Mixtures of succinate dehydrogenase inhibitors and picolinamides

Abstract

Compositions comprising (a1) a succinate dehydrogenase inhibitor (SDHI) and (a2) a picolinamide are disclosed. Also disclosed is a method for controlling plant disease caused by a fungal plant pathogen comprising applying to the plant or part thereof, or to the plant seed, a fungicidally effective amount of a composition comprising (a1) a succinate dehydrogenase inhibitor (SDHI) and (a2) picolinamide.

Description

Field of the Invention

[0001] The present invention relates to an agrochemical composition comprising a mixture of a succinate dehydrogenase inhibitor (SDHI) and a pyridinecarboxamide, and to a method of using such a mixture to protect plants or plant seeds against diseases caused by fungal pathogens. Background Art

[0002] The control of plant diseases caused by fungal plant pathogens is of utmost importance for achieving high crop efficiency. Damage to ornamental crops, vegetable crops, field crops, cereal crops, and fruit crops by plant diseases can result in significant yield losses, leading to increased costs for consumers. In addition to often being highly destructive, plant diseases can be difficult to control and may develop resistance to commercial fungicides. Many products are commercially available for these purposes, but there is a continuing need for novel fungicidal compounds that are more effective, lower in cost, less toxic, safer to the environment, or have different sites of action. In addition to the introduction of novel fungicides, combinations of fungicides are often used to facilitate disease control, broaden the control spectrum, and delay the development of resistance. Furthermore, certain rare combinations of fungicides exhibit greater than additive (i.e., synergistic) effects to provide a commercially important level of plant disease control. The advantages of specific fungicide combinations are recognized in the art as being different, depending on factors such as the specific plant species and the plant disease to be treated, whether the plant disease is from a fungal resistant strain, and whether the plant is treated before or after infection with the fungal plant pathogen. Thus, there is a need for novel advantageous combinations to provide a variety of options to best meet specific plant disease control needs. Such combinations have now been discovered.

[0003] PCT Patent Publication WO 2012 / 084812 and WO 2013 / 186325 disclose certain succinate dehydrogenase inhibitors (SDHIs) selected from pyrazole-4-carboxamide derivatives, mixtures thereof, and their use as fungicides.

[0004] PCT Patent Publication WO 2007 / 048556 discloses certain succinate dehydrogenase inhibitors (SDHIs) selected from heterocyclic carboxamide derivatives, mixtures thereof, and their use as fungicides.

[0005] U.S. Patent Publication US2008 / 0293798 discloses a fungicidal mixture comprising a succinate dehydrogenase inhibitor (SDHI) selected from 1-methylpyrazol-4-ylcarboxanilide derivatives.

[0006] PCT Patent Publications WO 2003 / 035617, WO 2016 / 109257, WO 2018 / 129237, and WO 2019 / 173665 disclose pyridinecarboxamide compounds, mixtures thereof, and their use as fungicides. Summary of the invention

[0007] The present invention relates to a fungicidal composition (i.e. combination, mixture) comprising:

[0008] (a1) succinate dehydrogenase inhibitors (SDHI); and

[0009] (a2) Pyridineamide.

[0010] The present invention also relates to a composition comprising: (a1) a succinate dehydrogenase inhibitor (SDHI); and (a2) a pyridine amide; and at least one component (b).

[0011] The present invention also relates to a composition comprising: (a1) a succinate dehydrogenase inhibitor (SDHI); and (a2) a pyridine amide, wherein the SDHI and the pyridine amide are present in synergistically effective amounts; and optionally at least one component (b).

[0012] The present invention also relates to a composition comprising one of the aforementioned compositions and at least one further component selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0013] The present invention also relates to a method for controlling plant diseases caused by fungal plant pathogens (including resistant strains of fungal pathogens), which method comprises applying to the plant or part thereof, or to the seed of the plant, a fungicidally effective amount of one of the aforementioned compositions.

[0014] The aforementioned method can also be described as a method for protecting plants or plant seeds from diseases caused by fungal pathogens, which method comprises applying to the plant (or part thereof) or plant seed a fungicidally effective amount of one of the aforementioned compositions (directly or through the environment of the plant or plant seed (e.g., the growing medium)). DETAILED DESCRIPTION

[0015] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation expressly stated. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

[0016] The connecting phrase "consisting of" excludes any unrecited element, step, or ingredient. If in a claim, such a phrase will render the claim closed, excluding materials other than those recited, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the claim body rather than immediately following the preamble, the phrase only limits the elements set forth in that clause; other elements are not excluded from the claim as a whole.

[0017] The connecting phrase "consisting essentially of" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect one or more of the basic and novel features of the claimed invention. The term "consisting essentially of" lies between "comprising" and "consisting of".

[0018] When the applicant has defined the invention or a part thereof using open - ended terms such as "comprising", it should be understood (unless otherwise specified) that the specification should also be interpreted as describing the invention using the terms "consisting essentially of" or "consisting of".

[0019] Furthermore, unless explicitly stated to the contrary, "or" means an inclusive or rather than an exclusive or. For example, the condition A or B is satisfied by any of the following conditions: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0020] In addition, the indefinite articles "a" and "an" before an element or component of the present invention are intended to be non - restrictive with respect to the number of instances (i.e., occurrences) of that element or component. Thus, "a" or "an" should be understood to include one or at least one, and the singular word form of an element or component also includes the plural, unless the number clearly means the singular.

[0021] The term "agronomy" refers to the production of field crops such as for food and fiber, and includes the growth of maize or corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other brassica crops), fruiting vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and cucurbit crops), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone, and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflowers, and olives).

[0022] The term "non - agronomic" refers to applications different from field crops, such as horticultural crops (e.g., greenhouse, nursery, or ornamental plants not grown in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored products, agroforestry and vegetation management, public health (i.e., human) and animal health (e.g., domestic animals such as pets, livestock, and poultry, non - domestic animals such as wild animals).

[0023] The term "crop vigor" refers to the growth rate or biomass accumulation of crop plants. "Increase in vigor" refers to an increase in growth or biomass accumulation of crop plants relative to untreated control crop plants. The term "crop yield" refers to the quantity and quality return of crop material obtained after harvesting crop plants. "Increase in crop yield" refers to an increase in crop yield relative to untreated control crop plants.

[0024] The term "biologically effective amount" refers to the amount of a biologically active compound that, when applied to (i.e., contacted with) a fungus to be controlled or its environment, or to a plant, the seed from which the plant grows, or the locus of the plant (e.g., growth medium), to protect the plant from damage by fungal diseases or for other desired effects (e.g., increasing plant vigor), is sufficient to produce the desired biological effect.

[0025] As mentioned in this disclosure and the claims, "plant" includes members of the plant kingdom at all life stages, particularly seed plants (Spermatopsida), and all life stages include young plants (e.g., germinated seeds developing into seedlings) and mature reproductive stages (e.g., flowering and seed - bearing plants). Plant parts include geotropic members typically growing below the surface of the growth medium (e.g., soil), such as roots, tubers, bulbs, and corms, as well as members growing above the growth medium, such as leaves (including stems and leaves), flowers, fruits, and seeds.

[0026] As mentioned herein, the term "seedling" used alone or in combination with words refers to a young plant developed from the embryo of a seed.

[0027] As mentioned herein, the term "broad - leaf" used alone or in words such as "broad - leaf crop" refers to dicotyledons or dicotyledonous plants, and this term is used to describe a group of angiosperms characterized by having an embryo with two cotyledons.

[0028] As mentioned in this disclosure, the terms "fungal pathogen" and "fungal plant pathogen" include pathogens in the phyla Ascomycota, Basidiomycota, and Zygomycota, as well as the fungus-like Oomycota, which are the causative agents of broad-spectrum plant diseases of economic importance that affect ornamental crops, turf crops, vegetable crops, field crops, cereal crops, and fruit crops. In the context of this disclosure, "protecting plants from disease" or "controlling plant disease" includes preventive actions (interrupting the cycle of fungal infection, colonization, symptom development, and spore production) and / or therapeutic actions (inhibiting colonization of plant host tissues).

[0029] As used herein, the term "mode of action" (MOA) is as defined by the Fungicide Resistance Action Committee (FRAC) and is used to distinguish fungicides based on their biochemical mode of action in the biosynthetic pathways of plant pathogens and their resistance risk. The modes of action defined by FRAC include (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell walls, (P) induction of host plant defenses, (U) unknown mode of action, (NC) unclassified, (M) multi-site contact activity, and (BM) biological agents with multiple modes of action. Each mode of action (i.e., letters A to BM) contains one or more subgroups (e.g., A includes subgroups A1, A2, A3, and A4), which are based on individually verified target sites of action or, in cases where the exact target site is unknown, on cross-resistance characteristics within the group or with other groups. Each of these subgroups (e.g., A1, A2, A3, and A4) is assigned a FRAC code (numbers and / or letters). For example, the FRAC code for subgroup A1 is 4. Additional information on target sites and FRAC codes can be obtained from publicly available databases maintained, for example, by FRAC.

[0030] As used herein, the term "cross-resistance" refers to the phenomenon that occurs when a pathogen becomes resistant to one fungicide and simultaneously becomes resistant to one or more other fungicides. These other fungicides typically but not always belong to the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.

[0031] In the present disclosure, phrases such as “fungicide resistance” or “fungicide-resistant strain” etc. refer to fungal pathogens that survive and reproduce in the presence of a fungicide. Resistance development is an evolutionary process that occurs after a pathogen is exposed to a fungicide for a period of time. For example, a pathogen that was initially sensitive to a fungicide becomes less sensitive over time and is no longer adequately controlled by the fungicide. Resistance can develop as qualitative resistance or quantitative resistance. Qualitative resistance is also known as monogenic or major gene resistance and occurs when a single mutation in a target gene results in loss of efficacy. Quantitative resistance is also known as polygenic resistance and occurs when the development of many individual genetic changes (such as mutations in target genes or overexpression of target genes) leads to a gradual decrease in sensitivity. FRAC regularly publishes additional information on fungal species that are resistant to fungicides and the corresponding gene mutations and makes it publicly available on its website.

[0032] The compounds of the invention can exist as one or more stereoisomers. Stereoisomers are isomers that have the same constitution but differ in the arrangement of their atoms in space and include enantiomers, diastereomers, cis- and trans-isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about a single bond where the rotational barrier is high enough to allow separation of the isomeric species. Those skilled in the art will understand that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to one or more other stereoisomers or when separated from one or more other stereoisomers. Additionally, those skilled in the art know how to separate, enrich, and / or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereochemistry, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0033] The present invention also includes compounds having the recited formulae, wherein one stereoisomer is enriched relative to one or more other stereoisomers. For example, the ratio of (Z)- to (E)-isomers in any compound having the recited formulae can take a wide range of values, whether stereoselective or non-stereoselective is produced. In addition, the present invention includes compounds enriched compared to the racemic mixture of enantiomers having the recited formulae. Also included are substantially pure enantiomers of compounds having the recited formulae. When the enantiomers are enriched, one enantiomer is present in a greater amount than the other, and the degree of enrichment can be defined by an expression of enantiomeric excess ("ee") defined as (2x - 1)·100%, where x is the mole fraction of the preponderant enantiomer in the mixture (e.g., 20% ee corresponds to a 60:40 ratio of enantiomers).

[0034] The compositions of the present invention can have an enantiomeric excess of at least 50% of the more active isomer; at least 75% enantiomeric excess; at least 90% enantiomeric excess; or at least 94% enantiomeric excess.

[0035] The compounds of the present invention can exist as one or more conformational isomers due to restricted rotation around the amide bond (e.g., C(=O)-N) in the recited formulae (or recited chemical names). The present invention includes mixtures of conformational isomers. In addition, the present invention includes compounds in which one conformational isomer is enriched relative to other conformational isomers.

[0036] The present invention includes all stereoisomers, conformational isomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.

[0037] Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides because the nitrogen requires an available lone pair of electrons to be oxidized to the oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art and include the use of peroxyacids such as peracetic acid and meta-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane to oxidize heterocycles and tertiary amines. These methods for preparing N-oxides have been widely described and reviewed in the literature, see for example: T.L. Gilchrist, Comprehensive Organic Synthesis, Volume 7, pages 748 - 750, edited by S.V. Ley, Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Volume 3, pages 18 - 20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimmett and B.R.T. Keene, Advances in Heterocyclic Chemistry, Volume 43, pages 149 - 161, edited by A.R. Katritzky, Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, Volume 9, pages 285 - 291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and G.W.H. Cheeseman and E.S.G. Werstiuk, Advances in Heterocyclic Chemistry, Volume 22, pages 390 - 392, edited by A.R. Katritzky and A.J. Boulton, Academic Press.

[0038] Those skilled in the art recognize that, since salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions, the salts share the biological utility of the non-salt forms. Accordingly, salts of a variety of compounds having the recited formula (or the recited chemical name) can be used to control plant diseases caused by fungal plant pathogens (i.e., are agriculturally suitable). Salts of compounds having the recited formula include acid addition salts formed with inorganic or organic acids, such acids as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid. When a compound having the recited formula contains an acidic moiety such as a carboxylic acid, the salts also include those formed with organic or inorganic bases, such bases as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention encompasses compounds selected from the recited formula, their N-oxides and agriculturally suitable salts and solvates.

[0039] Compounds selected from the recited formulas, their stereoisomers, tautomers, N-oxides, and salts typically exist in more than one form, and thus the recited formulas include all crystalline and non-crystalline forms of the compounds represented by the recited formulas. Non-crystalline forms include embodiments that are solids such as waxes and gums, and embodiments that are liquids such as solutions and melts. Crystalline forms include embodiments representative of substantially single crystal types and embodiments representative of mixtures of polymorphs (i.e., different crystal types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystalline forms, which forms have different molecular arrangements and / or conformations in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound within the crystal lattice. Polymorphs can differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. Those skilled in the art will understand that a polymorph of a compound represented by the recited formula can exhibit beneficial effects (e.g., suitability for the preparation of useful formulations, improved biological properties) relative to another polymorph or a mixture of polymorphs of the same compound represented by the recited formula. The preparation and isolation of a specific polymorph of a compound represented by the recited formula can be achieved by methods known to those skilled in the art, including, for example, crystallization using a selected solvent and temperature. For a comprehensive discussion of polymorphism, see R. Hilfiker, editor, Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

[0040] As described in the Summary of the Invention, aspects of the present invention relate to compositions comprising: (a1) a succinate dehydrogenase inhibitor (SDHI); and (a2) a pyridinecarboxamide, and at least one component (b). More particularly, the at least one component (b) is selected from the group consisting of:

[0041] (b1) a methyl benzimidazole carbamate (MBC) fungicide;

[0042] (b2) a dicarboximide fungicide;

[0043] (b3) a demethylation inhibitor (DMI) fungicide;

[0044] (b4) a phenylamide (PA) fungicide;

[0045] (b5) an amine / morpholine fungicide;

[0046] (b6) Phospholipid biosynthesis inhibitor fungicides;

[0047] (b7) Other succinate dehydrogenase inhibitor (SDHI) fungicides;

[0048] (b8) Hydroxy(2-amino)pyrimidine fungicides;

[0049] (b9) Anilinopyrimidine (AP) fungicides;

[0050] (b10) N-Phenyl carbamate fungicides;

[0051] (b11) Quinone outside inhibitor (QoI) fungicides;

[0052] (b12) Phenylpyrrole (PP) fungicides;

[0053] (b13) Quinazoline fungicides;

[0054] (b14) Cellular peroxidation inhibitor fungicides;

[0055] (b15) Melanin biosynthesis inhibitor - reductase (MBI-R) fungicides;

[0056] (b16a) Melanin biosynthesis inhibitor - dehydratase (MBI-D) fungicides;

[0057] (b16b) Melanin biosynthesis inhibitor - polyketide synthase (MBI-P) fungicides;

[0058] (b17) Keto reductase inhibitor (KRI) fungicides;

[0059] (b18) Squalene-epoxidase inhibitor fungicides;

[0060] (b19) Polyoxins fungicides;

[0061] (b20) Phenylurea fungicides;

[0062] (b21) Quinone inside inhibitor (QiI) fungicides;

[0063] (b22) Benzamide and thiazolecarboxamide fungicides;

[0064] (b23) Enolpyranosyluracil antibiotics fungicides;

[0065] (b24) Hexopyranosyl antibiotics fungicides;

[0066] (b25) Glucopyranosyl antibiotics: Protein synthesis fungicides;

[0067] (b26) Glucopyranosyl antibiotic fungicides;

[0068] (b27) Cyanoacetamide-oxime fungicides;

[0069] (b28) Carbamate fungicides;

[0070] (b29) Oxidative phosphorylation uncoupling fungicides;

[0071] (b30) Organotin fungicides;

[0072] (b31) Carboxylic acid fungicides;

[0073] (b32) Heteroaromatic fungicides;

[0074] (b33) Phosphonate fungicides;

[0075] (b34) Anthranilic acid fungicides;

[0076] (b35) Benzotriazine fungicides;

[0077] (b36) Benzene-sulfonamide fungicides;

[0078] (b37) Pyridazinone fungicides;

[0079] (b38) Thiophene-carboxamide fungicides;

[0080] (b39) Complex I NADH oxidoreductase inhibitor fungicides;

[0081] (b40) Carboxylic acid amide (CAA) fungicides;

[0082] (b41) Tetracycline antibiotic fungicides;

[0083] (b42) Thiocarbamate fungicides;

[0084] (b43) Benzamide fungicides;

[0085] (b44) Microbial fungicides;

[0086] (b45) Quinone outside inhibitor, strobilurin-binding type (QoSI) fungicides;

[0087] (b46) Plant extract fungicides;

[0088] (b47) Cyanoacrylate fungicides;

[0089] (b48) Polyene fungicides;

[0090] (b49) Oxysterol-binding protein inhibitor (OSBPI) fungicides;

[0091] (b50) Aryl-phenyl-ketone fungicides;

[0092] (b51) Host plant defense-inducing fungicides;

[0093] (b52) Multi-site active fungicides;

[0094] (b53) Biopreparations with multiple modes of action;

[0095] (b54) Fungicides other than the fungicides of component (a1), component (a2), and components (b1) to (b53); and

[0096] Salts of the compounds of (b1) to (b54).

[0097] It is noted that there are examples where component (b) contains at least one fungicidal compound from each of two different groups selected from (b1) to (b54).

