Fungicidal formulations containing ARYL amidines and methods of use and preparation
Fungicidal formulations with low moisture content and dehydrating agents, such as hydrochloride salt (Formula I-B), address stability and efficacy issues, maintaining effectiveness against fungal pathogens with minimal crop harm.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- CORTEVA AGRISCIENCE LLC
- Filing Date
- 2025-11-04
- Publication Date
- 2026-05-15
AI Technical Summary
Existing fungicidal formulations face challenges in achieving stability under storage conditions, ease of use, and effectiveness against agriculturally relevant fungi while minimizing harm to desirable crops.
Development of fungicidal formulations with low moisture content comprising compounds of Formula I and at least one dehydrating agent, which include hydrochloride salt (Formula I-B), providing improved stability and efficacy against fungal pathogens.
The formulations exhibit enhanced stability and fungicidal activity against agriculturally relevant fungi, ensuring minimal impact on desirable crops.
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Abstract
Description
FUNGICIDAL FORMULATIONS CONTAINING ARYL AMIDINES AND METHODS OF USE AND PREPARATIONCROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 718,608 filed November 9, 2024, which is expressly incorporated by reference herein.FIELD
[0002] The present disclosure is directed to fungicidal formulations containing 4- (difluoromethoxy)benzyl 4-(((ethyl(methyl)amino)methylene)amino)-2,5-dimethylbenzoate (Formula I) or an acceptable salt, solvate, or hydrate thereof, and at least one dehydrating agent. Also disclosed herein are fungicidal formulations with low moisture content, containing 4- (difluoromethoxy)benzyl 4-(((ethyl(methyl)amino)methylene)amino)-2,5-dimethylbenzoate (Formula I) or an acceptable salt, solvate, or hydrate thereof. Furthermore, this disclosure provides methods of treating and controlling plant derived fungal pathogens or diseases comprising contacting the crop or an area adjacent thereto with a fungi cidally effective amount of fungicidal formulations disclosed herein and methods of preparation of such fungicidal formulations.BACKGROUND
[0003] Many recurring problems in agriculture involve protecting and / or curing plants against damage caused by agriculturally relevant fungi. To help protecting and / or curing plants, researchers have produced a variety of fungicidal chemicals effective in protecting and / or curing plants against damage caused by agriculturally relevant fungi. While these fungicidal chemicals may be used neat, it is typically preferable to incorporate the fungicidal chemicals in formulations. Such formulations may be liquid formulations or solid formulations. Such formulations can be designed to be stable under typical storage conditions; easy for the end user to transport, dilute, mix, and apply; safe for the end user and the environment; effective in protecting and / or curing plants against damage caused by agriculturally relevant fungi; and no or minimum damage or injury on desirable crops. Achieving most or all of these goals can be challenging. It was an obj ect of the present disclosure to provide a fungicidal formulation which overcomes these challenges.SUMMARY
[0004] The present disclosure provides pesticidal formulations with low moisture content that comprise compounds of Formula I, and also pesticidal formulations the comprisingcompound of Formula I and at least one dehydrating agent. The disclosure also relates to processes for the preparation of these formulations, and to their use in the treatment and control of fungal diseases or disorders in agriculture.
[0005] In some aspects of the disclosure herein provide fungicidal formulations comprising a fungicidal compound of Formula I:Formula I or an acceptable salt, solvate, or hydrate thereof, and at least one dehydrating agent.
[0006] In some aspects of the disclosure herein provide fungicidal formulations comprising an acceptable fungicidal salt of a compound of Formula I and at least one dehydrating agent, wherein the acceptable fungicidal salts of Formula I include but not limited to hydrochloride, hydrobromide, sulfate, phosphate, trifluoroacetate, formate, citrate, maleate, oxalate, tartrate, fumarate, or combinations thereof.
[0007] In some aspects of the disclosure herein provide fungicidal formulations comprising an acceptable fungicidal salt of a compound of Formula I and at least one dehydrating agent, wherein the acceptable fungicidal salt of Formula I is the hydrochloride salt (Formula I-B):Formula I-B
[0008] Applicants have found that formulations comprising compounds of Formula I, or an acceptable salt, solvate, or hydrate thereof, and at least one dehydrating agent, disclosed in the present disclosure exhibit fungicidal activity against damage caused by agriculturally relevant fungi. In some aspects, the acceptable fungicidal salt of Formula I is the hydrochloride salt (Formula I-B).
[0009] Throughout the disclosure, reference to the compounds of Formula I is read as also including all acceptable salts, solvates, hydrates, and mixtures thereof; reference to the compounds of Formula I-B is read as also including all solvates, hydrates, and mixtures thereof.
[0010] Throughout the disclosure, reference to the compounds of Formula I and Formula I-B is read as also including all regioisomers, structural isomers, geometrical isomers, rotational isomers, tautomers, and stereoisomers, for example diastereomers, enantiomers, and mixtures thereof.
[0011] The compounds of Formula I and Formula I-B may also contain linkages (e.g., carbon-carbon bonds) wherein bond rotation is restricted about that particular linkage e.g., restriction resulting from the presence of a ring or a double bond. Accordingly, any cis / trans and E / Z isomers are expressly included in the present disclosure.
[0012] The compounds of Formula I and Formula I-B may also be present in multiple tautomeric forms. Where one or more tautomeric forms exist, the disclosure expressly includes all such tautomeric forms of the compounds described herein, even though only a single tautomeric form may be represented.
[0013] The compounds of Formula I and Formula I-B may exist in one or more crystalline or polymorphic forms. All crystalline forms and polymorphs of the compounds of the disclosure are expressly included in the present disclosure.
[0014] Surprisingly, substances typically used as dehydrating agents have shown capabilities of stabilizing the compound of Formula I or Formula I-B in some fungicidal formulations.
[0015] Also surprisingly, some fungicidal formulations comprising the compound of Formula I or Formula I-B show improved stability when the moisture content in such fungicidal formulations decreases.
[0016] In some aspects, the pesticidal formulation with low moisture content that comprises the compounds of Formula I may be present in suspended, emulsified, dissolved, or solid form. In some aspects, the pesticidal formulation with low moisture content that comprises compounds of Formula I-B may be present in suspended, emulsified, dissolved, or solid form. Exemplary formulations include, but are not limited to, soluble liquid concentrates, oil suspensions, emulsifiable concentrates, self-emulsifying formulations, pastes, gels, powders, dusts, granules, water-dispersible granules, wettable granules, wettable powders, and materials for spreading.
[0017] In some aspects, the pesticidal formulation comprising the compounds of Formula I and at least one dehydrating agent may be present in suspended, emulsified, dissolved, or solid form. In some aspects, the pesticidal formulation comprising the compounds of Formula I-B and at least one dehydrating agent may be present in suspended, emulsified, dissolved, or solid form. Exemplary formulations include, but are not limited to, soluble liquid concentrates, aqueous suspension concentrates, oil-in-water emulsions, oil-in-water microemulsions, aqueous suspo-emulsions, water-in-oil emulsion, water-in-oil microemulsions, oil suspensions, emulsifiable concentrates, self-emulsifying formulations, pastes, gels, powders, dusts, granules, water-dispersible granules, wettable granules, wettable powders, and materials for spreading.
[0018] In some aspects, the compound of Formula I may be present in a liquid formulation at a concentration from 0.006 to 1000 gram active ingredient per liter (g ai / L) of the liquid formulation. In some aspects, the pesticidal formulation comprises the compound of Formula I-B present in a liquid formulation at a concentration from 0.006 to 1000 gram active ingredient per liter (g ai / L) of the liquid formulation.
[0019] In some preferred aspects, the fungicidal formulation with low moisture content that comprises the compounds of Formula I can be provided in the form of liquid formulation. In some more preferred aspects, the fungicidal formulation with low moisture content that comprises the compounds of Formula I is provided in the form of emulsifiable concentrate (EC).
[0020] In some preferred aspects, the fungicidal formulation with low moisture content that comprises the compounds of Formula I-B can be provided in the form of liquid formulation. In some more preferred aspects, the fungicidal formulation with low moisture content that comprises the compounds of Formula I-B is provided in the form of emulsifiable concentrate (EC).
[0021] More surprisingly, substances typically used as dehydrating agents have shown capabilities of stabilizing compounds of Formula I or Formula I-B in fungicidal formulations in the form of emulsifiable concentrate (EC) or oil-in-water emulsion (EW).
[0022] In some preferred aspects, the fungicidal formulation comprising the compounds of Formula I and at least one dehydrating agent can be provided in the form of liquid formulation. In some more preferred aspects, the fungicidal formulation comprising the compounds ofFormula I and at least one dehydrating agent is provided in the form of emulsifiable concentrate (EC) or oil-in-water emulsion (EW).
[0023] In some preferred aspects, the fungicidal formulation comprising the compounds of Formula I-B and at least one dehydrating agent can be provided in the form of liquid formulation. In some more preferred aspects, the fungicidal formulation comprising the compounds of Formula I-B and at least one dehydrating agent is provided in the form of emulsifiable concentrate (EC) or oil-in-water emulsion (EW).
[0024] In some more preferred aspects, the fungicidal formulation of the present disclosure comprises the compounds of Formula I and at least one dehydrating agent, wherein the fungicidal formulation is in the form of emulsifiable concentrate (EC). In some alternatively more preferred aspects, the fungicidal formulation of the present disclosure comprises the compounds of Formula I-B and at least one dehydrating agent, wherein the fungicidal formulation is in the form of oil-in-water emulsion (EW).
[0025] In some aspects, the fungicidal formulation of the present disclosure comprises the compounds of Formula I, one or more additional pesticide active ingredients, and at least one dehydrating agent. The preferred additional pesticide active ingredients are fungicides including fenpicoxamid, florylpicoxamid, and metarylpicoxamid. The preferred additional fungicide is florylpicoxamid.
