungal species:

[0083] Botrytis cinerea (EPPO code: BOTRCI) Cryopreserved fungal conidia were mixed directly into nutrient liquid medium (Vogel's minimal medium). Test plates were incubated at 24°C and growth inhibition was determined photometrically after 72 hours.

[0084] result Table 3: Control of Botrytis cinerea for single compounds and mixtures. The plate design including the concentrations of streptimidon and malonomycin is shown in Table 1. Values ​​indicate the control of fungal growth (% reduction in growth in test wells compared to untreated controls).

[0085] [Table 3]

[0086] Table 4: Comparison of measured values ​​for disease control of Botrytis cinerea (as reported in Table 3) with calculated values ​​using the formula from Colby for the same mixtures. The numbers reported in the table represent the difference between measured efficacy (in %) and calculated efficacy (in %). Values ​​near 0 (zero) indicate additive activity, while positive values ​​suggest synergistic activity.

[0087] [Table 4]

[0088] Conclusion: Streptomycin and malonomycin can be mixed to obtain complete or partial control of fungal pathogens. The mixing ratio of the two compounds can vary widely in the mixture, but still result in over 50% control of fungal growth. Surprisingly, the efficacy of many mixtures was superior to that predicted based on calculations from Colby, indicating that mixtures of streptomidon and malonomycin have a synergistic effect on the control of fungal pathogens. This surprising synergy was observed in tests to control Botrytis cinerea.

[0089] 2. Fungicidal activity of mixtures with malonomycin in the leaf disc assay method: Streptomycin (CAS: 738-72-7) was purchased from a commercial supplier. A stock solution of streptimidon was prepared in DMSO (up to 10 mg / ml). Maronomycin was prepared according to Law et al., 2018 (Nature Catalyses | VOL 1 | DECEMBER 2018 | 977-984). A stock solution of maronomycin was prepared in water with 0.025% Tween 20.

[0090] An assay to test the effectiveness of a mixture of streptimidon in combination with malonomycin for control of fungal pathogens in a leaf disc assay was designed for two 24-well plates.

[0091] Tables 5 and 6: Overview of 24-well test plate (1) and test plate (2), including the concentration of compounds sprayed per well. The upper number in the cell indicates the streptimidon concentration (ppm), and the lower number indicates the malonomycin concentration (ppm). Column (1) holds the dilution series of streptimidon, while row (2-D) holds the dilution series of malonomycin. Well 2-D-(1) represents the untreated test. This design was applied to a test involving Puccinia recondita (EPPO code: PUCCRE) at preventive and curative spray timings.

[0092] [Table 5]

[0093] [Table 6]

[0094] Table 7: Compound mixture ratios sprayed in the 24-well plate assays outlined in Tables 5 and 6. Numbers represent the ratio of Compound 1:Compound 2. Compound 1 is malonomycin and Compound 2 is streptimidon. Plate designs across two 24-well plates span a wide range from 64:1 to 1:270.

[0095] [Table 7]

[0096] A first set of master plates was prepared containing a 1x concentrated spray solution of streptimidon stock diluted in water at the concentrations shown in Table 5 or Table 6, respectively. Each well contained 2% DMSO and 0.025% Tween 20. A second set of master plates was then prepared containing a 1x concentrated malonomycin stock diluted in water. Each well of the second set contained 0.025% Tween 20. Leaf sections placed on agar in a 24-well plate were sprayed with 8 μl of the solution from the master plate containing streptimidon, allowed to dry, and then sprayed 2 hours later with 8 μl of the solution from the master plate containing malonomycin. After the second spray had dried, the leaf sections were infected with fungal spores to provide a preventative application timing. Alternatively, leaf sections infected one day before spraying with the compound were used to provide a curative spray timing. Additionally, several plates were prepared in which leaf sections were sprayed twice in the absence of test compound (containing only DMSO and Tween 20) to represent untreated test samples. For each leaf section, the percentage leaf coverage of disease symptoms was assessed. The reduction in percentage leaf coverage relative to the untreated test was calculated. The efficacy of the mixtures was tested against different fungal species in duplicate. The reported efficacy values ​​are the average of the two replicate test results.

[0097] Preventive spray timing for Puccinia recondita (EPPO code: PUCCRE). Wheat (Kanzler variety) leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with the test solution (8 ul per well). After drying, the leaf segments are inoculated with a fungal spore suspension. After appropriate incubation, the activity of the compounds is evaluated 8 dpi (days post-inoculation) as preventative fungicidal activity.

