Fungicidal compositions comprising 5-fluoro-4-imino-3-methyl-1-(p-toluenesulfonyl) pyrimidin-2-one

Abstract

The present invention relates to a fungicidal composition comprising 5-fluoro-4-imino-3-methyl-1-(p-tolyl sulfonyl) pyrimidin-2-one (compound I) and at least one active compound II. The invention also relates to an agrochemical composition comprising the composition and a solvent of a solid carrier. In addition, the invention relates to the non-therapeutic use of the composition of the invention to control phytopathogenic harmful fungi.

Description

[0001] This invention relates to an antifungal composition comprising, as active ingredient 1), the following:

[0002] (I-1) 5-Fluoro-4-imino-3-methyl-1-(p-toluenesulfonyl)pyrimidin-2-one

[0003] As active component 2), at least one compound selected from the group consisting of, or its N-oxide, or an agriculturally useful salt.

[0004] (II-1) (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propionic acid [(1S)-2,2-bis(4-fluorophenyl)-1-methyl-ethyl] ester,

[0005] (II-2) Methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionate,

[0006] (II-3) methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionate,

[0007] (II-4) (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propionic acid [(1S)-2,2-bis(4-fluorophenyl)-1-methyl-ethyl] ester,

[0008] (II-5) 2-Methylpropionic acid (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxy-2-pyridyl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxane-7-yl ester,

[0009] (II-6) (2S)-2-[(4-methoxy-3-propanoyloxy-pyridine-2-carbonyl)amino]propionic acid [(1S,2S)-1-methyl-2-(o-tolyl)propyl] ester,

[0010] (II-7) (2RS)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)prop-2-ol,

[0011] (II-8) 3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1H-pyrazole-4-carboxamide,

[0012] (II-9) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydroinden-4-yl]pyrazole-4-carboxamide,

[0013] (II-10) 1-[2-({[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}methyl)-3-methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazole-5-one,

[0014] (II-11) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]prop-2-ol,

[0015] (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]prop-2-ol,

[0016] The weight ratio of compound I to compound II is 10:1 to 1:10.

[0017] This invention also relates to an agricultural chemical composition comprising a solvent of the composition and a solid carrier. Furthermore, this invention relates to the non-therapeutic use of the compositions of this invention for controlling pathogenic fungi of plants.

[0018] Compound I-1 as defined above with respect to component 1) is collectively referred to herein as "a compound having formula I" or "compound I". Compounds II-1 to II-12 as defined above with respect to component 2) are collectively referred to herein as "a compound having formula II" or "compound II".

[0019] Compound I-1 is known from WO 2014 / 105845 and WO 2022 / 234487. In addition, from WO 2014 / 105845, WO 2021 / 181274, WO 2022 / 234487, WO 2020 / 213739, WO 2021 / 230382, WO 2015 / 185485, WO 2017 / 211649, WO 2013 / 008162 and http: / / www.bcpcpesticidecompendium.org / Compounds II-1 to II-12 are known in this literature. The compositions are disclosed, for example, in WO 2018 / 145921, WO 2017 / 155091, WO 2018 / 109002, WO 2017 / 072166, WO 2022 / 130188, WO 2021 / 255070, and WO 2021 / 239766.

[0020] A typical problem in the field of pest control is the need to reduce the dosage rate of active ingredients in order to reduce or avoid adverse environmental or toxicological effects, while still allowing for effective pest control.

[0021] In this invention, the term "pest" includes harmful fungi and animal pests.

[0022] Another issue encountered involves the need for available pest control agents that can effectively resist broad-spectrum harmful fungi and harmful animal pests.

[0023] There is also a need for pest control agents that combine knockdown activity with long-term control (i.e., rapid action and sustained action).

[0024] Another difficulty associated with the use of pest control agents is that, in many cases, repeated and specific application of a single pest control compound leads to the rapid selection of pests (meaning animal pests and harmful fungi) that have developed natural or adaptive resistance to the active compound in question. Therefore, pest control agents that help prevent or overcome resistance are needed.

[0025] Controlling fungal diseases in soybeans, in particular, is a challenge, and now more than one active ingredient is needed to achieve sufficient activity. It is anticipated that all future products will consist of at least two active ingredients (binary compositions).

[0026] Therefore, the object of the present invention is to provide a composition that, from the perspective of effective resistance management and effective control of plant pathogenic harmful fungi, has improved antifungal activity (synergistic composition) and a broadened activity spectrum at the lowest possible application rate and with a reduced total amount of applied active compound.

[0027] Therefore, we have found that this objective is achieved by compositions as defined herein, which comprise compound I and at least one compound II.

[0028] In particular, it has been found that compositions as defined at the beginning exhibit significantly enhanced effects in pest control compared to control rates that could be achieved using individual compounds, and / or are suitable for improving plant health when applied to plants, plant parts, seeds or their growing sites.

