Bactericidal and fungicidal compositions

Abstract

A composition suitable for controlling diseases caused by plant pathogens, comprising: (A) Formula I JPEG2026500585000042.jpg3570 (in the formula, R 1 is halogen, C1-C6 alkyl or C3-C6 cycloalkyl, and R 2 and R 3 are each independently halogen or C1-6 alkyl; (B) at least one compound selected from compounds known for their fungicidal activity; and a method for controlling diseases on useful plants, in particular leaf spot, powdery mildew, and mold of fruits and vegetables, rice and cereals.

Description

[Technical Field]

[0001] The present invention relates to novel bactericidal and fungicidal compositions suitable for controlling diseases caused by plant pathogens, in particular plant pathogenic fungi, and to methods for controlling diseases in useful plants, in particular fruits and vegetables. [Background technology]

[0002] The biological activity of certain pyridazine derivatives and mixtures containing such pyridazine derivatives against plant pathogenic fungi is known from International Publication Nos. 2020 / 127780, 2021 / 255070, and 2021 / 255071. Meanwhile, various fungicidal compounds of different chemical classes are widely known as plant fungicides for use in various cultivated plant crops. However, crop tolerance and activity against plant pathogenic plant fungi do not necessarily meet the needs of agricultural practice in many cases and aspects. For example, the gray mold pathogen Botrytis cinerea has become an increasingly important problem in grape and fruit production, resulting in significant yield losses. In addition, Pyricularia oryzae, the causal agent of rice blast, Uncinula necator, the causal agent of grape powdery mildew, Zymoseptoria tritici, the causal agent of cereal leaf blight, and Cercospora kukuchii, the causal agent of soybean black leaf blight, cause economically important plant diseases that are becoming increasingly difficult to control. Many conventional fungicides are not suitable for controlling gray mold, rice blast, cereal leaf blight, and soybean black leaf blight, or their activity against Botrytis cinerea, Pyricularia oryzae, Uncinula necator, Zymoseptoria tritici, and Cercospora kukuchii is insufficient. Summary of the Invention [Means for solving the problem]

[0003] Therefore, in view of the above-mentioned demands of agricultural practice for increased crop tolerance and / or increased activity against plant pathogenic fungi, such as leaf spot, powdery mildew and mould, the present invention provides novel compositions suitable for controlling diseases caused by plant pathogens, comprising: (A) Formula I [ka] (In the formula, R 1 is halogen, C1-C6 alkyl, or C3-C6 cycloalkyl, and R 2 and R 3 are each independently halogen or C1-C6 alkyl; (B) at least one compound selected from the group consisting of benomyl, benzothiostrobin, carpropamid, diclocymet, fenoxanil, mepanipyrim, mepronil, picarbutrazox, pyribencarb, thifluzamide, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine; A novel composition is proposed which contains:

[0004] Because the compounds of formula I contain asymmetric carbon atoms, the compounds can exist in optically isomeric forms, i.e., enantiomeric or diastereomeric forms. As a result of restricted rotation about single bonds, atropisomers are also obtained. The present invention includes all of these possible isomeric forms of the compounds of formula I, as well as mixtures thereof. Similarly, formula I is intended to include all possible tautomers. The present invention also includes all possible tautomeric forms of the compounds of formula I, as well as racemates (i.e., mixtures of at least two enantiomers in a substantially 50:50 ratio).

[0005] In each case, the compounds of formula I according to the invention are in free form, in oxidized form as N-oxides, or in salt form, for example in agriculturally useful salt form.

[0006] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds, as described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0007] Preferred are (A) compounds of formula I [ka] (In the formula, R 1 is fluoro, chloro, or cyclopropyl; R 2 and R 3 are, independently of each other, chloro, bromo, or methyl; and (B) at least one compound selected from the group consisting of benomyl, carpropamid, diclocymet, fenoxanil, picarbutrazox, pyribencarb, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine; A composition comprising:

[0008] It has been discovered that using component (B) in combination with component (A) surprisingly and significantly increases the effectiveness of the latter against fungi, and vice versa. Furthermore, the compositions and methods of using the compositions of the present invention can be effective against a wider range of fungi than those that can be controlled using the active ingredients of the methods when used alone.