[0026] The description below sets forth details of one or more aspect of the present disclosure. Other features, objects, and advantages will be apparent from the description and from the claims.DETAILED DESCRIPTION
[0027] The present disclosure includes pesticidal formulations with low moisture content that comprise compounds of Formula I, and also pesticidal formulations the comprising compound of Formula I and at least one dehydrating agent. The present disclosure also includes methods of the preparation and use of pesticidal formulations disclosed herein to treat and control fungal diseases or disorders in agriculture.I. Definitions
[0028] Terms used herein will have their customary meaning in the art unless specified otherwise. The use of the terms “a”, “an”, “the”, “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to beconstrued to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. To the extent that the term "or" is employed (e.g., A or B) it is intended to mean "A orB or both." If this disclosure intends to indicate "only A or B but not both" then the term "only A or B but not both" will be employed. Thus, use of the term "or" herein is the inclusive and not the exclusive use. The term "about" when referring to a number or a numerical range means that the number or numerical range referred to is an approximation within experimental variability (or within statistical experimental error), and thus the number or numerical range, in some instances, will vary between 1% and 15% of the stated number or numerical range. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
[0029] The chemical moieties mentioned when defining variable positions within the general formulae described herein (e.g. , the term “alkyl”) are collective terms for the individual substituents encompassed by the chemical moiety. The prefix Cn-Cm preceding a group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows.
[0030] As used herein, the terms “pesticide” and “pesticidal active ingredient” refer to an active ingredient that controls or decreases the fitness (e.g., kills or inhibits the growth, proliferation, division, reproduction, or spread) of an agricultural, environmental, or domestic / household pest, such as an undesirable vegetation, insect, mollusk, nematode, fungus, bacterium, or virus. Pesticides are understood to encompass naturally occurring orsynthetic herbicides, fungicides, insecticides, insect growth regulators, acaricides (miticides), molluscicides, nematicides, ectoparasiticides, or bactericides. The terms “pesticide” and “pesticidal active ingredient” as used herein include fungicides and fungicidal active ingredients.
[0031] As used herein, the terms “fungicide,” “fungicidal chemical,” and “fungicidal active ingredient” may be understood to include an active ingredient that kills, controls, or otherwise adversely modifies the growth of agriculturally relevant fungi, when applied in an appropriate amount.
[0032] As used herein, the term “pesticidal formulation” may be understood to include compositions that comprise at least one pesticide and at least one additional component. A pesticidal formulation is understood to include a “fungicidal formulation”.
[0033] As used herein, the terms “fungicidal formulation” or “formulation” may be understood to include compositions that comprise at least one fungicide and at least one additional component. The additional component may be a solvent, a diluent, a carrier, an adjuvant, a surfactant, a dispersant, a chemical stabilizer, a physical stabilizer, an anti-foam agent, an emulsifier, an antifreeze agent, a dye or colorant, or other such component. The additional component may be another fungicide or another agricultural chemical, such as an insecticide, a fungicide, a fertilizer, a nematocide, a miticide, an arthropodicide, a bactericide, a plant growth regulator, or combinations thereof that are compatible with the formulations of the present disclosure.
[0034] As used herein, the terms “pesticidal formulation(s) with low moisture content,” “pesticidal formulation(s) with low water content,” “fungicidal formulation(s) with low moisture content,” and “fungicidal formulation(s) with low water content” refer to pesticidal or fungicidal formulation(s) that contain water at no more than 5% in weight percent based on the total weight of the formulation, preferably at no more than 2.5% in weight percent based on the total weight of the formulation, more preferably at no more than 1% in weight percent based on the total weight of the formulation, most preferably at no more than 0.5% in weight percent based on the total weight of the formulation, particularly preferably at no more than 0.1% in weight percent based on the total weight of the formulation.
[0035] As used herein, the term “tank mix” may be understood to refer to a fungicidal mixture prepared from the formulation disclosed herein by the end user, by diluting the formulation, adding other ingredients and additives, mixing the formulation ingredients, orother such activities before application. The end user may then apply the tank mix, as-is or with other additives, to the seed, the area adjacent to the plant, soil adapted to support growth of the plant, the root of the plant, and / or foliage of the plant.
[0036] As used herein, the term “adjuvant” may be understood to include additives to the formulation or tank mix that, while having no fungicidal effect in themselves, help to stabilize, improve, or otherwise enhance the fungicidal effect of the fungicidal active ingredient. For example, adjuvants may be surfactants that enhance the absorption of the fungicidal active ingredient into the plant. Adjuvants may be added to the formulation, or adjuvants may be added to the fungicidal tank mix by the end user prior to application of the tank mix. Adjuvants may also be included in the fungicidal formulation, in which case the adjuvant may be referred to as a “built-in adjuvant.”
[0037] As used herein, the term "applying" a fungicide or fungicidal formulation refers to delivering the fungicide or fungicidal formulation directly to the seed, the area adjacent to the plant, soil adapted to support growth of the plant, the root of the plant, and / or foliage of the plant, where control of fungal pathogens or diseases is desired.
[0038] As used herein, the term “vegetation” can include, for instance, dormant seeds, germinating seeds, emerging seedlings, plants propagating from vegetative propagules, immature vegetation, and established vegetation.
[0039] As used herein, the term "crop" refers to desired vegetation, for instance, plants that are grown to provide food, shelter, pasture, erosion control, etc. Example crops include row crops, maize, soy, canola, cotton, pulses, sunflower, sugar beet, wheat, barley, rice, sorghum, millet, oats, flax, cereals, legumes, vegetables, orchard and timber trees, grapevines, etc. Preferably, fungicides or fungicidal compositions have zero or minimal negative effect on crops.
[0040] As used herein, the terms "active ingredient" or "ai" may be understood to include a chemical compound or composition that has an effect on fungal pathogens or diseases. The term “active ingredient” or “ai” may also be used in expressions relating concentrations or applications rates, such as “grams active ingredient per hectare” or “g ai / ha” to clarify that the amount of the ingredient is measured as the compound as-is, including salts, esters, N-oxides, solvates, hydrates, etc.
[0001] As used herein, "acid equivalent" or "ae" may be understood to include the amount of the acid form of an active ingredient that is calculated from the amount of a salt, ester, N-oxide, solvates, or hydrate form of that active ingredient. For example, if the acid form of an active ingredient "Z " has a molecular weight of 100 Dalton, and the salt form of Z has a molecular weight of 130 Dalton, an application of 130 g ai / ha of the Z salt would be equal to applying 100 g ae / ha of the acid form of Z :130 g ai / ha Z salt * (100 Da Z acid / 130 Da Z salt) = 100 g ae / ha Z acid.The term “acid equivalent” or “ae” may also be used in expressions relating concentrations or applications rates, such as “grams acid equivalent per hectare” or “g ae / ha” to clarify that the amount of the ingredient is measured as the acid form of the compound, corrected to eliminate the mass contribution of associated salts, esters, N-oxides, solvates, hydrates, etc.
[0042] As used herein, “organic liquid” or “organic solvent” may be understood to refer to organic compounds (that is, compounds comprising carbon atoms) that are liquid at most or all typical ambient outdoor temperatures, such as from about -10 °C to 55 °C, about 0 °C to 40 °C, about 5 °C to about 50 °C, or about 8 °C to 38 °C. Organic liquids are frequently, although not always, hydrophobic and immiscible in water or aqueous liquids. It should be understood that the term “organic solvent” does not necessarily imply that any material mixed into the organic solvent dissolves in the organic solvent.
[0043] As used herein, “agriculturally acceptable salts, solvates, and hydrates” may be understood to include salts, solvates, and hydrates that exhibit fungicidal activity, or that are or can be converted in plants, water, or soil to the referenced fungicide.
[0044] As used herein, the terms “formulation” or “composition” refer to a mixture comprising at least one fungicide, and also comprising other ingredients used to enhance the properties or effectiveness of the mixture in some way. The other ingredients may include, but are not limited to, diluents, surfactants, adjuvants, anti-foam agents, emulsifiers, colorants, dispersants, antifreeze agents, and other such ingredients.
[0045] As used herein, the term “locus”, refers to the area in which the vegetation or plants are growing or will grow, typically a field.
[0046] As used herein, the term “dehydrating agent”, refers to substances that are used to absorb and remove water from gases or liquids. Examples of dehydrating agents include, but not limited to, activated alumina, activated carbon, benzophenone, clay, calcium salts (including, but not limited to, calcium chloride, calcium hydride, and calcium sulfate), carbodiimides, cobalt(II) chloride, copper sulfate, lithium salts (including, but not limited to, lithium chloride and lithium bromide), magnesium salts (including, but not limited to,magnesium chloride, magnesium sulfate, and magnesium perchlorate), metal hydroxides (including, but not limited to, potassium hydroxide and sodium hydroxide), metal oxides (including, but not limited to, calcium oxide, magnesium oxide, potassium oxide, and sodium oxide), molecular sieves (including, but not limited to, synthetic and natural zeolite materials), phosphorus pentoxide, potassium salts (including, but not limited to, potassium carbonate and potassium chloride), rice, silica gel, sodium salts (including, but not limited to, sodium chlorate, sodium chloride, and sodium sulfate), ion exchange resins, sucrose, sulfuric acid, and triethylene glycol.
[0047] As used herein, “carbodiimide” refers to compounds having the structure of R1N=C=NR2, wherein R1and R2are independently selected from the group consisting of H, (Ci-Cie)-alkyl, (C3-Cio)-cycloalkyl, (hetero)aryl, and substituted (hetero)aryl. Preferably, R1and R2are independently selected from the group consisting of (Ci-Cs)-alkyl, (C3-C10)- cycloalkyl, phenyl, and substituted phenyl. More preferably, R1and R2are independently selected from the group consisting of (Ci-Cs)-alkyl, (C3-Cs)-cycloalkyl, and substituted phenyl. Most preferably, R1and R2are the same group and selected from the group consisting of (Ci- Cs)-alkyl, (C3-Cs)-cycloalkyl, and phenyl that is substituted with at least one (Ci-Cs)-alkyl. Examples of carbodiimides include, but not limited to, A A-dicyclohexylcarbodiimide, N,N'~ diisopropylcarbodiimide, l-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and bis(2,6- diisopropylphenyl)carbodiimide.
[0048] As used herein, unless otherwise specified, “acyl” refers to formyl, C1-C3 alkylcarbonyl, and C1-C3 haloalkylcarbonyl. Ci-Ce acyl refers to formyl, C1-C5 alkylcarbonyl, and C1-C5 haloalkylcarbonyl (the acyl group contains a total of 1 to 6 carbon atoms).