[0029] Furthermore, we have found that simultaneous (i.e., combined or separate) application of Compound I and Compound II, or sequential application of Compound I and Compound II, allows for better control of harmful fungi compared to the control that may be achieved using only the individual compounds (synergistic composition). Therefore, in the context of this invention, the term "composition" should mean the physical composition of the components prior to application, or the result of simultaneous (i.e., combined or separate) application of Compound I and Compound II to fungi, their habitat or seeds, soil, or plants to be protected from fungal invasion.

[0030] Compound I and / or compound II can exist in different crystal forms (which may differ in biological activity).

[0031] The scope of this invention includes compositions of (R)- and (S)-isomers of compounds I and / or II having one or more chiral centers, as well as racemic mixtures. Due to the hindered rotation of asymmetric substituents, trans-restricted isomers of active compounds I and / or II may exist. They also form part of the subject matter of this invention.

[0032] Agriculturally acceptable salts of active compounds I and II particularly include salts of cations or acid addition salts of acids, where the cations and anions do not adversely affect the fungicidal activity of these active compounds. Therefore, suitable cations include, in particular, alkali metal (preferably sodium and potassium) ions, alkaline earth metal (preferably calcium, magnesium, and barium) ions, transition metal (preferably manganese, copper, zinc, and iron) ions, and also ammonium ions, which, if desired, may have one to four C1-C4-alkyl substituents and / or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, as well as phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfonium oxide ions, preferably tri(C1-C4-alkyl)sulfonium oxide. The available anions for acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and anions of C1-C4-alkyl acids, preferably formate, acetate, propionate, and butyrate. They can be formed by reacting compound I with an acid corresponding to the anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or nitric acid.

[0033] In binary mixtures, the weight ratio of component 1) to component 2) generally depends on the properties of the components used, typically in the range of 1:10,000 to 10,000:1, often in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, even more preferably in the range of 1:4 to 4:1, and particularly in the range of 1:2 to 2:1. According to another embodiment, the weight ratio of component 1) to component 2) is generally from 1000:1 to 1:1, often from 100:1 to 1:1, frequently from 50:1 to 1:1, preferably from 20:1 to 1:1, more preferably from 10:1 to 1:1, even more preferably from 4:1 to 1:1, and particularly in the range of 2:1 to 1:1. According to another embodiment, the weight ratio of component 1) to component 2) is typically from 20,000:1 to 1:10, often from 10,000:1 to 1:1, frequently from 5,000:1 to 5:1, preferably from 5,000:1 to 10:1, more preferably from 2,000:1 to 30:1, even more preferably from 2,000:1 to 100:1, and particularly in the range of 1,000:1 to 100:1. According to another embodiment, the weight ratio of component 1) to component 2) is typically from 1:1 to 1:1000, often from 1:1 to 1:100, frequently from 1:1 to 1:50, preferably from 1:1 to 1:20, more preferably from 1:1 to 1:10, even more preferably from 1:1 to 1:4, and particularly in the range of 1:1 to 1:2.

[0034] According to another embodiment, the weight ratio of component 1) to component 2) is typically from 10:1 to 1:20,000, often from 1:1 to 1:10,000, frequently from 1:5 to 1:5,000, preferably from 1:10 to 1:5,000, more preferably from 1:30 to 1:2,000, even more preferably from 1:100 to 1:2,000, and particularly in the range of 1:100 to 1:1,000.

[0035] According to another embodiment, compound I and compound II are typically present in a ratio of 20:1 to 1:20, often 15:1 to 1:15, more often 10:1 to 1:10, even more often 9:1 to 1:9, often 8:1 to 1:8, preferably 7:1 to 1:7, more preferably 6:1 to 1:6, even more preferably 5:1 to 1:5, most preferably 4:1 to 1:4, particularly preferably 3:1 to 1:3, especially 2:1 to 1:2, specifically 1:1.

[0036] Compound I and Compound II may also be present in a ratio of 20:1 to 1:1, often 15:1 to 1:1, more often 10:1 to 1:1, even more often 9:1 to 1:1, often 8:1 to 1:1, preferably 7:1 to 1:1, more preferably 6:1 to 1:1, even more preferably 5:1 to 1:1, most preferably 4:1 to 1:1, especially preferably 3:1 to 1:1, and particularly preferably 2:1 to 1:1.

[0037] Compound I and compound II may further exist in a ratio of 1:1 to 1:20, often 1:1 to 1:15, more often 1:1 to 1:10, even more often 1:1 to 1:9, often 1:1 to 1:8, preferably 1:1 to 1:7, more preferably 1:1 to 1:6, even more preferably 1:1 to 1:5, most preferably 1:1 to 1:4, particularly preferably 1:1 to 1:3, especially 1:1 to 1:2.

[0038] In a preferred aspect, the present invention relates to antifungal compositions M.1 to M.60, each identified in a row of Table M below, wherein components 1) and 2) are identified together with their relative amounts (weight ratios).