[0098] The "benzimidazole carbamate (MBC) fungicides (b1)" (FRAC code 1) inhibit mitosis by binding to β-tubulin during microtubule assembly. Inhibiting microtubule assembly can disrupt cell division, intracellular transport, and cell structure. Benzimidazole carbamate fungicides include benzimidazole and thiophanate fungicides. Benzimidazoles include benomyl, carbendazim, fenfuram, and thiabendazole. Thiophanates include thiophanate and thiophanate-methyl.

[0099] The "dicarboximide fungicides (b2)" (FRAC code 2) inhibit mitogen-activated protein (MAP) / histidine kinases in osmotic signal transduction. Examples include chlozolinate, dimethachlon, iprodione, procymidone, and vinclozolin.

[0100] "Demethylation inhibitor (DMI) fungicides (b3)" (FRAC code 3) (sterol biosynthesis inhibitor (SBI): class I) inhibit C14-demethylase, which plays a role in sterol production. Sterols, such as ergosterol, are required for membrane structure and function and are thus essential for the development of a functional cell wall. Exposure to these fungicides therefore leads to abnormal growth and eventual death of sensitive fungi. DMI fungicides are divided into several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles, and triazolethiones. Piperazines include triforine. Pyridines include buthiobate, fenpiclonil, fenamidone, and (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol. Pyrimidines include fenarimol, fluoroimide, and myclobutanil. Imidazoles include econazole, imazalil, oxpoconazole, blastmycin, prochloraz, and flutriafol. Triazoles include propiconazole, bitertanol, brefeldin A, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, metconazole, metconazole, picoxystrobin, penconazole, propiconazole, quinconazole, silthiofam, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazol-1-ethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazol-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole. Triazolethiones include prothioconazole. Biochemical studies have shown that all of the above fungicides are DMI fungicides, as described by K.H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

[0101] "Phenylamide (PA) fungicides (b4)" (FRAC code 4) are specific inhibitors of RNA polymerase in oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced ability to incorporate uridine into rRNA. The growth and development of sensitive fungi are prevented by exposure to fungicides of this class. Phenylamide fungicides include acylalanine, oxazolidinone, and butyrolactone fungicides. Acylalanine includes benalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyl, and metalaxyl-M (also known as mefenoxam). Oxazolidinone includes oxadixyl. Butyrolactone includes fuberidazole.

[0102] "Amine / morpholine fungicides (b5)" (FRAC code 5) (SBI: class II) inhibit two target sites within the sterol biosynthesis pathway, Δ 8 →Δ 7 isomerase and Δ 14 reductase. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of a functional cell wall. Thus, exposure to these fungicides results in abnormal growth and eventual death of sensitive fungi. Amine / morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine, piperidine, and spiroketal-amine fungicides. Morpholine includes aldimorph, dodemorph, fenpropimorph, tridemorph, and tridemorphamide. Piperidine includes fenpropidin and piperalin. Spiroketal-amine includes spiroxamine.

[0103] "Phospholipid biosynthesis inhibitor fungicides (b6)" (FRAC code 6) inhibit fungal growth by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phosphorothioate and dithiolane fungicides. Phosphorothioate includes edifenphos, isoprothiolane, and pyrazophos. Dithiolane includes isoprothiolane.

[0104] The "succinate dehydrogenase inhibitor (SDHI) fungicides (b7)" (FRAC code 7) inhibit complex II fungal respiration by disrupting a key enzyme called succinate dehydrogenase in the Krebs cycle (TCA cycle). Inhibiting respiration prevents the fungus from producing ATP and thus inhibits growth and reproduction. SDHI fungicides include phenylbenzamides, phenyl-oxo-ethyl thiopheneamides, pyridyl-ethyl-benzamides, furanamides, oxathiinecarboxamides, thiazolecarboxamides, pyrazole-4-carboxamides, N-cyclopropyl-N-benzyl-pyrazolecarboxamides, N-methoxy(phenylethyl)pyrazolecarboxamides, pyridinecarboxamides, and pyrazinecarboxamide fungicides. Phenylbenzamides include carboxin, flutolanil, and mepronil. Phenyl-oxo-ethyl thiopheneamides include isofetamid. Pyridyl-ethyl-benzamides include fluxapyroxad. Furanamides include mefuram. Oxathiinecarboxamides include carboxin and oxycarboxin. Thiazolecarboxamides include thifluzamide. Pyrazole-4-carboxamides include benzovindiflupyr, bixafen, fluxametamide (proposed common name, registration number 1676101-39-5), fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penthiopyrad, pyrisoxazole, pyrapropoyne (proposed common name, registration number 1803108-03-3), penflufen, and N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. N-cyclopropyl-N-benzyl-pyrazolecarboxamides include isoflucypram. N-methoxy(phenylethyl)pyrazolecarboxamides include fluxametamide. Pyridinecarboxamides include boscalid. Pyrazinecarboxamides include bixafen.

[0105] The "hydroxy(2-amino)pyrimidine fungicides (b8)" (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include ethirimol sulfate, dimethirimol, and ethirimol.

[0106] The "anilinopyrimidine (AP) fungicides (b9)" (FRAC code 9) are proposed to inhibit the biosynthesis of the amino acid methionine and disrupt the secretion of hydrolases that lyse plant cells during infection. Examples include cyprodinil, cymoxanil, and dimethirimol.

[0107] The "N-phenyl carbamate fungicides (b10)" (FRAC code 10) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Disrupting microtubule assembly can disrupt cell division, intracellular transport, and cell structure. Examples include diethofencarb.

[0108] "Quinone outside inhibitor (QoI) fungicides (b11)" (FRAC code 11) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. The oxidation of ubiquinol is blocked at the "quinone outside" (Qo) site of the cytochrome bc1 complex located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone outside inhibitor fungicides include methoxyacrylates, methoxyacetamides, methoxycarbamates, oxime acetates, oxime acetamides, and dihydrodioxazine fungicides (also collectively referred to as strobilurin fungicides), oxazolidinediones, imidazolinones, benzyl-carbamates, and tetrazolinone (subgroup A) fungicides. Methoxyacrylates include azoxystrobin, cispiramide, enoxastrobin (also known as enestroburin), fluoxastrobin, picoxystrobin, and pyraclostrobin. Methoxyacetamides include mandestrobin. Methoxy-carbamates include pyraclostrobin, pyribencarb, and picoxystrobin. Oxime-acetates include kresoxim-methyl and trifloxystrobin. Oxime-acetamides include dimoxystrobin, enoxastrobin, metominostrobin, and triclopyricarb. Dihydrodioxazine includes fluazinam. Oxazolidinediones include oxadixyl. Imidazolinones include imazalil. Benzyl-carbamates include pyriminobac-methyl. Tetrazolinone includes metconazole.

[0109] "Phenylpyrrole (PP) fungicides (b12)" (FRAC code 12) inhibit MAP / histidine kinases associated with osmotic signal transduction in fungi. Fuberidazole and fludioxonil are examples of this fungicide class.

[0110] "Phthalazinone fungicides (b13)" (FRAC code 13) are proposed to inhibit signal transduction by a currently unknown mechanism. They have been shown to interfere with the germination and / or appressorium formation of fungi causing powdery mildew diseases. Phthalazinone fungicides include aryloxyquinolines and quinazolinones. Aryloxyquinolines include quinoxyfen. Quinazolinones include propoxyquinoline.

[0111] "Cellular peroxidation inhibitor fungicides (b14)" (FRAC code 14) are proposed to inhibit lipid peroxidation that affects membrane synthesis in fungi. Members of this class, such as thiabendazole, can also affect other biological processes such as respiration and melanin biosynthesis. Cellular peroxidation fungicides include aromatic hydrocarbons and 1,2,4-thiadiazole fungicides. Aromatic hydrocarbon fungicides include biphenyl, chloroneb, dichlofluanid, quintozene, tecnazene, and tolclofos-methyl. 1,2,4-thiadiazole includes thiabendazole.

[0112] "Melanin Biosynthesis Inhibitor - Reductase (MBI - R) Fungicides (b15)" (FRAC code 16.1) inhibit the naphthalene aldehyde condensation reduction step in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin Biosynthesis Inhibitor - Reductase fungicides include isobenzofuranones, pyrroloquinolones, and triazolo - benzothiazole fungicides. Isobenzofuranones include tecnazene. Pyrroloquinolones include pyroquilon. Triazolo - benzothiazoles include tricyclazole.

[0113] "Melanin Biosynthesis Inhibitor - Dehydratase (MBI - D) Fungicides (b16a)" (FRAC code 16.2) inhibit the colletotrichum dehydratase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin Biosynthesis Inhibitor - Dehydratase fungicides include cyclopropanecarboxamides, formamides, and propionamides. Cyclopropanecarboxamides include carpropamid. Formamides include diclocymet. Propionamides include probenazole.

[0114] "Melanin Biosynthesis Inhibitor - Polyketide Synthase (MBI - P) Fungicides (b16b)" (FRAC code 16.3) inhibit the polyketide synthase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin Biosynthesis Inhibitor - Polyketide Synthase fungicides include trifluoroethyl carbamate fungicides. Trifluoroethyl carbamates include tolprocarb.

[0115] "Ketoreductase Inhibitor (KRI) Fungicides (b17)" (FRAC code 17) inhibit the 3 - ketoreductase during C4 - demethylation in sterol production. Ketoreductase Inhibitor fungicides (also known as Sterol Biosynthesis Inhibitors (SBI): Class III) include hydroxyanilines and amino - pyrazolinones. Hydroxyanilines include fenhexamid. Amino - pyrazolinones include amisulbrom. Additionally, Quinofumelin (proposed common name, registration number 861647 - 84 - 9) and ipflufenoquin (proposed common name, registration number 1314008 - 27 - 9) are considered ketoreductase inhibitor fungicides.

[0116] "Squalene - Epoxidase Inhibitor Fungicides (b18)" (FRAC code 18) (SBI: Class IV) inhibit squalene - epoxidase in the sterol biosynthesis pathway. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of a functional cell wall. Therefore, exposure to these fungicides leads to abnormal growth and eventual death of sensitive fungi. Squalene - epoxidase inhibitor fungicides include thiocarbamates and allylamines. Thiocarbamates include pebulate. Allylamines include naftifine and terbinafine.

[0117] The polyoxin fungicide (b19) (FRAC code 19) inhibits chitin synthase. Examples include polyoxins.

[0118] The phenylurea fungicide (b20) (FRAC code 20) has been proposed for affecting cell division. Examples include pencycuron.

[0119] The quinone inside inhibitor (QiI) fungicide (b21) (FRAC code 21) inhibits complex III mitochondrial respiration in fungi by affecting ubiquinol reductase. The reduction of ubiquinone is blocked at the "quinone inside" (Qi) site of the cytochrome bc1 complex located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone inside inhibitor fungicides include cyanoimidazoles, sulfamoyl-triazoles, and pyridinecarboxamides. Cyanoimidazoles include cyazofamid. Sulfamoyl-triazoles include amisulbrom. Pyridinecarboxamides include fenpicoxamid, florylpicoxamid, and metarylpicoxamid.

[0120] The benzamide and thiazolecarboxamide fungicides (b22) (FRAC code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Disrupting microtubule assembly can disrupt cell division, intracellular trafficking, and cell structure. Benzamides include tolylbenzamides such as zoxamide. Thiazolecarboxamides include ethylamino-thiazolecarboxamides such as ethaboxam.

[0121] The enopyranuronic acid antibiotic fungicide (b23) (FRAC code 23) inhibits fungal growth by affecting protein biosynthesis. Examples include blasticidin-S.

[0122] The hexopyranosyl antibiotic fungicide (b24) (FRAC code 24) inhibits the growth of fungi by affecting protein biosynthesis. Examples include kasugamycin.

[0123] The glucopyranosyl antibiotic: protein synthesis fungicide (b25) (FRAC code 25) inhibits the growth of fungi by affecting protein biosynthesis. Examples include streptomycin.

[0124] The glucopyranosyl antibiotic fungicide (b26) (FRAC code U18, previously FRAC code 26 reclassified as U18) has been proposed for inhibiting trehalase and inositol biosynthesis. Examples include validamycin.

[0125] The cyanoacetamide-oxime fungicide (b27) (FRAC code 27) includes cymoxanil.

[0126] The "carbamate fungicides (b28)" (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in the cell membrane, which then disrupts cell membrane permeability. Iodocarb, propamocarb, and thiofanox are examples of this fungicide class.

[0127] The "oxidative phosphorylation uncoupling fungicides (b29)" (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development. This class includes dinitrophenyl crotonates such as binapacryl, dinocap, and karathane, and 2,6-dinitroanilines such as fluazinam.

[0128] The "organotin fungicides (b30)" (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in the oxidative phosphorylation pathway. Examples include triphenyltin acetate, triphenyltin chloride, and triphenyltin hydroxide.

[0129] The "carboxylic acid fungicides (b31)" (FRAC code 31) inhibit fungal growth by affecting DNA topoisomerase type II (gyrase). Examples include oxolinic acid.

[0130] The "heteroaromatic fungicides (b32)" (FRAC code 32) are proposed to affect DNA / ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. Isoxazoles include hymexazol, and isothiazolones include octhilinone.

[0131] The "phosphonate fungicides (b33)" (FRAC code P07, previously FRAC code 33 reclassified as P07) include phosphorous acid and its various salts, including fosetyl-aluminum.

[0132] The "anthranilic acid fungicides (b34)" (FRAC code 34) include teclofthalam.

[0133] The "benzotriazine fungicides (b35)" (FRAC code 35) include azoxystrobin.

[0134] The "benzene-sulfonamide fungicides (b36)" (FRAC code 36) include flusulfamide.

[0135] The "pyridazinone fungicides (b37)" (FRAC code 37) include pyridaben.

[0136] The "thiophene-carboxamide fungicides (b38)" (FRAC code 38) are proposed to affect ATP production. Examples include silthiofam.

[0137] The "Complex I NADH oxidoreductase inhibitor fungicide (b39)" (FRAC code 39) inhibits electron transport in mitochondria and includes pyrimidine amines such as fluazinam, pyrazole-5-carboxamides such as clothianidin, and quinazolines such as quinothrin.

[0138] The "carboxylic acid amide (CAA) fungicide (b40)" (FRAC code 40) inhibits cellulose synthase, which prevents the growth of target fungi and causes the death of target fungi. Carboxylic acid amide fungicides include cinnamic acid amides, valinamide carbamates, and mandelic acid amide fungicides. Cinnamic acid amides include dimethomorph, flumorph, and pyrimorph. Valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, toprocarb, and valifenalate (also known as dimethomorph). Mandelic acid amides include mandipropamid, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, and N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

[0139] The "tetracycline antibiotic fungicide (b41)" (FRAC code 41) inhibits the growth of fungi by affecting protein synthesis. Examples include oxytetracycline.

[0140] The "thiocarbamate fungicide (b42)" (FRAC code M12, previously FRAC code 42 reclassified as M12) includes sulfallate.

[0141] The "benzamide fungicide (b43)" (FRAC code 43) inhibits fungal growth through the delocalization of spectrin-like proteins. Examples include pyridylmethylbenzamides, such as fluopicolide and fluoxastrobin.

[0142] The "microbial fungicide (b44)" (FRAC code BM02, previously FRAC code 44 reclassified as BM02) disrupts the cell membranes of fungal pathogens. Microbial fungicides include Bacillus species, such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB1600, D747, FCC1256 (deposited under ATCC number PTA-122162, disclosed in PCT / US2019 / 053424), TJ100 (also known as strain 1BE; known from EP2962568), and the fungicidal lipopeptides they produce.

[0143] The "quinone outside inhibitor, strobilurin-binding (QoSI) fungicide (b45)" (FRAC code 45) inhibits complex III mitochondrial respiration in fungi by affecting the ubiquinol reductase at the "quinone outside" (Qo) site of the cytochrome bc1 complex, the strobilurin-binding subsite. Inhibiting mitochondrial respiration prevents normal fungal growth and development. QoSI fungicides include triazolo-pyrimidinamines such as azoxystrobin.

[0144] The "plant extract fungicide (b46)" (FRAC code 46) causes cell membrane disruption. Plant extract fungicides include terpenes, terpenols, and terpene phenols such as extracts from Melaleuca alternifolia (tea tree) and vegetable oils (mixtures) such as eugenol, geraniol, and thymol.

[0145] The "cyanoacrylate fungicide (b47)" (FRAC code 47) binds to the myosin motor domain and affects motility and actin assembly. Cyanoacrylates include fungicides such as phenamacril.

[0146] The "polyene fungicide (b48)" (FRAC code 48) causes disruption of the fungal cell membrane by binding to the major sterol ergosterol in the membrane. Examples include natamycin (pimaricin).

[0147] The "oxysterol-binding protein inhibitor (OSBPI) fungicide (b49)" (FRAC code 49) binds to the oxysterol-binding protein in oomycetes, causing inhibition of zoospore release, zoospore motility, and sporangium germination. Oxysterol-binding fungicides include piperidyl-thiazole-isoxazolines such as oxathiapiprolin and fluoxapiprolin.

[0148] The "aryl-phenyl-ketone fungicide (b50)" (FRAC code 50, previously FRAC code U8 reclassified as 50) inhibits the growth of mycelia in fungi. Aryl-phenyl-ketone fungicides include benzophenones such as metrafenone, and benzoyl pyridines such as picoxystrobin.

[0149] The "host plant defense-inducing fungicide (b51)" induces the defense mechanism of the host plant. The host plant defense-inducing fungicides include benzothiadiazole (FRAC code P01), benzisothiazole (FRAC code P02), thiadiazole carboxamide (FRAC code P03), polysaccharide (FRAC code P04), plant extract (FRAC code P05), microorganism (FRAC code P06), and phosphonate fungicide (FRAC code P07, see above (b33)). Benzothiadiazole includes acibenzolar-S-methyl. Benzisothiazole includes thiabendazole. Thiadiazole carboxamide includes tiadinil and isotianil. Polysaccharide includes laminarin. The plant extract includes the extract of Reynoutria sachalinensis (giant knotweed). The microorganism includes the cell wall of Bacillus mycoides strain J and Saccharomyces cerevisiae strain LAS117.