[0009] Therefore, a further aspect of the present invention is a method for controlling diseases caused by plant pathogens on useful plants or on their propagation material, which method comprises applying to the useful plant, its locus, or its propagation material a composition according to the present invention.

[0010] Preferred is a method comprising applying a composition according to the invention to a useful plant or to the locus thereof, more preferably to a useful plant.

[0011] Further preferred is a method comprising applying a composition according to the invention to the propagation material of a useful plant.The present invention also relates to all stereoisomers and mixtures thereof, all tautomers, pesticide-useful acceptable salts, N-oxides, and tautomers of the subject compositions in any ratio, and their use for controlling diseases on useful plants or their propagation material caused by plant pathogens. DETAILED DESCRIPTION OF THE INVENTION

[0012] A preferred embodiment of the present invention is to use as component (A) a compound of formula (I) 1 is fluoro, chloro, or cyclopropyl; R 2 and R 3 are each independently chloro, bromo, or methyl, and most preferably R 1 is chloro or cyclopropyl, and R 2 is chloro or methyl, and R 3 is bromo or methyl).

[0013] Preferred compounds of formula (I) are Structure Ia: [ka] 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.1) according to Structure Ib: [ka] 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.2) according to and Structure Ic: [ka] 5-[(4-bromo-2-methyl-phenyl)methyl]-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.3) according to is.

[0014] Another preferred embodiment of the present invention is represented by a composition comprising as component (B) a fungicide selected from benomyl, carpropamid, diclocymet, fenoxanil, picalbutrazox, pyribencarb, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine.It may also be appropriate to use a mixture of compounds A and B.

[0015] Preferably, the composition comprises fungicidally effective amounts of components (A) and (B).

[0016] Particularly preferred compositions according to the invention comprise as component (A) 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.1), 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.2), and 5-[(4-bromo-2-methyl-phenyl)methyl]-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.3). 1.3), and as component (B) a compound selected from benomyl, carpropamid, diclocymet, fenoxanil, picarbutrazox, pyribencarb, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine.

[0017] Compound A-1.1 can be advantageously prepared in a manner similar to that outlined in WO 2021 / 255070. Compounds A-1.2 and A-1.3 can also be advantageously prepared in a manner similar to that outlined in WO 2021 / 255070. Component (B) is known. Some of the compounds of component (B) are referred to herein above by their so-called "ISO common names," or other "common names" used in individual cases, or by their trade names.

[0018] The following preferred ingredients (B) are included in the Pesticide Manual Online ("E-Pesticide Manual") by the British Crop Production Council and in the Compendium of Pesticide Common Names by Alan Wood: benomyl, benzothiostrobin, carpropamid, diclocymet, fenoxanil, mepanipyrim, mepronil, picarbutrazox, pyribencarb, thifluzamide, tolylfluanid.

[0019] Further preferred compounds include 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine, all of which are disclosed in WO 2020 / 178307.

[0020] Throughout this specification, the expression "composition" refers to various mixtures or combinations of components (A) and (B), for example, in a single "ready-mix" form, in combined spray mixtures such as "tank mixes" composed of separate formulations of a single active ingredient, and in sequential manner, i.e., in combination with a single active ingredient when applied one after the other over a reasonably short period of time, such as a few hours or days. The order in which components (A) and (B) are applied is not critical to the practice of this invention.

[0021] Examples of compounds that are particularly suitable as component (B) are compounds selected from the following group P: benomyl, benzothiostrobin, carpropamid, diclocymet, fenoxanil, mepanipyrim, mepronil, picarbutrazox, pyribencarb, thifluzamide, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine.

[0022] Further examples of compositions according to the invention comprising three active ingredients are defined as embodiments E1, E2 and E3.