[0049] As used herein, “alkyl” refers to saturated, straight-chained or branched saturated hydrocarbon moieties. Unless otherwise specified, C1-C16 alkyl groups are intended. Examples include methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1- dimethyl-ethyl, pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl- pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 1,3- dimethyl-butyl, 2,2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1 -ethyl -butyl, 2- ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl, 1 -ethyl- 1-methyl-propyl, and 1- ethyl-2-methyl-propyl.
[0050] As used herein, “haloalkyl” refers to straight-chained or branched alkyl groups, where in these groups the hydrogen atoms may be substituted partially or entirely with halogen atoms. Unless otherwise specified, C1-C16 groups are intended. Examples include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluorom ethyl, chlorofluoromethyl, di chlorofluoromethyl, chlorodifluoromethyl, 1- chloroethyl, 1 -bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- trichloroethyl, pentafluoroethyl, and l,l,l-trifluoroprop-2-yl.
[0051] As used herein, “alkenyl” refers to unsaturated, straight-chained, or branched hydrocarbon moieties containing a double bond. Unless otherwise specified, C3-C16 alkenyl are intended. Alkenyl groups may contain more than one unsaturated bond. Examples include ethenyl, 1 -propenyl, 2-propenyl, 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl- 1 -propenyl, 2-methyl-l -propenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2- pentenyl, 3 -pentenyl, 4-pentenyl, 1 -methyl- 1-butenyl, 2-methyl-l-butenyl, 3 -methyl- 1- butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2- methyl-3-butenyl, 3-methyl-3-butenyl, l,l-dimethyl-2-propenyl, 1,2-dimethyl-l -propenyl, l,2-dimethyl-2-propenyl, 1 -ethyl- 1 -propenyl, l-ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3- hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl- 1 -pentenyl, 2-m ethyl- 1 -pentenyl, 3 -methyl- 1- pentenyl, 4-methyl-l -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, l-methyl-3 -pentenyl, 2-methyl-3 -pentenyl, 3-methyl-3- pentenyl, 4-methyl-3 -pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4- pentenyl, 4-methyl-4-pentenyl, l,l-dimethyl-2-butenyl, l,l-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, l,2-dimethyl-2-butenyl, l,2-dimethyl-3-butenyl, 1,3 -dimethyl- 1-butenyl, 1,3- dimethyl-2-butenyl, l,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3 -dimethyl- 1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl- 1-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl- 1-butenyl, 2-ethyl-2- butenyl, 2-ethyl-3-butenyl, l,l,2-trimethyl-2-propenyl, 1 -ethyl- l-methyl-2-propenyl, 1-ethyl-2-methyl-l -propenyl, and l-ethyl-2-methyl-2-propenyl. Vinyl refers to a group having the strutcture -CEUCH2; 1 -propenyl refers to a group with the structure-CEUCH-CEE; and 2- propenyl refers to a group with the structure -CH2-CEUCH2.
[0052] As used herein, “alkynyl” represents straight-chained or branched hydrocarbon moieties containing a triple bond. Unless otherwise specified, C3-C16 alkynyl groups are intended. Alkynyl groups may contain more than one unsaturated bond. Examples include C2-Ce-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3- butynyl, l-methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3 -pentynyl, 4-pentynyl, 3 -methyl- 1- butynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l,l-dimethyl-2- propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3- m ethyl- 1 -pentynyl, 4-methyl-l -pentynyl, l-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1- methyl-3 -pentynyl, 2-methyl-3 -pentynyl, l-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3- methyl-4-pentynyl, l,l-dimethyl-2-butynyl, l,l-dimethyl-3-butynyl, l,2-dimethyl-3-butynyl,2.2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2- ethyl-3-butynyl, and 1 -ethyl- l-methyl-2-propynyl.
[0053] As used herein, “alkoxy” refers to a group of the formula R-O-, where R is alkyl as defined above. Unless otherwise specified, alkoxy groups wherein R is a Ci-Cio alkyl group are intended. Examples include methoxy, ethoxy, propoxy, 1 -methyl-ethoxy, butoxy, 1- methyl-propoxy, 2-methyl-propoxy, 1,1 -dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2- methyl-butoxy, 3-methyl-butoxy, 2,2-dimethyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1- dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy, 3-methyl- pentoxy, 4-methyl-pentoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy,2.2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethyl- butoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1 -ethyl- 1-methyl-propoxy, and 1- ethyl-2-methyl-propoxy.
[0054] As used herein, “haloalkoxy” refers to a group of the formula R-O-, where R is haloalkyl as defined above. Unless otherwise specified, haloalkoxy groups wherein R is a Ci- Cio alkyl group are intended. Examples include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, di chlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1- bromoethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2- chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2- trichloroethoxy, pentafluoroethoxy, and l,l,l-trifluoroprop-2-oxy.
[0055] As used herein, “alkylthio” refers to a group of the formula R-S- where R is alkyl as defined above. Unless otherwise specified, alkylthio groups wherein R is a Ci-Cio alkyl group are intended. Examples include methylthio, ethylthio, propylthio, 1 -methylethylthio, butylthio, 1-methyl-propylthio, 2-m ethylpropylthio, 1,1 -dimethylethylthio, pentylthio, 1- methylbutylthio, 2-m ethylbutylthio, 3 -methylbutylthio, 2,2-dimethylpropylthio, 1- ethylpropylthio, hexylthio, 1,1 -dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3 -methylpentylthio, 4-methylpentylthio, 1,1- dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3- dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2- trimethylpropylthio, 1,2,2-trimethylpropylthio, 1 -ethyl- 1 -methylpropylthio, and l-ethyl-2- methylpropylthio.
[0056] As used herein, “haloalkylthio” refers to an alkylthio group as defined above wherein the carbon atoms are substituted partially or entirely with halogen atoms. Unless otherwise specified, haloalkylthio groups wherein R is a Ci-Cs alkyl group are intended. Examples include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chi orofluorom ethylthio, dichlorofluorom ethylthio, chi orodifluorom ethylthio, 1- chloroethylthio, 1 -bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2- dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and 1,1,1- trifluoroprop-2-ylthio.
[0057] As used herein, “aryl”, as well as derivative terms such as aryloxy, refers to a phenyl, indanyl or naphthyl group with phenyl being preferred. The term heteroaryl, as well as derivative terms such as heteroaryloxy, refers to a 5- or 6-membered aromatic ring containing one or more heteroatoms, viz., N, O or S; these aromatic and heteroaromatic rings may be fused to other aromatic and / or heteroaromatic systems. The aryl or heteroaryl substituents may be unsubstituted or substituted with one or more substituents selected from halogen, hydroxy, nitro, cyano, formyl, Ci-Ce alkyl, C2-C6 alkenyl, C2-C6 alkynyl, Ci-Ce alkoxy, Ci-Ce haloalkyl, Ci-Ce haloalkoxy, Ci-Ce acyl, Ci-Ce alkylthio, Ci-Ce alkylsulfinyl, Ci-Ce alkylsulfonyl, Ci-Ce alkoxycarbonyl, Ci-Ce (thio)carbamoyl, hydroxycarbonyl, Ci-Ce alkylcarbonyl, aminocarbonyl, Ci-Ce alkylaminocarbonyl, Ci-Ce dialkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.
[0058] As used herein, “alkylcarbonyl” refers to an alkyl group bonded to a carbonyl group. C1-C3 alkylcarbonyl and C1-C3 haloalkylcarbonyl refer to groups wherein a C1-C3 alkyl group is bonded to a carbonyl group (the group contains a total of 2 to 4 carbon atoms).0
[0059] As used herein, “alkoxy carbonyl” refers to a group of the formulawherein R is alkyl.
[0060] As used herein, “arylalkyl” refers to an alkyl group substituted with an aryl group. For example, “C7-C10 arylalkyl” refers to a group wherein the total number of carbon atoms in the group is 7 to 10.
[0061] As used herein, “alkylamino” refers to an amino group substituted with one or two alkyl groups, which may be the same or different.
[0062] As used herein, “haloalkylamino” refers to an alkylamino group wherein the alkyl carbon atoms are substituted partially or entirely with halogen atoms.
[0063] As used herein, “Ci-Ce alkylaminocarbonyl” refers to a group of the formula RNHC(O)- wherein R is Ci-Ce alkyl, and Ci-Ce dialkylaminocarbonyl refers to a group of the formula R2NC(O)- wherein each R is independently Ci-Ce alkyl.
[0064] As used herein, “alkylcarbamyl” refers to a carbamyl group substituted on the nitrogen with an alkyl group.O ll— S-RII
[0065] As used herein, “alkyl-sulfonyl” refers to a group of the formula O , where R is alkyl.
[0066] As used herein, “carbamyl” (also referred to as carbamoyl and aminocarbonyl) o refers to a group of the formulao11— P- OR
[0067] As used herein, “dialkylphosphonyl” refers to a group of the formula OR where R is independently alkyl in each occurrence.
[0068] As used herein, “Ci-Ce trialkyl silyl” refers to a group of the formula -SiRs wherein each R is independently a Ci-Ce alkyl group (the group contains a total of 3 to 18 carbon atoms).
[0069] As used herein, “Me” refers to a methyl group; “OMe” refers to a methoxy group; and “i-Pr” refers to an isopropyl group.
[0070] As used herein, the term “halogen” including derivative terms such as halo refers to fluorine, chlorine, bromine and iodine.
[0071] Substituted groups may be selected from any of the groups disclosed herein and / or any functional groups generally known in the art of organic chemistry.II. Aryl Amidines Pesticides
[0072] Formulations and methods of the present disclosure include pesticidal formulations comprising a compound of Formula I and at least one dehydrating agent to control fungal pathogens and diseases in various locations, such as croplands, orchards, lawns, pastures, gardens, and recreational areas. Also disclosed herein are pesticidal formulations comprising a compound of Formula I-B and at least one dehydrating agent to control fungal pathogens and diseases in various locations, such as croplands, orchards, lawns, pastures, gardens, and recreational areas.
[0073] In some aspects of the disclosure herein provide fungicidal formulations comprising a fungicidal compound of the Formula I:Formula I or an acceptable salt, solvate, or hydrate thereof, and at least one dehydrating agent.
