Fungicidal compositions

Abstract

Disclosed is a composition suitable for controlling diseases caused by plant pathogens, the composition comprising: (A) which is a compound of formula (I), wherein R is C1-C6 alkyl, C1-C6 alkoxy or C3-C6 cycloalkyl, and X is CH or N; and (B) at least one compound selected from compounds known for their fungicidal activity; and a method of controlling diseases on useful plants, in particular rust diseases on soybean or cereals.

Description

[0001] This invention relates to novel fungicidal compositions suitable for controlling diseases caused by plant pathogenic fungi, particularly Phakopsorapachyrhizi (the pathogen of Asian soybean rust), and to a method for controlling diseases on useful plants, particularly soybeans.

[0002] As known from WO 2020 / 097012 and WO 2021 / 226234, certain carbamate derivatives and mixtures containing said carbamate derivatives possess biological activity against plant pathogenic fungi. On the other hand, various fungicides of different chemical classes are well known to be applied as plant fungicides to a wide range of cultivated plant crops. However, crop tolerance and activity against plant pathogenic fungi do not always meet the needs of agricultural practice in many situations and aspects. For example, *Phyllostachys spp.* (the pathogen of Asian soybean rust) has become an increasingly important problem in soybean production, causing considerable yield losses. Many conventional fungicides are unsuitable for controlling Asian soybean rust, or their effectiveness against *Phyllostachys spp.* is unsatisfactory.

[0003] In light of the above-mentioned agricultural practices requiring improved crop tolerance and / or enhanced activity against plant pathogenic fungi (such as *Dioscorea beanus* rust), a novel composition suitable for controlling diseases caused by plant pathogens is proposed according to the present invention.

[0004] The composition according to the invention comprises: (A) a compound having formula I

[0005]

[0006] Wherein R is a C1-C6 alkyl, C1-C6 alkoxy, or C3-C6 cycloalkyl, and X is CH or N; and

[0007] (B) At least one compound selected from the group consisting of fluoxazine and pyridine.

[0008] In the presence of an asymmetric carbon atom in a compound having Formula I, the compound may exist in optical isomeric form (i.e., enantiomers or diastereomers). As a result of restricted rotation around the single bond, a trans-blocking isomer may also exist. This invention includes all possible isomeric forms of compounds having Formula I and mixtures thereof. Similarly, Formula I is intended to include all possible tautomers. This invention includes all possible tautomeric forms of compounds having Formula I, and also includes racemic compounds, i.e., mixtures of at least two enantiomers in a substantially 50:50 ratio.

[0009] In each case, the compound of formula I according to the invention is in a free form, an oxidized form (such as an N-oxide), or a salt form (e.g., an agronomically available salt form).

[0010] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. For example, they are described by A. Albini and S. Pietra in their 1991 book, "Heterocyclic N-oxides," published by CRC Press in Boca Raton.

[0011] Preferred compositions comprise: (A) a compound having formula I

[0012]

[0013] Wherein R is a C1-C3 alkyl, C1-C3 alkoxy, or C3-C4 cycloalkyl, and X is CH; and

[0014] (B) At least one compound selected from the group consisting of fluoxazine and pyridine.

[0015] It has been found that the combined use of component (B) and component (A) unexpectedly and significantly enhances the latter's effectiveness against fungi, and vice versa. Furthermore, the composition and the method of using the composition of the present invention are effective against a broader spectrum of such fungi compared to those that can be combated by the active ingredients of this method when used alone or independently.

[0016] Therefore, another aspect of the present invention is a method for controlling diseases caused by plant pathogens on useful plants or their propagation material, the method comprising applying a composition according to the invention to such useful plants, their sites or their propagation material.

[0017] A preferred method is one in which the composition according to the invention is applied to the useful plants or to their location, more preferably to the useful plants.

