Fungicidal composition

Abstract

A composition suitable for controlling diseases caused by plant pathogens, the composition comprising (A) a compound of formula I (I) wherein R1 is halogen, C1-C6 alkyl or C3-C6 cycloalkyl, and R2 and R3 are, independently of each other, halogen or C1-C6 alkyl; and (B) at least one compound selected from compounds of which their fungicidal activity is known; and a method of controlling diseases on useful plants, in particular leaf spot, powdery mildew and mold on fruits and vegetables, rice and cereals.

Description

[0001] This invention relates to novel fungicidal compositions suitable for controlling diseases caused by plant pathogens, particularly plant pathogenic fungi, and to methods for controlling diseases on useful plants, particularly fruits and vegetables.

[0002] As known from WO 2020 / 127780, WO 2021 / 255070, and WO 2021 / 255071, certain pyridazine derivatives and mixtures containing said pyridazine derivatives possess biological activity against plant pathogenic fungi. On the other hand, various fungicides of different chemical classes are well known as plant fungicides for application in 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, *Botrytis cinerea*, the pathogen of gray mold, has become an increasingly important problem in grape and fruit production, leading to considerable yield losses. Furthermore, *Pyrrosia lingua*, the pathogen of rice blast, *Hypophthalmia spp.*, the pathogen of grape powdery mildew, *Syndromea spp.*, the pathogen of cereal leaf spot, *Syndromea spp.*, and *Cercospora kikuchi*, the pathogen of soybean leaf blight, cause economically important plant diseases that are becoming increasingly difficult to control. Many commonly used fungicides are unsuitable for controlling gray mold, rice blast, cereal leaf spot, and soybean leaf blight, or their effectiveness against Botrytis cinerea, Pyrocystis oryzae, Botrytis cinerea, Sinapis oryzae, and Cercospora kikuchi is unsatisfactory.

[0003] In light of the aforementioned agricultural practices requiring enhanced crop tolerance and / or increased activity against plant pathogenic fungi (such as leaf spot, powdery mildew, and mold), this invention provides a novel composition suitable for controlling diseases caused by plant pathogens, comprising:

[0004] (A) Compounds having formula I

[0005]

[0006] Where R 1 It is a halogen, a C1-C6 alkyl or a C3-C6 cycloalkyl, and R 2 and R 3 Each is independently a halogen or a C1-C6 alkyl group; and

[0007] (B) At least one compound selected from the group consisting of: benomyl, thiamethoxam, cyclopropionylamine, diclofenac, isoprothiolane, pyrimethanil, methamidophos, tetrazolium pyraclostrobin, pyribencarb, thifluzamide, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline.

[0008] Because compounds of Formula I contain asymmetric carbon atoms, they can exist as optical isomers (i.e., enantiomers or diastereomers). As a result of restricted rotation around the single bond, turn-blocked isomers may also exist. This invention includes all those possible isomeric forms of compounds of Formula I and mixtures thereof. Similarly, Formula I is intended to include all possible tautomers. This invention includes all possible tautomeric forms of compounds of 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] Where R 1 It is fluorine, chlorine, or cyclopropyl, and R 2 and R 3 Each of the following is independently chlorine, bromine, or methyl; and

[0014] (B) At least one compound selected from the group consisting of: benomyl, cyproconazole, cyhalothrin, isoprothiolane, tetrazolium pyraclostrobin, pyraclostrobin, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline.

[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 one in which the composition according to the invention is applied to the propagation material of a useful plant. 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 their propagation material.

[0019] Preferred embodiments of the present invention include compositions comprising a compound having formula (I) as component (A), wherein R 1 It is fluorine, chlorine, or cyclopropyl, and R 2 and R 3 Each of the elements is independently chlorine, bromine, or methyl, and most preferably R is wherein 1 It is chlorinated or cyclopropyl, R 2 It is chlorine or methyl and R 3 It is either bromine or methyl.

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

[0021] Based on structure Ia, 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):

[0022]

[0023] Based on structure Ib, 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):

[0024]

[0025] And according to structure Ic, 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):

[0026]

[0027] Another preferred embodiment of the invention is represented by compositions comprising a fungicide as component (B), the fungicide being selected from benomyl, cyproconazole, cyhalofop-p-ethyl, isoprothiolane, tetrazolium acetamiprid, pyraclostrobin, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoline-3-amine. Furthermore, mixtures of compounds A and B are also 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 a compound selected from the group consisting of: 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), and a compound selected from the following as component (B): benomyl, cyproconazole, cyhalothrin, isoprothiolane, tetrazolium pyraclostrobin, pyraclostrobin, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline.