[0023] Preferred embodiment E1: As used herein, the term "TX1" means "Compound A-1.1 + a compound selected from Group P." Preferred examples include the following compositions: benomyl + TX1, benzothiostrobin + TX1, carpropamid + TX1, diclocymet + TX1, fenoxanil + TX1, mepanipyrim + TX1, mepronil + TX1, picarbutrazox + TX1, pyribencarb + TX1, thifluzamide + TX1, tolylfluanid + TX1, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl -quinoline + TX1, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine + TX1, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine + TX1, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine + TX1.

[0024] Preferred embodiment E2: As used herein, the term "TX2" means "compound A-1. 2 + a compound selected from group P." Preferred examples include the following compositions: benomyl + TX2, benzothiostrobin + TX2, carpropamid + TX2, diclocymet + TX2, fenoxanil + TX2, mepanipyrim + TX1, mepronil + TX1, picarbutrazox + TX1, pyribencarb + TX1, thifluzamide + TX2, tolylfluanid + TX2, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl -quinoline + TX2, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine + TX2, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine + TX2, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine + TX2.

[0025] Preferred embodiment E3: As used herein, the term "TX3" means "Compound A-1.3 + a compound selected from Group P." Preferred examples include the following compositions: benomyl + TX3, benzothiostrobin + TX3, carpropamid + TX3, diclocymet + TX3, fenoxanil + TX3, mepanipyrim + TX3, mepronil + TX3, picarbutrazox + TX3, pyribencarb + TX3, thifluzamide + TX3, tolylfluanid + TX3, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl -quinoline + TX3, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine + TX3, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine + TX3, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine + TX3.

[0026] Preferred embodiments E1, E2, and E3 define compositions according to the invention comprising three active ingredients. In these embodiments, the mixing partners selected from group P must be different from the other listed mixing partners. For example, the composition "benomyl + TX1" refers to a composition comprising benomyl, compound A-1.1, and a compound selected from group P as active ingredients. In this composition, the compound selected from group P is different from benomyl.

[0027] The following compositions are particularly preferred: (A) a composition comprising compound A-1.1, compound A-1.2, or compound A-1.3, and (B) a compound selected from group P. An example of such a composition is a composition comprising compound A-1.1 and a first compound from group P, which is benomyl.

[0028] The compositions according to the present invention are effective against harmful microorganisms, such as those causing phytopathogenic diseases, in particular phytopathogenic fungi and bacteria.

[0029] The compositions according to the invention are particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycete (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula, Pyrenophora); Basidiomycete (e.g. Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia genera); Fungi imperfecti (e.g. Fungi of the genera Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); imperfecti (also known as Deuteromycetes; e.g., Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Zymoseptoria, Cercospora, Alternaria, Pyricularia, and Pseudocercosporella); Oomycetes (e.g., Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).

[0030] 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 fodder beets; fruits, such as pome fruits, drupes, or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, or blackberries; legumes, such as beans, lentils, peas, or soybeans; oil plants, such as rapeseed, mustard, poppy, olives, sunflowers, coconuts, castor beans, cocoa beans, or groundnuts; cucumber plants. Examples of suitable plants include: plants such as mallow, cucumber, or melon; fiber plants such as cotton, flax, hemp, or jute; citrus fruits such as oranges, lemons, grapefruit, or mandarins; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, melons, or peppers; lauraceae plants such as avocados, cinnamon, or camphor trees; corn; tobacco; nuts; coffee; sugarcane; tea; vines; hops; durian; bananas; rubber plants; turf or ornamental plants such as flowers, shrubs, broadleaf trees, or evergreen plants such as conifers. This list is not intended to be limiting.

[0031] The term "useful plants" should also be understood to include useful plants which 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, etc.) or PPO (protoporphyrinogen oxidase) inhibitors, as a result of conventional methods of breeding or genetic engineering. An example of a crop which has been rendered tolerant to imidazolinones, such as imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been genetically engineered to tolerate herbicides or classes of herbicides include glyphosate- and glufosinate-tolerant corn varieties available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0032] The term "useful plants" should also be understood to include useful plants which 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, in particular those of the genus Bacillus.