[0039] Table M

[0040]

[0041]

[0042] Some of the binary compositions and agrochemical compositions according to the invention are systemic and can be used as foliar fungicides, seed dressing fungicides, and soil fungicides for crop protection. Furthermore, they are suitable for controlling harmful fungi, particularly those found in wood or plant roots.

[0043] The binary compositions and their agrochemical compositions according to the present invention are particularly important for controlling a variety of plant pathogenic fungi on various cultivated plants, including: cereals such as wheat, rye, barley, triticale, oats, or rice; sugar beets such as sugar beets or forage beets; fruits such as pome, drupes, or berries such as apples, pears, plums, peaches, apricots, cherries, strawberries, raspberries, blackberries, or gooseberries; legumes such as lentils, peas, alfalfa, or soybeans; oilseed plants such as rapeseed, mustard, olives, sunflowers, coconuts, cocoa beans, castor oil plants, oil palms, peanuts, or soybeans; cucurbits such as pumpkins, cucumbers, or melons; and fiber plants such as cotton, flax, and millet. 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; laurel plants such as avocados, cinnamon, or camphor; energy and raw material plants such as corn, soybeans, rapeseed, sugarcane, or oil palm; corn; tobacco; nuts; coffee; tea; bananas; grapevines (table grapes and grape juice vines); hops; turfgrass; stevia (also known as stevia); natural rubber plants or ornamental and forestry plants such as flowers, shrubs, broad-leaved trees, or evergreens such as conifers; and plant propagation materials such as seeds, and crop materials of these plants.

[0044] Preferably, the binary composition and its agrochemical composition according to the present invention are used to control a variety of fungi on field crops such as: potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugarcane; fruits; vines; ornamental plants; or vegetables such as cucumbers, tomatoes, green beans or pumpkins.

[0045] More preferably, the binary composition and its agrochemical composition according to the present invention are used to control various fungi on grains, corn, fruits, vegetables, rice, and soybeans.

[0046] Even more preferably, the binary composition and its agrochemical composition according to the present invention are used to control various fungi on wheat, barley, corn, tomato, potato, rice, melon, cucumber, pumpkin, squash, pepper, grape, and soybean.

[0047] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control plant pathogenic harmful fungi on wheat.

[0048] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control plant pathogenic harmful fungi on barley.

[0049] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control plant pathogenic harmful fungi on grapes.

[0050] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control plant pathogenic fungi on soybeans.

[0051] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control plant pathogenic harmful fungi on rice.

[0052] Preferably, the binary composition and its agrochemical composition according to the present invention are used to control the following pathogenic factors of plant diseases:

[0053] White rust (A. candida) species on ornamental plants, vegetables (e.g., white rust fungus), and sunflowers (e.g., white rust fungus *A. tragopogonis*); *Albugo* species (white rust disease) on vegetables (e.g., *Albugo* dauci or *Albugo* porri), rapeseed (*Albugo* brassicicola or *Albugo* brassicae), sugar beets (*Albugo* tenuis), fruits (e.g., *Albugo* grandis), rice, soybeans, potatoes, and tomatoes (e.g., *Albugo* solani, *Albugo* or *Albugo* alternata), tomatoes (e.g., *Albugo* solani or *Albugo* alternata), and wheat (e.g., *Albugo* wheat). Alternaria species on *Alternaria triticina* (Alternaria leaf spot); Aphanomyces species on sugar beets and vegetables; Ascochyta species on cereals and vegetables, such as *A. tritici* on wheat (anthracnose) and *A. hordei* on barley; *Aureobasidium zeae* (synonym *Kapatiella zeae*) on maize; Bipolaris and Drechslera species (sexual form: *Cochliobolus* species), such as *D. maydis* (maize leaf spot) or *B. zeicola* (maize leaf spot), such as *B. zeicola* (wheat root rot). Sorokiniana) and, for example, B. oryzae on rice and turfgrass; Blumeria graminis (formerly known as Erysiphe graminis) (powdery mildew) on cereals (e.g., wheat or barley); Botrytiscinerea (sexual form: Botryotinia fuckeliana: gray mold) on fruits and berries (e.g., strawberries), vegetables (e.g., lettuce, carrots, celery, and cabbage); Botrytiscinerea (sexual form: Botryotinia fuckeliana: gray mold) on onion family plants, rapeseed, ornamental plants (e.g., Botrytis eliptica), vines, forest plants, and wheat; Botrytis squamosa or Botrytis rotundifolia (B. eliptica).* *allii*; *Bremia lactucae* on lettuce (downy mildew); *Ceratocystis* species (synonym *Ophiostoma*) on broadleaf and evergreen trees (rot or wilting), such as *C. ulmi* on elm trees (Dutch elm disease); maize (e.g., gray leaf spot: *C. zeae-maydis*), rice, sugar beets (e.g., *C. beticola*), sugarcane, vegetables, coffee, soybeans (e.g., *C. sojina* or *C. kikuchii*) and *Cercospora* species on rice (Cercospora leaf spot); *Cladobotryum* species (synonym *Dactylium*) on mushrooms (e.g., *C. mycophilum*).