[0030] Compound A-1.1 can be advantageously prepared in a manner similar to that outlined in WO 2021 / 255070. Furthermore, compounds A-1.2 and A-1.3 can be advantageously prepared in a manner similar to that outlined in WO 2021 / 255070.

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

[0032] The following preferred components (B) are included in the UK Crop Production Council's Pesticide Manual Online ("E-pesticide Manual") and Alan Wood's Compendium of Pesticide Common Names: benomyl, thiamethoxam, cyproconazole, cyhalofop-ethyl, isoprothiolane, pyraclostrobin, cymoxanil, tetrazolium, pyraclostrobin, thifluzamide, and parathion.

[0033] 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-quinoxaline-2-amine, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline-2-amine and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline-3-amine, all as disclosed in WO 2020 / 178307.

[0034] 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 formulations of separate single active ingredient components) (e.g., "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.

[0035] Examples of particularly suitable compounds as component (B) are those selected from group P: benomyl, thiamethoxam, cyclopropionylamine, diclofenac, isoprothiolane, pyraclostrobin, cymoxanil, tetrazolium, pyraclostrobin, thifluzamide, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline.

[0036] Further examples of compositions comprising three active ingredients according to the present invention are defined in Examples E1, E2, and E3:

[0037] Preferred embodiment E1:

[0038] The term "TX1" herein means: "Compound A-1.1 + a compound selected from group P". Preferred examples include the following compositions: benomyl + TX1, benomyl + TX1, cyproconazole + TX1, cyhalofop-p-ethyl + TX1, isoprothiolane + TX1, pyraclostrobin + TX1, cymoxanil + TX1, tetrazolium + TX1, pyraclostrobin + TX1, thifluzamide + TX1, parathion + TX1, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl The following are listed: 3-quinoline + TX1, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxaline-2-amine + TX1, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline-2-amine + TX1, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoline-3-amine + TX1.

[0039] Preferred embodiment E2:

[0040] The term "TX2" herein refers to "compound A-1.2 + compounds selected from group P". Preferred examples include the following compositions: benomyl + TX2, benomyl + TX2, cyclopropionylamine + TX2, cyhalothrin + TX2, isoprothiolane + TX2, pyraclostrobin + TX1, cymoxanil + TX1, tetrazolium + TX1, pyraclostrobin + TX1, thifluzamide + TX2, parathion + TX2, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl The following compounds are listed: 2-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxaline-2-amine + TX2, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline-2-amine + TX2, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline-3-amine + TX2.

[0041] Preferred embodiment E3:

[0042] The term "TX3" in this document means: "Compound A-1.3 + a compound selected from group P". Preferred examples include the following compositions: benomyl + TX3, benomyl + TX3, cyproconazole + TX3, cyhalofop-p-ethyl + TX3, isoprothiolane + TX3, pyraclostrobin + TX3, cymoxanil + TX3, tetrazolium + TX3, pyraclostrobin + TX3, thifluzamide + TX3, parathion + TX3, 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl]methyl]-7,8-difluoro-2-methyl The following compounds are listed: 3-quinoline + TX3, N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl-quinoxaline-2-amine + TX3, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline-2-amine + TX3, and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoline-3-amine + TX3.

[0043] Preferred embodiments E1, E2, and E3 define compositions comprising three active ingredients according to the present invention. In these embodiments, the mixture selected from group P must be different from the other mixtures described. For example, the composition “benzyl + TX1” means a composition comprising benzyl, 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 benzyl.

[0044] The following compositions are particularly preferred: compositions comprising (A) 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).

[0045] The compositions according to the invention are effective against harmful microorganisms, such as those that cause plant pathogenic diseases, particularly plant pathogenic fungi and bacteria.

[0046] 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 (also known as Hemimycetes; e.g., *Botrytis*, *Hemiphagus*, *Rhizoctonia*, *Fusarium*, *Zymoseptoria*, *Cercospora*, *Alternaria*, *Pyrophagus*, and *Pseudocercospora*); Oomycetes (e.g., *Phytophthora*, *Peronospora*, *Pseudorhyx*, *Euphorbia*, *Plasmodium*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*).

[0047] 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, olives, sunflowers, coconuts, castor oil plants, cocoa beans, or peanuts; and cucurbitaceous plants, such as zucchini. Reeds, cucumbers, or melons; 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, melons, 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 limitation.

[0048] The term "useful plants" should be understood to also include useful plants that have developed tolerance to herbicides (like bromobenzonitrile) or herbicide classes (such as HPPD inhibitors, ALS inhibitors like flusulfuron, flusulfuron, and triflusulfuron, EPSPS (5-enol-pyruvyl-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 (e.g., methoxyfenozide) through conventional breeding methods (mutation) are... Summer rapeseed (Canola). 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.