[0018] A further preferred method is the application of the composition according to the invention to the propagation material of these useful plants. The invention also relates to all stereoisomers of the subject composition and mixtures thereof, any tautomers, chemically useful and acceptable salts, N-oxides, and tautomers (in any ratio), and their use in controlling diseases caused by plant pathogens on useful plants or on their propagation material.

[0019] Preferred embodiments of the present invention include compositions comprising a compound having formula (I) as component (A), wherein R is isopropyl, methoxy, or cyclopropyl and X is CH, and most preferably wherein R is isopropyl or cyclopropyl and X is CH.

[0020] The preferred compound having formula (I) is:

[0021] According to structure Ia, N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.1):

[0022]

[0023] Based on structure Ib, N-[[5-[1-(2,6-difluoro-4-methoxy-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.2):

[0024]

[0025] And according to structure Ic, N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.3):

[0026]

[0027] Further preferred embodiments of the invention are represented by compositions comprising: a fungicide as component (B), the fungicide being selected from fluopyram and pyrimethanil. Furthermore, mixtures of compounds A and B may also be applicable.

[0028] Preferably, the composition comprises a fungicide effective amount of components (A) and (B).

[0029] A particularly preferred composition according to the invention comprises the following: a compound as component (A) selected from N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.1), N-[[5-[1-(2,6-difluoro-4-methoxy-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.2) and N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.3); and a compound as component (B) selected from fluopyram and pyridoxine.

[0030] Compound A-1.1 can be advantageously prepared in a manner similar to that outlined in WO 2021 / 226234. Furthermore, compounds A-1.2 and A-1.3 can be advantageously prepared in a manner similar to that outlined in WO 2021 / 226234.

[0031] Component (B) is known and is mentioned above by the so-called "ISO common name" or, in some cases, another "common name" or trademark name.

[0032] Component (B), including preferred components (B) included in the online pesticide handbook (“E-pesticide handbook”) published by the UK Crop Production Council and Alan Wood’s compilation of pesticide generic names: flufenoxuron and pyridine.

[0033] Throughout this document, the term "composition" refers to various mixtures or combinations of components (A) and (B), for example, in a single "ready-to-use with water" form, in a combined spray mixture (consisting of separate formulations of individual active ingredient components) (e.g., a "tank mix"), and when used in a sequential manner (i.e., one after another over a suitably short period of time, such as hours or days). For the purposes of this invention, the order in which components (A) and (B) are applied is not critical.

[0034] Further examples of compositions according to the invention comprise three or more active ingredients. Therefore, particularly preferred compositions comprise compositions comprising the following as active ingredients: (i) methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.1), fluopyram, and pyridinesulfuron. Further preferred compositions comprise the following as active ingredients: (ii) methyl N-[[5-[1-(2,6-difluoro-4-methoxy-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.2), fluopyram, and pyridinesulfuron. A further preferred composition comprises the following as active ingredients: (iii) methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (compound A-1.3), fluoxazine, and pyridinesulfuron.

[0035] The compositions according to the invention are effective against harmful microorganisms, such as microorganisms that cause plant pathogenic diseases, especially plant pathogenic fungi and bacteria.

[0036] The compositions according to the invention are particularly effective against plant pathogenic fungi belonging to the following classes: Ascomycetes (e.g., *Aureobasidium*, *Cyclocarya*, *Erythrophagus*, *Pseudomonas*, *Cyclocarya*, *Uncaria*, *Sclerotium*); Basidiomycetes (e.g., *Hemileia*, *Rhizoctonia*, *Laminaria*, *Pseudomonas*, *Ustilago*, *Ustilago*); Deuteromycetes (e.g., *Botrytis*, *Helix*, *Rhizoctonia*, *Fusarium*, *Zymoseptoria*, *Cercospora*, *Alternaria*, *Pyrophora*, and *Pseudocercospora*); Oomycetes (e.g., *Phytophthora*, *Peronospora*, *Pseudorhyx*, *Euphorbia*, *Plasmodium*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*).