[0054] (Formerly known as *Dactylium dendroides*, sexual forms: *Nectria albertinii*, *Nectria rosella*, synonym *Hypomyces rosellus*; *Craniopyriformes* species on tomatoes (e.g. *C. fulvum*: leaf mold) and cereals, such as *C. herbarum* on wheat (smut); *Clavicepspurpurea* on cereals (ergot); *C. carbonum* on maize, cereals (e.g. *C. sativus*, asexual form: *B. sorokiniana*) and rice (e.g. *C. miyabeanus*, asexual form: *H.*) Species of the genus *Helminthosporium* (asexual form: *Bipolaris*) on *oryzae* (leaf spot); cotton (e.g., *C. gossypii*), maize (e.g., *C. graminicola*, anthracnose stem rot), berries, potatoes (e.g., *C. coccodes*, black spot), beans (e.g., *C. lindemuthianum*), soybeans (e.g., *C. truncatum* or *C. gloeosporioides*), vegetables (e.g., *C. lagenarium* or *C. capsici*), fruits (e.g., *C. acutatum*), coffee (e.g., *C. coffeanum* or *C. coffeanum*, coffee berry anthracnose). Colletotrichum species (sexual form: Glomerella) on kahawae (anthracnose) and Colletotrichum discoidus on various crops; Corticium species, such as C. sasakii on rice (sheath blight); Corynesporacassiicola on soybeans, cotton and ornamental plants (leaf spot); Cycloconium species, such as C. oleaginum on olive trees; fruit trees, vines (e.g. C.*Liriodendri* (sexual form: *Neonectrialiriodendri*: blackfoot disease) and *Cylindrocarpon* species on ornamental plants (e.g., fruit tree canker or young vine decline disease, sexual form: *Nectria* or *Neonectria* species); *Dematophora necatrix* on soybean (sexual form: *Rosellinia necatrix*) (root and stem rot); *Diaporthe* species, such as *D. phaseolorum* on soybean (damping-off); maize, cereals such as barley (e.g., *D. teres*, net blotch disease) and wheat (e.g., *D. teres*, wheat blotch disease). tritici-repentis: brown spot disease), Drechslera species (synonym: Helminthosporium) on rice and turfgrass, sexual type: Pyrenophora species; Esca disease on vines (apical dieback, apoplexy) caused by Formicaria punctata (synonym Phellinus punctata), F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa; pear fruit (E. scabia). Species of the genus *Elsinoe* on berries (*E. veneta*): anthracnose and vines (*E. ampelina*): anthracnose; *Entyloma oryzae* on rice (leaf smut); species of the genus *Epicoccum* on wheat (black mold); sugar beets (*E. betae*), vegetables (e.g., pea powdery mildew), gourds (e.g., *E. cichoracearum*), cabbage, rapeseed (e.g., cruciferous powdery mildew).Powdery mildew species (Erysiphe) on *Cytosporina cruciferarum*; grape vine rot (Eutypa lata) (grape canker or shoot dieback, asexual form: *Cytosporina lata*, synonym *Libertella blepharis*) on fruit trees, vines, and ornamental trees; *Exserohilum* species (synonym *Helminthosporium*) on maize (e.g., *E. turcicum*); *Fusarium* species (sexual form: *Gibberella*) on various plants (wilt, root or stem rot), such as *F. graminearum* or *F. culmorum* on cereals (e.g., wheat or barley) (root rot, scab, or wilt), and *F. oxysporum* on tomatoes. *Fusarium oxysporum*, *F. solani* (a soybean-specific fungus, now synonymous with *F. virguliforme*) and *F. tucumaniae* (the South American soybean sudden death syndrome pathogen), as well as *F. brasiliense*, and *F. verticillioides* on corn; *Gaeumannomyces graminis* (take-all disease) on cereals (e.g., wheat or barley) and corn; *Gibberella* species on cereals (e.g., *G. zeae*) and rice (e.g., *G. fujikuroi*: Bakanae disease); *Glomerella cingulata* on vines, pome fruits and other plants, and *G. gossypii* on cotton; grain-stained complexes on rice. Complex); *Guignardia bidwellii* on vines (black rot); *Gymnosporangium* species on Rosaceae and juniper, such as *G. sabinae* on pears (rust); *Helminthosporium* species (synonym *Drechslera*, sexual form: *Cochliobolus*) on corn, cereals, potatoes, and rice; *Hemileia* species, such as *Hemileia coffeeensis* on coffee.Vastatrix (coffee leaf rust); Isariopsis clavispora (synonym Cladosporium vitis) on vines; Macropomina phaseolina (synonym Macropomina phaseoli) on soybeans and cotton (root and stem rot); Microdochium nivale (synonym Fusarium nivale) on cereals (e.g., wheat or barley) (powdery mildew); Microsphaera diffusa on soybeans (powdery mildew); Monilinia species on drupes and other Rosaceae plants, such as M. laxa, M. fructicola, and M. fructicola. *Mycosphaerella* species on cereals, bananas, berries, and peanuts, such as *M. graminicola* (asexual form: *Zymoseptoria tritici*, formerly known as *Septoria tritici*: leaf spot) on wheat, or *M. fijiensis* (synonym: *Pseudocercospora fijiensis*: black leaf spot) and *M. musicola* on bananas, *M. arachidicola* (synonym: *M. arachidis* or *Cercospora arachidis*) and *M. berkeleyi* on peanuts, and *M. berkeleyi* on peas. Downy mildew (P. brassiciola) on rapeseed (e.g., P. brassicae), rapeseed (e.g., P. parasitica), onion (e.g., P. destructor), tobacco (P. tabacina), and soybean (e.g., P. manshurica); soybean rust fungi P. meibomiae (soybean rust); and species of the genus Phialophora, such as P. tracheiphila and P. tetrasporophora.On *P. tetraspora* and soybeans (e.g., *P. gregata*: stem rot); on rapeseed and cabbage, *Phoma lingam* (synonyms *Leptosphaeria biglobosa* and *L. maculans*: root and stem rot), on sugar beets, *P. betae* (root rot, leaf spot, and damping-off), and on corn, *P. zeae-maydis* (synonym *Phyllosticazeae*); on sunflowers, vines (e.g., *P. viticola*: can and leafspot), and soybeans (e.g., stem rot: *P. lentina*). Phaseoli, sexual form: *Phomopsis* species on the interpoda of common beans (Diaporthephaseolorum); *Physodermamaydis* on maize (brown spot); *Phytophthora* species on various plants (wilt, roots, leaves, fruits, and stems), such as red peppers and gourds (e.g. *P. capsici*), soybeans (e.g. *P. megasperma*, synonym *P. sojae*), potatoes and tomatoes (e.g. *P. infestans*: late blight), and broadleaf trees (e.g. *P. ramorum*: oak sudden death); *Plasmodiophora brassicae* (club rot) on cabbage, rapeseed, radish, and other plants. root); Plasmopara species, such as *P. viticola* (grape downy mildew) on vines and *P. halstedii* on sunflowers; Podosphaera species (powdery mildew) on Rosaceae plants, hops, pome fruits, and berries, such as *P. leucotricha* on apples and *P. xanthii* on gourds; Polymyxa species on cereals such as barley and wheat (*P. graminis*) and sugar beets (*P. betae*), and the viral diseases transmitted by them; Pseudocercosporella herpotrichoides (synonym Oculimacula yallundae) on cereals such as wheat or barley.*Acuformis*: eye spot disease, sexual form: *Tapesia yallundae*; *Pseudoperonospora* (downy mildew) on various plants, such as *P. cupensis* on gourd or *P. humili* on hops; *Pseudopezicula tracheiphila* (red fire disease or rotbrenner) on vines, asexual form: *Phialophora*; *Puccinia* species (rust) on various plants, such as *P. triticina* (brown rust or leaf rust) on cereals (e.g., wheat, barley, or rye), *P. striiformis* (stripe rust or yellow rust), and *P. barley* (…). *Pseudomonas hordei* (dwarf rust), *P. graminis* (stem rust or black rust), or *P. recondita* (brown rust or leaf rust); *P. kuehnii* (citrus rust) on sugarcane and *P. asparagi* (Asparagus rust) on asparagus; species of *Pyrenopeziza*, such as *P. brassicae* on rapeseed; *Pyrenophora tritici-repentis* (asexual form: *Drechsleratritici-repentis*) on wheat (brown spot) or *P. teres* (net blotch) on barley; species of *Pyricularia* on rice, such as *P. oryzae* (sexual form: *Magnaporthe*). *Grisea*: rice blast, and *P. grisea* on turfgrass and cereals; *Pythium* species (damping-off) on turfgrass, rice, corn, wheat, cotton, rapeseed, sunflower, soybean, sugar beet, vegetables, and many other plants (e.g., *P. ultimum* or *P. aphanidermatum*) and *P. oligandrum* on mushrooms; *Ramularia* species, such as *R. collo-cygni* on barley (*Ramularia* leaf spot, physiological leaf spot), *R. areola* on cotton (sexual form: *Mycosphaerella areola*), and *R. beetroot* on sugar beet.beticola); Rhizoctonia species on cotton, rice, potatoes, turfgrass, corn, rapeseed, sugar beets, vegetables, and many other plants, such as Rhizoctonia solani (root and stem rot) on soybeans, Rhizoctonia solani (sheath blight) on rice, or Rhizoctonia cerealis (rhizoctonia leaf blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines, and tomatoes; Rhynchosporium secalis and Rhizoctonia commune (scald) on barley, rye, and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; and S. minor and S. attenuatum on vegetables. *Sclerotinia* species (stalk rot or white mold) on field crops such as rapeseed, sunflower (e.g., *Sclerotinia*) and soybean; *S. rolfsii* (synonym *Athelia rolfsii*) on soybean, peanut, vegetables, corn, cereals, and ornamental plants; *Septoria* species on various plants, such as *S. glycines* (brown spot) on soybean, *S. tritici* (synonym *S. tritici*, *S. noodorum* (synonym *Stagonospora nodorum*, *Stagonosporablotch*) on wheat; *Uncinula necator* (synonym *Erysiphenecator*, powdery mildew, asexual form: *Oidium*) on vines. tuckeri); maize (e.g., S. turcicum, synonym Helminthosporium turcicum) and Setosphaeria species on turfgrass (leaf blight); maize (e.g., S. smut).*Reiliana*, synonyms for *Ustilago reiliana* (corn smut), species of *Sphacelotheca* on sorghum and sugarcane (smut); *Sphaerotheca fuliginea* on gourds (synonym *Podosphaera xanthii* (powdery mildew); *Spongospora subterranea* on potatoes (powdery mildew) and the viral diseases transmitted by it; species of *Stagonospora* on cereals, such as *S. nodorum* on wheat (sex form: *Leptosphaeria nodorum* [synonym *Phaeosphaeria nodorum*], synonym *Septoria nodorum*); endophytic chytrium on potatoes. endobioticum (potato cancer); species of the genus *Taphrina*, such as *T. deformans* on peaches (leaf curl) and *T. pruni* on plum trees (plum pocket); species of the genus *Thielaviopsis* on tobacco, pome, vegetables, soybeans, and cotton (black root rot), such as *T. basicola* (synonym *Chalara elegans*); *Tilletia spp.* on cereals (wheat smut or wheat smut), such as *T. caries* on wheat (synonym *T. caries*, wheat smut) and *T. controversa* (wheat dwarf smut); *Trichoderma harzianum* on mushrooms; *Typhula incarnata* on barley or wheat (grey snow mold). Snowmold); species of the genus *Urocystis*, such as *U. occulta* on rye (stem smut); species of the genus *Uromyces* on vegetables (rust diseases), such as *U. appendiculatus* (a synonym of *U. phaseoli*), beets (such as *U. betae* or *U. beticola*), and legumes (such as *U. vignae* and *U. stilbene*).*Ustilago* species (loosesmut) on grains (e.g., *Ustilago nuda* and *Ustilago avaenae*), maize (e.g., *Ustilago maydis*: maize smut), and sugarcane; *V. inaequalis* species (scab) on apples (e.g., *V. inaequalis*) and pears; and *V. verticillium* species (wilt) on various plants such as fruits and ornamental plants, vines, berries, vegetables, and field crops, such as *V. longisporum* on rapeseed, *V. dahliae* on strawberries, rapeseed, potatoes, and tomatoes, and *V. dahliae* on mushrooms. (Fungicola); wheat fermentation shell spores on grains.