[0074] In some aspects of the disclosure herein provide fungicidal formulations comprising an acceptable fungicidal salt of a compound of Formula I, where the acceptable fungicidal salts of Formula I include but not limited to hydrochloride, hydrobromide, sulfate, phosphate, trifluoroacetate, formate, citrate, maleate, oxalate, tartrate, fumarate, or combinations thereof.[0075 J In some aspects of the disclosure herein provide fungicidal formulations comprising an acceptable fungicidal salt of a compound of Formula I and at least one dehydrating agent, wherein the acceptable fungicidal salts of Formula I is the hydrochloride salt (Formula I-B):Formula I-B
[0076] In some aspects, the formulations comprise, in weight percent based on the total weight of the formulation, from about 0.1% to about 99% of the compound of Formula I or Formula I-B (e.g., about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, , 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 82.5%, 85%, 87.5%, 90%, 92.5%, or 95% of the compound of Formula I or Formula I-B), or within any range defined from any two of the forgoing values, such as from about 1% to about 95%, from about 10% to about 60%, from about 20% to about 45%, from about 55% to about 82.5%, or from about 12.5% to about 50% of the compound of Formula I or Formula I-B, by weight percent based on the total weight of the formulation. In some aspects, the formulations comprise, in grams active ingredient per liter (g ai / L) of the formulation, a concentration from about 1 g ai / L to about 850 g ai / L of the compound of Formula I or Formula I-B (e.g., about 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 12.5, 15, 17.5, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 110, 112, 115, 117, 120, 125, 130, 140, 150, 160, 170, 175, 180, 190, 200, 210, 215, 220, 225, 230, 240, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 800, or 850 g ai / L of the compound of Formula I or Formula I-B), or within any range defined from any two of the forgoing values, such as from about 1 g ai / L to about 750 g ai / L, from about 1 g ai / L to about 600 g ai / L, from about 1 g ai / L to about 500 g ai / L, from about 1 g ai / L to about 450 g ai / L, from about 10 g ai / L to about 350 g ai / L, from about 20 g ai / L to about 150 g ai / L, or from about 112 g ai / L to about 250 g ai / L of the compound of Formula I or Formula LB.
[0077] In some preferred aspects, the formulations comprise, in weight percent based on the total weight of the formulation, from about 0.1% to about 99% of the compound of Formula I (e.g., about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, , 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 82.5%, 85%, 87.5%, 90%, 92.5%, or 95% of the compound of Formula I), or within any range defined from any two of the forgoing values, such as from about 1% to about 95%, from about 10% to about 60%, from about 20% to about 45%, from about 55% to about 82.5%, or from about 12.5% to about 50% of the compound of Formula I, by weight percent based on the total weight of the formulation. In some aspects, the formulations comprise, in grams active ingredient per liter (g ai / L) of the formulation, a concentration from about 1 g ai / L to about 850 g ai / L of the compound of Formula I (e.g., about 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 12.5, 15, 17.5, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 110, 112, 115, 117, 120, 125, 130,140, 150, 160, 170, 175, 180, 190, 200, 210, 215, 220, 225, 230, 240, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 800, or 850 g ai / L of the compound of Formula I), or within any range defined from any two of the forgoing values, such as from about 1 g ai / L to about 750 g ai / L, from about 1 g ai / L to about 600 g ai / L, from about 1 g ai / L to about 500 g ai / L, from about 1 g ai / L to about 450 g ai / L, from about 10 g ai / L to about 350 g ai / L, from about 20 g ai / L to about 150 g ai / L, or from about 112 g ai / L to about 250 g ai / L of the compound of Formula I.III. Formulations
[0078] The present disclosure provides pesticidal formulations with low moisture content that comprise compounds of Formula I, and also pesticidal formulations the comprising compound of Formula I and at least one dehydrating agent. The disclosure also relates to processes for the preparation of these formulations, and to their use in the treatment and control of fungal diseases or disorders in agriculture.; and methods of use of the pesticidal formulation disclosed herein to control fungal pathogens and diseases.A. Physical States
[0079] In some aspects, the pesticidal formulation of compounds of Formula I with low moisture content may be present in suspended, emulsified, dissolved, or solid form. Exemplary formulations include, but are not limited to, soluble liquid concentrates, oil suspensions, emulsifiable concentrates, self-emulsifying formulations, pastes, gels, powders, dusts, granules, water-dispersible granules, wettable granules, wettable powders, and materials for spreading. A comprehensive list of formulation types with official definitions is available from CropLife International (croplife.org / wp-content / uploads / 2017 / 04 / Technical-Monograph-2- 7th-Edition-Revi sed-March-2017.pdf) .
[0080] In some aspects, the pesticidal formulation of compounds of Formula I and at least one dehydrating agent, may be present in suspended, emulsified, dissolved, or solid form. Exemplary formulations include, but are not limited to, soluble liquid concentrates, aqueous suspension concentrates, oil-in-water emulsions, oil-in-water microemulsions, aqueous suspo- emulsions, water-in-oil emulsion, water-in-oil microemulsions, oil suspensions, emulsifiable concentrates, self-emulsifying formulations, pastes, gels, powders, dusts, granules, water- dispersible granules, wettable granules, wettable powders, and materials for spreading. A comprehensive list of formulation types with official definitions is available from CropLifeInternational (croplife.org / wp-content / uploads / 2017 / 04 / Technical-Monograph-2-7th-Edition- Revi sed-March-2017. pdf) .
[0081] In some aspects, the pesticidal formulation is a liquid formulation that can be diluted before use. Exemplary liquid formulations include, but are not limited to, soluble liquid concentrates, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, microemulsions, suspension concentrates, capsule suspensions, suspo-emulsions, oil dispersions. The liquid formulation may be diluted with a carrier such as water by the end user, and then applied by the end user as needed. Exemplary liquid formulations with low moisture content include, but are not limited to, soluble liquid concentrates, emulsifiable concentrates, and oil dispersions.
[0082] Soluble liquid concentrates are liquid, homogenous formulations in water or one or more water miscible solvent or their mixtures that become homogenous solution when diluted with water or a liquid by the end user. Emulsifiable concentrates are liquid, homogeneous formulations in hydrophobic organic liquids that become oil-in-water emulsions when diluted with water or an aqueous liquid by the end user. Emulsions are two-phase (or more phases) liquid mixtures containing two or more immiscible liquid phases, with fine droplets of one immiscible liquid dispersed in a continuous phase of the other immiscible liquid. The diluted emulsion is then applied by the end user as needed. Oil-in-water emulsions are liquid, heterogeneous formulations containing an organic liquid dispersed as fine droplets in a continuous water or aqueous liquid phase. In one aspect, the fungicide may be dissolved or dispersed in the organic liquid droplets dispersed in an oil-in-water emulsion. In another aspect, the fungicide may be dissolved or dispersed in the continuous water or aqueous liquid phase of an oil-in-water emulsion. Water-in-oil emulsions are liquid, heterogeneous formulations containing water or an aqueous liquid dispersed as fine droplets in a continuous hydrophobic organic liquid phase. In one aspect, the fungicide may be dissolved or dispersed in the water or aqueous liquid droplets dispersed in a water-in-oil emulsion. In another aspect, the fungicide may be dissolved or dispersed in the continuous organic liquid phase of a water-in-oil emulsion. Multi-phase emulsions, such as water-in-oil-in-water emulsions, are also known. The size of the dispersed droplets in these emulsions (also called “conventional emulsions”) is typically in the range of about 0.1 to 100 pm in diameter. A microemulsion is a clear to opalescent liquid containing both organic liquid and water or an aqueous liquid. The microemulsion may be oil- in-water or water-in-oil emulsions, where the dispersed globules are very small, typically less than 1 pm or less than 0.1 pm. Microemulsions differ from conventional emulsions in that: a)the droplet size in microemulsions is smaller; b) microemulsions are typically clear or opalescent, whereas conventional emulsions are cloudy or milky; and c) microemulsions are thermodynamically stable and remain dispersed, whereas conventional emulsions are kinetically stable but thermodynamically unstable, and typically require mixing energy, such as high-shear mixing, to maintain the emulsion droplets dispersed within the continuous liquid phase.
[0083] Formulations with low moisture content that comprise compounds of Formula I or Formula I-B, and also formulations comprising compound of Formula I or Formula I-B and at least one dehydrating agent, may be emulsifiable concentrates, where the compound of Formula I or Formula I-B, is dissolved in one or more organic liquid(s) or solvent(s). The emulsifiable concentrate forms an oil-in-water emulsion when diluted with water before use. The emulsifiable concentrate (EC) formulation may also include one or more emulsifiers, and optionally, one or more co-solvent(s), built-in adjuvant(s), antifoam agent(s), or other components.