[0037] According to the present invention, "useful plants" typically include the following plant species: grapevines; cereals, such as wheat, barley, rye, or oats; beets, such as sugar beets or forage beets; fruits, such as pome, drupe, or soft fruits, for example, apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, or blackberries; legumes, such as beans, lentils, peas, or soybeans; oil crops, such as rapeseed, mustard, poppies, olives, sunflowers, coconuts, castor oil plants, cocoa beans, or peanuts; and cucumber-like plants, such as... Gourds, cucumbers, or cantaloupes; fiber plants such as cotton, flax, hemp, or jute; citrus fruits such as oranges, lemons, grapefruits, or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, gourds, or peppers; Lauraceae, such as avocados, cinnamon, or camphor; corn; tobacco; nuts; coffee; sugarcane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamental plants such as flowering plants, shrubs, broadleaf trees, or evergreens, such as conifers. This list does not represent any restrictions.

[0038] The term "useful plant" should be understood to include useful plants that have developed tolerance to herbicides (like bromuconazole) or herbicide classes (such as HPPD inhibitors, ALS inhibitors, such as flusulfuron, fluprosulfuron, and triflusulfuron, EPSPS (5-enol-acetone-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthase) inhibitors, or PPO (protoporphyrinogen oxidase) inhibitors) through conventional breeding or genetic engineering methods. Examples of crops that have been induced to tolerate imidazolinones (such as methoxyfenozide) through conventional breeding methods (mutation) are... Summer rapeseed (Carnora). Examples of crops that have been genetically engineered to be resistant to herbicides or herbicides include glyphosate-resistant and glufosinate-resistant maize varieties, marketed under trade names. Herculex and Available for commercial purchase.

[0039] The term “useful plant” should be understood to also include useful plants that have been transformed by the use of recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to come from toxin-producing bacteria, especially those of the genus Bacillus.

[0040] The term “useful plant” should be further understood to include useful plants that have been transformed by the use of recombinant DNA technology to enable them to synthesize pathogen-resistant substances with selective action, such as so-called “pathogenesis-associated proteins” (PRPs, see, for example, EP-A-0 392 225).

[0041] Examples of such pathogen-resistant substances and transgenic plants capable of synthesizing such pathogen-resistant substances are known, for example, from EP-A-0392 225, WO 95 / 33818 and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the disclosures mentioned above.

[0042] As used herein, the term "site" for useful plants is intended to include places where useful plants grow, where plant propagation material of useful plants is sown, or where plant propagation material of useful plants will be placed in the soil. An example of such a site is a field on which crop plants grow.

[0043] The term "plant propagation material" should be understood to refer to the reproductive parts of a plant, such as seeds, which can be used for plant propagation, as well as nutrient materials, such as cuttings or tubers (e.g., potatoes). References may include, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of the plant. References may also include germinating plants and young plants that will be transplanted after germination or emergence. These young plants may be protected before transplanting by complete or partial treatment with maceration. Preferably, "plant propagation material" should be understood to refer to seeds.

[0044] On the other hand, this application also relates to plant propagation materials coated with compositions according to the invention.

[0045] These compositions of the present invention can also be used in the field of protecting stored goods from fungal attack. According to the present invention, the term "stored goods" should be understood to refer to natural substances of plant and / or animal origin and their processed forms, derived from their natural life cycle and intended for long-term protection. Plant-derived stored goods (such as plants or parts thereof, e.g., stems, leaves, tubers, seeds, fruits, or grains) can be protected in a freshly harvested state or in a processed form (e.g., pre-dried, moistened, crushed, ground, pressed, or baked). Also falling under the definition of stored goods is timber, whether in log form, such as building timber, transmission towers, and fences, or in the form of finished products, such as furniture or objects made of wood. Animal-derived stored goods are hides, leather, fur, hair, etc. The compositions according to the present invention can prevent adverse effects such as decay, fading, or mold.