[0033] The term "useful plants" should also be understood to include useful plants that have been genetically modified using recombinant DNA techniques so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenesis-specific proteins" (PRPs, see, for example, EP-A-0 392 225).

[0034] Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP 0 392 225, WO 95 / 33818 and EP 0 353 191. Methods for producing such transformed plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications.

[0035] As used herein, the term "locus" of a useful plant is intended to include the location where the useful plant is growing, the location where the plant propagation material of the useful plant is planted, or the location where the plant propagation material of the useful plant is to be placed in soil. An example of such a location is a field where crop plants are growing.

[0036] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, and vegetative bodies, such as cuttings or tubers (e.g., potatoes), which can be used for their propagation. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and plant parts may be mentioned. Germinated plants and seedlings that will be transplanted after germination or emergence from the soil may also be mentioned. These seedlings may be protected by a complete or partial treatment by immersion before transplanting. Preferably, "plant propagation material" is understood to refer to seeds.

[0037] In a further aspect, the present application also relates to a plant propagation material coated with a composition according to the invention.

[0038] The compositions of the present invention may be used in the field of protecting stored goods from fungal attack. In the present invention, the term "storage goods" is understood to mean natural substances of plant and / or animal origin and their processed forms, derived from their natural life cycle, for which long-term protection is desired. Stored goods of plant origin, 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, such as pre-dried, moistened, crushed, ground, pressed, or roasted. The definition of stored goods also includes wood in the form of raw wood (e.g., construction timber, electricity transmission towers, and fences) and wood in the form of finished products (e.g., furniture or wooden products). Stored goods of animal origin include leather, leather products, fur, and hair. The compositions according to the present invention are capable of preventing adverse effects such as decay, discoloration, or mold.

[0039] Preferably, "storage products" is understood to mean natural substances of plant origin and / or their processed forms, more preferably fruits and their processed forms, such as pome fruits, stone fruits, soft fruits and citrus fruits and their processed forms. In another preferred embodiment of the invention, "storage products" is understood to mean trees.

[0040] Therefore, a further aspect of the present invention is a method for protecting stored goods, which comprises applying to the stored goods a composition of the present invention.

[0041] The composition of the present invention can also be used in the field of protecting industrial raw materials from fungal attack. In the present invention, the term "industrial raw materials" includes paper; carpets; buildings; cooling and heating systems; wallboards; ventilation and air-conditioning systems, etc.; preferably, "industrial raw materials" is understood to mean wallboards. The composition of the present invention can prevent adverse effects such as corrosion, discoloration, or mold.

[0042] The compositions according to the invention are effective against Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurea, Cochliobolus sativus, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium arginum ... solani, Fusarium subglutinans, Gaeumannomyces graminis, Helminthosporium spp., Microdochium nivale, Phoma spp., Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Zymoseptoria spp., Sphacelotheca reilliana, Tilletia spp., Typhula incarnata, Urocystis occulta, Ustilago spp. or Verticillium spp.) and soil-borne diseases; especially against pathogens of cereals such as wheat, barley, rye or oats; corn; rice; cotton; soybeans; turf; sugar beet; oilseed rape; potato; peas, lentils or chickpeas; and sunflower.

[0043] The compositions according to the invention are effective against Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicillium italicum, Penicillium solitum, Penicillium digitatum or Penicillium exopansum. expansum), in particular against pathogens of pome fruits, e.g. apple and pear, stone fruits, e.g. peaches and plums, citrus fruits, melons, papayas, kiwi, mango, berries, e.g. strawberries, avocados, pomegranates and bananas, and nuts.

[0044] The compositions according to the invention are particularly useful for controlling the following diseases on the following crops: Alternaria spp. in fruit and vegetables and potato; Botrytis cinerea in strawberry, tomato, sunflower, cereals, vegetables and grapes; Rhizoctonia solani in potato and vegetables, Uncinula necator in grapes, Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium in cucurbits and solanaceous crops, Leveillula taurica in cucurbits and solanaceous crops. taurica, Fusarium spp. in cereals, Leptosphaeria spp., Zympseptoria tritici etc. in cereals, Septoria spp., Septoria glycines etc. in cereals, Septoria spp. in oil crops, Mycosphaerella arachidicola etc. in peanuts, Cercospora spp. in tomatoes, pulses, peanuts and oil crops, or Cercospora sojinae and Cercospora kikuchii in soybean.