[0150] "Multi-site active fungicide (b52)" inhibits fungal growth through multiple sites of action and has contact / preventive activity. Multi-site active fungicides include copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfonamide fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code M11), and thiocarbamate (FRAC code M12, see above (b42)) fungicides. Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate, and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate). Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur. Dithiocarbamate fungicides contain a dithiocarbamate moiety; examples include ferbam, mancozeb, maneb, metiram, propineb, thiram, thiazole zinc, zineb, and ziram. Phthalimide fungicides contain a phthalimide moiety; examples include folpet, captan, and captafol. Chloronitrile fungicides contain an aromatic ring substituted with chlorine and a cyano group; examples include chlorothalonil. Sulfonamide fungicides include dichlofluanid and tolylfluanid. Multi-site contact guanidine fungicides include biguanides, guazatine besilate, and guazatine triacetate. Triazine fungicides include anilazine. Quinone fungicides include dithianon. Quinoxaline fungicides include quinomethionate (also known as chinomethionate). Maleimide fungicides include fluazinam.

[0151] "Biological agents with multiple modes of action (b53)" include agents from biological sources that exhibit multiple mechanisms of action without evidence of a primary mode of action. Fungicides in this category include polypeptides (lectins), phenols, sesquiterpenes, triterpenoids, and coumarin fungicides (FRAC code BM01), such as extracts from the cotyledons of lupin seedlings. This category also includes microbial fungicides (FRAC code BM02, see above (b44)).

[0152] "Fungicides other than the fungicides of components (a1) and (a2) and components (b1) to (b53); (b54)"; includes certain fungicides whose mode of action may be unknown. These include: (b54.1) "phenyl-acetamide fungicides" (FRAC code U06), (b54.2) "guanidine fungicides" (FRAC code U12), (b54.3) "thiazolidine fungicides" (FRAC code U13), (b54.4) "pyrimidinone-hydrazone fungicides" (FRAC code U14), (b54.5) "4-quinolyl acetate fungicides" (FRAC code U16), (54.6) "tetrazole-oxime fungicides" (FRAC code U17) and "glucopyranosyl antibiotic fungicides" (FRAC code U18, see (b26) above). Phenyl-acetamide includes cyflufenamid. Guanidine includes dodine. Thiazolidine includes flutianil. Pyrimidinone-hydrazone includes ferimzone. 4-quinolyl acetate includes tebufloquin. Tetrazole-oxime includes picarbutrazox.

[0153] (b54) category also includes bethoxazin, dichlobentiazox (proposed common name, registration number 957144-77-3), dipyridone (proposed common name, registration number 16114-35-5), flumequin, ferric methylarsonate, nitroprid, metsulfenamide (registration number 304911-98-6), N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]-4-fluorophenylcarbamate, N′-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methyl-methylformamidine, N′-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methyl-methylformamidine, and N′-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methyl-methylformamidine.

[0154] Additional "fungicides other than the fungicides of categories (1) to (54)" whose mode of action may be unknown or may not yet be classified include fungicidal compounds selected from components (b54.8) to (b54.14) discussed below.

[0155] Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional common name pyridachlometyl, registration number 1358061-55-8), which is considered to be a promoter of tubulin polymerization and exhibits antifungal activity against fungal species belonging to the Ascomycota and Basidiomycota phyla.

[0156] Component (54.10) relates to aminopyrifen (provisional common name) (registration number 1531626-08-0, CAS name methyl 2-amino-6-methylpyridine-3-carboxylate (4-phenoxyphenyl)), which is considered to inhibit the GWT-1 protein in the biosynthesis of glycosylphosphatidylinositol-anchors in Neurospora crassa.

[0157] Component (b54.11) relates to a compound having the formula b54.11

[0158]

[0159] wherein

[0160] R b1 and R b3 are each independently halogen; and

[0161] R b2 is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl.

[0162] Examples of compounds having the formula b54.11 include (b54.11a) methyl N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11b) methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11c) methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11d) methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11e) methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, and (b54.11f) methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate. Compounds having the formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT patent publications WO 2008 / 124092, WO 2014 / 066120, and WO 2020 / 097012.

[0163] Component (b54.12) relates to compounds having the formula b54.12

[0164]

[0165] wherein

[0166] R b4 is

[0167]

[0168] R b6 is C2-C4 cyanoalkyl, C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;

[0169] L is CH2 or CH2O, where the right-hand atom is attached to the benzene ring in the formula b54.12; and

[0170] R b5 is

[0171]

[0172] Examples of compounds having the formula b54.12 include (b54.12a) N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, (b54.12b) ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, (b54.12c) 3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1H-pyrazole-1-acetonitrile, and (b54.12d) N-(2,2,2-trifluoroethyl)-5-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-oxadiazole-3-carboxamide. Compounds having the formula b54.12, their use as fungicides and methods of preparation are generally known; see, for example, PCT patent publication WO 2020 / 056090.

[0173] Component (b54.13) relates to compounds having the formula b54.13

[0174]

[0175] wherein

[0176] R b7 , R b8 and R b9 are each independently H, halogen or cyano; and

[0177] R b10 and R b11 are each independently H, halogen, C1-C3 alkyl or C1-C3 methoxy.

[0178] Examples of compounds having the formula b54.13 include (b54.13a) 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (b54.13b) 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (b54.13c) 3,5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile, (b54.13d) N-(2-chloro-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (b54.13e) 4-(2-chloro-4,6-difluorophenyl)-1,3-dimethyl-N-(2-nitrophenyl)-1H-pyrazol-5-amine, and (b54.13f) 4-(2-chloro-4,6-difluorophenyl)-1,3-dimethyl-N-(4-methyl-2-nitrophenyl)-1H-pyrazol-5-amine. Compounds having the formula b54.13, their use as fungicides and methods of preparation are generally known; see, for example, PCT patent publication WO 2020051402.

[0179] Component (54.14) relates to N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (common name fluopyram, registration number 1839120-27-2), which is considered a class II histone deacetylase (HDAC) inhibitor.

[0180] The embodiments of the present disclosure can be combined in any way, provided that these combinations result in obtaining the compositions and methods claimed herein.

[0181] Embodiments of the invention as described in the Summary of the Invention include those described below. In the following embodiments, unless further defined in the embodiments, the recited formulas include their stereoisomers, N-oxides and salts, and references to "compounds having the formula I" or "compounds having the formula II" include the definitions of the substituents specified in the Summary of the Invention.

[0182] Example A1. A composition as described in the Summary of the Invention, wherein the SDHI is selected from:

[0183] (a1-a) phenylbenzamide, carboxin, flutolanil, mepronil, phenyl-oxo-ethylthiophenecarboxamide, isofetamid, fluxapyroxad, furametpyr, dimethirimol, oxycarboxin and oxycarboxin oxide, thiazole carboxamide, thifluzamide, pyrazole-4-carboxamide, benzovindiflupyr, bixafen, fluopyram, fluindapyr, flutriafol, furametpyr, inpyrfluxam, isopyrazam, penthiopyrad, pyrisoxazole, trifloxystrobin, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-cyclopropyl-N-benzyl-pyrazole carboxamide, isoflucypram, N-methoxy(phenylethyl)pyrazole carboxamide, fluxametamide, pyridine carboxamide, boscalid, pyrazine carboxamide fungicides and bixafen; and

[0184] (a1-b) aminoindanamide having the structure of formula (I):

[0185]

[0186] wherein

[0187] R 1 、R 2 、R 3 and R 4 are each independently H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl;

[0188] R 5 and R 7 are each independently H, C1-C4 alkyl or C1-C4 haloalkyl;

[0189] R 6 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio;

[0190] R 8 is halogenated, -OH, -SH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio; and

[0191] n is from 0 to 3, and

[0192] (a1-c) their combinations.

[0193] Example A2. The composition according to Example A1, wherein the SDHI is aminoindanamide having the structure of formula (I):

[0194]

[0195] wherein

[0196] R 1 、R 2 、R 3 and R 4 are each independently H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl;

[0197] R 5 and R 7 are each independently H, C1-C4 alkyl or C1-C4 haloalkyl;

[0198] R 6 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio;

[0199] R 8 is halo, -OH, -SH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio; and

[0200] n is from 0 to 3.

[0201] Example A3. The composition according to Example A2, wherein

[0202] R 1 、R 2 、R 4 and R 6 are each independently C1-C4 alkyl;

[0203] R 3 is H, C1-C4 alkyl or C1-C4 haloalkyl;

[0204] R 5 and R 7 are each independently H, C1-C4 alkyl or C1-C4 haloalkyl;

[0205] R 8 is halo, C1-C4 alkyl or C1-C4 haloalkyl; and

[0206] n is from 0 to 3.

[0207] Example A4. The composition according to Example A2, wherein R 1 、R 2, R 4 and R 6 are each methyl.

[0208] Example A5. The composition according to Example A2, wherein R 3 is H.

[0209] Example A6. The composition according to Example A2, wherein R 7 is methyl, difluoromethyl or trifluoromethyl.

[0210] Example A7. The composition according to Example A2, wherein R 5 is H or methyl.

[0211] Example A8. The composition according to Example A2, wherein n is from 1 to 3.

[0212] Example A9. The composition according to Example A2, wherein R 8 is halo.

[0213] Example A10. The composition according to Example A2, wherein R 8 is F.

[0214] Example A11. The composition according to Example A2, wherein the indanamine amide of formula (I) is

[0215]

[0216] Example A12. The composition according to Example A2 or A11, wherein the indanamine amide of formula (I) is (fluopyram)

[0217]

[0218] Example A13a. The composition according to Example A2, wherein n is 0.

[0219] Example A13b. The composition according to Example A2, wherein n is 1.

[0220] Example A14a. A composition as described in Example A1, wherein the SDHI is selected from phenylbenzamide, carboxin, flutolanil, mepronil, phenyl-oxo-ethylthiophenecarboxamide, isofetamid, pyridyl-ethyl-benzamide, fluxapyroxad, furametpyr, dimethachlon, oxycarboxin and oxycarboxin oxide, thiazolecarboxamide, thifluzamide, pyrazole-4-carboxamide, benzovindiflupyr, bixafen, fluxametamide, fluindapyr, fluxazolamide, furpicoxamid, ipfencarbazone, sedaxane, penthiopyrad, isopyrazam, fluopyram, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-cyclopropyl-N-benzyl-pyrazolecarboxamide, isoflucypram, N-methoxy(phenylethyl)pyrazolecarboxamide, fluxametamide, pyridinecarboxamide, boscalid, pyrazinecarboxamide fungicides and bixafen.

[0221] Example A14b. A composition as described in Example A14a, wherein the SDHI is selected from benzovindiflupyr, bixafen, fluindapyr, fluxazolamide, ipfencarbazone, isoflucypram, fluxametamide and boscalid.

[0222] Example A14c. A composition as described in Example A14b, wherein the SDHI is selected from benzovindiflupyr, bixafen, fluindapyr, fluxazolamide and boscalid.

[0223] Example A14d. A composition as described in Example A14c, wherein the SDHI is selected from benzovindiflupyr, fluindapyr and fluxazolamide.

[0224] Example A15. A composition as described in Example A14a, wherein the SDHI is selected from phenylbenzamide.

[0225] Example A16. A composition as described in Example A14a, wherein the SDHI is carboxin.

[0226] Example A17. A composition as described in Example A14a, wherein the SDHI is flutolanil.

[0227] Example A18. A composition as described in Example A14a, wherein the SDHI is mepronil.

[0228] Example A19. A composition as described in Example A14a, wherein the SDHI is selected from phenyl-oxo-ethylthiophenecarboxamide.

[0229] Example A20. A composition as described in Example A14a, wherein the SDHI is isofetamid.

[0230] Example A21. The composition according to Example A14a, wherein the SDHI is selected from pyridyl-ethyl-benzamides.

[0231] Example A22. The composition according to Example A14a, wherein the SDHI is fluxapyroxad.

[0232] Example A23. The composition according to Example A14a, wherein the SDHI is selected from furan-carboxamides.

[0233] Example A24. The composition according to Example A14a, wherein the SDHI is fenfuram.

[0234] Example A25. The composition according to Example A14a, wherein the SDHI is selected from oxathiins-carboxamides.

[0235] Example A26. The composition according to Example A14a, wherein the SDHI is carboxin.

[0236] Example A27. The composition according to Example A14a, wherein the SDHI is oxycarboxin.

[0237] Example A28. The composition according to Example A14a, wherein the SDHI is selected from thiazole-carboxamides.

[0238] Example A29. The composition according to Example A14a, wherein the SDHI is thifluzamide.

[0239] Example A30. The composition according to Example A14a, wherein the SDHI is selected from pyrazole-4-carboxamides.

[0240] Example A31. The composition according to Example A14a, wherein the SDHI is benzovindiflupyr.

[0241] Example A32. The composition according to Example A14a, wherein the SDHI is bixafen.

[0242] Example A33. The composition according to Example A14a, wherein the SDHI is fluxametamide.

[0243] Example A34. The composition according to Example A14a, wherein the SDHI is fluindapyr.

[0244] Example A35. The composition according to Example A14a, wherein the SDHI is fluopyram.

[0245] Example A36. The composition according to Example A14a, wherein the SDHI is furametpyr.

[0246] Example A37. A composition as described in Example A14a, wherein the SDHI is fluxapyroxad.

[0247] Example A38. A composition as described in Example A14a, wherein the SDHI is isopyrazam.

[0248] Example A39. A composition as described in Example A14a, wherein the SDHI is penthiopyrad.

[0249] Example A40. A composition as described in Example A14a, wherein the SDHI is pythiathion.

[0250] Example A41. A composition as described in Example A14a, wherein the SDHI is sedaxane.

[0251] Example A42. A composition as described in Example A14a, wherein the SDHI is N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.

[0252] Example A43. A composition as described in Example A14a, wherein the SDHI is selected from N-cyclopropyl-N-benzyl-pyrazole carboxamide.

[0253] Example A44. A composition as described in Example A14a, wherein the SDHI is ipfencarbazone.

[0254] Example A45. A composition as described in Example A14a, wherein the SDHI is selected from N-methoxy(phenylethyl)pyrazole carboxamide.

[0255] Example A46. A composition as described in Example A14a, wherein the SDHI is fluxametamide.

[0256] Example A47. A composition as described in Example A14a, wherein the SDHI is selected from pyridine carboxamide.

[0257] Example A48. A composition as described in Example A14a, wherein the SDHI is boscalid.

[0258] Example A49. A composition as described in Example A14a, wherein the SDHI is selected from pyridine carboxamide fungicides.

[0259] Example A50. A composition as described in Example A14a, wherein the SDHI is bixafen.

[0260] Example B1. A composition as described in the Summary of the Invention, wherein the pyridine carboxamide is selected from:

[0261] (a2-a) Fempizole, picoxystrobin, [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl] (2S)-2-[(3-acetoxy-4-methoxypyridine-2-carbonyl)amino]propionate, [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl] (2S)-2-[[3-(acetoxymethoxy)-4-methoxypyridine-2-carbonyl]amino]propionate, and [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl] (2S)-2-[(3-hydroxy-4-methoxypyridine-2-carbonyl)amino]propionate;

[0262] (a2-b) Picolinafen;

[0263] (a2-c) A pyridine amide having the structure of formula (II):

[0264]

[0265] wherein

[0266] R 9 is H or alkyl, substituted with zero, one or more R 19 substituents;

[0267] R 10 and R 11 are independently selected from C2-C6 alkyl, C3-C6 cycloalkyl, aryl or heteroaryl, each optionally substituted with zero, one or more substituents selected from R 19 substituents, and R 10 and R 11 together form a 3- to 6-membered saturated or partially saturated carbocyclic or heterocyclic ring, optionally substituted with zero, one or more R 19 substituents;

[0268] R 12 is aryl or heteroaryl, each optionally substituted with zero, one or more R 19 substituents;

[0269] R 13 is H or alkyl, each substituted with zero, one or more R 19 substituents;

[0270] R 14 is H or C(O)R 16 ;

[0271] R 15 is H, C(O)R 16 or Q;

[0272] Q is

[0273]

[0274] wherein Z is N or N + →O - , and W is O or S;

[0275] R 16 is an alkoxy or benzyloxy, each optionally substituted by 0, 1 or more R 19 substituents;

[0276] R 17 is H, alkoxy or halo, each optionally substituted by 0, 1 or more R 19 substituents;

[0277] R 18 is from H, -C(O)R 20 , or -CH2OC(O)R 20 ;

[0278] R 19 is H, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclic group, each optionally substituted by 0, 1 or more R 21 substituents;

[0279] R 20 is alkyl, alkoxy or aryl, each optionally substituted by 0, 1 or more R 19 substituents; and

[0280] R 21 is H, alkyl, aryl, acyl, halo, alkenyl, alkoxy or heterocyclic group; and

[0281] (a2-d) their combinations.

[0282] Example B2. The composition according to Example B1, wherein the pyridinecarboxamide is a pyridinecarboxamide having the structure of formula (II):

[0283]

[0284] wherein

[0285] R 9 is H or alkyl, substituted by 0, 1 or more R 19 substituents;

[0286] R 10 and R 11 are C2-C6 alkyl, C3-C6 cycloalkyl, aryl or heteroaryl, each optionally substituted by 0, 1 or more R 19 substituents, or R 10 and R 11Together form a 3- to 6-membered saturated or partially saturated carbocyclic or heterocyclic ring, optionally substituted with 0, 1 or more R 19 substituted;

[0287] R 12 is aryl or heteroaryl, each optionally substituted with 0, 1 or more R 19 substituted;

[0288] R 13 is H or alkyl, each substituted with 0, 1 or more R 19 substituted;

[0289] R 14 is H or C(O)R 16 ;

[0290] R 15 is H, C(O)R 16 or Q;

[0291] Q is

[0292]

[0293] wherein Z is N or N + →O - and W is O or S;

[0294] R 16 is alkoxy or benzyloxy, each optionally substituted with 0, 1 or more R 19 substituted;

[0295] R 17 is H, alkoxy or halo, each optionally substituted with 0, 1 or more R 19 substituted;

[0296] R 18 is H, -C(O)R 20 or -CH2OC(O)R 20 ;

[0297] R 19 is H, alkyl, aryl, acyl, halo, alkenyl, alkynyl, alkoxy, cyano or heterocyclic group, each optionally substituted with 0, 1 or more R 21 substituted;

[0298] R 20 is alkyl, alkoxy or aryl, each optionally substituted with 0, 1 or more R 19 substituted; and

[0299] R 21 is selected from H, alkyl, aryl, acyl, halo, alkenyl, alkoxy or heterocyclic group.