[0046] Preferably, "stored goods" should be understood to mean natural substances of plant origin and / or their processed forms, more preferably fruits and their processed forms (such as pome, stone fruit, berries, and citrus fruits and their processed forms). In another preferred embodiment of the invention, "stored goods" should be understood to mean timber.

[0047] Therefore, another aspect of the present invention is a method for protecting stored goods, the method comprising applying a composition according to the present invention to the stored goods.

[0048] The compositions of this invention can also be used in the field of protecting technical materials from fungal attack. According to the invention, the term "technical material" includes paper; blankets; buildings; cooling and heating systems; wall panels; ventilation and air conditioning systems, etc.; preferably, "technical material" should be understood to refer to wall panels. The compositions according to the invention can prevent adverse effects such as decay, fading, or mold growth.

[0049] Furthermore, the compositions according to the invention are particularly effective against seed-borne and soil-borne diseases, such as those caused by *Alternaria* spp., *Ascochyta* spp., *Botrytis cinerea*, *Cercospora* spp., *Ervectomyces violaceum*, *Colletotrichum* spp., *Epicoccum* spp., *Fusarium graminearum*, *Fusarium moniliforme*, *Fusarium oxysporum*, *Fusarium proliferatum*, *Fusarium solani*, and *Fusarium glomeratum*. *graminis*, *Helminthosporium* spp., *Rhizoctonia graminea*, *Phoma* spp., *Pyrenophora graminea*, *Pyrenophora graminea*, *Rhizoctonia cerealis*, *Sclerotinia* spp., *Zymoseptoria* spp., *Ustilago*, *Tilletia* spp., *Typhula incarnata*, *Ustilago*, *Verticillium* spp.; particularly resistant to pathogens in cereals such as wheat, barley, rye, or oats; corn; rice; cotton; soybeans; turf; sugar beets; rapeseed; potatoes; and legumes. Crops such as peas, lentils, or chickpeas; and sunflowers.

[0050] Furthermore, the compositions according to the invention are particularly effective against the following postharvest diseases, such as Botrytis cinerea, Banana anthracnose, Curvularia crescentis, Fusarium semitecum, Geotrichum candida, brown rot fungi, brown rot fungi of apples, Sclerotinia sclerotiorum of stone fruits, Mucor pyriformis, Penicillium italicum, Penicillium detachment, Penicillium fingering, or Penicillium expansum; especially against pathogens of fruits such as pome (e.g., apples and pears), stone fruits (e.g., peaches and plums), citrus, melons, papayas, kiwifruit, mangoes, berries (e.g., strawberries), avocados, pomegranates, and bananas, as well as nuts.

[0051] The compositions according to the invention are particularly useful for controlling the following diseases in the following crops: Blumeria graminis in cereals; Uncinula necator in grapes; Sphaerotheca fuliginea in gourds; Puccinia species in cereals; and Phakopsora pachyrhizi in soybeans.

[0052] However, in addition to the actual synergistic effect relative to the fungicidal activity, the compositions according to the invention may also have other unexpectedly advantageous properties. Examples of such advantageous properties that may be mentioned are: more favorable biodegradability; improved toxicological and / or ecotoxicological behavior; or improved characteristics of useful plants, including: emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, less basal leaf mortality, stronger tillering, greener leaf color, less fertilizer required, less seed required, more tillering, earlier flowering, earlier grain maturity, less lodging, enhanced bud growth, improved plant vigor, and earlier germination.

[0053] Some compositions according to the present invention have systemic action and can be used as fungicides for leaf, soil and seed treatment.

[0054] Using the composition according to the invention, plant pathogenic microorganisms present on various useful plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) can be inhibited or destroyed, while also protecting later-growing plant parts from attack by plant pathogenic microorganisms.

[0055] The compositions according to the invention can be applied to plant pathogens, useful plants threatened by microbial attack, their sites, their propagation materials, stored goods or technical materials.