[0049] Herculex and Available for commercial purchase.

[0050] 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.

[0051] 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).

[0052] Examples of such pathogen-resistant substances and transgenic plants capable of synthesizing such pathogen-resistant substances are known, for example, from EP-A-0 392 225, 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 in, for example, the disclosures mentioned above.

[0053] As used herein, the term "site" for useful plants is intended to include places on which useful plants grow, where plant propagating material of useful plants is sown, or where plant propagating material of useful plants will be placed in the soil. An example of such a site is a field on which crop plants grow.

[0054] 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 vegetarian material, 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 can be protected before transplanting by complete or partial treatment via maceration. Preferably, "plant propagation material" should be understood to mean seeds.

[0055] On the other hand, this application also relates to plant propagation materials coated with the composition according to the invention.

[0056] The compositions of this invention can also be used in the field of protecting stored goods from fungal attack. According to the 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 for which long-term protection is desired. 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, or baked). Also falling under the definition of stored goods is timber, whether in log form, such as construction timber, transmission towers, and fences, or in finished product form, such as wooden furniture or objects. Animal-derived stored goods are raw hides, leather, fur, hair, etc. The compositions according to the invention can prevent adverse effects such as decay, fading, or mold.

[0057] 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 wood.

[0058] 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.

[0059] 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.

[0060] 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*, *Colletotrichum* spp., *Epicoccum* spp., *Fusarium graminearum*, *Fusarium moniliforme*, *Fusarium oxysporum*, *Fusarium proliferatum*, *Fusarium solani*, *Colletotrichum*, and *Carex spp.* *graminis*, *Helminthosporium* spp., *Phoma* spp., *Pyrenophora graminea*, *Pyrenophora graminea*, *Rhizoctonia cerealis*, *Sclerotinia* spp., *Zymoseptoria* spp., *Ustilago* spp., *Tilletia* spp., *Typhulaincarnata*, *Ustilago* spp., or *Verticillium* (spp.); particularly effective against pathogens of cereals such as wheat, barley, rye, or oats; corn; rice; cotton; soybeans; turf; sugar beets; rapeseed; potatoes; legumes such as peas, lentils, or chickpeas; and sunflowers.

[0061] Furthermore, the compositions according to the invention are particularly effective against postharvest diseases such as *Botrytis cinerea*, *Colletotrichum musae*, *Curvularialunata*, *Fusarium semitecum*, *Geotrichum candida*, *Brachystomum rubrum*, *Streptococcus sclerotiorum*, *Streptococcus sclerotiorum*, *Mucor piriformis*, *Penicilium italicum*, *Penicilium solidum*, *Penicilium fingeriformis*, or *Penicilium expansum*; especially against pathogens of fruits such as pomegranates (e.g., apples and pears), stone fruits (e.g., peaches and plums), citrus fruits, melons, papayas, kiwifruit, mangoes, berries (e.g., strawberries), avocados, pomegranates, and bananas, as well as nuts.

[0062] The compositions according to the invention are particularly useful for controlling the following diseases on the following crops: *Alternaria* species on fruits and vegetables and potatoes; *Botrytis cinerea* on strawberries, tomatoes, sunflowers, legumes, vegetables, and grapes; *Rhizoctonia solani* in potatoes and vegetables; *Hydrocotyle spp.* in grapes; *Aureobasidium aeruginosa*, *Aureobasidium monnieri*, *Powdery mildew*, and *Anthracnose* in gourds; *Erythrina tartare* in gourds and solanaceous crops; *Fusarium* species in cereals; *Cercospora* species in cereals; *Syngonium* species in cereals, such as *Syngonium leaf blight*; *Syngonium* species in oilseed crops, such as *Syngonium spp.*; *Cercospora* species in tomatoes, legumes, peanuts, and oilseed crops, such as *Cercospora arachinensis* in peanuts, or *Cercospora sojinae* and *Cercospora purpureus* in soybeans.

[0063] 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.

[0064] Some compositions according to the present invention have systemic effects and can be...

[0065] Used as a fungicide for treating leaves, soil, and seeds.

[0066] 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.

[0067] The compositions according to the invention can be applied to plant pathogenic microorganisms, useful plants threatened by microbial attack, their sites, their propagation materials, stored goods or technical materials.

[0068] 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.

[0069] 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.