[0300] Example B3. The composition according to Example B2, wherein R 14 is H, and R 15 is Q.

[0301] Example B4. The composition according to Example B2, wherein Z is N.

[0302] Example B5. The composition according to Example B2, wherein W is O.

[0303] Example B6. The composition according to Example B2, wherein R 17 is an alkoxy group.

[0304] Example B7. The composition according to Example B2, wherein R 18 is H.

[0305] Example B8. The composition according to Example B2, wherein R 9 and R 13 are independently selected from H or alkyl, R 10 and R 11 are independently selected from C2-C6 alkyl or together form a 3- to 6-membered saturated carbocyclic ring, each optionally substituted with zero, one or more R 19 substituents, and R 12 is an aryl group, optionally substituted with zero, one or more R 19 substituents.

[0306] Example B9. The composition according to Example B1, wherein the pyridinecarboxamide is selected from fenpicoxamid, picoxystrobin, [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl] (2S)-2-[(3-acetoxy-4-methoxypyridine-2-carbonyl)amino]propionate, [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl] (2S)-2-[[3-(acetoxymethoxy)-4-methoxypyridine-2-carbonyl]amino]propionate, and [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl] (2S)-2-[(3-hydroxy-4-methoxypyridine-2-carbonyl)amino]propionate.

[0307] Example B10. The composition according to Example B9, wherein the pyridinecarboxamide is fenpicoxamid.

[0308] Example B11. The composition according to Example B9, wherein the pyridinecarboxamide is picoxystrobin.

[0309] Example B12. The composition according to Example B9, wherein the pyridinecarboxamide is [(1S,2S)-2-(4-fluoro-2-methyl-phenyl)-1,3-dimethyl-butyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propionate.

[0310] Example B13. The composition according to Example B9, wherein the pyridinecarboxamide is [(1S,2S)-2-(4-fluoro-2-methyl-phenyl)-1,3-dimethyl-butyl] (2S)-2-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]propionate.

[0311] Example B14. The composition according to Example B9, wherein the pyridinecarboxamide is [(1S,2S)-2-(4-fluoro-2-methyl-phenyl)-1,3-dimethyl-butyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propionate.

[0312] Example B15. The composition according to Example B1, wherein the pyridinecarboxamide is picolinafen.

[0313] The examples of the present invention (including the above examples and any other examples described herein) can be combined in any way, and the descriptions of the variables in these examples relate not only to the composition comprising (a1) a succinate dehydrogenase inhibitor (SDHI) and (a2) a pyridinecarboxamide, but also to the composition comprising (a1) a succinate dehydrogenase inhibitor (SDHI) and (a2) a pyridinecarboxamide and at least one invertebrate pest control compound or agent. In addition, the examples of the present invention (including the above examples and any other examples described herein) and any combination thereof relate to the methods of the present invention. Therefore, as additional examples, it should be noted that the compositions disclosed above, which comprise (a1) a succinate dehydrogenase inhibitor (SDHI) and (a2) a pyridinecarboxamide, and at least one invertebrate pest control compound or agent.

[0314] Example C1. The composition according to the Summary of the Invention, which further comprises at least one component (b).

[0315] Example C2. The composition according to Example C1, wherein the composition further comprises at least one component (b) selected from the following:

[0316] (b1) Methyl benzimidazole carbamate (MBC) fungicide;

[0317] (b2) Dicarboximide fungicide;

[0318] (b3) Demethylation inhibitor (DMI) fungicide;

[0319] (b4) Phenylamide (PA) fungicides;

[0320] (b5) Amine / morpholine fungicides;

[0321] (b6) Phospholipid biosynthesis inhibitor fungicides;

[0322] (b7) Additional succinate dehydrogenase inhibitor (SDHI) fungicides;

[0323] (b8) Hydroxy (2-amino) pyrimidine fungicides;

[0324] (b9) Anilinopyrimidine (AP) fungicides;

[0325] (b10) N-Phenyl carbamate fungicides;

[0326] (b11) Quinone outside inhibitor (QoI) fungicides;

[0327] (b12) Phenylpyrrole (PP) fungicides;

[0328] (b13) Quinazoline fungicides;

[0329] (b14) Cellular peroxidation inhibitor fungicides;

[0330] (b15) Melanin biosynthesis inhibitor - reductase (MBI-R) fungicides; (b16a) Melanin biosynthesis inhibitor - dehydratase (MBI-D) fungicides; (b16b) Melanin biosynthesis inhibitor - polyketide synthase (MBI-P) fungicides; (b17) Keto reductase inhibitor (KRI) fungicides;

[0331] (b18) Squalene-epoxidase inhibitor fungicides;

[0332] (b19) Polyoxins fungicides;

[0333] (b20) Phenylurea fungicides;

[0334] (b21) Quinone inside inhibitor (QiI) fungicides;

[0335] (b22) Benzamide and thiazolecarboxamide fungicides;

[0336] (b23) Enolpyranosyluracil antibiotics fungicides;

[0337] (b24) Hexopyranosyl antibiotics fungicides;

[0338] (b25) Glucopyranosyl antibiotics: Protein synthesis fungicides;

[0339] (b26) Glucopyranosyl antibiotic fungicides;

[0340] (b27) Cyanoacetamide-oxime fungicides;

[0341] (b28) Carbamate fungicides;

[0342] (b29) Oxidative phosphorylation uncoupling fungicides;

[0343] (b30) Organotin fungicides;

[0344] (b31) Carboxylic acid fungicides;

[0345] (b32) Heteroaromatic fungicides;

[0346] (b33) Phosphonate fungicides;

[0347] (b34) Anthranilic acid fungicides;

[0348] (b35) Benzotriazine fungicides;

[0349] (b36) Benzene-sulfonamide fungicides;

[0350] (b37) Pyridazinone fungicides;

[0351] (b38) Thiophene-carboxamide fungicides;

[0352] (b39) Complex I NADH oxidoreductase inhibitor fungicides;

[0353] (b40) Carboxylic acid amide (CAA) fungicides;

[0354] (b41) Tetracycline antibiotic fungicides;

[0355] (b42) Thiocarbamate fungicides;

[0356] (b43) Benzamide fungicides;

[0357] (b44) Microbial fungicides;

[0358] (b45) Quinone outside inhibitor, strobilurin binding type (QoSI) fungicides;

[0359] (b46) Plant extract fungicides;

[0360] (b47) Cyanoacrylate fungicides;

[0361] (b48) Polyene fungicides;

[0362] (b49) Oxysterol-binding protein inhibitor (OSBPI) fungicides;

[0363] (b50) Aryl-phenyl-ketone fungicides;

[0364] (b51) Host plant defense-inducing fungicides;

[0365] (b52) Multi-site active fungicides;

[0366] (b53) Biopesticides with multiple modes of action;

[0367] (b54) Fungicides other than the fungicides of component (a1), component (a2), and components (b1) to (b53); and

[0368] Salts of the compounds of (b1) to (b54).

[0369] Example C3. The composition according to Example C2, wherein component (b) comprises at least one fungicidal compound from each of two different groups selected from (b1) to (b54).

[0370] Example C4. The composition according to Example C1, wherein component (b) comprises at least one compound selected from: (b1) benzimidazole carbamate fungicides such as benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate and thiophanate-methyl.

[0371] Example C5. The composition according to Example C1, wherein component (b) comprises at least one compound selected from: (b2) dicarboximide fungicides such as chlozolinate, dimethachlon, iprodione, procymidone and vinclozolin.

[0372] Example C6. The composition according to Example C1, wherein component (b) comprises at least one compound selected from: (b3) demethylation inhibitor fungicides such as azaconazole, bitertanol, bixafen, boscalid, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), econazole, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, isopyrazam, metconazole, myclobutanil, oxpoconazole, penconazole, prochloraz, propiconazole, pyrifenox, pyriofenone, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, uniconazole and uniconazole-P.

[0373] Example C7. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b4) phenylamide fungicides such as benalaxyl, benalaxyl-M, ofurace, metalaxyl, metalaxyl-M, furathiocarb, and oxadixyl.

[0374] Example C8. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b5) amine / morpholine fungicides such as aldimorph, dodemorph, fenpropidin, fenpropimorph, piperalin, spiroxamine, tridemorph, and tridemorphamide.

[0375] Example C9. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b6) phospholipid biosynthesis inhibitor fungicides such as edifenphos, isoprothiolane, isoprothiolane, and pyrazophos.

[0376] Example C10. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b7) succinate dehydrogenase inhibitor fungicides such as carboxin, benzovindiflupyr, bixafen, boscalid, carboxin, dimethachlon, fluopyram, fluxapyroxad, flutolanil, flutriafol, furametpyr, ipfencarbazone, isofetamid, isopyrazam, metconazole, oxycarboxin, penthiopyrad, pythiathion, sedaxane, pyraclostrobin, fluxapyroxad, and thifluzamide.

[0377] Example C11. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b8) hydroxy(2-amino)pyrimidine fungicides such as ethirimol bluestone, dimethirimol, and ethirimol.

[0378] Example C12. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b9) anilinopyrimidine fungicides such as cyprodinil, cymoxanil, and dimethirimol.

[0379] Example C13. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b10) N-phenyl carbamate fungicides such as diethofencarb.

[0380] Example C14. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b11) quinone outside inhibitor fungicides, such as azoxystrobin, carylex, enestrobin, enoxastrobin, famoxadone, fenamidone, enamine, fluoxastrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, tetraconazole, orysastrobin, pyraclostrobin, pyribencarb, picoxystrobin, triclopyricarb, and trifloxystrobin.

[0381] Example C15. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b12) phenylpyrrole fungicide compounds, such as fenpiclonil and fludioxonil.

[0382] Example C16. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b13) quinoxaline fungicides, such as quinoxyfen and propoxyquinoline.

[0383] Example C17. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b14) cell peroxidation inhibitor fungicides, such as biphenyl, chloroneb, dichlofluanid, etridiazole, quintozene, tecnazene, and tolclofos-methyl.

[0384] Example C18. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b15) melanin biosynthesis inhibitor - reductase fungicides, such as phthalide, pyroquilon, and tricyclazole.

[0385] Example C19a. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b16a) melanin biosynthesis inhibitor - dehydratase fungicides, such as carpropamid, diclocymet, and blastoxamide.

[0386] Example C19b. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b16b) melanin biosynthesis inhibitor - polyketide synthase fungicides, such as toprol.

[0387] Example C20. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b17) ketoreductase inhibitor fungicides, such as fenhexamid, amisulbrom, fluopicolide, and quinofumelin.

[0388] Example C21. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b18) squalene-epoxidase inhibitor fungicides such as naftifine, pyributicarb, and terbinafine.

[0389] Example C22. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b19) polyoxin fungicides such as polyoxin.

[0390] Example C23. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b20) phenylurea fungicides such as pencycuron.

[0391] Example C24. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b21) quinone inside inhibitor fungicides such as indaziflam, cyazofamid, fenpicoxamid, and picarbutrazox.

[0392] Example C24a. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b21) quinone inside inhibitor fungicides such as picoxystrobin.

[0393] Example C25. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b22) benzamide and thiazolecarboxamide fungicides such as ethaboxam and zoxamide.

[0394] Example C26. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b23) enolpyranosyluronic acid antibiotic fungicides such as blasticidin-S.

[0395] Example C27. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b24) hexopyranosyl antibiotic fungicides such as kasugamycin.

[0396] Example C28. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b25) glucopyranosyl antibiotic: protein synthesis fungicides such as streptomycin.

[0397] Example C29. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides such as validamycin.

[0398] Example C30. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b27) cyanoacetamide-oxime fungicides, such as cymoxanil.

[0399] Example C31. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b28) carbamate fungicides, such as iodopropargyl butylcarbamate, propamocarb, and thiabendazole.

[0400] Example C32. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b29) oxidative phosphorylation uncoupling fungicides, such as binapacryl, dicofol, fluazinam, and dinocap.

[0401] Example C33. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b30) organotin fungicides, such as triphenyltin acetate, triphenyltin chloride, and triphenyltin hydroxide.

[0402] Example C34. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b31) carboxylic acid fungicides, such as oxolinic acid.

[0403] Example C35. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b32) heteroaromatic fungicides, such as hymexazol and octhilinone.

[0404] Example C36. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b33) phosphonate fungicides, such as phosphorous acid and its various salts, including fosetyl-aluminum.

[0405] Example C37. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b34) o-carbamoylbenzoic acid fungicides, such as tetcyclacis.

[0406] Example C38. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b35) benzotriazine fungicides, such as azoxystrobin.

[0407] Example C39. The composition as described in Example C1, wherein component (b) comprises at least one compound selected from the following: (b36) benzene-sulfonamide fungicides, such as sulfametamide.

[0408] Example C40. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b37) pyridazinone fungicides such as pyridazinol.

[0409] Example C41. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b38) thiophene-carboxamide fungicides such as silthiofam.

[0410] Example C42. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b39) Complex I NADH oxidoreductase inhibitor fungicides such as fluazinam, clofentazine and tolfenpyrad.

[0411] Example C43. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b40) carboxamide fungicides such as benthiavalicarb, benthiavalicarb-isopropyl, dimethomorph, flumorph, iprodione, mandipropamid, pyrimorph, toclophos-methyl and valifenalate.

[0412] Example C44. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b41) tetracycline antibiotic fungicides such as oxytetracycline.

[0413] Example C45. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b42) thiocarbamate fungicides such as ethiozole.

[0414] Example C46. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b43) benzamide fungicides such as fluopicolide and fluoxastrobin.

[0415] Example C47. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b44) microbial fungicides such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, D747, F727, FCC1256, FZB24, FZB42, MB1600, QST713, RTI301, RTI472, TJ100 (also known as strain 1BE; known from EP2962568), and the fungicidal lipopeptides produced by them.

[0416] Example C48. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b45) quinone outside inhibitor, strobilurin-binding fungicides such as azoxystrobin.

[0417] Example C49. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b46) plant extract fungicides such as eugenol, geraniol, and thymol.

[0418] Example C50. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b47) cyanoacrylate fungicides such as phenamacril.

[0419] Example C51. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b48) polyene fungicides such as natamycin.

[0420] Example C52. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b49) oxysterol-binding protein inhibitor fungicides such as fluopyram and fluxapyroxad.

[0421] Example C53. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b50) aryl-phenyl-ketone fungicides such as benzophenone and fenpyrazamine.

[0422] Example C54. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b51) host plant defense-inducing fungicides such as acibenzolar-S-methyl, thiabendazole, tiadinil, isotianil, laminarin, extract from Reynoutria japonica, and cell walls of Bacillus mycoides strain J and Saccharomyces cerevisiae strain LAS117.

[0423] Example C55. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b52) multi-site active fungicides such as copper oxychloride, copper sulfate, copper hydroxide, Bordeaux mixture (tribasic copper sulfate), elemental sulfur, ferric dimethyldithiocarbamate, mancozeb, maneb, metiram, propineb, thiram, thiazole zinc, zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, captan, folpet, dichlofluanid, tolylfluanid, biguanide salts, guazatine benzenesulfonate, guazatine triacetate, anilazine, dithianon, ferimzone, and fluazinam.

[0424] Example C56. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b53) biogenic fungicides with multiple modes of action such as extract from the cotyledons of lupin seedlings.

[0425] Example C57. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the following: (b54) fungicides other than the fungicides of component (a1), component (a2), and components (b1) to (b53), such as besoxazin, cyflufenamid, dichlobenzoxazide, dipyrithione, dodine, ferimzone, flumequin, fluoxastrobin, ferric methylarsonate, tebuconazole, pyrrolnitrin, triforine, metsulfovax, N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, and 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate (XR-539).

[0426] Example C58. The composition according to Example C1, wherein component (b) comprises 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (proposed common name: pyridachlometyl).

[0427] Example C59. The composition according to Example C1, wherein component (b) comprises aminopyrine.

[0428] Example C60. The composition according to Example C1, wherein component (b) comprises at least one fungicidal compound (fungicide) selected from the group consisting of azoxystrobin, benzovindiflupyr, boscalid (nicobifen), bixafen, bromuconazole, carbendazim, chlorothalonil, copper sulfate, cyflufenamid, cyproconazole, difenoconazole, enestroburin, epoxiconazole, fluazinam, fludioxonil, flusilazole, flutriafol, fluxapyroxad, hexaconazole, ipfencarbazone, ipconazole, isofetamid, kresoxim-methyl, mancozeb, metconazole, metiram, pyraclostrobin, tebuconazole, tetraconazole, tricyclazole, trifloxystrobin, triflumizole, triticonazole, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, and ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate.

[0429] Example C61. The composition according to Example C60, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper sulfate, cyflufenamid, cyproconazole, difenoconazole, enestroburin, epoxiconazole, fluazinam, fluoxastrobin, fluquinconazole, flutriafol, fluxapyroxad, ipfencarbazone, isoflucypram, kresoxim-methyl, mancozeb, maneb, metconazole, metrafenone, metominostrobin, picoxystrobin, propiconazole, proquinazid, prothioconazole, pyraclostrobin, pyraflufen-ethyl, pyribencarb, quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, and ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate.

[0430] Example C62. The composition according to Example C61, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper sulfate, cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flutriafol, fluxapyroxad, ipfencarbazone, isoflucypram, mancozeb, metconazole, metrafenone, metominostrobin, picoxystrobin, prothioconazole, pyraclostrobin, pyraflufen-ethyl, pyribencarb, quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, and ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate.

[0431] Example C63. The composition according to Example C62, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper sulfate, cyproconazole, difenoconazole, epoxiconazole, fenpropimorph, picoxystrobin, fluindapyr, isoflucypram, mancozeb, florylpicolide, metconazole, picoxystrobin, prothioconazole, fluxapyroxad, pyraclostrobin, tebuconazole, and tricyclazole.

[0432] Example C64. The composition according to Example C63, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, difenoconazole, epoxiconazole, fenpropimorph, fluindapyr, fludioxonil, mancozeb, florylpicolide, picoxystrobin, prothioconazole, fluxapyroxad, tebuconazole, and tricyclazole.

[0433] Example C65. The composition according to Example C1, wherein component (b) comprises at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, difenoconazole, epoxiconazole, fenpropimorph, fluindapyr, fludioxonil, mancozeb, florylpicolide, picoxystrobin, prothioconazole, fluxapyroxad, tebuconazole, and tricyclazole.