[0045] However, in addition to the actual synergistic effect on fungicidal activity, the compositions according to the present invention may also have surprising 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, fewer seeds required, more productive tillers, earlier flowering, earlier grain maturation, less plant lodging (lodging), increased shoot growth, improved plant vigor, and earlier germination.

[0046] Some compositions according to the invention have systemic action and can be used as foliar, soil and seed treatment fungicides.

[0047] The compositions according to the invention make it possible to inhibit or eliminate phytopathogenic microorganisms occurring in plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plants, while at the same time also protecting subsequently growing plant parts from attack by phytopathogenic microorganisms.

[0048] The compositions according to the invention can be applied to phytopathogenic microorganisms, to useful plants threatened by microbial attack, their habitat, their propagation material, storage articles or technical material.

[0049] The compositions according to the invention can be applied before or after the infection of useful plants, their propagation material, storage items or technical material by microorganisms.

[0050] The amount of the composition according to the invention to be applied depends on various factors, such as the compound used; the object of treatment, e.g., plants, soil or seeds; the type of treatment, e.g., spraying, dusting or seed dressing; the purpose of the treatment, e.g., preventive or curative; the type of fungus to be controlled or the time of application.

[0051] When applied to useful plants, component (A) is typically applied in an amount of 5 to 2000 g ai / ha, especially 10 to 1000 g ai / ha, for example 50, 75, 100, or 200 g ai / ha, typically with component (B) at 1 to 5000 g ai / ha, especially 2 to 2000 g ai / ha, for example 100, 250, 500, 800, 1000, 1500 g ai / ha.

[0052] In agricultural practice, the application rates of the compositions according to the invention depend on the type of effect desired and typically range from 20 to 4000 g of total composition per hectare.

[0053] When the compositions according to the invention are used for seed treatment, an amount of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g per kg of seed of the compound of component (A), and 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g per kg of seed of the compound of component (B) will generally be sufficient.

[0054] As used herein, the term "compound" also refers to any agrochemically acceptable salts, n-oxides, and tautomers thereof.

[0055] The compositions of the present invention may be in any conventional form, for example, in a twin dosage form. The compounds may be used in the form of a dry seed treatment powder (DS), a seed treatment emulsion (ES), a seed treatment flowable (FS), a seed treatment solution (LS), a water-dispersible seed treatment powder (WS), a seed treatment capsule suspension (CF), a seed treatment gel (GF), an emulsifiable concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), an oil dispersion (OD), an oil-mix flowable (OF), an oil-mix liquid (OL), a soluble concentrate (SL), a super fine suspension (SU), a super fine liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or in any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0056] Such compositions can be prepared in a conventional manner, for example, by mixing the active ingredient with at least one suitable inert formulation adjuvant (e.g., 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 used when efficacy is intended to last for a long period of time. In particular, formulations applied in the form of sprays, 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 that provide auxiliary effects, such as condensation products of formaldehyde with naphthalenesulfonates, alkylarylsulfonates, ligninsulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0057] The compositions according to the invention may also comprise a further pesticide, such as, for example, a fungicide, insecticide or herbicide.

[0058] The seed dressing formulation is applied to seeds in a known manner using the composition according to the present invention and a diluent in a suitable seed dressing formulation form, for example, as an aqueous suspension or in the form of a dry powder 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.