[0084] Suitable organic solvents for forming emulsifiable concentrates of the compound ofFormula I, or an acceptable salt, solvate, or hydrate thereof, include, but are not limited to: long-chain alkyl amides, such as N,N-dimethylalkyl amide, Agnique® AMD 810 or Agnique AMD 10 (Agnique® is a registered trademark of BASF Corporation, Florham Park, NJ, USA), Hallcomid® M-10 or Hallcomid® M-8-10 or Hallcomid M8-10 Ultra or Hallcomid-M-12-14 or Hallocmid-M-12 (Hallcomid® is a registered trademark of Stepan Company, Northfield, Illinois, USA), Genagen PA or Genagen® 4166 (Genagen® is a registered trademark of Clariant Produkte (Deutschland) GmbH, Frankfurt am Main, Germany) or Armid® DM810 (Armid® is a registered trademark of Nouryon, Amsterdam, Netherlands); methylated seed oils, such as Agnique® 610 U, Agnique® ME18 RD-F, Agnique® ME18 S-U, Agnique® ME 2337 , or Agnique® ME 1218; fatty acid or triglyceride esters, such as Steposol® ME, Steposol® C-48, Stepan® C-25, Stepan® 108 (Steposol® and Stepan® are registered trademarks of Stepan Company, Northfield, Illinois, USA); fatty acid morpholine amide, such as Jeffsol® AG 1730 (Jeffsol® is a registered trademark of Huntsman Petrochemical Corporation, Salt Lake City, Utah, USA); ketones such as 2-heptanone, cyclopentanone, acetophenone, or Cyrene® (Cyrene® is a registered trademark of Circa Group Pty Ltd, Coburg, Victoria, Australia); or phosphate triesters, such as DisflamollTOF (Disflamoll® is a registered trademark of Lanxess Corporation, Pittsburgh, PA, USA), or Amgard® TBEP (Amgard® is a trademark of Syensqo S.A., Brussels, Belgium); aromatic solvents, such as Aromatic 100,Aromatic 150, Aromatic 150 ND, Aromatic 200, or Aromatic 200 ND (Aromatic solvents are available from ExxonMobil Chemical Company, Spring, TX, USA), or Solvesso™ 100, or Solvesso™ 150, Solvesso™ 150ND, Solvesso™ 200, Solvesso™ 200ND (Solvesso™ is a trademark of ExxonMobil Chemical Company, Spring, TX, USA); or aliphatic / paraffinic oils, such as Isopar® M, Isopar N, or Exxsol® DI 30 (Isopar®, and Exxsol® are trademarks of ExxonMobil Corporation, Irving, Texas, USA); or alkyl alcohol, such as 2-ethylhexanol; alkyl benzoate or dibenzoate, such as Surfonic® AG 1700 (Surfonic® is a trademark of Indorama, The Woodlands, TX, USA) or Zendex® DB-120 (Zendex® is a trademark of Eastman Chemical Company, Kingsport, TN, USA); alkyl lactates, such as Agnique® AE 3-2EH, or Purasolv® EHL (Purasolv® is a registered trademark of Purac Biochem B.V., Gorinchem, Netherlands); ester solvents, such as Rhodiasolv® RPDE (Rhodiasolv® is a trademark of Syensqo S.A., Brussels, Belgium), or benzyl acetate, or triethyl citrate, or Isobomyl acetate, or ethyl 5-methyl-2-furoate; p-anisaldehyde. Suitable co-solvents for the emulsifiable concentrates of the compound of Formula I, or an acceptable salt, solvate, or hydrate thereof, s include, but are not limited to: alkyl pyrrolidone, such as Genagen NBP and Tamisolve® NxG (Tamisolve is a registered trademark of Eastman Chemical Company, Kingsport, TN, USA), l-dodecyl-2-pyrrolidone, or N-octyl-2-pyrrolidione; ether solvents, such as Atlox® Solvall™ BDE l-LQ-(AP) (Atlox® and Solvall™ are trademarks of Croda Inc., Edison, NJ, USA); aprotic glycol ethers, such as Dowanol DPM, or butyl Cellosolve™ solvent, or Carbitol™ solvent, or Proglyde® DMM (Dowanol, Cellosolve™, Carbitol™ and Proglyde® are registered trademarks of Dow Chemical Company, Midland, Michigan, USA); glycol ether acetate, such as Dowanol® PMA; alkanol solvent, such as hexylene glycol; N,N-dimethyl lactamide, such as Agnique® AMD 3L; alkylene carbonates, such as Jeffsol® AG 1505 or Jeffsol® AG 1555; alkyl lactates, such as Purasolv® EL; lactone solvent, such as y- butyrolactone, y-caprolactone, d-valerolactone; cyclohexanone; or diamides and ester amides, such as Rhodiasolv® PolarClean; Augeo® SL191 (Augeo® is a trademark of Syensqo S.A., Brussels, Belgium); ester solvent, such as UCAR™ Filmer IBT (UCAR™ is a trademark of the Dow Chemical Company, Midland, MI, USA); N-formylmorpholine; or benzyl alcohol.
[0085] Suitable emulsifiers include, but are not limited to, non-ionic, anionic, and polymeric emulsifiers. Suitable non-ionic emulsifiers include: ethoxylated castor oil, such as Agnique® CSO-25, Toximul® 8240 (Toximul® is a registered trademark of Stepan Company, Northfield, Illinois, USA), or Etocas™ 29 (Etocas™ is a trademark of Croda International Pic, Goole, East Yorkshire, UK); or ethoxylated fatty alcohols / fatty acids, such as, Makon® DA-6(Makon® is a registered trademark of Stepan Company, Northfield, Illinois, USA), Synperonic® 13 / 12 (Synperonic® is a registered trademark of Croda International Pic, Goole, East Yorkshire, UK), Ecosurf™ SA-4 (Ecosurf™ is a registered trademark of Dow Chemical Company, Midland, Michigan, USA), or Tergitol 15-S-12 (Tergitol® is a registered trademark of Union Carbide Corporation, Midland, Michigan, USA); or alkoxylated fatty alcohols, such as Dehypon® LS 54 (Dehypon® is a registered trademark of BASF Corporation, Mount Olive, New Jersey, USA), Genapol® EP 2552 (Genapol® is a registered trademark of Clariant); or sorbitan ester ethoxylate / alkoxylate, such as Tween® 80 (Tween® is a registered trademark of Croda International Pic, Goole, East Yorkshire, UK); or sorbitan esters, such as Span® 80 (Span® is a registered trademark of Uniqema Americas LLC, Wilmington, Delaware, USA); or polyglycerol ester, such as Break-thru® SP 133 (Break-thru® is a registered trademark of Evonik Operations GmbH, Essen, Germany); or Trisiloxane / Polysiloxane, such as Break- thru® OE 446, Break-thru® S 233, Break-thru® S 240, or Silwet®-L77 (Silwet® is a registered trademark of Momentive). Suitable polymeric emulsifiers include: EO / PO block copolymers, such as Toximul® 8320, Termul® 5500 (Termul® is a registered trademark of Indorama Ventures Oxides LLC, The Woodlands, Texas, USA), Ethylan™ NS-500LQ (Ethylan™ is a trademark of Nouryon Surface Chemistry LLC, Chicago, Illinois, USA), Tergitol® XD (Tergitol® is a registered trademark of Union Carbide Corporation, Midland, Michigan, USA), Pluronic® P-105 (Pluronic® is a registered trademark of BASF Corporation, Mount Olive, New Jersey, USA), or Atlas® G-5002L (Atlas® is a registered trademark of Croda International Pic, Goole, East Yorkshire, UK); or other polymeric surfactants, such as Atlox® 4912 or Atlox® 4914. Suitable anionic emulsifiers include: various salts of dodecylbenzene sulfonates, such as Bio-Soft® N-411 (Bio-Soft® is a registered trademark of Stepan Company, Northfield, Illinois, USA), Nansa® EVM 70 / 2E (Nansa® is a trademark of Innospec Performance Chemicals Europe Ltd, Cheshire, UK); or sodium dioctyl sulfosuccinates, such as Geropon® SDS (Geropon® is a registered trademark of Rhodia Chimie SAS, Aubervilliers, France), Lankropol™ KPH 70 (Lankropol™ is a trademark of Nouryon Surface Chemistry LLC, Chicago, Illinois, USA) , or Aerosol OT (Aerosol OT is available from Syensqo S.A., Brussels, Belgium); or sodium lauryl sulfonates, such as Stepanol® ME Dry (Stepanol® is a registered trademark of Stepan Company, Northfield, Illinois, USA); or phosphate ester, such as STEPFAC™ 8180 (STEPFAC™ is a registered trademark of Stepan Company, Northfield, Illinois, USA), or Rhodafac® RS 610 (Rhodafac® is a registered trademark of Syensqo S.A., Brussels, Belgium). Some emulsifiers can bemultifunctional. For example, some Trisiloxane / Polysiloxane, such as Break-thru® OE 446, Break-thru® S 233, and Break-thru® S 240, are also recognized adjuvants.
[0086] Suitable antifoam agents include polydimethylsiloxanes emulsified in water, such as Foamaster® UDB (Foamaster® is a registered trademark of BASF Corporation, Florham Park, NJ, USA), or SAG™ 1572, or SAG™ 1538, or SAG™ 1599 (SAG™ is a trademark of Momentive Performance materials, Friendly, WV, USA), or Xiameter™ ACP-0001, or Xiameter™ ACP-0100, or Xiameter™ ACP-1400, or Xiameter™ AFE-0010, or Xiameter™ AFE-0300 (Xiameter™ is a trademark of the Dow Chemical Company, Midland, MI, US), or Antifoam 10, or Antifoam 100, or Antifoam 8810 IND, or Antifoam 8830 IND, or Silfar® S 184; or Silfar® SE 4; or Silfoam® SC 132, or Silfoam® SE-23 (Silfar® and Silfoam® are trademarks of Wacker Silicones, Adrian, MI, USA); or Break-thru® AF 9902, or Break-thru® AF 9903, or Break-thru® AF 9905.
[0087] Suitable built-in adjuvants can be any of the agriculturally acceptable adjuvants disclosed herein above. Exemplary built-in adjuvants include: methylated seed oils, including Cl 8 soyate and Cl 8 rapeate, such as Agnique® ME 18 RD-F, Agnique® ME 18 SD-F, Agnique® ME 2337, or Edenor® ME 12-18; non-ionic surfactants, including ethoxylated castor oils such as Agnique® CSO-25, Etocas™ 10, Etocas™ 29, or Etocas™ 40; C16-C18 alcohol ethoxylate propoxylate ether, such as Agnique@ BP-420 manufactured and sold by BASF; ethoxylated fatty alcohols, such as Synperonic® 13 / 12; polysorbates, such as Tween® 80 (Tween® is a registered trademark of Croda International Pic, Goole, East Yorkshire, UK); sorbitan esters, such as Span® 80 (Span® is a registered trademark of Uniqema Americas LLC, Wilmington, Delaware, USA); and phosphates, such as tris(2-ethylhexyl) phosphate (TEHP).