[0055] More preferably, the binary composition and its agrochemical composition according to the present invention are used to control the following pathogenic factors of plant diseases:

[0056] Rust diseases on soybeans and cereals (e.g., *Puccinia tritici* and *P. striiformis* on soybeans; *Puccinia tritici* and *P. striiformis* on wheat); mildew diseases on specialty crops, soybeans, rapeseed, and sunflowers (e.g., *Botrytis cinerea* on strawberries and vines; *Sclerotium rolfsii*, *Sclerotium sclerotiorum*, and *S. rolfsii* on rapeseed, sunflower, and soybeans); Fusarium diseases on cereals (e.g., *Fusarium graminearum* and *Fusarium graminearum* on wheat); downy mildew on specialty crops (e.g., *Monosporium variegatum* on vines, *Phytophthora infestans* on potatoes); powdery mildew on specialty crops and cereals (e.g., *Hypericum variegatum* on vines, various powdery mildew species on specialty crops, *Brucella variegata* on cereals); and leaf spot diseases on cereals, soybeans, and maize (e.g., *Synthia scabra* and *Synthia scabra* on cereals, *Synthia scabra* on soybeans, *Cercospora* species on maize and soybeans).

[0057] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control grape monococcidioidomycetes.

[0058] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control wheat scab.

[0059] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control rust fungi in the potato layer.

[0060] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control Sclerotinia sclerotiorum.

[0061] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control circocytozoon bacteria.

[0062] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control Cercospora species, such as Cercospora betaecarpa, Cercospora davidii, Cercospora davidii, and Cercospora zea-maydis.

[0063] According to a preferred embodiment of the present invention, compositions M.1 to M.60 are used to control Botrytis cinerea.

[0064] According to a preferred embodiment of the invention, compositions M.1 to M.60 are used to control *Plasmodium* species, such as *Plasmodium barbarum*.

[0065] In one aspect of the invention, the amount of compound I-1 in compositions M.1 to M.60 is between 40 and 200 g / ha, preferably between 60 and 120 g / ha, and more preferably 100 g / ha.