[0434] Example C66. The composition according to Example C1, wherein component (b) comprises

[0435] at least two fungicidal compounds selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper sulfate, cyproconazole, difenoconazole, epoxiconazole, fenpropimorph, picoxystrobin, fluindapyr, isoflucypram, mancozeb, florylpicolide, metconazole, picoxystrobin, prothioconazole, fluxapyroxad, pyraclostrobin, tebuconazole, and tricyclazole.

[0436] It should be noted that for the compositions of any of the embodiments described herein, the reference to formula I or formula II includes their salts but not their N-oxides; thus, the phrases "compound having formula I" or "compound having formula II" may be replaced by the phrases "compound having formula I or its salt" or "compound having formula II or its salt".

[0437] Also noteworthy as an example is the fungicidal composition of the present invention, which comprises a fungicidally effective amount of the composition of any of the embodiments described herein, and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0438] Embodiments of the present invention further include methods for controlling plant diseases caused by fungal plant pathogens, which include applying a fungicidally effective amount of the composition of any one of the embodiments described herein to the plant or a part thereof, or to the plant seeds or seedlings. Embodiments of the present invention also include methods for protecting plants or plant seeds from diseases caused by fungal pathogens, which include applying a fungicidally effective amount of the composition of any one of the embodiments described herein to the plant or the plant seeds.

[0439] Some embodiments of the present invention relate to controlling plant diseases that primarily affect plant leaves or protecting against plant diseases that primarily affect plant leaves and / or applying the composition of the present invention to plant leaves (i.e., plants rather than seeds). Preferred methods of use include those involving the preferred compositions described above; and diseases that are particularly effectively controlled include plant diseases caused by fungal plant pathogens. The combination of fungicides used according to the present invention can promote disease control and delay the development of resistance. Additionally, the combination of fungicides used according to the present invention can be particularly effective against fungal species that are resistant to fungicides.

[0440] Example D1. A composition as described in the Summary of the Invention, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 20:1 to about 1:20.

[0441] Example D2. A composition as described in Example D1, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 10:1 to about 1:10.

[0442] Example D3. A composition as described in Example D2, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 9:1 to about 1:9.

[0443] Example D4. A composition as described in Example D3, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 8:1 to about 1:8.

[0444] Example D5. A composition as described in Example D4, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 7:1 to about 1:7.

[0445] Example D6. A composition as described in Example D5, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 6:1 to about 1:6.

[0446] Example D7. A composition as described in Example D6, wherein the SDHI and the pyridine amide are present in an SDHI:pyridine amide ratio in the range of from about 5:1 to about 1:5.

[0447] Example D8. A composition as described in Example D7, wherein the SDHI and the pyridinecarboxamide are present in an SDHI:pyridinecarboxamide ratio in the range of from about 4:1 to about 1:4.

[0448] Example D9. A composition as described in Example D8, wherein the SDHI and the pyridinecarboxamide are present in an SDHI:pyridinecarboxamide ratio in the range of from about 3:1 to about 1:3.

[0449] Example D10. A composition as described in Example D9, wherein the SDHI and the pyridinecarboxamide are present in an SDHI:pyridinecarboxamide ratio in the range of from about 2:1 to about 1:2.

[0450] Example D11. A composition as described in Example D10, wherein the SDHI and the pyridinecarboxamide are present in an SDHI:pyridinecarboxamide ratio of about 1.5:1.

[0451] The method examples further include:

[0452] Example E1. A method for protecting plants against diseases selected from rust, powdery mildew, Septoria diseases and Botrytis diseases, the method comprising applying to the plant a fungicidally effective amount of a composition as described in any of the embodiments of the Summary of the Invention or herein.

[0453] Example E2. The method as described in Example E1, wherein the disease is rust and component (b) of the composition comprises at least one fungicidal compound selected from the following: (b3) demethylation inhibitor (DMI) fungicides, (b5) amine / morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b11) quinone outside inhibitor (QoI) fungicides, (b13) benzimidazole methylcarbamate fungicides and (b52) multi-site active fungicides.

[0454] Example E3. The method as described in Example E2, wherein component (b) of the composition comprises at least one fungicidal compound selected from the following: (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b11) quinone outside inhibitor (QoI) fungicides and (b52) multi-site active fungicides.

[0455] Example E4. The method as described in Example E3, wherein component (b) of the composition comprises at least one fungicidal compound selected from the following: (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides and (b11) quinone outside inhibitor (QoI).

[0456] Example E5. The method as described in Example E1, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, benzovindiflupyr, bixafen, cyproconazole, difenoconazole, epoxiconazole, fenpropimorph, picoxystrobin, fluindapyr, flutriafol, fluxapyroxad, pyraflufen-ethyl, iprovalicarb, mancozeb, cyflufenamid, metconazole, fluopyram, pyraclostrobin, tebuconazole, and triticonazole.

[0457] Example E6. The method as described in Example E5, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, benzovindiflupyr, cyproconazole, epoxiconazole, fenpropimorph, flutriafol, fluxapyroxad, metconazole, fluopyram, pyraclostrobin, tebuconazole, and triticonazole.

[0458] Example E7. The method as described in Example E2, wherein the disease is Asian soybean rust caused by Phakopsora pachyrhizi.

[0459] Example E8. The method as described in Example E2, wherein the disease is wheat leaf rust caused by Puccinia recondita.

[0460] Example E9. The method as described in Example E1, wherein the disease is powdery mildew and component (b) of the composition comprises at least one fungicidal compound selected from the following: (b3) demethylation inhibitor (DMI) fungicides, (b11) quinone outside inhibitor (QoI) fungicides, (b13) quinazoline fungicides, and (b52) multi-site active fungicides.

[0461] Example E10. The method as described in Example E9, wherein component (b) of the composition comprises at least one fungicidal compound selected from the following: (b3) demethylation inhibitor (DMI) fungicides, (b11) quinone outside inhibitor (QoI) fungicides, and (b52) multi-site active fungicides.

[0462] Example E11. The method as described in Example E9, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, chlorothalonil, copper sulfate, cyproconazole, difenoconazole, epoxiconazole, flutriafol, mancozeb, cyflufenamid, metconazole, fluopyram, pyraclostrobin, tebuconazole, and triticonazole.

[0463] Example E12. The method according to Example E11, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, flutriafol, mancozeb, prothioconazole, tebuconazole, and trifloxystrobin.

[0464] Example E13. The method according to Example E10, wherein component (b) of the composition comprises at least one fungicidal compound selected from (b3) DMI fungicides.

[0465] Example E14. The method according to Example E13, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, flutriafol, prothioconazole, and tebuconazole.

[0466] Example E15. The method according to Example E10, wherein component (b) of the composition comprises at least one fungicidal compound selected from (b11) QoI fungicides.

[0467] Example E16. The method according to Example E15, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, picoxystrobin, pyraclostrobin, and trifloxystrobin.

[0468] Example E17. The method according to Example E9, wherein the disease is powdery mildew of wheat caused by Erysiphe graminis.

[0469] Example E18. The method according to Example E1, wherein the disease is a Septoria disease and component (b) of the composition comprises at least one fungicidal compound selected from the following: (b3) demethylation inhibitor (DMI) fungicides and (b11) quinone outside inhibitor (QoI) fungicides.

[0470] Example E19. The method according to Example E18, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of azoxystrobin, cyproconazole, difenoconazole, epoxiconazole, flutriafol, fenpropimorph, picoxystrobin, metconazole, metominostrobin, picoxystrobin, prothioconazole, pyraclostrobin, tebuconazole, and trifloxystrobin.

[0471] Example E20. The method according to Example E18, wherein the disease is leaf blotch of wheat caused by Zymoseptoria tritici.

[0472] Example E21. The method as described in Example E1, wherein the disease is a Botrytis disease and component (b) of the composition comprises at least one fungicidal compound selected from the following: (b11) quinone outside inhibitor (QoI) fungicides and (b52) multi-site active fungicides.

[0473] Example E22. The method as described in Example E21, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, chlorothalonil, mancozeb, metconazole, picoxystrobin, pyraclostrobin, and trifloxystrobin.

[0474] Example E23. The method as described in Example E22, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, mancozeb, and trifloxystrobin.

[0475] Example E24. The method as described in Example E1, wherein components (a1), (a2), and (b) are applied in synergistically effective amounts (and in synergistic ratios relative to each other).

[0476] The method examples also include:

[0477] Example F1. A method for protecting plants against diseases caused by at least one fungal resistant strain, the method comprising applying to the plant a fungicidally effective amount of a composition as described in the Summary of the Invention or in any of the examples herein.

[0478] Example F2. The method as described in Example F1, wherein the fungal resistant strain is the result of cross-resistance.

[0479] Example F3. The method as described in Example F1, wherein the fungal resistant strain is the result of one or more gene mutations.

[0480] Example F4. The method as described in any one of Examples F1 to F3, wherein the fungal resistant strain is resistant to at least one SDHI fungicide (succinate dehydrogenase inhibitor).

[0481] Example F5. The method as described in Example F4, wherein when the wild-type fungal resistant strain is sensitive to the fungicide, the resistant strain is resistant to at least one SDHI fungicide.

[0482] Example F6. The method according to any one of Examples F1 to F5, wherein the fungal resistant strain is selected from Alternaria alternata, Alternaria solani, Aspergillus oryzae, Botrytis cinerea, Corynespora cassiicola, Didymella bryoniae, Erysiphe necator, soybean rust, Podosphaera xanthii, Puccinia hordei, Puccinia triticina, Pyrenophora teres, Ramularia collo-cygni, Rhynchosporium secalis, Sclerotinia sclerotiorum, Stemphylium botryose, Ustilago maydis, Venturia inaequalis, and wheat leaf blight pathogen.

[0483] Example F7. The method according to any one of Examples F1 to F5, wherein the fungal resistant strain is selected from Alternaria alternata, Alternaria solani, Aspergillus oryzae, Botrytis cinerea, Botrytis elliptica, Corynespora cassiicola, Didymella bryoniae, Mycosphaerella graminicola, Podosphaera xanthii, Sclerotinia sclerotiorum, Stemphylium botryose, Ustilago maydis, and wheat leaf blight pathogen.

[0484] Example F8. The method according to Examples F6 and F7, wherein the fungal resistant strain is the wheat leaf blight pathogen.

[0485] Example F9. The method according to Example F8, wherein the wheat leaf blight pathogen is strain IPO323.

[0486] Example F10. The method according to Example F8, wherein the wheat leaf blight pathogen comprises at least one mutation in the CYP51 gene.

[0487] Example F11. The method according to Example F8, wherein the wheat leaf blight pathogen comprises at least two mutations in the CYP51 gene.

[0488] Example F12. The method as described in Example F8, wherein the wheat leaf blight pathogen is strain TriR6.

[0489] Example F12. The method as described in Example F8, wherein the wheat leaf blight pathogen is strain TriR10.

[0490] It is noteworthy that the examples corresponding to Examples E1 to E24 and Examples F1 to F12 relate to methods for controlling plant diseases caused by fungal plant pathogens, which methods comprise applying a fungicidally effective amount of the fungicidal composition of the present invention to the plant or a part thereof.

[0491] Preparation / Effect

[0492] As described in the Summary of the Invention, (a1) SDHI and (a2) pyridine carboxamide will generally be used as the fungicidal active ingredients in the composition (i.e., formulation), and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents is used as a carrier. The formulation or composition components are selected to be consistent with the physical properties of the active ingredients, the application method, and environmental factors such as soil type, moisture, and temperature.

[0493] The mixtures of components (a1) and (a2) with component (b) (e.g., selected from (b1) to (b54) and their salts as described above) and / or one or more other biologically active compounds or agents (i.e., insecticides, other fungicides, nematicides, acaricides, herbicides, and other biological agents) can be formulated in a variety of ways, including:

[0494] (i) Component (a1), component (a2), component (b), and / or one or more other biologically active compounds or agents can be formulated separately and applied separately or simultaneously in appropriate weight ratios, for example, as a tank mix; or

[0495] (ii) Component (a1), component (a2), component (b), and / or one or more other biologically active compounds or agents can be formulated together in appropriate weight ratios.

[0496] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates) which can optionally be thickened into gels, suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspoemulsions), etc. General types of aqueous liquid compositions are soluble concentrates, thick suspensions, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspoemulsions. General types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0497] The general types of solid compositions are powders, dusts, granules, pellets, prills, tablets, filled films (including seed coatings), etc., which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. One or more active ingredients can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively, the entire formulation of the active ingredient can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations. High-strength compositions are mainly used as intermediates for further formulations.

[0498] In one embodiment of the composition, granules of a solid composition comprising component (a1) and component (a2) are mixed with granules of a solid composition comprising component (b). These mixtures can be further mixed with granules containing additional agricultural protectants. Alternatively, two or more agricultural protectants (e.g., component (a1), component (a2), component (b) compounds, agricultural protectants other than component (a1) or (a2) or (b)) can be combined in a solid composition of a group of granules, and then it is mixed with granules of one or more groups of solid compositions containing one or more additional agricultural protectants. These granule mixtures can be the general granule mixture disclosure according to PCT patent publication WO 94 / 24861, or more preferably the homogeneous granule mixture teaching of US Patent 6,022,552.

[0499] Sprayable formulations are typically dispersed in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily dilutable in a spray medium, usually water, but occasionally another suitable medium such as aromatic hydrocarbons or paraffinic hydrocarbons or vegetable oils. The spray volume can range from about one to several thousand liters per hectare, but more typically ranges from about ten to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment by air or ground application, or for application to the growth medium of plants. Liquid and dry formulations can be metered directly into drip irrigation systems, or metered into furrows during planting. Liquid and solid formulations can be applied as a seed treatment to the seeds of crops and other desired vegetation before planting to protect the developing roots and other below-ground plant parts and / or leaves by systemic absorption.

[0500] Formulations will typically contain up to 100 weight percent of an effective amount of one or more active ingredients, diluents, and surfactants in the following approximate ranges. As defined herein, an effective amount of one or more active ingredients includes a single amount of a single active ingredient or a combined amount of more than one active ingredient.

[0501]

[0502]

[0503] Solid diluents include, for example, clays (such as bentonite, montmorillonite, attapulgite and kaolin), gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (such as lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey.

[0504] Liquid diluents include, for example, water, N,N-dimethylalkanamides (such as N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (such as N-methylpyrrolidone), alkyl phosphates (such as triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (such as white mineral oil, n-alkanes, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, de-aromatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactates, diesters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols which may be straight-chain, branched-chain, saturated or unsaturated such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecanol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acids (typically C6-C 22The glycerides of (), such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (maize oil), peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., tallow, lard, pig fat, fish liver oil, fish oil), and mixtures thereof. The liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, where the fatty acids can be obtained by hydrolysis of glycerides from plant and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0505] The solid and liquid compositions of the present invention generally contain one or more surfactants. When added to a liquid, surfactants (also called "surface-active agents") generally alter, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be used as wetting agents, dispersants, emulsifiers, or defoaming agents.

[0506] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alcohol alkoxylates, such as those based on natural and synthetic alcohols (which can be branched or straight-chain) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and inverse block polymers in which the terminal block is prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated triphenylvinylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters); other sorbitan derivatives such as sorbitan esters; polymeric surfactants, such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (peg); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives, such as sucrose esters, alkyl polyglycosides; alkyl polysaccharides; and glucamides, such as a mixture of octyl-N-methyl glucamide and decyl-N-methyl glucamide (e.g., products available under the GA name from Clariant).

[0507] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrenylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrenylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

[0508] Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylene triamine, and dipropylene tetramine, and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quats, ethoxylated quats, and diquats; and amine oxides, such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0509] Mixtures of nonionic surfactants and anionic surfactants, or mixtures of nonionic surfactants and cationic surfactants, may also be used in the compositions of the present invention. Nonionic surfactants, anionic surfactants, and cationic surfactants and their recommended uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, annual American and International Editions, published by The Manufacturing Confectioner Publishing Co., McCutcheon Division; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, 7th Edition, John Wiley and Sons, New York, 1987.

[0510] The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as adjuvants (some of which may also be considered to act as solid diluents, liquid diluents or surfactants). Such formulation aids and additives may control: pH (buffering agents), foaming during processing (defoaming agents such as polyorganosiloxanes), sedimentation of the active ingredient (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), elution (film-forming or adhesive agents), evaporation (evaporation retardants), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those listed in the following: McCutcheon’s Volume 2: Functional Materials, annual International and North American editions, published by the McCutcheon division of The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03 / 024222.

[0511] Typically, components (a1) and (a2) and any other active ingredients are incorporated into the compositions of the invention by dissolving the active ingredients in a solvent or by grinding in a liquid or dry diluent. Solutions including emulsifiable concentrates can be prepared by simply mixing these ingredients. If the solvent of the liquid composition intended to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added to emulsify the solvent containing the active ingredient upon dilution with water. An active ingredient slurry with a particle size up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average particle size below 3 μm. An aqueous slurry can be made into a finished thick suspension (see, e.g., U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations generally require a dry milling process, resulting in an average particle size in the range of 2 to 10 μm. Dusts and powders can be prepared by blending and typically by grinding (e.g., with a hammer mill or a fluid energy mill). Granules and pellets can be prepared by spraying the active substance onto a preformed granule carrier or by an agglomeration technique. See Browning, “Agglomeration,” Chemical Engineering, December 4, 1967, pp. 147-48; Perry’s Chemical Engineer’s Handbook, 4th Edition, McGraw-Hill, New York, 1963, pp. 8-57 et seq., and WO 91 / 13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442, and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701, and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

[0512] One embodiment of the invention relates to a method for controlling fungal pathogens, the method comprising diluting a fungicidal composition of the invention (a formulation of components (a1) and (a2) together with a surfactant, a solid diluent, and a liquid diluent, or a formulated mixture of components (a1) and (a2) and at least one other fungicide) with water, and optionally adding adjuvants to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of the diluted composition.

[0513] Although the spray composition formed by diluting the fungicidal composition of the present invention with water at a sufficient concentration can provide sufficient efficacy in controlling fungal pathogens, separately formulated adjuvant products can also be added to the spray tank mix. These additional adjuvants are commonly referred to as "spray adjuvants" or "tank mix adjuvants" and include any substances that are mixed in the spray tank to improve the performance of the pesticidal agent or to alter the physical characteristics of the spray mixture. Adjuvants can be anionic or non-ionic surfactants, emulsifiers, petroleum-based crop oils, crop-derived seed oils, acidifying agents, buffers, thickeners, or defoamers. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, penetration, coverage uniformity, and protection durability), or to minimize or eliminate spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization, and degradation. To obtain optimal performance, adjuvants are selected based on the characteristics of the active ingredient, formulation, and target (e.g., crop, insect pest).