[0088] Formulations comprising the compound of Formula I or Formula LB and at least one dehydrating agent of the present disclosure may be oil-in-water emulsions (EWs), where the compound of Formula I or Formula I-B, is dissolved in the dispersed droplets of the organic liquid phase. The emulsion formation may contain: the organic liquid; an emulsifier; and water, aqueous liquid, or other diluent. Suitable organic liquids and emulsifiers may be chosen from the solvents, co-solvents, and emulsifiers listed for emulsifiable concentrates. The oil-in-water emulsion formulation may also contain one or more of antimicrobial agent(s), viscosity modifier(s), antifreeze(s), pH modifier(s), antifoam agent(s), or built-in adjuvant(s). Suitable antimicrobial agents include: l,2-benzisothiazolin-3-one, such as Proxel® GXL (Proxel® is a registered trademark of Arch UK Biocides Ltd, Castleford, West Yorkshire, UK); 5-chloro-2- methyl-4-isothiazolin-3-one; or 2-methyl4-isothiazolin-3-one, such as Kathon® CG / ICP(Kathon® is a registered trademark of Rohm and Haas Company, Philadelphia, Pennsylvania, USA). Suitable viscosity modifiers include: smectite clay, such as Veegum® (Veegum® is a registered trademark of Vanderbilt Minerals LLC, Norwalk, Connecticut, USA); microcrystalline cellulose, such as Avicel® CL-611 (Avicel® is a registered trademark of DuPont Nutrition USA, Wilmington, Delaware, USA); xantham gum, such as Rhodopol® 23, Rhodopol® Extra 2, or Rhodicare® CFT (Rhodopol® and Rhodicare® are registered trademarks of Rhodia Chimie Corporation, Aubervilliers, France); or diutan gum. Suitable antifreeze compounds include: propylene glycol; glycerol; or electrolyte-based antifreeze, such as sodium chloride or sodium acetate. Suitable pH modifiers include agriculturally-acceptable weak acidic or basic buffers, such as sodium phosphate, potassium phosphate, phosphoric acid, sodium citrate, potassium citrate, citric acid, sodium lactate, potassium lactate, or lactic acid. Suitable antifoam agents include polydimethylsiloxanes emulsified in water, such as Foamaster® UDB (Foamaster® is a registered trademark of BASF Corporation, Florham Park, NJ, USA), or SAG™ 1572, or SAG™ 1538, or SAG™ 1599 (SAG™ is a trademark of Momentive Performance materials, Friendly, WV, USA), or Xiameter™ ACP-0001, or Xiameter™ ACP-0100, or Xiameter™ ACP-1400, or Xiameter™ AFE-0010, or Xiameter™ AFE-0300 (Xiameter™ is a trademark of the Dow Chemical Company, Midland, MI, US), or Antifoam 10, or Antifoam 100, or Antifoam 8810 IND, or Antifoam 8830 IND, or Silfar® S 184; or Silfar® SE 4; or Silfoam® SC 132, or Silfoam® SE-23 (Silfar® and Silfoam® are trademarks of Wacker Silicones, Adrian, MI, USA); or Break-thru® AF 9902, or Break-thru® AF 9903, or Break-thru® AF 9905. For diluents, water, an aqueous liquid, or a polar solvent that is not miscible with the organic phase can be selected. Suitable built-in adjuvants include: methylated seed oils, including C18 soyate and Cl 8 rapeate, such as Agnique® ME 18 RD-F, Agnique® ME 18 SD-F, Agnique® ME 2337, or Edenor® ME 12-18; ethoxylated castor oils such as Agnique® CSO-25, Etocas™ 10, Etocas™ 29, or Etocas™ 40; ethoxylated fatty alcohols, such as Synperonic® 13 / 12; polysorbates, such as Tween® 80; sorbitan esters, such as Span® 80; and phosphates, such as tris(2-ethylhexyl) phosphate.
[0089] In some aspects, the formulations disclosed herein comprise, in weight percent based on the total weight of the formulation, from about 0.1% to about 99% of the compound of Formula I (e.g., about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, , 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 82.5%, 85%, 87.5%, 90%, 92.5%, or 95% of the compound of Formula I), or within any range defined from any two of the forgoing values, such as from about 1% to about95%, from about 10% to about 60%, from about 20% to about 45%, from about 55% to about 82.5%, or from about 12.5% to about 50% of the compound of Formula I, by weight percent based on the total weight of the formulation. In some aspects, the liquid formulations comprise, in grams active ingredient per liter (g ai / L) of the formulation, a concentration from about 1 g ai / L to about 850 g ai / L of the compound of Formula I, or an acceptable salt, solvate, or hydrate thereof, (e.g., about 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 12.5, 15, 17.5, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 110, 112, 115, 117, 120, 125, 130, 140, 150, 160, 170, 175, 180, 190, 200, 210, 215, 220, 225, 230, 240, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 800, or 850 g ai / L of the compound of Formula I), or within any range defined from any two of the forgoing values, such as from about 1 g ai / L to about 750 g ai / L, from about 1 g ai / L to about 600 g ai / L, from about 1 g ai / L to about 500 g ai / L, from about 1 g ai / L to about 450 g ai / L, from about 10 g ai / L to about 350 g ai / L, from about 20 g ai / L to about 150 g ai / L, or from about 112 g ai / L to about 250 g ai / L of the compound of Formula I. In a formulation designed to be employed as a concentrate, the concentrate can be diluted with an inert carrier, such as water or an aqueous liquid, to form a tank mix prior to application. The tank mix applied to the area adjacent to the plant or soil adapted to support growth of the plant, or directly upon to the seed, the root of the plant, and / or foliage of the plant, can contain from about 0.006 to about 80 g ai / L of the compound of Formula I, or an acceptable salt, solvate, or hydrate thereof, (e.g., about 0.01, 0.05, 0.1, 0.25, 0.5, 0.75, 1, 1.5, 2, 2.5, 5, 7.5, 10, 11, 12, 12.5, 13, 14, 15, 16, 17, 17.5, 18, 19, 20, 22, 22.5, 24, 25, 26, 27.5, 28, 30, 32, 32.5, 34, 35, 36, 37.5, 38, 40, 42, 44, 45, 46, 48, 50, 52.5, 55, 57.5, 60, 62.5, 65, 67.5, 70, 72.5, 75, or 77.5 g ai / L of compound of Formula I), or within any range defined from any two of the forgoing values, such as from about 0.01 g ai / L to about 30 g ai / L, about 7.5 g ai / L to about 25 g ai / L, about 7.5 g ai / L to about 75 g ai / L, or about 0.25 g ai / L to about 5 g ai / L of the compound of Formula I in the tank mix.
[0090] In some aspects, the formulations disclosed herein comprise, in weight percent based on the total weight of the formulation, from about 0.1% to about 99% of the compound of Formula LB (e.g., about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, , 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 82.5%, 85%, 87.5%, 90%, 92.5%, or 95% of the compound of Formula LB), or within any range defined from any two of the forgoing values, such as from about 1% to about 95%, from about 10% to about 60%, from about 20% to about 45%, from about 55% to about 82.5%, or from about 12.5% to about 50% of the compound of Formula LB, by weightpercent based on the total weight of the formulation. In some aspects, the liquid formulations comprise, in grams active ingredient per liter (g ai / L) of the formulation, a concentration from about 1 g ai / L to about 850 g ai / L of the compound of Formula B (e.g., about 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 12.5, 15, 17.5, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 110, 112, 115, 117, 120, 125, 130, 140, 150, 160, 170, 175, 180, 190, 200, 210, 215, 220, 225, 230, 240, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 800, or 850 g ai / L of the compound of Formula I-B), or within any range defined from any two of the forgoing values, such as from about 1 g ai / L to about 750 g ai / L, from about 1 g ai / L to about 600 g ai / L, from about 1 g ai / L to about 500 g ai / L, from about 1 g ai / L to about 450 g ai / L, from about 10 g ai / L to about 350 g ai / L, from about 20 g ai / L to about 150 g ai / L, or from about 112 g ai / L to about 250 g ai / L of the compound of Formula B. In a formulation designed to be employed as a concentrate, the concentrate can be diluted with an inert carrier, such as water or an aqueous liquid, to form a tank mix prior to application. The tank mix applied to the area adjacent to the plant or soil adapted to support growth of the plant, or directly upon to the seed, the root of the plant, and / or foliage of the plant, can contain from about 0.006 to about 80 g ai / L of the compound of Formula B (e.g., about 0.01, 0.05, 0.1, 0.25, 0.5, 0.75, 1, 1.5, 2, 2.5, 5, 7.5, 10, 11, 12, 12.5, 13, 14, 15, 16, 17, 17.5, 18, 19, 20, 22,22.5, 24, 25, 26, 27.5, 28, 30, 32, 32.5, 34, 35, 36, 37.5, 38, 40, 42, 44, 45, 46, 48, 50, 52.5, 55,57.5, 60, 62.5, 65, 67.5, 70, 72.5, 75, or 77.5 g ai / L of compound of Formula LB), or within any range defined from any two of the forgoing values, such as from about 0.01 g ai / L to about 30 g ai / L, about 7.5 g ai / L to about 25 g ai / L, about 7.5 g ai / L to about 75 g ai / L, or about 0.25 g ai / L to about 5 g ai / L of the compound of Formula B, in the tank mix.B. Additives
[0091] The pesticidal formulations containing the compound of Formula I, or an acceptable salt, solvate, or hydrate thereof, disclosed herein can also comprise one or more additives, such as the additives described herein above. In some aspects, the additive is premixed with the compound of Formula I, or an acceptable salt, solvate, or hydrate thereof. In some aspects, the additive is added sequentially. In some aspects, the additive is added simultaneously.1. Dehydrating Agents
[0092] Some aspects of the described fungicidal formulations include adding at least one dehydrating agent to the fungicidal formulations.
[0093] In some aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I and at least one dehydrating agent. In some alternative aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I-B and at least one dehydrating agent.
[0094] In some preferred aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I and at least one dehydrating agent.
[0095] Examples of dehydrating agents include, but not limited to, activated alumina, activated carbon, alkyl orthoesters, bicyclic oxazolidine derivatives, benzophenone, clay, calcium salts (including, but not limited to, calcium chloride, calcium hydride, and calcium sulfate), carbodiimides (including polycarbodiimides), cobalt(II) chloride, copper sulfate, lithium salts (including, but not limited to, lithium chloride and lithium bromide), magnesium salts (including, but not limited to, magnesium chloride, magnesium sulfate, and magnesium perchlorate), metal hydroxides (including, but not limited to, potassium hydroxide and sodium hydroxide), metal oxides (including, but not limited to, calcium oxide, magnesium oxide, potassium oxide, and sodium oxide), molecular sieves (including, but not limited to, synthetic and natural zeolite materials), organosilanes, phosphorus pentoxide, potassium salts (including, but not limited to, potassium carbonate and potassium chloride), rice, silica gel, sodium salts (including, but not limited to, sodium chlorate, sodium chloride, and sodium sulfate), sucrose, sulfuric acid, and tri ethylene glycol. Preferred examples of dehydrating agents are activated alumina, alkyl orthoesters, bicyclic oxazolidine derivatives, carbodiimides (including polycarbodiimides), molecular sieves, organosilanes, and silica gels. Preferred dehydrating agents include alkyl orthoesters, bicyclic oxazolidine derivatives, carbodiimides (including polycarbodiimides), molecular sieves, and organosilanes. The most preferred examples are alkyl orthoesters, carbodiimides, molecular sieves, and organosilanes.