[0066] The binary compositions and agrochemical compositions according to the invention may also be used as fungicides in the form of premixes with other active substances (e.g., with herbicides, insecticides, growth regulators, fungicides or otherwise with fertilizers), or, if appropriate, until immediately before use (tank mix).

[0067] In many cases, mixing active compounds I and II, as well as compositions comprising the compositions, in their intended form as fungicides with other fungicides results in an expansion of the fungicidal activity spectrum or prevents the development of fungicide resistance. Furthermore, synergistic effects are often observed.

[0068] The binary compositions according to the invention can be converted into commonly used types of agrochemical compositions, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, tablets, capsules, and combinations thereof. Examples of composition types are suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), tablets (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations for treating plant propagation materials such as seeds (e.g., GF). These and other composition types are defined in “Catalogue of pesticide formulation types and international coding system”, Technical Monograph, Vol. 2, 6th edition, May 2008, CropLife International.

[0069] These compositions are prepared in known ways, as described in: Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

[0070] The binary compositions of the active compounds described herein can be prepared by conventional means, such as those given herein for the composition of compound I, into compositions comprising at least one inert component (adjuvant) in addition to the active ingredient. For the general composition of such compositions, refer to the explanation given for the composition containing compound I.

[0071] Suitable additives include solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, auxiliary agents, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, viscous agents, and adhesives.

[0072] Agricultural chemical compositions typically contain between 0.01% and 95% by weight, preferably between 0.1% and 90%, more preferably between 1% and 70%, and particularly between 10% and 60% of an active substance. The active substance is used with a purity of 90% to 100%, preferably 95% to 100% (based on NMR spectra).

[0073] For the purpose of treating plant propagating material, especially seeds, seed treatment solutions (LS), suspension emulsions (SE), flowable concentrates (FS), dry treatment powders (DS), water-dispersible powders (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are commonly used. After dilution two to ten times, the concentration of the active compound in the ready-to-use formulation of the compositions under discussion is 0.01% to 60% by weight, preferably 0.1% to 40%. Application can be carried out before or during sowing. Methods for applying compound I and its compositions separately to plant propagating material, especially seeds, include seed dressing, coating, granulation, dusting, soaking, and furrow application. Preferably, the binary composition or its composition according to the invention is applied to the plant propagating material by methods that do not induce germination, such as seed dressing, granulation, coating, and dusting.

[0074] When used for plant protection, the amount of active substance applied is 0.001 to 2 kg / ha, preferably 0.005 to 2 kg / ha, more preferably 0.05 to 0.9 kg / ha, and especially 0.1 to 0.75 kg / ha, depending on the type of effect desired.

[0075] In the treatment of plant propagation material such as seeds, for example by dusting, coating or soaking, the amount of active compound is typically required for every 100 kg of plant propagation material (preferably seeds), ranging from 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g, and most preferably 5 to 100 g.

[0076] When used for the protection of materials or stored products, the amount of active compound applied depends on the type of application and the desired effect. Typically, the amount applied for the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active compound per cubic meter of treated material.

[0077] By applying the binary composition according to the invention, a synergistic effect can be obtained, that is, a simple summation of more than a single effect (synergistic composition).

[0078] This can be achieved by applying the binary composition according to the invention in combination (e.g., as a barrel mix) or separately, or sequentially, wherein the time interval between individual applications is chosen to ensure that the initially applied active compound remains present at the site of action in sufficient quantity when the other active substance is applied. The order of application is not important for the implementation of the invention.

[0079] When the binary composition according to the invention is applied sequentially, the time between two applications can vary, for example, from 2 hours to 7 days. A range of 0.25 hours to 30 days, preferably 0.5 hours to 14 days, particularly 1 hour to 7 days or 1.5 hours to 5 days, and even more preferably a wider range of 2 hours to 1 day is also possible.

[0080] Biological testing

[0081] Microtest

[0082] The active compound was prepared separately as a stock solution with a concentration of 10,000 ppm in dimethyl sulfoxide.

[0083] Mix the stock solution according to the specified ratio, transfer it to a microtiter plate (MTP) using a pipette, and dilute it with water to the specified concentration.

[0084] Example 1 - Antimicrobial activity against Cercospora soybean in microtiter plate test

[0085] Then add a spore suspension of *Cercospora sojae* in a biological malt aqueous solution or a yeast-bacterial peptone-sodium acetate solution.

[0086]

[0087] Example 2 - Activity against Colletotrichum orbiculare in microtiter plate test

[0088] Then add a spore suspension of *Colletotrichum cucurbita* in a biological malt aqueous solution, yeast-bacterial peptone-glycerol solution, or DOB solution.

[0089]

[0090] Example 3 - Anti-Septoria tritici activity in microtiter plate test

[0091] Then add a spore suspension of wheat husk spores in a biological malt aqueous solution or a yeast-bacterial peptone-glycerol or DOB solution.