[0059] Typically, the formulations contain 0.01 to 90% by weight of active agent, 0 to 20% by weight of agriculturally acceptable surfactant, and 10 to 99.99% by weight of solid or liquid formulation inactive materials and adjuvants, where the active agent consists of at least the compound of component (A) together with the compound of component (B), and optionally other active agents, particularly microbicides or preservatives. A concentrate-form composition generally contains about 2 to 80%, preferably about 5 to 70% by weight of active agent. The application form of the formulation may contain, for example, 0.01 to 20%, preferably 0.01 to 5% by weight of active agent. Commercially available products will preferably be formulated as concentrates, but end users will typically use diluted formulations. Further features of compositions containing a compound of formula (I), their methods of application to plants, and their amounts to be used are as described for compositions containing a compound of formula (I) and at least one additional component (B) described above. These applications may be both before and after fungal infection of the plant or its part. Treatment is preferably carried out before infection. When the compound of formula (I) is used per se, the application rate in the method according to the present invention is as described above, e.g., 5 to 2000 g ai / ha, particularly 10 to 1000 g ai / ha, e.g., 50, 75, 100, or 200 g ai / ha, being typical. The compound of formula (I) can be applied to the plant once or more than once during the growing season. For use in the method according to the present invention, the compound of formula (I) can be converted into the above-mentioned conventional formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes, and granules. The application form will depend on the specific intended purpose; in each case, it is necessary to ensure a fine and uniform distribution of the compound of formula (I). As used herein, the term "plant" includes fruit and vegetable seedlings, bushes, and crops.

[0060] The following examples serve to illustrate the present invention, and "active ingredient" refers to a mixture of component (A) and component (B) in a specific mixing ratio. The same formulation can be used for a composition containing only the compound of formula (I) as the active ingredient.

[0061] [Table 1]

[0062] The active ingredient is thoroughly mixed with the other formulation ingredients, and the mixture is thoroughly ground in a suitable mill to provide a wettable powder that can be diluted with water to give a suspension of the desired consistency.

[0063] [Table 2]

[0064] The active ingredient is thoroughly mixed with the other formulation ingredients and the mixture is thoroughly ground in a suitable mill to provide a powder that can be used directly for seed treatment. emulsifiable concentrate Active ingredients (A):B) = 1:6) 10% Octylphenol polyethylene glycol ether 3% (ethylene oxide 4-5 mol) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0065] Emulsions of any desired dilution that can be used for plant protection can be obtained from this concentrate by dilution with water.

[0066] [Table 3]

[0067] Ready-to-use dusts can be obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry seed dressing. Extruded Granules % w / w Active ingredients (A):B) = 2:1) 15% Sodium lignosulfonate 2% Sodium alkylnaphthalene sulfonate 1% Kaolin 82%

[0068] The active ingredient is mixed with the other formulation ingredients, milled, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Suspension concentrate Active ingredients (A):B) = 1:8) 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% Water: 32%

[0069] The finely divided active ingredient is homogeneously mixed with other formulation ingredients to provide a suspension concentrate that can be diluted in water at any desired rate to treat growing plants, as well as plant propagation material, by spraying, pouring, or immersion to protect them from microbial infestation. Flowable seed treatment Active ingredients (A):B) = 1:8) 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrenephenol ethoxylate (containing 10-20 moles of EO) 2% 1,2-Benzisothiazolin-3-one 0.5% Monoazo dye calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0070] The finely divided active ingredient is mixed homogeneously with the other formulation ingredients to obtain a suspension concentrate, which can be further diluted with water before application to seeds. Such dilution allows the propagation material to be treated by spraying, pouring, or immersion to protect it from microbial infestation.

[0071] Thus, a further aspect of the invention is a method for controlling leaf spot diseases on plants, which method comprises applying to the plant, its locus or its propagation material a composition comprising a compound of formula (I).

[0072] Preferred are methods in which plant pathogens attack plants, causing diseases such as leaf spot, powdery mildew, mould and blight.

[0073] Preferred is a method which comprises applying a composition comprising a compound of formula (I) to the plant or its locus, preferably the plant.

[0074] Further preferred is a method comprising applying to the propagation material of the plant a composition comprising a compound of formula (I).

[0075] The method according to the invention also allows good control of other harmful fungi which often occur in plants, in particular when the compounds of formula (I) are used in combination with at least one of the above-mentioned compounds (B).