[0514] The amount of adjuvant added to the spray mixture is typically in the range of about 0.1% to 2.5% by volume. The application rate of the adjuvant added to the spray mixture is typically between about 1 L and 5 L per hectare. Representative examples of spray adjuvants include: (Syngenta) 47% methylated rapeseed oil in a liquid hydrocarbon, (Helena Chemical Company) polyether-modified heptamethyltrisiloxane, and (BASF) a 17% surfactant blend in 83% paraffinic mineral oil.

[0515] One method of seed treatment is to spray or dust the seeds with the compound of the present invention (i.e., as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment typically contain a film-forming agent or binder. Thus, typically, the seed coating composition of the present invention contains a biologically effective amount of component (a1) and component (a2) and a film-forming agent or binder. Seeds can be coated by spraying a flowable thick suspension directly onto a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wet powders, solutions, suspension emulsions, emulsifiable concentrates, and emulsions in water can be sprayed onto the seeds. This method is particularly useful for applying film coatings to seeds. Those skilled in the art can use a variety of coating machines and methods. Suitable methods include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Monograph No. 57 and the references listed therein.

[0516] For further information in the area of formulations, see “The Formulator’s Toolbox–Product Forms for Modern Agriculture” in T.S. Woods, Pesticide Chemistry and Bioscience, The Food–Environment Challenge, edited by T. Brooks and T.R. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, column 6, lines 16 to column 7, line 19 and Examples 10-41; U.S. 3,309,192, column 5, line 43 to column 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, column 3, line 66 to column 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81–96; Hance et al., Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0517] Water-soluble and water-dispersible formulations are typically diluted with water prior to application to form an aqueous composition. An aqueous composition (e.g., a spray tank composition) applied directly to a plant or a part thereof typically contains at least about 1 ppm or more (e.g., 1 ppm to 100 ppm) of one or more compounds of the present invention.

[0518] Seeds are generally treated at a rate of from about 0.001 g (more typically about 0.1 g) to about 10 g / kg of seeds (i.e., from about 0.0001% to 1% by weight of the seeds prior to treatment). A flowable suspension formulated for seed treatment typically comprises from about 0.5% to about 70% active ingredient, from about 0.5% to about 30% film-forming binder, from about 0.5% to about 20% dispersant, from 0% to about 5% thickener, from 0% to about 5% pigment and / or dye, from 0% to about 2% defoamer, from 0% to about 1% preservative, and from 0% to about 75% volatile liquid diluent.

[0519] The compositions of the present invention can be used as plant disease control agents. Accordingly, the present invention further includes a method for controlling plant diseases caused by fungal plant pathogens, which method comprises applying to a plant to be protected or a part thereof or to a plant seed to be protected an effective amount of a compound of the present invention or a fungicidal composition containing said compound. The compounds and / or compositions of the present invention provide control of diseases caused by broad-spectrum fungal plant pathogens in the classes Ascomycota, Basidiomycota, Zygomycota phyla, and fungal-like Oomycota. They are effective in controlling a broad spectrum of plant diseases, especially leaf pathogens of ornamental crops, turf crops, vegetable crops, field crops, cereal crops, and fruit crops. These pathogens include, but are not limited to, those listed in Table 1-1. For Ascomycetes and Basidiomycetes, the names of the sexual / teleomorphic / sexual stage and the asexual / anamorphic / asexual stage (in parentheses) are listed where known. Synonymous names of pathogens are indicated by an equal sign. For example, following the sexual / teleomorphic / sexual stage name Phaeosphaeria nodorum is the corresponding asexual / anamorphic / asexual stage name Stagnospora nodorum and the synonymous old name Septoria nodorum.

[0520] Table 1-1

[0521]

[0522]

[0523]

[0524] In addition to their fungicidal activity, the compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae and other related species. By controlling harmful microorganisms, the compositions of the present invention can be used to increase (i.e., raise) the ratio of beneficial to harmful microorganisms in contact with crop plants or their propagules (e.g., seeds, bulbs, corms, tubers, cuttings) or in the agronomic environment of crop plants or their propagules.

[0525] The compositions of the present invention can be used to treat all plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional breeding and propagation methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant or seed genome. The transgene defined by the specific location of the transgene in the plant genome is called a transformation or transgenic event.

[0526] Genetically modified plant cultivars that can be treated according to the present invention include those that are resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those that contain other desired characteristics. Plants can be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, modified oil characteristics or drought tolerance.

[0527] Treatment of genetically modified plants and seeds with the compounds of the present invention can result in supra-additive or enhanced effects. For example, a reduction in application rate, an extended activity spectrum, an increased tolerance to biotic / abiotic stresses or an enhanced storage stability can be greater than that expected from the simple additive effect of applying the compounds of the present invention on genetically modified plants and seeds.

[0528] The compounds and compositions of the present invention can be used in seed treatment to protect seeds from plant diseases. In the context of the present disclosure and claims, treating seeds means contacting the seeds with a biologically effective amount of a compound of the present invention typically formulated as a composition of the present invention. Such seed treatment protects the seeds from soil-borne disease pathogens and generally can also protect the roots and other plant parts in contact with the soil of the seedlings developed from the germinated seeds. Seed treatment can also provide protection to the leaves by translocating the compound of the present invention or a second active ingredient into the developing plant. Seed treatment can be applied to all types of seeds, including those that will germinate to form genetically transformed plants expressing specific traits. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxins, or those expressing herbicide resistance, such as glyphosate acetyltransferase providing glyphosate resistance. Seed treatment using the compounds and compositions of the present invention can also increase the vigor of the plants grown from the seeds.

[0529] The compounds and compositions of the present invention can be particularly used in seed treatment agents for crops including, but not limited to, maize or corn, soybeans, cotton, cereals (e.g., wheat, oats, barley, rye, and rice), potatoes, vegetables, and oilseed rape.

[0530] In addition, the compounds and compositions of the present invention can be used to treat post-harvest diseases of fruits and vegetables caused by fungi, oomycetes, and bacteria. These infections can occur before, during, and after harvest. For example, the infection can occur before harvest and then remain dormant until a point during ripening (e.g., the host begins to undergo tissue changes in a way that the infection can proceed or the conditions become conducive to disease development); the infection can also be caused by surface wounds resulting from mechanical or insect damage. In this regard, the compositions of the present invention can reduce losses (i.e., losses in quantity and quality) caused by post-harvest diseases that can occur at any time from harvest to consumption. Treating post-harvest diseases with the compounds of the present invention can increase the period of time during which perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) can be stored frozen or unfrozen after harvest and remain edible and free from significant or harmful degradation or contamination by fungi or other microorganisms. Treating edible plant parts before or after harvest with the compounds of the present invention can also reduce the formation of toxic metabolites of fungi or other microorganisms, e.g., mycotoxins such as aflatoxin.

[0531] Plant disease control is typically achieved by applying an effective amount of a compound of the present invention to parts of the plant to be protected, such as roots, stems, leaves, fruits, seeds, tubers or bulbs, before or after infection, or to the medium (soil or sand) in which the plant to be protected grows. These compounds can also be applied to seeds to protect the seeds and the seedlings developed from the seeds. The compounds can also be applied by irrigation water to treat the plants. Control of post-harvest pathogens that infect post-harvest products is typically achieved by on-site application of the compounds of the present invention, and in cases where infection occurs post-harvest, these compounds can be applied to the harvested crop as dips, sprays, fumigants, treatment wraps and box liners.

[0532] The compounds and compositions of the present invention can also be applied using an unmanned aerial vehicle (UAV) to disperse the compositions disclosed herein over a planting area. In some embodiments, the planting area is an area containing a crop. In some embodiments, the crop is selected from monocot or dicot. In some embodiments, the crop is selected from rice, corn, barley, soybeans, wheat, vegetables, tobacco, tea plants, fruit trees and sugarcane. In some embodiments, the compositions disclosed herein are formulated for ultra-low volume spraying. The products applied by drone can use water or oil as a spray carrier. Typical spray volumes (including product) for global drone applications are 5.0 liters per hectare - 100 liters per hectare (approximately 0.5 gpa - 10 gpa). This includes the range from ultra-low spray volume (ULV) to low spray volume (LV). Although not common, there may be cases where even lower spray volumes as low as 1.0 liter per hectare (0.1 gpa) can be used.

[0533] Suitable application rates of component (a1) and component (a2) (e.g., a fungicidally effective amount), as well as suitable application rates of mixtures and compositions comprising component (a1) and component (a2) according to the invention (e.g., a biologically effective amount, a fungicidally effective amount or an insecticidally effective amount) can be affected by factors such as the plant diseases to be controlled (including diseases developed from known fungal resistant strains), the plant species to be protected, the population structure of the pathogen to be controlled, environmental humidity and temperature, etc. and should be determined under actual use conditions. A person skilled in the art can easily determine the fungicidally effective amount necessary for the desired level of plant disease control through simple experiments. When treated at a rate of the active ingredient of less than about 1 g / ha to about 5,000 g / ha, the leaves can generally be protected. When seeds are treated at a rate of about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seeds, the seeds and seedlings can generally be protected. A person skilled in the art can easily determine the application rates of component (a1) and component (a2) and their mixtures and compositions, containing a specific combination of the active ingredients according to the invention required to provide a spectrum of desired plant protection and control of plant diseases and optionally other plant pests.

[0534] The compounds and compositions of the invention can also be used to increase the vigor of crop plants. The method comprises contacting a crop plant (e.g., leaves, flowers, fruits or roots) or the seeds from which the crop plant grows with an amount (i.e., a biologically effective amount) of a composition comprising component (a1) and component (a2) sufficient to achieve the desired plant vigor effect. Typically, component (a1) and component (a2) are applied in a formulated composition. Although component (a1) and component (a2) are typically applied directly to the crop plant or its seeds, they can also be applied to the locus of the crop plant, i.e., the environment of the crop plant, particularly sufficiently close to allow component (a1) and component (a2) to migrate to the parts of the crop plant's environment. The locus relevant to this method most commonly includes the growth medium (i.e., the medium that provides nutrients for the plant), typically the soil in which the plant grows. Thus, the treatment of a crop plant to increase its vigor comprises contacting the crop plant, the seeds from which the crop plant grows or the locus of the crop plant with a biologically effective amount of component (a1) and component (a2).

[0535] Increasing crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence, and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass, and total dry weight of the vegetative parts of the crop; (c) improved crop yield as demonstrated by flowering time, flowering duration, number of flowers, total biomass accumulation (i.e., yield), and / or marketability of the product grade of fruits or grains (i.e., quality and quantity); (d) enhanced ability of the crop to tolerate or prevent infection by plant diseases and infestation by arthropod, nematode, or mollusk pests; and (e) increased ability of the crop to tolerate environmental stresses such as exposure to extreme heat, sub-optimal moisture, or phytotoxic chemicals.

[0536] Compared to untreated plants, the compounds and compositions of the present invention can increase the vigor of treated plants by preventing and / or controlling plant diseases caused by fungal plant pathogens in the plant environment. In the absence of such control of plant diseases, the diseases reduce plant vigor by consuming plant tissue or sap, or by spreading plant pathogens such as viruses. Even in the absence of fungal plant pathogens, the compounds of the present invention can increase plant vigor by altering the metabolism of the plant. Generally, if a plant is grown in a non-ideal environment, i.e., an environment that contains one or more aspects that are not conducive to the plant achieving its full genetic potential as it would exhibit in an ideal environment, then the vigor of the crop plant will be most significantly increased by treating the plant with the compounds of the present invention.

[0537] Noteworthy are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that includes a plant disease caused by a fungal plant pathogen. Also noteworthy are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that does not include a plant disease caused by a fungal plant pathogen. Also noteworthy are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that includes a moisture amount less than the ideal moisture amount to support crop plant growth.

[0538] The compounds and compositions of the present invention can also be mixed with one or more other biologically active compounds or agents to form multi-component pest control agents, thereby conferring even broader agricultural protection. These biologically active compounds or agents include fungicides, insecticides, nematicides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemical sterilants, chemical pheromones, repellents, attractants, pheromones, feeding stimulants, phyto-nutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi. Accordingly, the present invention also relates to a composition comprising component (a1) and component (a2) (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount), and the composition may further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated into a composition comprising at least one of a surfactant, a solid or liquid diluent. For the mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with component (a1) and component (a2) to form a premix, or one or more other biologically active compounds or agents can be formulated separately from component (a1) and component (a2) and the formulations combined together prior to application (e.g., in a spray tank), or alternatively, applied sequentially.

[0539] As mentioned in the Summary of the Invention, one aspect of the present invention is a fungicidal composition comprising component (a1) and component (a2), and at least one other fungicide (i.e., component (b)). Of note are such combinations wherein the other fungicidal active ingredient has a different site of action from component (a1) and / or component (a2). In certain cases, combinations with at least one other fungicidal active ingredient having a similar control spectrum but a different site of action will be particularly advantageous for resistance management. Accordingly, the compositions of the present invention can further comprise at least one additional fungicidal active ingredient in a fungicidally effective amount having a similar control spectrum but a different site of action.

[0540] Examples of component (b) fungicides include benalaxyl-S-methyl, aldimorph, amisulbrom, amisulflor, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), carboxin, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, besoxyazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride, copper sulfate, coumethoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, fluazinam, dimethirimol, dimethomorph, enestrobin, enilconazole (also known as enilconazole), epoxiconazole, etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenbuconazole, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, ferbam, fenpyrazamine, fluazinam, fludioxonil, fluindapyr, fluopicolide, flumorph, fluopyram, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthiacet-methyl, flutolanil, folpet, phthalide, fenoxanil, furalaxyl, furametpyr, guazatine, hexaconazole, hymexazol, imazalil, imibenconazole, guazatine acetate, guazatine trisacetate, iodopropynyl butylcarbamate, ipconazole, ipfencillin triazole, isoprothiolane, iprodione, iprovalicarb, isoconazole, isoprothiolane, isofetamid, isopyrazam, isofetamid, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, mandrobin, mancozeb, mepanipyrim, mepronil, meptyldinocap, metalaxyl (including metalaxyl-M / mefenoxam), cefluconazole, metconazole, methasulfocarb, maneb, metominostrobin, metrafenone, miconazole, myclobutanil, naftifine, methylarsenic acid iron ammonium salt, fluoromide, ofurace, orysastrobin, oxadixyl, fluopyram, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, pyroquilon, penconazole, pencycuron, penthiopyrad, pyrasulfotole, phosphorous acid (including its salts, e.g., fosetyl-aluminum), tetraconazole, picoxystrobin, piperalin, polyoxins, thiabendazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propoxyquinoline, promecarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyrimethanil, pyribenzoxim, pyributicarb, pyrifenox, dimethachlon, picobenzamid, pyridinitril, quinazoline,Quinofumelin (Registration No. 861647-84-9), Chinomethionat, Quinoxyfen, quintozene, fluxapyroxad, silthiofam, silafluofen, spiroxamine, streptomycin, sulfur, tebuconazole, tefurylquinoline, tetrachloroisophthalonitrile, terbinafine, fluconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiophanate, thiram, tiadinil, tolclofos-methyl, metosulam, toprocarb, tolylfluanid, triadimefon, triadimenol, myclobutanil, triticonazole, azoxystrobin, tridemorph, trifloxystrobin, fluotrimazole, dimethomorph, uniconazole, uniconazole-P, validamycin, valifenalate (also known as dimethomorph), vinclozolin, zineb, ziram, zoxamide, N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butyramide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butyramide, N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-(3',4′-difluoro[1,1′-biphenyl]-2-yl)-3-(trifluoromethyl)-2-pyrazinecarboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]ethyl]-4-quinazolinamine, 1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, and [[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxacyclononan-3-yl]amino]carbonyl]-3-pyridyl]oxy]methyl 2-methylpropanoate. Therefore, it is worth noting that the fungicidal composition comprises component (a1) and component (a2) and at least one fungicide selected from the aforementioned list as component (b). ,

[0541] Particularly noteworthy is the combination of component (a1) and component (a2) with component (b) compounds selected from the following: aminopyrine (registration number 1531626 - 08 - 0), azoxystrobin, benzovindiflupyr, bixafen, captan, cyproconazole, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, dichlorobenzene azo (registration number 957144 - 77 - 3), diethofencarb, difenoconazole, dimethomorph, dipyridione, epoxiconazole, ethaboxam, fenarimol, fenhexamid, fluazinam, fludioxonil, fluindapyr, fluopyram, flusilazole, fluthiacet - methyl, flutriafol, fluxapyroxad, folpet, fluorobenzene quinoline (registration number 1314008 - 27 - 9), iprodione, isofetamid, isoflupredone, isopyrazam, kresoxim - methyl, mancozeb, mandestrobin, metiram, metalaxyl (including metalaxyl - M / mefenoxam), chlorfludioxonil, metconazole, metrafenone, tetraconazole (registration number 1472649 - 01 - 6), myclobutanil, fluopyramide, penthiopyrad, picoxystrobin, propiconazole, propoxyquinoline, prothioconazole, pyridine chloromethyl (registration number 1358061 - 55 - 8), pyraclostrobin, propiolic (registration number 1803108 - 03 - 3), dimethirimol, flutriafol, spiroxamine, sulfur, tebuconazole, thiophanate - methyl, trifloxystrobin, zoxamide, α-(1 - chlorocyclopropyl)-α-[2-(2,2 - dichlorocyclopropyl)ethyl]-1H - 1,2,4 - triazole - 1 - ethanol, N-[2-(2,4 - dichlorophenyl)-2 - methoxy - 1 - methylethyl]-3-(difluoromethyl)-1 - methyl - 1H - pyrazole - 4 - carboxamide, 3-(difluoromethyl)-N-(2,3 - dihydro - 1,1,3 - trimethyl - 1H - indene - 4 - yl)-1 - methyl - 1H - pyrazole - 4 - carboxamide, 1-[4-[4-[5R-(2,6 - difluorophenyl)-4,5 - dihydro - 3 - isoxazolyl]-2 - thiazolyl]-1 - piperidinyl]-2-[5 - methyl - 3-(trifluoromethyl)-1H - pyrazol - 1 - yl]ethanone, N-[6 - [[[[(1 - methyl - 1H - tetrazol - 5 - yl)phenylmethylene]amino]oxy]methyl]-2 - pyridinyl]carbamic acid 1,1 - dimethylethyl ester, 5 - fluoro - 2 - [(4 - fluorophenyl)methoxy]-4 - pyrimidinamine, (αS)-[3-(4 - chloro - 2 - fluorophenyl)-5-(2,4 - difluorophenyl)-4 - isoxazolyl]-3 - pyridinemethanol, rel - 1 - [[(2R,3S)-3-(2 - chlorophenyl)-2-(2,4 - difluorophenyl)-2 - epoxyethyl]methyl]-1H - 1,2,4 - triazole, rel - 2 - [[(2R,3S)-3-(2 - chlorophenyl)-2-(2,4 - difluorophenyl)-2 - epoxyethyl]methyl]-1,2 - dihydro - 3H - 1,2,4-Triazole-3-thione and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranylmethyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole (i.e., as component (b) in the composition).