[0056] The composition according to the invention can be applied before or after useful plants, their propagation materials, stored goods or technical materials are infected by microorganisms.

[0057] The amount of the composition according to the invention to be applied will depend on various factors, such as the compound used; the object to be treated, such as plants, soil or seeds; the type of treatment, such as spraying, dusting or seed dressing; the purpose of the treatment, such as prevention or treatment; the type of fungus to be controlled or the time of application.

[0058] Typically, when applied to useful plants in combination with component (B) which is typically 1 to 5000 g ai / ha, particularly 2 to 2000 g ai / ha, such as 100, 250, 500, 800, 1000, or 1500 g ai / ha, component (A) is typically applied at a ratio of 5 to 2000 g ai / ha, particularly 10 to 1000 g ai / ha, such as 50, 75, 100, or 200 g ai / ha.

[0059] In agricultural practice, the application rate of the composition according to the invention depends on the type of desired effect and typically ranges from 20 to 4000 g of total composition per hectare.

[0060] When the composition according to the invention is used to treat seeds, a ratio of 0.001 to 50 g of component (A) compound / kg seed, preferably 0.01 to 10 g / kg seed, and 0.001 to 50 g of component (B) compound / kg seed, preferably 0.01 to 10 g / kg seed, is generally sufficient.

[0061] The term "compound" in this article also refers to any of its agrochemically acceptable salts, n-oxides, and tautomers.

[0062] The compositions of the present invention can be used in any conventional form, for example, in the form of double-packaged powders (DS) for dry seed treatment, emulsions (ES) for seed treatment, flowable concentrates (FS) for seed treatment, solutions (LS) for seed treatment, water-dispersible powders (WS) for seed treatment, capsule suspensions (CF) for seed treatment, gels (GF) for seed treatment, emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), dispersible oil suspensions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical grade (TK), dispersible concentrates (DC), wettable powders (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0063] Such compositions can be produced in conventional ways, for example by mixing the active ingredient with at least one suitable inert formulation adjuvant (e.g., diluent, solvent, filler, and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, adhesives, thickeners, and compounds that provide auxiliary effects). Conventional sustained-release formulations designed for long-term sustained efficacy can also be used. In particular, formulations intended for application in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, may contain surfactants such as wetting agents and dispersants, and other compounds that provide auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0064] The compositions according to the invention may also contain additional pest control agents, such as fungicides, insecticides, or herbicides.

[0065] Using the composition and diluent according to the invention, the seed dressing is applied to seeds in a suitable seed dressing form, such as an aqueous suspension or dry powder having good adhesion to seeds, in a manner known to the art. Such seed dressings are known in the art. The seed dressing may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as sustained-release capsules or microcapsules.

[0066] Typically, the formulation comprises, by weight, 0.01% to 90% of an active agent, 0% to 20% of an agriculturally acceptable surfactant, and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being composed of at least the compound of component (A) together with the compound of component (B), and optionally other active agents (particularly microbicides or preservatives, etc.). The concentrated form of the composition typically contains between about 2% and 80%, preferably between about 5% and 70%, of the active agent by weight. The application form of the formulation may, for example, contain 0.01% to 20%, preferably 0.01% to 5% of the active agent by weight. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations. Further characteristics of compositions comprising compounds having formula (I), methods of application to plants, and the application ratios thereof are as described for compositions comprising compounds having formula (I) and at least one other component (B) as described above. Their application can be performed before and after the plants or parts thereof are infected by fungi. Preferably, treatment is carried out before infection. When a compound having formula (I) is used on its own, the application ratio in the method according to the invention is as described above, typically from 5 to 2000 g ai / ha, particularly from 10 to 1000 g ai / ha, for example, ratios of 50, 75, 100, or 200 g ai / ha. During the growing season, the compound having formula (I) can be applied to these plants once or more. For use in the method according to the invention, the compound having formula (I) can be converted into the conventional formulations described above, such as solutions, emulsions, suspensions, dusts, powders, pastes, and granules. The form of use will depend on the specific intended purpose; in each case, it should ensure a fine and uniform distribution of the compound having formula (I).