[0092]

[0093] These plates were placed in a water vapor saturated chamber at 18°C. MTP was measured at 405 nm using an absorbance spectrophotometer 7 days post-inoculation.

[0094] The measured parameters were compared with the growth rate (100%) of the control variant of the inactive compound and the blank value of the fungus-free compound to determine the relative growth rate (in %) of pathogens in the corresponding active compound.

[0095] Translate these percentages into benefits.

[0096] Efficacy 0 means that the growth level of the pathogen corresponds to the growth level of the untreated control; efficacy 100 means that the pathogen did not grow.

[0097] The expected efficacy of mixtures of active compounds was determined using the Colby formula [RS Colby, “Calculating synergistic and antagonistic responses of herbicide combinations”, Weeds 15, 20-22 (1967)] and compared with observed efficacy.

Claims

1. A fungicidal composition comprising as active component 1) the following (I-1) 5-fluoro-4-imino-3-methyl-1-(p-tolylsulfonyl)pyrimidin-2-one as active component 2) at least one compound selected from the group consisting of (II-1) (2S)-2-[(3-acetyloxy-4-methoxy-pyridine-2-carbonyl)amino]propionic acid [(1S)-2,2-bis(4-fluorophenyl)-1-methyl-ethyl] ester, (II-2) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester, (II-3) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester, (II-4) (2S)-2-[(3-acetyloxy-4-methoxy-pyridine-2-carbonyl)amino]propionic acid [(1S)-2,2-bis(4-fluorophenyl)-1-methyl-ethyl] ester, (II-5) 2-methylpropionic acid (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxy-2-pyridyl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl ester, (II-6) (2S)-2-[(4-methoxy-3-propionyloxy-pyridine-2-carbonyl)amino]propionic acid [(1S,2S)-1-methyl-2-(o-tolyl)propyl] ester, (II-7) (2RS)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (II-8) 3-(difluoromethyl)-1-methyl-N-(3',4',5'-trifluorobiphenyl-2-yl)-1H-pyrazole-4-carboxamide, (II-9) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydroinden-4-yl]pyrazole-4-carboxamide, (II-10) 1-[2-({[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}methyl)-3-methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazol-5-one, (II-11) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]propan-2-ol, (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]propan-2-ol, wherein the weight ratio of compound I to compound II is from 20 : 1 to 1 :

20.

2. The composition of claim 1, wherein, active component 2) is selected from the group consisting of (II-2) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1- yl)propanoic acid methyl ester, (II-3) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1- yl)propanoic acid methyl ester, (II-7) (2RS)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4- triazol-1-yl)propan-2-ol, (II-8) 3-(Difluoromethyl)-1-methyl-N-(3',4',5'-trifluorobiphenyl-2-yl)-1H- pyrazole-4-carboxamide, (II-10) 1-[2-({[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}methyl)-3-methylphenyl]- 1,4-dihydro-4-methyl-5H-tetrazol-5-one, (II-11) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]propan-2-ol. (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]propan-2-ol.

3. The composition according to claim 1 or 2, wherein, active ingredient 2) is selected from the group consisting of: (II-7) (2RS)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4- triazol-1-yl)propan-2-ol, (II-10) 1-[2-({[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}methyl)-3-methylphenyl]- 1,4-dihydro-4-methyl-5H-tetrazol-5-one, (II-11) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (II-12) 2-[2-(7,8-difluoro-2-methylquinolin-3-yl)oxy-6-fluorophenyl]propan-2-ol.

4. The composition according to any one of claims 1 to 3, comprising compound I and compound II in a weight ratio of 5 : 1 to 1 :

5.

5. The composition according to any one of claims 1 to 4, comprising compound I and compound II in a weight ratio of 4 : 1 to 1 :

4.

6. The composition according to any one of claims 1 to 5, comprising compound I and compound II in a weight ratio of 2 : 1 to 1 :

2.

7. An agrochemical composition comprising a solvent or solid carrier and a composition according to any one of claims 1 to 6.

8. The agrochemical composition according to claim 7, further comprising a seed in an amount of 1 g to 1000 g active ingredient per 100 kg of seed.

9. Non-therapeutic use of a composition according to any one of claims 1 to 8 for controlling phytopathogenic harmful fungi.

10. The non-therapeutic use according to claim 9 for controlling phytopathogenic harmful fungi on cereals, maize, fruits, vegetables, rice, soybeans.

11. The non-therapeutic use according to any one of claims 10 to 11 for controlling phytopathogenic harmful fungi on wheat, barley, maize (Zea mays), rice, grape, soybean.

12. The non-therapeutic use according to any one of claims 10 to 12 for controlling a disease selected from the group consisting of Plasmopara viticola, Septoria tritici, Cylindrocarpon spp. like Cylindrocarpon ampullarioides, Botrytis cinerea, Sclerotinia sclerotiorum, Phakopsora pachyrizi, Cercospora spp. like Cercospora beticola, Cercospora sojina, Cercospora sojae, Cercospora zeae-maydis.

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