[0070] When applied to beneficial plants, component (A) is typically applied in combination with component (B) 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, typically at a ratio of 1 to 5000 g ai / ha, particularly 2 to 2000 g ai / ha, such as 100, 250, 500, 800, 1000, 1500 g ai / ha.

[0071] 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.

[0072] 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.

[0073] The term "compound" in this article also refers to any of its agrochemically acceptable salts, n-oxides, and tautomers.

[0074] The compositions of the present invention can be used in any conventional form, for example, in the following forms: double packaging, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), seed treatment solution (LS), seed treatment water-dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspension emulsion (SE), capsule suspension (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), dispersible oil suspension (OD), oil suspension (OF), oil-soluble liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical material (TK), dispersible concentrate (DC), wettable powder (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0075] 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 adjuvant effects). Conventional sustained-release formulations designed for long-term sustained efficacy can also be used. In particular, formulations intended for spray application, 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 adjuvant effects, such as condensation products of formaldehyde and naphthalene sulfonates, alkyl aryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0076] The compositions according to the invention may also contain additional pest control agents, such as fungicides, insecticides, or herbicides.

[0077] 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 a dry powder with 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.

[0078] Typically, formulations comprise 0.01% to 90% by weight of an active agent, 0% to 20% by weight of an agriculturally acceptable surfactant, and 10% to 99.99% by weight 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.). Concentrated forms of the composition typically contain between about 2% and 80% by weight, preferably between about 5% and 70% by weight of an active agent. Application forms of the formulation may, for example, contain 0.01% to 20% by weight, preferably 0.01% to 5% by weight of an active agent. 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 applying them to plants, and their application ratios are as described for compositions comprising compounds having formula (I) and additionally at least one 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 5 to 2000 g ai / ha, particularly 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 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).

[0079] As used in this article, the term "plant" includes seedlings, shrubs, and crops of fruits and vegetables.

[0080] 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.

[0081] Examples of preparations

[0082]

[0083] 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.

[0084]

[0085] 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.

[0086] Emulsifiable concentrate

[0087]

[0088] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0089]

[0090] A 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.

[0091]

[0092] 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.

[0093] suspension concentrate

[0094]

[0095] 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.

[0096] Flowable concentrate for seed treatment

[0097]

[0098]

[0099] 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.

[0100] 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.

[0101] A preferred method is one in which plant pathogens attack plants and cause diseases such as leaf spot, powdery mildew, mold, and fungal wilt.

[0102] A preferred method includes applying a composition comprising a compound having formula (I) to a plant or its site, preferably to such plants.

[0103] 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.

[0104] 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.

[0105] 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.

[0106]

[0107] Where R 1 It is fluorine, chlorine, or cyclopropyl, and R 2 and R 3 They are chlorine, bromine, or methyl, each independent of the other.

[0108] 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.

[0109] 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 rate 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 rates, the mixture of active ingredients still achieves a high degree of plant pathogen control. Second, by significantly broadening the spectrum of controllable plant pathogens.

[0110] A synergistic effect exists as long as the combined effect of the 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):

[0111] ppm = number of milligrams of active ingredient (=ai) per liter of spray mixture

[0112] X = the percentage of active ingredient A, using p ppm of active ingredient.

[0113] Y = the percentage of active ingredient B, using q ppm of active ingredient.

[0114] According to Colby, using p+q ppm of active ingredients, the expected effect of (additive) active ingredient (A)+(B) is:

[0115] 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 perfectly complementary superposition of activities (expected activity), the difference (OE) is zero. A negative value of the difference (OE) indicates a loss of activity compared to the expected activity.

[0116] Biological examples

[0117] Alternaria alternata (tomato / potato early blight):

[0118] 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.

[0119]

[0120]

[0121] Glomerellalagenarium, also known as Colletotrichum, is a fungus that causes anthracnose in cucurbits. (Anthracnose of Cucurbitaceae family):

[0122] 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.

[0123] Compound A-1.1 Pyrafenib Observed Expected Colby ppm ppm active(%) active(%) 0.1 90 0.01 20 0.22 20 0.1 0.22 100 92 0.01 0.22 50 36

[0124] Compound A-1.1 Para-methyl antibacterial agent Observed Expected Colby ppm ppm active(%) active(%) 0.1 90 0.01 20 0.074 50 0.1 0.074 100 95 0.01 0.074 90 60

[0125]

[0126]

[0127] Compound A-1.2 Pyraclostrobin Observed Expected Colby ppm ppm active(%) active(%) 0.02 90 0.002 20 0.22 20 0.02 0.22 100 92 0.002 0.22 50 36

[0128] Compound A-1.2 Para-methyl antibacterial agent Observed Expected Colby ppm ppm active(%) active(%) 0.002 20 0.074 50 0.025 20 0.002 0.074 100 60 0.002 0.025 50 36

[0129]

[0130]

[0131] Mycosphaerella arachidis, also known as peanut brown spot fungus (Cercospora achidicola) (brown leaf spot disease of peanuts):

[0132] 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.