[0096] Preferred alkyl orthoesters are alkyl orthoesters of acetic acid. More preferred alkyl orthoesters are C1-C8 alkyl orthoesters of acetic acid. The most preferred alkyl orthoester is triethyl orthoacetate.
[0097] Preferred bicyclic oxazolidine derivatives are alkylbicyclooxazolidines. More preferred bicyclic oxazolidine derivatives are 7-alkylbicyclooxazolidines. The most preferred bicyclic oxazolidine derivatives are 7-Cl-C8-alkylbicyclooxazolidines. The particularly preferred bicyclic oxazolidine derivative is 7-ethylbicyclooxazolidine.
[0098] Preferred carbodiimides are N,N'-dicyclohexylcarbodiimide (DCC), N,N'- diisopropylcarbodiimide (DIC), l-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N- cyclohexyl-N'-(2-morpholinoethyl)carbodiimide methyl- / ?-toluenesulfonate (Morpho CDI), N,N-ditritylcarbodiimide (N,N-ditrityl CDI), and bis(2,6-diisopropylphenyl)carbodiimide (DIPPC). More preferred carbodiimides are N,N'-dicyclohexylcarbodiimide (DCC), N,N'- diisopropylcarbodiimide (DIC), N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide methyl- / ?- toluenesulfonate (Morpho CDI), N,N-ditritylcarbodiimide (N,N-ditrityl CDI), and bis(2,6- diisopropylphenyl)carbodiimide (DIPPC). The most preferred carbodiimides are N,N'- dicyclohexylcarbodiimide (DCC), N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide methyl- -toliienesulfonate (Morpho CDI), and N,N-ditritylcarbodiimide (N,N-ditrityl CDI). The particularly preferred carbodiimide is N,N'-dicyclohexylcarbodiimide (DCC).
[0099] In some aspects, carbodiimides herein may be polycarbodiimides. Polycarbodiimides are oligomers or polymers that contain on average two or more carbodiimide groups. Examples of polycarbodiimides include, but not limited to, RelcaLink® carbodiimide crosslinkers that can be purchased from Stahl, such as Picassian® XL-701, Picassian® XL-702, Picassian® XL-725, Picassian® XL-732, RelcaLink® 70, RelcaLink® 71, RelcaLink® 72, and RelcaLink® 90.
[0100] Examples of molecular sieves include, but not limited to, molecular sieves in types of molecular sieve 3 A, molecular sieve 4A, molecular sieve 5 A, and molecular sieve 13X. Preferred molecular sieves are molecular sieve 3A and molecular sieve 4A. More preferred molecular sieve is molecular sieve 3 A. Molecular sieves can be purchased commercially from Sigma-Aldrich, Fisher Scientific, and alike. For example, molecular sieve 3A can be purchased from Sigma-Aldrich under the Brand SIGALD with the product name Molecular sieves, 3 , which has the CAS number of 308080-99-1.
[0101] Preferred organosilanes are vinyltrimethoxysilane, triethoxyphenylsilane, triethoxy(4-methoxyphenyl)silane, cyclohexyltrimethoxysilane, isooctyl trimethoxysilane, 3- (triethoxysilyl)propionitrile, (N,N-dimethylaminopropyl)trimethoxysilane, 2-(2- (trimethoxysilyl)ethyl)pyridine, and l-(3-(trimethoxysilyl)propyl)-lH-imidazole. More preferred organosilanes are vinyltrimethoxysilane, triethoxyphenylsilane, triethoxy(4- methoxyphenyl)silane, cyclohexyltrimethoxysilane, isooctyl trimethoxysilane, 3- (triethoxysilyl)propionitrile, and 2-(2-(trimethoxysilyl)ethyl)pyridine. The most preferred organosilanes are vinyltrimethoxysilane and triethoxyphenylsilane.
[0102] In some aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I or Formula I-B, and at least one dehydrating agent selected from the group consisting of alkyl orthoesters, bicyclic oxazolidine derivatives, carbodiimides, molecular sieves, organosilanes, and mixtures thereof. In some preferred aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I and at least one dehydrating agent selected from the group consisting of C1-C8 alkyl orthoesters of acetic acid, 7-alkylbicyclooxazolidines, N,N'-dicyclohexylcarbodiimide (DCC), N-cyclohexyl-N'-(2- morpholinoethyl)carbodiimide methyl- / ?-toluenesulfonate (Morpho CDI), N,N- ditritylcarbodiimide (N,N-ditrityl CDI), N,N'-diisopropylcarbodiimide (DIC), l-ethyl-3-(3- dimethylaminopropyl)carbodiimide (EDC), bis(2,6-diisopropylphenyl)carbodiimide (DIPPC), molecular sieve 3 A, molecular sieve 4A, molecular sieve 5 A, molecular sieve 13X, vinyltrimethoxysilane, triethoxyphenylsilane, triethoxy(4-methoxyphenyl)silane, cyclohexyltrimethoxysilane, isooctyl trimethoxysilane, 3-(triethoxysilyl)propionitrile, (N,N- dimethylaminopropyl)trimethoxy silane, 2-(2-(trimethoxysilyl)ethyl)pyridine, l-(3-(trimethoxysilyl)propyl)-lH-imidazole, and mixtures thereof. In some more preferred aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I and at least one dehydrating agent selected from the group consisting of triethyl orthoacetate, 7- ethylbicyclooxazolidine, N,N'-dicyclohexylcarbodiimide (DCC), N-cyclohexyl-N'-(2- morpholinoethyl)carbodiimide methyl- / ?-toluenesulfonate (Morpho CDI), N,N- ditritylcarbodiimide (N,N-ditrityl CDI), molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, vinyltrimethoxysilane, triethoxyphenylsilane, triethoxy(4-methoxyphenyl)silane, cyclohexyltrimethoxy silane, isooctyl trimethoxy silane, 3 -(tri ethoxy silyl)propionitrile, 2-(2- (trimethoxysilyl)ethyl)pyridine, and mixtures thereof. In some most preferred aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I and at least one dehydrating agent selected from the group consisting of triethyl orthoacetate, N,N'- dicyclohexylcarbodiimide (DCC), molecular sieve 3A, molecular sieve 4A, vinyltrimethoxysilane, triethoxyphenylsilane, and mixtures thereof. In some particularly preferred aspects, the fungicidal formulations of the present disclosure comprise compounds of Formula I and at least one dehydrating agent selected from the group consisting of triethyl orthoacetate, N,N'-dicyclohexylcarbodiimide (DCC), molecular sieve 3 A, molecular sieve 4A, vinyltrimethoxysilane, and triethoxyphenylsilane.[01.03] The total amount of the at least one dehydrating agent present in the fungicidal formulation of the present disclosure is, in weight percent based on the total weight of theformulation, from about 0.001% to about 50% (e.g., about 0.002%, 0.005%, 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, , 30%, 35%, 40%, 45%, or 47.5%), or within any range defined from any two of the forgoing values, such as from about 1% to about 45%, from about 10% to about 30%, from about 20% to about 47.5%, from about 12.5% to about 20%, or from about 2% to about 15%, by weight percent based on the total weight of the formulation.
[0104] In some aspects, the dehydrating agents disclosed herein are readily soluble in the resulting fungicidal formulations comprising compounds of Formula I or Formula I-B.
[0105] In some aspects, the dehydrating agents disclosed herein are not soluble in the resulting fungicidal formulations comprising compounds of Formula I or Formula I-B. The undissolved dehydrating agents may be removed from the fungicidal formulations before storage or transportation or the application in the field.
[0106] In some aspects, the dehydrating agents disclosed herein may improve the chemical stability of the fungicidal formulations of the present disclosure via various mechanisms. For example, carbodiimides such N,N'-dicyclohexylcarbodiimide (DCC), N-cyclohexyl-N'-(2- morpholinoethyl)carbodiimide methyl- / ?-toluenesulfonate (Morpho CDI), and N,N- ditritylcarbodiimide (N,N-ditrityl CDI), preferably N,N'-dicyclohexylcarbodiimide (DCC), could act in a role of removing or de-activating acid impurities and thus improve the stability of the fungicidal formulations of the present disclosure.2. Other Pesticides
[0107] Some aspects of the described pesticidal formulations include adding one or more additional pesticide active ingredients to the pesticidal formulations. These pesticide active ingredients may include one or more of a herbicide, an insecticide, a fungicide, a nematocide, a miticide, an arthropodicide, a bactericide, a plant growth regulator, or combinations thereof that are compatible with the formulations of the present disclosure.