[0067] As used in this article, the term "plant" includes seedlings, shrubs, and crops of fruits and vegetables.

[0068] The following examples illustrate the present invention. "Active ingredient" refers to a mixture of component (A) and component (B) in a specific mixing ratio. The same formulation can be used in compositions containing only a compound having formula (I) as an active ingredient.

[0069] Examples of preparations

[0070]

[0071] The active ingredient is thoroughly mixed with other formulation components and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder, which can be diluted with water to provide a suspension with the desired concentration.

[0072]

[0073] The active ingredient is thoroughly mixed with other formulation components and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be used directly for seed treatment.

[0074] Emulsifiable concentrate

[0075]

[0076] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0077]

[0078] Ready-to-use dust is obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry seed dressing.

[0079]

[0080] The active ingredient is mixed and ground with other formulation components, and the mixture is moistened with water. The mixture is then extruded and dried in an air stream.

[0081] suspension concentrate

[0082]

[0083] The finely ground active ingredient is thoroughly mixed with other formulation components to obtain a suspension concentrate, which can be diluted in water at any desired ratio. Using such a dilution, living plants and plant propagation material can be treated and protected from microbial contamination by spraying, watering, or immersion.

[0084] Flowable concentrate for seed treatment

[0085]

[0086]

[0087] The finely ground active ingredient is thoroughly mixed with other formulation components to obtain a suspension concentrate, which can be further diluted in water for application to seeds. Using such a dilution, propagation material can be treated and protected from microbial contamination by spraying, watering, or soaking.

[0088] Therefore, another aspect of the present invention is a method for controlling leaf spot disease on plants, the method comprising applying a composition comprising a compound having formula (I) to a plant, its site or its propagation material.

[0089] The preferred method is that the plant pathogen is *Dioscorea beanus* rust fungus.

[0090] A preferred method is one in which a composition comprising a compound having formula (I) is applied to a plant or its site, preferably to such plants.

[0091] A further preferred method is one in which a composition comprising a compound having formula (I) is applied to the propagation material of a plant.

[0092] The method according to the invention, especially when a compound having formula (I) is used in combination with at least one compound (B) as described above, also allows for good control of other harmful fungi frequently encountered in plants.

[0093] A preferred method for controlling diseases on soybeans, particularly those caused by rust, comprises applying a composition containing a compound having formula (I) to the useful plant, its location, or its propagation material.

[0094]

[0095] Where R is a C1-C6 alkyl, C1-C6 alkoxy, or C3-C6 cycloalkyl, and X is CH or N.

[0096] Typically, the weight ratio of component (A) to component (B) is in the range of 2000:1 to 1:1000. The weight ratio of component (A) to component (B) is preferably 100:1 to 1:100; more preferably 20:1 to 1:50; even more preferably 12:1 to 1:25; even more preferably 10:1 to 1:10; still more preferably 5:1 to 1:15; and most preferably 2:1 to 1:5.

[0097] It has been discovered, unexpectedly, that certain weight ratios of component (A) to component (B) can produce synergistic activity. Therefore, another aspect of the invention is a composition in which components (A) and (B) are present in amounts that produce a synergistic effect. This synergistic activity is evident from the fact that the fungicidal activity of the composition comprising components (A) and (B) is greater than the sum of the fungicidal activities of components (A) and (B) alone. This synergistic activity extends the scope of action of components (A) and (B) in two ways. First, by reducing the application ratio of components (A) and (B) while maintaining the same level of effectiveness, meaning that even if the two individual components become completely ineffective at such low application ratios, the mixture of active ingredients still achieves a high degree of plant pathogen control. Second, by significantly broadening the spectrum of plant pathogens that can be controlled.