[0076] A method for controlling diseases on soybeans, particularly those caused by rust, comprising administering to a useful plant, its locus or its propagation material a compound of formula (I). [ka] (In the formula, R 1 is fluoro, chloro, or cyclopropyl; R 2 and R 3 are, independently of each other, chloro, bromo, or methyl. A method comprising applying a composition comprising a compound of formula (I) is preferred.

[0077] Generally, 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, even more preferably 5:1 to 1:15, and most preferably 2:1 to 1:5.

[0078] Surprisingly, it has been found that a certain weight ratio of component (A) to component (B) can result in synergistic activity. Therefore, a further aspect of the present invention is a composition in which component (A) and component (B) are present in a synergistic amount. This synergistic activity is evident from the fact that the fungicidal activity of a composition containing component (A) and component (B) is higher than the sum of the fungicidal activities of components (A) and (B). This synergistic activity extends the range of action of components (A) and (B) in two ways. First, the application rates of components (A) and (B) can be reduced while still maintaining equally good activity, meaning that even at low application rates where the two individual components are completely ineffective, the active ingredient mixture still achieves a high level of plant pathogen control. Second, the range of plant pathogens that can be controlled is substantially expanded.

[0079] A synergistic effect exists whenever the effect of a combination of active ingredients is greater than the sum of the effects of the individual ingredients. The expected effect E for 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.

[0080] According to COLBY, the expected (additive) effect of active ingredients (A) + (B) using p + q ppm of active ingredients is:

number

[0081] 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). In the case of a purely complementary addition of activities (expected activity), the difference (OE) is zero. A negative value for the difference (OE) indicates a loss of activity compared to the expected activity. [Example]

[0082] Biological Examples Alternaria solani (tomato / potato late blight): Fungal conidia from cryogenic storage were mixed directly into nutrient broth (PDB potato dextrose broth). DMSO solutions of test compounds were placed in microtiter plates (96-well format), and nutrient liquid medium containing fungal spores was added. Test plates were incubated at 24°C, and growth inhibition was determined photometrically after 48 hours.

[0083] [Table 4]

[0084] [Table 5]

[0085] [Table 6]

[0086] Glomerella lagenarium syn. Colletotrichum lagenarium (cucurbit anthracnose): Fungal conidia from cryogenic storage were mixed directly into nutrient broth (PDB potato dextrose broth). DMSO solutions of test compounds were placed in microtiter plates (96-well format), and nutrient broth containing fungal spores was added. Test plates were incubated at 24°C, and growth inhibition was measured photometrically at 620 nm after 72 hours.

[0087] [Table 7]

[0088] [Table 8]

[0089] [Table 9]

[0090] [Table 10]

[0091] [Table 11]

[0092] [Table 12]

[0093] [Table 13]

[0094] [Table 14]

[0095] [Table 15]

[0096] Mycosphaerella arachidis syn. Cercospora arachidicola (brown leaf spot of peanut): Fungal conidia from cryogenic storage were mixed directly into nutrient broth (PDB potato dextrose broth). DMSO solutions of test compounds were placed in microtiter plates (96-well format), and nutrient liquid medium containing fungal spores was added. Test plates were incubated at 24°C, and after 5–6 days, growth inhibition was measured photometrically at 620 nm.

[0097] [Table 16]

[0098] [Table 17]

[0099] Sclerotinia sclerotiorum (cotton rot, mildew, etc.): Fungal mycelial fragments prepared from fresh liquid cultures were mixed directly into nutrient broth (PDB potato dextrose broth). DMSO solutions of test compounds were placed in microtiter plates (96-well format), and nutrient broth containing fungal spores was added. Test plates were incubated at 24°C, and growth inhibition was determined photometrically at 620 nm after 72 hours.