[0542] Mixtures of component (a1) and component (a2) with fungicidal compounds selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, boscalid, carbendazim, chlorothalonil, copper sulfate, cymoxanil, cyproconazole, difenoconazole, dimethomorph, enestroburin, epoxiconazole, fenpropimorph, fluopyram, fludioxonil, fluindapyr, fluquinconazole, fluopicolide, flutriafol, fluxapyroxad, ipfencarbazone, isopyrazam, kresoxim-methyl, mancozeb, metalaxyl, metconazole, metominostrobin, picoxystrobin, prothioconazole, pyraclostrobin, pyribencarb, pyraflufen-ethyl, tebuconazole, thiabendazole, thiophanate-methyl, tricyclazole, trifloxystrobin, and triadimenol are generally preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower application rates or broader spectra of controlled plant pathogens) or resistance management.

[0543] In the fungicidal compositions of the invention, component (a1) and component (a2) and component (b) are present in fungicidally effective amounts. The weight ratio of component (a1) and / or component (a2) to component (b) (i.e., one or more additional fungicidal compounds) is generally between about 1:3000 and about 3000:1, and more typically between about 1:500 and about 500:1. Of note are compositions in which the weight ratio of component (a1) and / or component (a2) to component (b) is from about 125:1 to about 1:125. Particularly notable are compositions in which the weight ratio of component (a1) and / or component (a2) to component (b) is from about 25:1 to about 1:25, or from about 5:1 to about 1:5. Those skilled in the art can readily determine, by simple experimentation, the weight ratios and application rates of the fungicidal compounds required for the desired fungicidal protection and control spectrum. It will be apparent that including additional fungicidal compounds as component (b) can extend the plant disease control spectrum beyond that of component (a1) and / or component (a2) alone. In addition, Tables A1, B1, and C1 illustrate the weight ratio combinations of the fungicidal compounds of the invention. Further, Table B1 lists the typical, more typical, and most typical ratio ranges for specific fungicidal compounds involving component (b).

[0544] In the fungicidal composition of the present invention, components (a1) and (a2) are present in synergistically effective amounts. The weight ratio of component (a1) to component (a2) is generally between about 1:3000 and about 3000:1, and more typically between about 1:500 and about 500:1. Of note are compositions in which the weight ratio of component (a1) to component (a2) is from about 125:1 to about 1:125. Particularly notable are compositions in which the weight ratio of component (a1) to component (a2) is from about 25:1 to about 1:25, or from about 5:1 to about 1:5.

[0545] In some embodiments, components (a1) and (a2) are present and / or applied in a ratio of component (a1):component (a2) in the following ranges: from about 30:1, about 29:1, about 28:1, about 27:1, about 26:1, about 25:1, about 24:1, about 23:1, about 22:1, about 21:1, about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1.75:1, about 1.5:1, about 1.25:1, or about 1:1 to about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, about 1:21, about 1:22, about 1:23, about 1:24, about 1:25, about 1:26, about 1:27, about 1:28, about 1:29, or about 1:30.

[0546] As described above, the present invention includes embodiments in which the composition comprises components (a1) and (a2) and (b), wherein component (b) comprises at least one fungicidal compound selected from (b1) to (b54). Of particular note are the compositions of the present invention in which component (b) has a different site of action from component (a1) and / or component (a2). In certain cases, combinations with at least one other fungicidal compound having a similar control spectrum but a different site of action will be particularly advantageous for resistance management. Thus, the compositions of the present invention may advantageously comprise at least one fungicidally active compound selected from the group consisting of (b1) to (b54) as described above, which has a similar control spectrum to components (a1) and / or (a2) but a different site of action.

[0547] The composition of component (a1) and component (a2), or component (a1) and component (a2) and component (b) can be further mixed with one or more other biologically active compounds or agents to form a multi-component pestcide, thereby conferring even broader agricultural protection. These biologically active compounds or agents include insecticides, nematicides, fungicides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and root stimulants, chemical sterilants, chemical pheromones, repellents, attractants, pheromones, feeding stimulants, phytohormones, other biologically active compounds or entomopathogenic bacteria, viruses or fungi. Accordingly, the present invention also relates to a composition comprising a fungicidally effective amount of component (a1) and component (a2), or component (a1) and component (a2) and component (b), and a biologically effective amount of a mixture of at least one additional biologically active compound or agent, and may further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can also be formulated separately into a composition comprising at least one of a surfactant, a solid or a liquid diluent. For the compositions of the present invention, one or more other biologically active compounds or agents can be formulated together with one or both of components (a1) and (a2) and (b) to form a premix, or one or more other biologically active compounds or agents can be formulated separately from components (a1) and (a2) and (b) and the formulations combined together prior to application (e.g., in a spray tank), or alternatively, applied sequentially.

[0548] Examples of such biologically active compounds or agents that can be formulated together with component (a1) and component (a2) or the composition of component (a1) and component (a2) with component (b) are: insecticides such as abamectin, acephate, acequinocyl, acetamiprid, allethrin, acynonapyr, alanidipine, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, benzpyrimoxan, bifenthrin, κ-bifenthrin, bifenazate, bistrifluron, borate, broflanilide, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlordimeform, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chloroprallethrin, chlorpyrifos, chlorpyrifos-e, chlorpyrifos-methyl, chromafenozide, clofentezine, chloroprallethrin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyflumetofen, cyhalothrin, lambda-cyhalothrin, cyhalodiamide, deltamethrin, emamectin, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, ethofenprox, ε-methoxybenzylfluthrin, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flufenerim, flupenthrin, flupyrazofos, flupyradifurone, flupyrimin, fluvalinate, τ-fluvalinate, flutriafol, fonofos, formetanate, fosthiazate, lambda-cyhalothrin, halofenozide, heptaflumethrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isofenphos, isoxazoline, κ-heptafluthrin, lambda-cyhalothrin, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxybenzylfluthrin, methoxyfenozide, ε-methoxybenzylfluthrin, ε-fluoro-α-cyano-3-phenoxybenzyl 2,2,3,3-tetrafluoropropionate, monocrotophos, monofluorothrin, nicotine, nitenpyram, nitrothal-isopropyl, novaluron, noviflumuron, oxamyl, oxazosulfyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,Pirimicarb, profenofos, cyfluthrin, propargite, empenthrin, tebufenpyrad, pymetrozine, flonicamid, pyrethrins, pyridaben, pyridalyl, pyflubumide, pyrimidifen, pyrafluprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spiropidion, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, pyridaben, chlorfluazuron, heptafluthrin, κ-heptafluthrin, terbufos, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, tetraflumizole, tetraniliprole, thiacloprid, thiamethoxam, thiodicarb, bisultap, thiazosulfuron, tolfenpyrad, tetrabromomethrin, triazamate, trichlorfon, triflumezopyrim, triflumuron, ticlopyrazoflor, ζ-cypermethrin, Bacillus thuringiensis δ-endotoxin, entomopathogenic bacteria, entomopathogenic viruses or entomopathogenic fungi.

[0549] An example of a biopesticide for mixing with the compounds of the present disclosure includes entomopathogenic bacteria such as Bacillus thuringiensis, and encapsulated δ-endotoxins of Bacillus thuringiensis prepared by processes, such as and Biological insecticides ( and are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (naturally occurring and genetically modified) viruses, including baculoviruses, nucleopolyhedroviruses (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granuloviruses (GV) such as Cydia pomonella granulosisvirus (CpGV).

[0550] General references for these agricultural protectants (i.e., insecticides, fungicides, nematicides, acaricides, herbicides, and biopesticides) include The Pesticide Manual, 13th Edition, edited by C.D.S. Tomlin, British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, edited by L.G. Copping, British Crop Protection Council, Farnham, Surrey, U.K., 2001.

[0551] For embodiments in which one or more of the invertebrate pest control compounds are used, the weight ratio of these compounds (in total) to the compounds of component (a1) and component (a2) is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). A person skilled in the art can readily determine the biologically effective amount of the active ingredient required for the desired biological activity profile by simple experimentation.

[0552] The compounds of component (a1) and component (a2) and / or their combination with the compound of component (b) and / or one or more other biologically active compounds or agents can be applied to plants that have been genetically transformed to express a protein toxic to invertebrate pests (such as Bacillus thuringiensis δ-endotoxin). The action of the separately applied component (a1) and component (a2) of the present invention or in combination with component (b) can act synergistically with the expressed toxin protein.

[0553] It should be noted that the combination or composition containing component (a1) and component (a2) or components (a1) and (a2) and (b) as described in the Summary of the Invention further comprises at least one invertebrate pest control compound or agent (e.g., insecticide, acaricide). Particularly notable is the composition containing component (a1) and component (a2) and at least one (i.e., one or more) invertebrate pest control compound or agent, which can then be subsequently combined with component (b) to provide a composition containing components (a1), (a2), (b), and one or more invertebrate pest control compounds or agents. Alternatively, without first mixing with component (b), a biologically effective amount of a composition containing component (a1) and component (a2) and at least one invertebrate pest control agent can be applied to the plant or plant seed (directly or through the environment of the plant or plant seed) to protect the plant or plant seed from diseases caused by fungal pathogens and damage caused by invertebrate pests.

[0554] It should be noted that the composition of the present invention, in addition to component (a1) and component (a2) (alone or in combination with component (b)), further comprises at least one invertebrate pest control compound or agent selected from the group consisting of: abamectin, acetamiprid, fluvalinate, avermectin, cyantraniliprole, amitraz, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, broflanilide, cadusafos, carbaryl, cartap hydrochloride, chlorantraniliprole, d-cis-trans allethrin, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, deltamethrin, dieldrin, dinotefuran, phenthoate, emamectin benzoate, endosulfan, epsilon-methoprene, esfenvalerate, ethiprole, ethofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flufiprole, flonicamid, flubendiamide, fluthiacet-methyl, flufenoxuron, fluacrypyrim, flufenerim, flupyrazofos, flupyradifurone, formetanate hydrochloride, fosthiazate, lambda-cyhalothrin, heptaflumethrin, flucycloxuron, indoxacarb, isoxazoline, kappa-cyhalothrin, lambda-cyhalothrin, lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl, methoprene, monocrotophos, nitenpyram, nithiazine, novaluron, oxamyl, pyraflufen-ethyl, pymetrozine, pyrethrins, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spirotetramat, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetraflumizone, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim, triflumuron, Tolfenpyrad, zeta-cypermethrin, Bacillus thuringiensis delta-endotoxin, all strains of Bacillus thuringiensis, and all strains of nuclear polyhedrosis virus.

[0555] In certain cases, the combination of component (a1) and component (a2) of the present invention (alone or in admixture with component (b)) with other biologically active (especially fungicidal) compounds or agents (i.e., active ingredients) can produce a greater than additive (i.e., synergistic) effect. Reducing the amount of active ingredient released into the environment while ensuring effective pest control has always been desirable. Such combinations can be advantageously used to reduce crop production costs and environmental burden when the fungicidal active ingredient produces an enhanced effect at an application rate that achieves an agronomically satisfactory level of fungal control.

[0556] Compositions comprising components (a1) and (a2) useful for seed treatment can further comprise bacteria and fungi that have the ability to provide protection against the deleterious effects of phytopathogenic fungi or bacteria and / or soil-dwelling animals such as nematodes. Bacteria exhibiting nematicidal properties can include, but are not limited to, Bacillus firmus, Bacillus cereus, Bacillus subtiliis, and Pasteuria penetrans. A suitable strain of Bacillus firmus is the strain commercially available as BioNem TM strain CNCM I-1582 (GB-126). A suitable strain of Bacillus cereus is strain NCMM I-1592. Both Bacillus strains are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are Bacillus amyloliquefaciens IN937a and Bacillus subtilis strain GB03. Bacteria exhibiting fungicidal properties can include, but are not limited to, Bacillus pumilus strain GB34. Fungal species exhibiting nematicidal properties can include, but are not limited to, Myrothecium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum.

[0557] Seed treatment can also comprise one or more nematicides of natural origin, such as the elicitor protein known as harpin, which is isolated from certain bacterial plant pathogens such as Erwinia amylovora. An example is the harpin-N-Tek seed treatment technology available as N-Hibit TM Gold CST.

[0558] Seed treatment can also comprise one or more leguminous plant nodulating bacterial species, such as the microsymbiotic nitrogen-fixing bacterium Bradyrhizobium japonicum. These inoculants can optionally comprise one or more lipochitooligosaccharides (LCO), which are nodulation (Nod) factors produced by rhizobial bacteria during nodule formation induction on the roots of leguminous plants. For example, the branded seed treatment technology combines LCO promoters in combination with the inoculant Technology TM .

[0559] Seed treatment may also comprise one or more isoflavones, which may increase the level of root colonization by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing the uptake of nutrients such as water, sulfate, nitrate, phosphate, and metals by the roots. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin, and trifolin. Formononetin is available as an active ingredient in mycorrhizal inoculant products such as PHC AG.

[0560] Seed treatment may also comprise one or more plant activators that cause systemic acquired resistance in plants upon contact with a pathogen. An example of a plant activator that causes such a protective mechanism is acibenzolar-S-methyl.

[0561] In the fungicidal compositions of the present invention, component (a1) and component (a2) may act synergistically with additional fungicidal compounds of component (b) to provide beneficial results such as broadening the spectrum of plant diseases controlled, extending the duration of preventive and therapeutic protection, and inhibiting the proliferation of resistant fungal pathogens. In particular embodiments, compositions are provided according to the present invention that comprise component (a1) and component (a2) and component (b) in proportions that are particularly useful for controlling specific fungal diseases (such as Alternaria solani, Blumeria graminis f.sp. tritici, Botrytis cinerea, Puccinia recondita f.sp. tritici, Rhizoctonia solani, Septoria nodorum, Septoria tritici).

[0562] Mixtures of fungicides can also provide significantly better disease control than might be expected based on the activity of the individual components. This synergism has been described as "the cooperative action of the two components of the mixture such that the total effect is greater than or exceeds the sum of the individual effects of the two (or more) components" (see P.M.L. Tames, Neth. J. Plant Pathology [Dutch Journal of Plant Pathology] 1964, 70, 73-80). In a method of providing plant disease control, where synergism is exhibited from a combination of active ingredients (e.g., fungicidal compounds) applied to a plant or seed, the active ingredients are applied in a weight ratio that is synergistic and in an amount that is synergistic (i.e., synergistically effective). The measures of disease control, suppression, and prevention cannot exceed 100%. Thus, the expression of substantial synergism typically requires the use of application rates of the active ingredients where the active ingredients individually provide far less than 100% of the effect, such that their additive effect is substantially less than 100%, to allow for the possibility of an increased effect due to synergism. On the other hand, too low an application rate of the active ingredients may not show much activity in the mixture even with the benefit of synergism. A person skilled in the art can readily determine and optimize the weight ratio and application rate (i.e., amount) of the fungicidal compounds that provide synergism through simple experiments.

[0563] Synergism exists whenever the action of a combination of active components is greater than the sum of the actions of each component alone. Thus, a synergistic combination is a combination of active components having an action greater than the sum of the actions of each active component alone, and a synergistically effective amount is the effective amount of the synergistic combination. Well-known methods for determining the existence of synergism include the Colby method, the Tammes method, and the Wadley method, all of which are described below. Any of these methods can be used to determine whether there is synergism between compounds A and B.

[0564] In the Colby method, also known as the Limpels method, the expected action E of a given combination of active ingredients follows the so-called Colby formula. According to Colby, the expected action of active ingredients A + B using p + q ppm of active ingredients is:

[0565]

[0566] where ppm = milligrams of active ingredient (a.i.) per liter of spray mixture X = percent of the effect of component A using p ppm of active ingredient Y = percent of the effect of component B using q ppm of active ingredient. If the ratio R, defined as the ratio of the actually observed effect (O) divided by the expected effect (E), is > 1, then the combined effect is supra-additive, i.e., there is a synergistic effect. For a more detailed description of the Colby formula, see Colby, S.R. "Calculating synergistic and antagonistic responses of herbicide combination," Weeds, Vol. 15, pp. 20-22; 1967; also see Limpel et al., Proc. NEWCC 16:48-53 (1962).

[0567] The Tammes method uses a graphical representation to determine if there is a synergistic effect. See "Isoboles, a graphic representation of synergism in pesticides," Netherlands Journal of Plant Pathology, 70 (1964) pp. 73-80.

[0568] The Wadley method is based on a comparison of the observed EC50 value (i.e., the concentration providing 50% control) obtained from experimental data using dose-response curves with the expected EC50 calculated theoretically according to the following formula:

[0569]

[0570] where a and b are the weight ratios of compounds A and B in the mixture, and EC50obs is the experimentally determined EC50 value obtained using the dose-response curves of the individual compounds. The EC50(A + B) 预期值 / EC50(A + B) observed value ratio represents the interaction factor (F) (synergistic factor). In the case of synergism, F is > 1. For a more detailed description of the Wadley method, see Levi et al., EPPO - Bulletin 16, 1986, 651-657.

[0571] Without further elaboration, it is believed that those skilled in the art can make the most of the present invention using the previously described. However, the following examples should be construed as merely illustrative and in no way limit this disclosure in any way.

[0572] Biological Examples of the Invention

[0573] The following tests demonstrated the control efficacy of the compositions (i.e., mixtures) of the present invention against specific fungal pathogens. In particular, the efficacy of the compositions against pathogen strains that have been identified as sensitive or resistant biotypes and are associated with control failures of previously effective fungicides was evaluated. For example, fungicides identified by FRAC.