[0098] A synergistic effect exists as long as the combined effect of active ingredients is greater than the sum of the effects of the individual components. For a given combination of active ingredients, the expected effect E follows the so-called Colby formula and can be calculated as follows (COLBY, SR, "Calculating synergistic and antagonistic responses of herbicide combination," Weeds, Vol. 15, pp. 20-22; 1967):

[0099] ppm = number of milligrams of active ingredient (=ai) per liter of spray mixture

[0100] X = % effect of active ingredient (based on active ingredient A) using p ppm.

[0101] Y = % effect of active ingredient (based on active ingredient B) using q ppm of active ingredient.

[0102] According to Colby, using p+q ppm of active ingredients, the expected effect of (additive) active ingredient (A)+(B) is:

[0103] If the observed effect (O) is greater than the expected effect (E), then the combined effect is superadditive, i.e., a synergistic effect exists. Mathematically, a synergistic effect corresponds to a positive value of the difference (OE). In the case of purely complementary addition of the active ingredient (expected activity), the difference (OE) is zero. A negative value of the difference (OE) indicates a loss of activity compared to the expected activity.

[0104] Biological examples

[0105] Alternaria alternata (tomato / potato early blight):

[0106] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well size), and nutrient liquid medium containing fungal spores was added. These test plates were incubated at 24°C, and the inhibition of growth was determined photometrically after 48 hours.

[0107]

[0108]

[0109] Compound A-1.1 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 0 0.66 50 0.22 20 0.074 0 0.005 0.66 70 50 0.005 0.22 50 20 0.005 0.074 20 0

[0110] Botrytis cinerea (gray mold):

[0111] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well size), and nutrient liquid medium containing fungal spores was added. These test plates were incubated at 24°C, and the inhibition of growth was determined photometrically after 72 hours.

[0112]

[0113]

[0114] Compound A-1.1 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 0 0.22 50 0.074 20 0.0246 0 0.005 0.22 70 50 0.005 0.074 50 20 0.005 0.0246 20 0

[0115] Glomerella lagenarium, also known as Colletotrichum glomeratus, is a fungus that causes anthracnose in cucurbits. (Anthracnose of Cucurbitaceae family):

[0116] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well size), and nutrient liquid medium containing fungal conidia was added. These test plates were incubated at 24°C, and the inhibition of growth was determined spectrophotometrically at 620 nm after 72 hours.

[0117]

[0118]

[0119] Compound A-1.1 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 0 0.001 0 2 70 0.66 0 0.22 0 0.005 2 100 70 0.005 0.66 100 0 0.005 0.22 100 0 0.001 2 100 70 0.001 0.66 90 0 0.001 0.22 50 0

[0120] Mycosphaerella arachidis, also known as Cercospora, is a fungus that causes peanut brown spot. (arachidicola) (brown leaf spot disease of peanuts):

[0121] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well size), and nutrient liquid medium containing fungal spores was added. These test plates were incubated at 24°C, and the inhibition of growth was determined photometrically at 620 nm after 5–6 days.

[0122] Compound A-1.3 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 50 0.001 0 0.0246 50 0.0080 20 0.005 0.0246 100 75 0.005 0.0080 90 60 0.001 0.0246 90 50 0.001 0.0080 70 20

[0123] Compound A-1.1 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 20 0.001 0 0.0246 50 0.0080 20 0.005 0.0246 90 60 0.005 0.0080 70 36 0.001 0.0246 70 50 0.001 0.0080 50 20

[0124] Phakopsora pachyrhizi (soybean rust fungus):

[0125] Four weeks after planting, whole soybean plants were treated with the described active ingredient. One day after spraying, leaf discs were cut from the first leaf with three leaves. Five replicates were performed at each ratio. One day after treatment, the leaf discs were inoculated with *Soybean rust* (Asian soybean rust). The leaf discs were evaluated 11 to 14 days after inoculation, and the activity was derived from the infection test between the treated and untreated plants. The ratios of active ingredients used are given in the table as g active ingredient (ai) / ha.