[0100] [Table 18]

[0101] Table 19

[0102] Table 20

[0103] Table 21

[0104] Table 22

[0105] Table 23

[0106] Table 24

[0107] Table 25

[0108] Table 26

[0109] Table 27

[0110] Septoria tritici (leaf blight): Fungal conidia from cryogenic storage were mixed directly into nutrient broth (PDB potato dextrose broth). DMSO solutions of test compounds were placed in microtiter plates (96-well format), and nutrient broth containing fungal spores was added. Test plates were incubated at 24°C, and growth inhibition was determined photometrically after 72 hours.

[0111] [Table 28]

[0112] [Table 29]

Claims

1. A composition for controlling diseases caused by plant pathogens, comprising: (A) at least one compound of Formula I: 【Chemistry 1】 (In the formula, R 1 is a halogen, C 1 ~C 6 Alkyl or C 3 ~C 6 is cycloalkyl, and R 2 and R 3 are each independently a halogen or C 1 ~C 6 alkyl) or an agrochemically acceptable salt or N-oxide thereof; (B) at least one compound selected from benomyl, benzothiostrobin, carpropamid, diclocymet, fenoxanil, mepanipyrim, mepronil, picarbutrazox, pyribencarb, thifluzamide, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine, or a combination thereof; A composition comprising:

2. In compound (A), R 1 represents fluoro, R 2 and R 3 The composition of claim 1 , wherein each is independently chloro, bromo, or methyl.

3. In compound (A), R 1 represents chloro, R 2 and R 3 3. The composition of claim 1, wherein each of the groups is independently chloro, bromo, or methyl.

4. In compound (A), R 1 represents cyclopropyl, R 2 and R 3 The composition of any one of claims 1 to 3, wherein are, independently of each other, chloro, bromo, or methyl.

5. (A) is Structure I. a: 【Chemistry 2】 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.1) according to Structure I. b: 【Transformation 3】 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.2) according to and structure I.c: 【Chemistry 4】 5-[(4-bromo-2-methyl-phenyl)methyl]-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound A-1.3) according to or an agrochemically acceptable salt or N-oxide thereof; or a mixture of compounds A-1.1, A-1.2, and A-1.3, or an agrochemically acceptable salt or N-oxide thereof.

6. 6. The composition of any one of claims 1 to 5, comprising as component (B) a fungicidally effective amount of a compound selected from benomyl, carpropamid, diclocymet, fenoxanil, picarbutrazox, pyribencarb, tolylfluanid, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl-quinoline, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxalin-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2-amine, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine, or combinations thereof.

7. The composition of any one of claims 1 to 6, wherein the weight ratio of component (A) to component (B) is in the range of 2000:1 to 1:1000.

8. A composition according to any one of claims 1 to 7, comprising one or more further pesticides, preferably one or more further fungicides, insecticides or herbicides.

9. A method for controlling diseases caused by plant pathogens on useful plants or on their propagation material, the method comprising applying to said useful plants, their locus, or their propagation material a composition according to any one of claims 1 to 8.

10. 10. The method of claim 9, wherein the plant pathogen attacks the plant and causes disease.

11. 11. The method of claim 9 or 10, comprising applying component (A) in an amount of from 5 to 2000 g ai / ha in combination with component (B) of from 1 to 5000 g ai / ha.

12. 12. The method according to any one of claims 9 to 11, which, when used to treat seeds, comprises applying from 0.001 to 50 g per kg of seeds of at least the compound of component (A) and from 0.001 to 50 g per kg of seeds of at least the compound of component (B).

13. A coated plant propagation material, wherein the coating comprises a composition according to any one of claims 1 to 8.

14. Use of a composition according to any one of claims 1 to 8 for controlling diseases caused by plant pathogens on useful plants or their propagation material.

15. 15. Use of the composition of claim 14 for controlling leaf spot, powdery mildew, and mold on fruits and vegetables, rice and cereals.

16. Phytopathogenic fungi belonging to the following classes: Ascomycetes, preferably Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula; Basidiomycetes, preferably the genera Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia; Fungi imperfecti imperfecti or Deuteromycetes, preferably Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Zymoseptoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella 16. Use of a composition according to claim 14 or 15 for the control of Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, and / or Plasmopara.

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