[0133]

[0134]

[0135] Compound A-1.3 Para-methyl antibacterial agent Observed Expected Colby ppm ppm active(%) active(%) 0.2 0 0.02 0 0.66 90 0.22 20 0.2 0.66 100 90 0.2 0.22 50 20 0.02 0.66 100 90 0.02 0.22 20 20

[0136] Sclerotinia sclerotiorum (cottonymycosis, white rot, etc.):

[0137] Mycelial fragments of fungi prepared from fresh liquid cultures were directly mixed into nutrient broth (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.

[0138] Compound A-1.2 Tetrazopyridine Observed Expected Colby ppm ppm active(%) active(%) 0.02 20 20 0 6.66 0 0.02 20 50 20 0.02 6.66 50 20

[0139]

[0140]

[0141]

[0142] Compound A-1.3 Pyraclostrobin Observed Expected Colby ppm ppm active(%) active(%) 0.2 70 0.02 20 0.008 20 0.2 0.008 90 76 0.02 0.008 50 36

[0143]

[0144]

[0145] Wheat leaf spot disease (Syndrome aureus):

[0146] 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.

[0147]

[0148]

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 or N-oxide thereof: Where R 1 It is a halogen, a C1-C6 alkyl or a C3-C6 cycloalkyl, and R 2 and R 3 They are halogens or C1-C6 alkyl groups, each independent of the other; as well as (B) At least one compound selected from the following: benomyl, thiamethoxam, cyclopropionylamine, diclofenac, isoprothiolane, pyraclostrobin, cymoxanil, tetrazolium pyraclostrobin, pyraclostrobin, thifluzamide, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline; or combinations thereof.

2. The composition according to claim 1, wherein, In compound (A), R 1 It represents fluorine, and R 2 and R 3 They are chlorine, bromine, or methyl, each independent of the other.

3. The composition according to claim 1 or claim 2, wherein, In compound (A), R 1 It represents chlorine, and R 2 and R 3 They are chlorine, bromine, or methyl, each independent of the other.

4. The composition according to claims 1 to 3, wherein, In compound (A), R 1 It represents cyclopropyl, and R 2 and R 3 They are chlorine, bromine, or methyl, each independent of the other.

5. The composition according to any one of claims 1 to 4, wherein, (A) Contains a compound selected from the following or an agriculturally chemically acceptable salt or N-oxide thereof: Based on structure Ia, 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): Based on structure Ib, 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 according to structure Ic, 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): Or a mixture of compounds A-1.1, A-1.2 and A-1.3, or a mixture of their chemically acceptable salts or N-oxides for agricultural use.

6. The composition according to any one of claims 1 to 5, comprising an effective amount of a compound selected from the group consisting of: benomyl, cyproconazole, cyhalofop-ethyl, isoprothiolane, tetrazolium acetamiprid, pyraclostrobin, parathion, 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-quinoxaline, 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxaline and N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinoxaline, or combinations thereof.

7. The composition according to 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. The composition according to any one of claims 1 to 7, comprising one or more additional pest control agents, preferably one or more additional fungicides, insecticides or herbicides.

9. 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 8 to said useful plant, its location, or its propagation material.

10. The method according to claim 9, wherein, The plant pathogens attack plants and cause diseases.

11. The method according to any one of claims 9 and 10, 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.

12. The method according to any one of claims 9 to 11, 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.

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

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

16. Use of the composition according to claim 14 or 15 for controlling plant pathogenic fungi belonging to the following classes: Ascomycetes, preferably *Agromycetes*, *Cytomyces*, *Erythrophagus*, *Pseudomonas*, *Cytomyces*, *Hypophthalmia*; Basidiomycetes, preferably *Russula*, *Rhizoctonia*, *Laminaria*, *Pseudomonas*, *Ustilago*, *Ustilago*; Incomplete or Deuteromycetes, preferably *Botrytis*, *Helicobacter*, *Rhizoctonia*, *Fusarium*, *Rhizoctonia*, *Cercospora*, *Alternaria*, *Pyrophagus*, and *Pseudocercospora*; and / or Oomycetes, preferably *Phytophthora*, *Peronospora*, *Pseudorhyx*, *Euphorbia*, *Plasmodium*, *Pythium*, *Pseudorhyx*, and / or *Monocotyle*.

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