[0126] Compound A-1.3 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 1 2 0.5 0 0.5 34 0.25 0 1 0.50 78 35 1 0.25 13 2 0.5 0.50 54 34 0.5 0.25 12 0

[0127] Compound A-1.3 Fluopyram Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 1 2 0.5 0 0.50 10 0.25 0 1 0.50 78 11 1 0.25 13 2 0.5 0.50 54 10 0.5 0.25 12 0

[0128]

[0129]

[0130] Sclerotinia sclerotiorum (cottonymycosis, white rot, etc.):

[0131] Mycelial fragments of fungi prepared from fresh liquid culture were directly mixed into nutrient liquid medium (PDB potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well size), and nutrient liquid medium containing fungal spores was added. These test plates were incubated at 24°C, and the inhibition of growth was determined spectrophotometrically at 620 nm after 72 hours.

[0132] Compound A-1.3 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 0 0.001 0 2 50 0.005 2 70 50 0.001 2 70 50

[0133] Compound A-1.1 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.005 0 0.001 0 2 50 0.005 2 70 50 0.001 2 70 50

[0134] Wheat leaf spot disease caused by *Syngonium spp.*

[0135] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well size), and nutrient liquid medium containing fungal spores was added. These test plates were incubated at 24°C, and the inhibition of growth was determined photometrically after 72 hours.

[0136] Compound A-1.3 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.001 50 0.074 70 0.0246 50 0.008 20 0.001 0.074 90 85 0.001 0.0246 90 75 0.001 0.008 70 60

[0137] Compound A-1.1 Pyridine amide Observed Expected Colby (g ai / ha) (g ai / ha) active(%) active(%) 0.001 20 0.074 70 0.0246 50 0.008 20 0.001 0.074 90 76 0.001 0.0246 70 60 0.001 0.008 70 36 .

Claims

1. A composition for controlling diseases caused by plant pathogens, comprising: (A) At least one compound having formula I or an agriculturally chemically acceptable salt thereof: ， Where R represents isopropyl or cyclopropyl, and X represents CH; and (B) At least one compound selected from fluoxazine and pyridine, wherein the weight ratio of component (A) to component (B) is in the range of 5:1 to 1:1000.

2. The composition according to claim 1, wherein, (A) Contains a compound selected from the following or an agriculturally chemically acceptable salt thereof: Based on the N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate of structure Ia: ； Or, based on structure Ic, N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate: ； Or a mixture of the above compounds, or a mixture of their chemically acceptable salts for agricultural use.

3. The composition according to claim 1 or 2, comprising the following as an active ingredient: (i) N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate, fluopyram, and pyridinesulfuron; or (ii) N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate, fluoxazine and pyridinesulfuron.

4. The composition according to claim 1, wherein it comprises one or more additional pest control agents.

5. The composition according to claim 1, wherein it comprises one or more other fungicides, insecticides, or herbicides.

6. A method for controlling diseases caused by plant pathogens on useful plants or their propagation material, the method comprising applying a composition according to any one of claims 1 to 5 to said useful plant, its location, or its propagation material.

7. The method according to claim 6, wherein, The plant pathogens attack plants and cause diseases, including rust.

8. The method according to claim 7, wherein, The plants include soybeans and / or grains.

9. The method according to any one of claims 6 to 8, comprising applying component (A) in combination with component (B) at a ratio of 5 to 2000 g ai / ha to 1 to 5000 g ai / ha.

10. The method according to claim 6, comprising, when used for seed treatment, applying 0.001 to 50 g of at least one compound of component (A) per kg of seed, and 0.001 to 50 g of at least one compound of component (B) per kg of seed.

11. Use of the composition according to any one of claims 1 to 5 for controlling diseases caused by plant pathogens.

12. The use according to claim 11, for controlling rust on useful plants.

13. The use according to claim 11, for controlling diseases caused by plant pathogens on soybeans and / or grains.

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