[0098] Puccinia recondita (EPPO code: PUCCRE) with therapeutic spray timing. Wheat (Kanzler variety) leaf segments are placed on agar in a multi-well plate (24-well format). The leaf segments are then inoculated with a fungal spore suspension. One day after inoculation, the test solution is sprayed (8 ul per well). After appropriate incubation, the activity of the compound is evaluated 8 dpi (days after inoculation) as curative fungicidal activity.

[0099] result Table 8: (Preventive) control of Puccinia recondita for single compounds and mixtures. Plate designs with concentrations of streptimidon and malonomycin are shown in Tables 5 and 6. Values ​​indicate control of fungal growth (% reduction of symptoms on leaf sections compared to untreated tests).

[0100] [Table 8]

[0101] Table 9: Comparison of measured values ​​for (preventive) disease control of Puccinia recondita (as reported in Table 8) with calculated values ​​using the formula from Colby for the same mixtures. The numbers reported in the table represent the difference between the measured efficacy (in %) and the calculated efficacy (in %). Values ​​near 0 (zero) indicate additive activity, while positive values ​​suggest synergistic activity.

[0102] [Table 9]

[0103] Table 10: (Curative) control of Puccinia recondita for single compounds and mixtures. Plate designs with concentrations of streptimidon and malonomycin are shown in Tables 5 and 6. Values ​​indicate control of fungal growth (% reduction of symptoms on leaf sections compared to untreated tests).

[0104] [Table 10]

[0105] Table 11: Comparison of measured (curative) disease control of Puccinia recondita (as reported in Table 10) with calculated values ​​using the formula from Colby for the same mixtures. The numbers reported in the table represent the difference between the measured efficacy (in %) and the calculated efficacy (in %). Values ​​near 0 (zero) indicate additive activity, while positive values ​​suggest synergistic activity.

[0106] [Table 11]

[0107] Conclusion: Streptomydon and malonomycin can be mixed to obtain complete or partial control of fungal pathogens. The mixing ratio of the two compounds can vary widely in the mixture, but still results in greater than 50% control of fungal growth when sprayed on leaves. Surprisingly, the efficacy of many mixtures was superior to that predicted based on calculations from Colby, indicating that mixtures of streptomidon and malonomycin have a synergistic effect on the control of fungal pathogens when sprayed on leaves. This surprising synergy was observed in tests to control Puccinia recondita.

Claims

1. A composition comprising streptimidon and malonomycin.

2. 2. The composition of claim 1, wherein the ratio of streptimidon to malonomycin is from 10:1 to 1:500 by weight.

3. 3. The composition of claim 2, wherein the ratio of streptimidon to malonomycin is from 1:1 to 1:300 by weight.

4. A pesticide composition comprising a fungicidally effective amount of a mixture comprising streptimidon and malonomycin.

5. 5. The pesticide composition of claim 4, further comprising an agrochemically acceptable diluent or carrier.

6. The pesticide composition according to claim 4 or 5, comprising the composition according to any one of claims 1 to 3.

7. 10. A method for controlling or preventing fungal infestation of plants, wherein a fungicidally effective amount of a composition according to any one of claims 1 to 6 is applied to the plant, its parts or its habitat.

8. 8. The method of claim 7, wherein the composition is applied to plants at a rate of 0.1 g to 6 kg of the combined weight of streptimidon and malonomycin per hectare.

9. 8. The method of claim 7, wherein the composition is applied to seeds at a rate of 0.001 to 100 g of the total weight of streptimidon and malonomycin per kg of seeds.

10. The method according to any one of claims 7 to 9, wherein the plant is selected from the group consisting of cereals and pulses.

11. The fungus may be selected from the group consisting of Fusarium avenaceum, Fusarium culmorum, Fusarium langsethiae, Fusarium poae, Fusarium sporotrichioides, Fusarium tricinctum, Fusarium virguliforme, Fusarium verticillioides, Fusarium subglutinans, and the like.

11. The method according to any one of claims 7 to 10, wherein the selected fungus is selected from the group consisting of Puccinia tritici, Puccinia triticina (= P. recondita), Mycosphaerella fijiensis, Puccinia striiformis, Magnaporthe grisea and Rhizoctonia solani.

12. Use of a composition comprising streptimidon and malonomycin according to any one of claims 1 to 3 as an antifungal or fungicidal agent.

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