[0574] The sources of the strains of Septoria tritici blotch (synonym Mycosphaerella graminicola) expressing one or more gene mutations used for inoculation in the tests below are as follows.

[0575] The isolate of Septoria tritici blotch IPO323 (phenotype of Mycosphaerella graminicola) is from the Westerdijk Fungal Biodiversity Institute (CBS, Netherlands), which acts as an International Depository Authority (IDA) under the provisions of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure. The isolate was deposited in the CBS collection on July 5, 1981, with the reference number CBS115943.

[0576] The strains of Septoria tritici blotch TriR6 and TriR10 (two phenotypes from the TriMR group expressing CYP51 mutations) are from INRAE (France’s National Research Institute for Agriculture, Food and Environment). All isolates were maintained at –80 °C in glycerol and brought to room temperature before use in the tests. The isolates were used after one transfer to Petri dishes.

[0577] The TriMR group encompasses many different phenotypes, each with known fungicide resistance factors. For further information on phenotype classes and their fungicide resistance factors, see: Evolution of resistance to fungicides in populations of Mycosphaerella graminicola: emergence of new phenotypes highly resistant to DMIs, Conference: EPPO workshop on Azole fungicide and Septoria leaf blotch control, December 2010; Leroux et al., Pest Management Science, 2007, 63, 688 - 98; and Walker, Pest Management Science, 2011, 67, 44 - 59.

[0578] The strains identified as 20, 30, 39, and 97 in the tests below are field isolates with target site mutations that reduce sensitivity to SDHI fungicides. These isolates were collected and characterized during resistance monitoring in Europe in 2021. The following table summarizes the mutations detected for each of these strains and the country of origin of the isolates.

[0579] Strain Mutation Country Sampling Date 20 N86S Ireland 2021 30 F23S, I29V, N33T, N34T, H152R UK 2021 39 H152R UK 2021 97 T79N Germany 2021

[0580] The general protocol for preparing the test compositions used in Tests A - G was as follows. Indifloxycarb was prepared and formulated as an emulsifiable concentrate (100EC) for industrial use. Fenpicoxamid was obtained as a formulated product (as Questar TM commercially available). The product was dispersed in sufficient water to reach the desired concentration, and no organic solvents or surfactants were added to the suspension. The resulting test mixture was then used in Tests A - H and sprayed at a volume of 250 L / ha using a tunnel sprayer. The application rates of indifloxycarb were 50 and 150 g a.i. / ha, and the application rates of fenpicoxamid were 33.3 and 100 g a.i. / ha.

[0581] Test compositions:

[0582] Composition 1

[0583]

[0584] Composition 2

[0585]

[0586] The test results for Tests A to G are provided in the table below. The results in each table correspond to a set of evaluations conducted together at the same time. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the untreated control). The column labeled "Observed Efficacy" indicates the mean of the results observed in independent tests on individual plants (the number of replicates is indicated below). The column labeled "Expected Efficacy" indicates the expected value for each treatment mixture using the Colby formula, as described above.

[0587] Test A

[0588] The test compositions were sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain IPO323) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table A below are the mean of four tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0589] Table A

[0590] Compositions 1 and 2, used alone and in mixtures, in the control of Septoria tritici blotch caused by Septoria tritici (strain

[0591] IPO323), observed and expected efficacy

[0592]

[0593] Test B

[0594] The test suspensions were sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain TriR6) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table B below are the mean of two tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0595] Table B

[0596] Observed and expected effects of Compositions 1 and 2, used alone and in mixture, in controlling Septoria tritici blotch caused by Mycosphaerella graminicola (strain

[0597] TriR6)

[0598]

[0599]

[0600] Test C

[0601] The test suspensions were sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Mycosphaerella graminicola (strain TriR10) (the causal agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table C are the mean of two tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0602] Table C

[0603] Observed and expected effects of Compositions 1 and 2, used alone and in mixture, in controlling Septoria tritici blotch caused by Mycosphaerella graminicola (strain

[0604] TriR10)

[0605]

[0606] Test D

[0607] The test suspensions were sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Mycosphaerella graminicola (strain 20, with mutation N86S) (the causal agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table D are the mean of three tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0608] Table D

[0609] Observed and expected effects of Compositions 1 and 2, used alone and in mixture, in controlling Septoria tritici blotch caused by Mycosphaerella graminicola (strain 20, with mutation N86S)

[0610]

[0611] Test E

[0612] The test suspension was sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain 30, having mutations F23S, I29V, N33T, N34T, and H152R) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table E below are the average of three tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0613] Table E

[0614] Observed and expected effects of Compositions 1 and 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici (strain 30, having mutations F23S, I29V, N33T, N34T, and H152R)

[0615]

[0616] Test F

[0617] The test suspension was sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain 39, having mutation H152R) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table F below are the average of three tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0618] Table F

[0619] Observed and expected effects of Compositions 1 and 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici (strain 39, having mutation H152R)

[0620]

[0621] Test G

[0622] The test suspension was sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici blotch pathogen (strain 97, with mutation T79N) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table G below are the average of three tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0623] Table G

[0624] Observed and expected effects of Composition 1 and Composition 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici blotch pathogen (strain 97, with mutation T79N)

[0625]

[0626]

[0627] The general protocol for preparing the test compositions used in Tests H to N was as follows. Benzovindiflupyr was obtained as a formulated product (as PLUS is commercially available). Fenpicoxamid was used for Composition 2 as described above. The product was dispersed in sufficient water to reach the desired concentration, and neither organic solvents nor surfactants were added to the suspension. The resulting test mixture was then used in Tests H - N and sprayed at a volume of 250 L / ha using a tunnel sprayer. The application rate of benzovindiflupyr was 25 and 75 g a.i. / ha, and the application rate of fenpicoxamid was 33.3 and 100 g a.i. / ha.

[0628] Test compositions:

[0629] Composition 3

[0630]

[0631] Composition 2

[0632]

[0633] The test results of Tests H to N are provided in the following tables. The results in each table correspond to a set of evaluations carried out together at the same time. In the tables, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the untreated control). The column labeled "Observed Efficacy" indicates the mean of the results observed in independent tests on individual plants (the number of replicates is indicated below). The column labeled "Expected Efficacy" indicates the expected value for each treatment mixture using the Colby formula, as described above.

[0634] Test H

[0635] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Mycosphaerella graminicola (strain IPO323) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table H below are for individual tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0636] Table H

[0637] Compositions 3 and 2, used alone and in mixtures, in the control of Septoria tritici blotch caused by Mycosphaerella graminicola (strain

[0638] IPO323), observed and expected efficacies

[0639]

[0640] Test I

[0641] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Mycosphaerella graminicola (strain mutant TriR6) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table I below are for individual tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0642] Table I

[0643] Compositions 3 and 2, used alone and in mixtures, in the control of Septoria tritici blotch caused by Mycosphaerella graminicola (strain mutant TriR6), observed and expected efficacies

[0644]

[0645]

[0646] Test J

[0647] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain mutant TriR10) (the pathogen of Septoria tritici blotch), the causal agent of wheat Septoria blotch, and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table J below are for individual tests, with four replicates (i.e., pots) for each test for each composition, where each replicate (i.e., pot) contained five plants.

[0648] Table J

[0649] Observed and expected efficacy of Compositions 3 and 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici (strain mutant TriR10)

[0650]

[0651] Test K

[0652] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain 20, with mutation N86S) (the pathogen of Septoria tritici blotch), the causal agent of wheat Septoria blotch, and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table K below are for individual tests, with four replicates (i.e., pots) for each test for each composition, where each replicate (i.e., pot) contained five plants.

[0653] Table K

[0654] Observed and expected efficacy of Compositions 3 and 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici (strain 20, with mutation N86S)

[0655]

[0656] Test L

[0657] The test suspension was sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain 30, having mutations F23S, I29V, N33T, N34T, and H152R) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table L below were for individual tests, with four replicates (i.e., pots) for each test for each composition, where each replicate (i.e., pot) contained five plants.

[0658] Table L

[0659] Observed and expected efficacy of Composition 3 and Composition 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici (strain 30, having mutations F23S, I29V, N33T, N34T, and H152R)

[0660]

[0661] Test M

[0662] The test suspension was sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain 39, having mutation H152R) (the causative agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table M below were for individual tests, with four replicates (i.e., pots) for each test for each composition, where each replicate (i.e., pot) contained five plants.

[0663] Table M

[0664] Observed and expected efficacy of Composition 3 and Composition 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici (strain 39, having mutation H152R)

[0665]

[0666] Test N

[0667] The test suspension was sprayed onto 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici (strain 97, with mutation T79N) (the causal agent of Septoria tritici blotch) and incubated for 48 h in a saturated atmosphere at 20 °C and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table N were for individual tests, with each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0668] Table N

[0669] Observed and expected efficacy of compositions 3 and 2, alone and in mixture, in controlling Septoria tritici blotch caused by Septoria tritici (strain 97, with mutation T79N)

[0670]

[0671]

[0672] The general protocol for preparing the test compositions used in tests O - Q was as follows. Fluxapyroxad was obtained as a formulated product (as commercially available). Fenpicoxamid was used for composition 2 as described above. The product was dispersed in sufficient water to achieve the desired concentration, and neither organic solvents nor surfactants were added to the suspension. The resulting test mixture was then used in tests O - Q, sprayed at a volume of 250 L / ha using a tunnel sprayer. The application rates of fluxapyroxad were 41.67, 62.5, and 125 g a.i. / ha, and the application rates of fenpicoxamid were 33.3, 75, and 100 g a.i. / ha.

[0673] Test compositions:

[0674] Composition 4

[0675]

[0676] Composition 2

[0677]

[0678] Test O

[0679] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici blotch pathogen (strain 20 with mutation N86S) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, followed by visual disease rating. The test results provided in Table O are the average of two tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contains five plants.

[0680] Table O

[0681] Observed and expected efficacy of Composition 4 and Composition 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici blotch pathogen (strain 20 with mutation N86S)

[0682]

[0683] Test P

[0684] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici blotch pathogen (strain 30 with mutations F23S, I29V, N33T, N34T and H152R) and incubated for 48 h in a saturated atmosphere at 20 °C, and then transferred to a growth chamber at 20 °C for 21 days, followed by visual disease rating. The test results provided in Table P are the average of two tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contains five plants.

[0685] Table P

[0686] Observed and expected efficacy of Composition 4 and Composition 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici blotch pathogen (strain 30 with mutations F23S, I29V, N33T, N34T and H152R)

[0687]

[0688]

[0689] Test Q

[0690] The test suspension was sprayed on 6-day-old wheat seedlings. The next day, the seedlings were inoculated with a spore suspension of Septoria tritici blotch pathogen (strain 97, with mutation T79N) and incubated for 48 h in a saturated atmosphere at 20 °C and then transferred to a growth chamber at 20 °C for 21 days, after which visual disease ratings were made. The test results provided in Table Q are the average of two tests, each test having four replicates (i.e., pots) for each composition, where each replicate (i.e., pot) contained five plants.

[0691] Table Q

[0692] Observed and expected efficacy of compositions 4 and 2 used alone and in mixtures in controlling Septoria tritici blotch caused by Septoria tritici blotch pathogen (strain 97, with mutation T79N)

[0693]

Claims

1. A composition, comprising: (a1) A succinate dehydrogenase inhibitor (SDHI); and (a2) A pyridinecarboxamide.

2. The composition according to claim 1, wherein the SDHI is selected from (a1-a) Phenylbenzamides, carboxin, flutolanil, mepronil, phenyl-oxo-ethylthiophenecarboxamide, isofetamid, pyridyl-ethyl-benzamide, fluopyram, furametpyr, mefurthiapropyl, oxathiapiprolin, carboxin and oxycarboxin, thifluzamide, thiamet-G, pyrazole-4-carboxamide, benzovindiflupyr, bixafen, fluxapyroxad, fluopyram, ipfencarbazone, sedaxane, pyriofenone, fluoxastrobin, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-cyclopropyl-N-benzyl-pyrazolecarboxamide, isoflucypram, N-methoxy(phenylethyl)pyrazolecarboxamide, fluxametamide, pyridinecarboxamide, boscalid, pyrazinecarboxamide fungicides and bixazox; and (a1-b) Indanamine carboxamides having the structure of formula (I): Wherein R 1 、R 2 、R 3 and R 4 each independently is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl; R 5 and R 7 each independently is H, C1-C4 alkyl or C1-C4 haloalkyl; R 6 is a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group or a C1-C4 haloalkylthio group; R 8 is halogenated, -OH, -SH, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio; and n is from 0 to 3; and (a1-c) Combinations thereof.

3. The composition according to claim 1, wherein the SDHI indanamine carboxamide of formula (I) is fluoxastrobin having the following structure:

4. The composition according to claim 1, wherein the SDHI is benzovindiflupyr.

5. The composition according to claim 1, wherein the SDHI is fluxapyroxad.

6. The composition according to claim 1, wherein the pyridinecarboxamide is selected from (a2-a) Fempizone, picoxystrobin, [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl](2S)-2-[(3-acetoxy-4-methoxypyridine-2-carbonyl)amino]propionate, [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl](2S)-2-[[3-(acetoxymethoxy)-4-methoxypyridine-2-carbonyl]amino]propionate, and [(1S,2S)-2-(4-fluoro-2-methylphenyl)-1,3-dimethylbutyl](2S)-2-[(3-hydroxy-4-methoxypyridine-2-carbonyl)amino]propionate.

7. The composition according to claim 1, wherein the pyridinecarboxamide is selected from (a2-a) Fempizone and picoxystrobin and (a2-b) pyridoxamide.

8. The composition according to claim 7, wherein the pyridinecarboxamide is fempizone.

9. The composition according to claim 7, wherein the pyridinecarboxamide is picoxystrobin.

10. The composition according to claim 7, wherein the pyridinecarboxamide is pyridoxamide.

11. The composition according to claim 1, wherein the SDHI is selected from (a1-a) benzovindiflupyr, fluxapyroxad, and fluxametamide, and the pyridinecarboxamide is selected from (a2-a) fenpicoxamid and picoxystrobin and (a2-b) pyriftalid.

12. The composition according to claim 11, wherein the SDHI is fluxapyroxad.

13. The composition according to claim 11, wherein the pyridinecarboxamide is fenpicoxamid.

14. The composition according to claim 1, which further comprises at least one component (b) selected from the following: (b1) benzimidazole methylcarbamate (MBC) fungicides; (b2) dicarboximide fungicides; (b3) demethylation inhibitor (DMI) fungicides; (b4) phenylamide (PA) fungicides; (b5) amine / morpholine fungicides; (b6) phospholipid biosynthesis inhibitor fungicides; (b7) additional succinate dehydrogenase inhibitor (SDHI) fungicides; (b8) hydroxy(2-amino)pyrimidine fungicides; (b9) anilinopyrimidine (AP) fungicides; (b10) N-phenyl carbamate fungicides; (b11) quinone outside inhibitor (QoI) fungicides; (b12) phenylpyrrole (PP) fungicides; (b13) quinazoline fungicides; (b14) cell peroxidation inhibitor fungicides; (b15) melanin biosynthesis inhibitor - reductase (MBI-R) fungicides; (b16a) melanin biosynthesis inhibitor - dehydratase (MBI-D) fungicides; (b16b) melanin biosynthesis inhibitor - polyketide synthase (MBI-P) fungicides; (b17) ketoreductase inhibitor (KRI) fungicides; (b18) squalene-epoxidase inhibitor fungicides; (b19) polyoxins fungicides; (b20) phenylurea fungicides; (b21) quinone inside inhibitor (QiI) fungicides; (b22) benzamide and thiazolecarboxamide fungicides; (b23) enolpyranosyluracil antibiotics fungicides; (b24) hexopyranosyl antibiotics fungicides; (b25) glucopyranosyl antibiotics: protein synthesis fungicides; (b26) glucopyranosyl antibiotics fungicides; (b27) cyanoacetamide-oxime fungicides; (b28) carbamate fungicides; (b29) oxidative phosphorylation uncoupler fungicides; (b30) organotin fungicides; (b31) carboxylic acid fungicides; (b32) heteroaromatic fungicides; (b33) phosphonate fungicides; (b34) anthranilic acid fungicides; (b35) benzotriazine fungicides; (b36) benzene-sulfonamide fungicides; (b37) pyridazinone fungicides; (b38) thiophene-carboxamide fungicides; (b39) complex I NADH oxidoreductase inhibitor fungicides; (b40) carboxylic acid amide (CAA) fungicides; (b41) tetracycline antibiotics fungicides; (b42) thiocarbamate fungicides; (b43)Benzamide fungicides; (b44)Microbial fungicides; (b45)Quinone outside inhibitors, strobilurin-binding (QoSI) fungicides; (b46)Plant extract fungicides; (b47)Cyanacrylate fungicides; (b48)Polyene fungicides; (b49)Oxysterol-binding protein inhibitors (OSBPIs) fungicides; (b50)Aryl-phenyl-ketone fungicides; (b51)Host plant defense induction fungicides; (b52)Multi-site active fungicides; (b53)Biological agents with multiple modes of action; (b54)Fungicides other than the fungicides of component (a1), component (a2), and components (b1) to (b53); and salts of the compounds of (b1) to (b54).

15. The composition according to claim 1 and at least one additional component selected from surfactants, solid diluents, and liquid diluents.

16. The composition according to claim 1, wherein the SDHI and the pyridinecarboxamide are present in an SDHI:pyridinecarboxamide ratio in the range of about 2:1 to about 1:

1.

17. The composition according to claim 1, wherein the SDHI and the pyridinecarboxamide are present in an SDHI:pyridinecarboxamide ratio of about 1.5:

1.

18. The composition according to claim 1, wherein the SDHI is in a form selected from the group consisting of concentrated suspension, capsule suspension, emulsifiable concentrate, granule, wettable granule, and combinations thereof.

19. The composition according to claim 1, wherein the pyridinecarboxamide is in a form selected from the group consisting of concentrated suspension, capsule suspension, emulsifiable concentrate, granule, wettable granule, and combinations thereof.

20. A method for protecting plants or plant seeds against diseases caused by fungal pathogens, the method comprising applying a fungicidally effective amount of the composition according to claim 1 to the plants or plant seeds.

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