[0108] Examples of additional pesticides include: (3-ethoxypropyl)mercury bromide, 1,2- dibromoethane, 1,2-dichloroethane, 1,2-di chloropropane, 1,3 -di chloropropene, 1-MCP, 1- methylcyclopropene, 1-naphthol, 2-(octylthio)ethanol, 2,3,3-TPA, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA, 2,4, 5-T, 2,4,5-TB, 2,4,5-TP, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2,4-MCPA, 2,4-MCPB, 2iP, 2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, 3,4- DB, 3,4-DP, 3,6-dichloropicolinic acid, 4-aminopyridine, 4-CPA, 4-CPB, 4-CPP, 4- hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline,abamectin, abamectin-aminomethyl, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetofenate, acetophos, acetoprole, acibenzolar, acifluorfen, aclonifen, ACN, acrep, acrinathrin, acrolein, acrylonitrile, acynonapyr, acypetacs, afidopyropen, afoxolaner, alachlor, alanap, alanycarb, albendazole, aldicarb, aldicarb sulfone, aldimorph, aldoxycarb, aldrin, allethrin, allicin, allidochlor, allosamidin, alloxydim, allyl alcohol, allyxycarb, alorac, a / / ra-cypermethrin, a / / ?Aa-endosulfan, alphamethrin, altretamine, aluminium phosphide, aluminum phosphide, ametoctradin, ametridione, ametryn, ametryne, amibuzin, amicarbazone, amicarthiazol, amidithion, amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor, aminopyralid, aminopyrifen, aminotriazole, amiprofos-methyl, amiprophos, amiprophos-methyl, amisulbrom, amiton, amitraz, amitrole, ammonium sulfamate, amobam, amorphous silica gel, amorphous silicon dioxide, ampropylfos, AMS, anabasine, ancymidol, anilazine, anilofos, anisflupurin, anisuron, anthraquinone, antu, apholate, aramite, arprocarb, arsenous oxide, asomate, aspirin, asulam, athidathion, atraton, atrazine, aureofungin, avermectin Bl, AVG, aviglycine, azaconazole, azadirachtin, azafenidin, azamethiphos, azidithion, azimsulfuron, azinphosethyl, azinphos-ethyl, azinphosmethyl, azinphos-methyl, aziprotryn, aziprotryne, azithiram, azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban, barbanate, barium hexafluorosilicate, barium polysulfide, barium silicofluoride, barthrin, basic copper carbonate, basic copper chloride, basic copper sulfate, BCPC, beflubutamid, beflubutamid-M, benalaxyl, benalaxyl-M, benazolin, bencarbazone, benclothiaz, bendaqingbingzhi, bendiocarb, bendioxide, benefin, benfluralin, benfuracarb, benfuresate, benmihuangcaoan, benodanil, benomyl, benoxacor, benoxafos, benquinox, benquitrione, bensulfuron, bensulide, bensultap, bentaluron, bentazon, bentazone, benthiavalicarb, benthiazole, benthiocarb, bentioflumin, bentranil, benzadox, benzalkonium chloride, benzamacril, benzamizole, benzamorf, benzene hexachloride, benzfendizone, benzimine, benzipram, benzobicyclon, benzoepin, benzofenap, benzofluor, benzohydroxamic acid, benzomate, benzophosphate, benzothiadi azole, benzovindiflupyr, benzoximate, benzoylprop, benzpyrimoxan, benzthiazuron, benzuocaotong, benzyl benzoate, benzyladenine, berberine, beta-cyfluthrin, Z>eta-cypermethrin, bethoxazin, BHC, bialaphos, bicyclopyrone, bifemetstrobin, bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos, binapacryl, bingqingxiao, bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bipyrazone, bisazir, bismerthiazol, bismerthiazol-copper, bisphenylmercury methylenedi(x-naphthalene-y- sulphonate), bispyribac, bistrifluron, bisulflufen, bisultap, bitertanol, bithionol, bixafen, bixlozone, blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid, BPPS, brassinolide, brassinolide-ethyl, brevicomin, broclozone, brodifacoum, brofenprox, brofenvalerate,broflanilide, brofluthrinate, bromacil, bromadiolone, bromchlophos, bromethalin, bromethrin, bromfenvinfos, bromoacetamide, bromobonil, bromobutide, bromociclen, bromocyclen, bromo-DDT, bromofenoxim, bromofos, bromomethane, bromophos, bromophos-ethyl, bromopropylate, bromothalonil, bromoxynil, brompyrazon, bromuconazole, bronopol, BRP, BTH, bucarpolate, bufencarb, buminafos, bupirimate, buprofezin, Burgundy mixture, busulfan, busulphan, butacarb, butachlor, butafenacil, butam, butamifos, butane-fipronil, butathiofos, butenachlor, butene-fipronil, butethrin, buthidazole, buthiobate, buthiuron, butifos, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butrizol, butroxydim, buturon, butylamine, butylate, butylchlorophos, butylene-fipronil, cacodylic acid, cadusafos, cafenstrole, calciferol, calcium arsenate, calcium chlorate, calcium cyanamide, calcium cyanide, calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor, captafol, captan, carbarn, carbamorph, carbanolate, carbaril, carbaryl, carbasulam, carbathion, carbendazim, carbendazol, carbetamide, carbofenotion, carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide, carbophenothion, carbophos, carbosulfan, carboxazole, carboxide, carboxin, carfentrazone, carpropamid, cartap, carvacrol, carvone, CAVP, CDAA, CDEA, CDEC, cellocidin, CEPC, ceralure, cerenox, cevadilla, Cheshunt mixture, chinalphos, chinalphos-methyl, chinomethionat, chinomethionate, chiralaxyl, chitosan, chi obenthi azone, chlomethoxyfen, chloralose, chloramben, chloramine phosphorus, chloramphenicol, chloraniformethan, chloranil, chloranocryl, chlorantraniliprole, chlorazifop, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chlorempenthrin, chloretazate, chi or ethephon, chlorethoxyfos, chloreturon, chlorfenac, chlorfenapyr, chlorfenazole, chlorfenethol, chlorfenidim, chlorfenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfenvinphos-methyl, chlorfluazuron, chlorflurazole, chlorflurecol, chlorfluren, chlorflurenol, chloridazon, chlorimuron, chlorinate, chlor-IPC, chlormephos, chlormequat, chlormesulone, chlormethoxynil, chlornidine, chlornitrofen, chloroacetic acid, chlorobenzilate, chlorodinitronaphthalenes, chlorofenizon, chloroform, chloroinconazide, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophos, chloropicrin, chloropon, chloroprallethrin, chloropropylate, chlorothalonil, chlorotoluron, chloroxifenidim, chloroxuron, chloroxynil, chlorphonium, chlorphoxim, chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal, chlorthiamid, chlorthiophos, chlortoluron, chlozolinate, chitosan, cholecalciferol, choline chloride, chromafenozide, cicloheximide, cimectacarb, cimetacarb, cinerin I, cinerin II, cinerins, cinflubrolin, cinidon-ethyl, cinmethylin, cinosulfuron, cintofen, ciobutide, cisanilide,cismethrin, clacyfos, clefoxydim, clenpirin, clenpyrin, clethodim, climbazole, cliodinate, clodinafop, cloethocarb, clofencet, clofenotane, clofentezine, clofenvinfos, clofibric acid, clofop, clomazone, clomeprop, clonitralid, cloprop, cloproxydim, clopyralid, cloquintocet, cloransulam, closantel, clothianidin, clotrimazole, cloxyfonac, cloxylacon, clozylacon, CMA, CMMP, CMP, CMU, codlelure, colecalciferol, colophonate, copper 8-quinolinolate, copper acetate, copper acetoarsenite, copper arsenate, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper sulfate, basic, copper zinc chromate, coumachlor, coumafene, coumafos, coumafuryl, coumaphos, coumatetralyl, coumethoxystrobin, coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, cresylic acid, crimidine, crotamiton, crotoxyfos, crotoxyphos, crufomate, cryolite, cue-lure, cufraneb, cumyleron, cumyluron, cuprobam, cuprous oxide, curcumenol, CVMP, cyanamide, cyanatryn, cyanazine, cyanofenphos, cyanogen, cyanophos, cyanthoate, cyantraniliprole, cyanuric acid, cyazofamid, cybenzoxasulfyl, cybutryne, cyclafuramid, cyclanilide, cyclaniliprole, cyclethrin, cycloate, cyclobutrifluram, cycloheximide, cycloprate, cycloprothrin, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyetpyrafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalodiamide, cyhalofop, cyhalothrin, cyhexatin, cymiazole, cymoxanil, cyometrinil, cypendazole, cypermethrin, cyperquat, cyphenothrin, cyprazine, cyprazole, cyproconazole, cyprodinil, cyproflanilide, cyprofuram, cypromid, cyprosulfamide, cypyrafluone, cyromazine, cythioate, cytrex, daimuron, dalapon, daminozide, dayoutong, dazomet, DBCP, tZ-camphor, DCB, DCIP, DCPA (Japan), DCPA (USA), DCPTA, DCU, DDD, DDPP, DDT, DDVP, debacarb, decafentin, decamethrin, decarbofuran, deet, dehydroacetic acid, deiquat, delachlor, delnav, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl sulphone, demeton-S-methylsulphon, DEP, depallethrine, derris, desmedipham, desmetryn, desmetryne, d-fanshiluquebingjuzhi, diafenthiuron, dialifor, dialifos, diallate, di-allate, diamidafos, dianat, diatomaceous earth, diatomite, diazinon, dibrom, dibutyl phthalate, dibutyl succinate, dicamba, dicapthon, dichlobenil, dichlobentiazox, dichlofenthion, dichlofluanid, dichlone, dichloralurea, dichlorbenzuron, dichlorfenidim, dichlorflurecol, di chlorflurenol, dichlormate, dichlormid, dichloromethane, dichlorophen, dichlorprop, dichlorprop-P, dichlorvos, dichlozolin, dichlozoline, diclobutrazol, diclocymet, diclofop, diclomezine, dicloran, dicloromezotiaz, diclosulam, dicofol, dicophane, dicoumarol, dicresyl, dicrotophos, dicryl, dicumarol, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat, diethatyl, diethion, diethion, diethofencarb, dietholate, diethon, diethyl pyrocarbonate, diethyltoluamide, difenacoum,difenoconazole, difenopenten, difenoxuron, difenzoquat, difethialone, diflovidazin, diflubenzuron, diflufenican, diflufenicanil, diflufenzopyr, diflumetorim, dikegulac, dilor, dimatif, dimefluthrin, dimefox, dimefuron, dimehypo, dimepiperate, dimesulfazet, dimetachlone, dimetan, dimethacarb, dimethachlone, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate, dimethyl disulfide, dimethyl phthalate, dimethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin, dimpropyridaz, dimpylate, dimuron, dinex, dingjunezuo, diniconazole, diniconazole-M, dinitramine, dinitrophenols, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinosulfon, dinotefuran, dinoterb, dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion, dioxation, dioxopyritrione, diphacin, diphacinone, diphenadione, diphenamid, diphenamide, diphenyl sulfone, diphenylamine, diphenylsulphide, diprogulic acid, dipropalin, dipropetryn, dipterex, dipymetitrone, dipyrithione, diquat, disodium tetraborate, disosultap, disparlure, disugran, disul, disulfiram, disulfoton, ditalimfos, dithianon, dithicrofos, dithioether, dithiometon, dithiopyr, diuron, dixanthogen, d-limonene, DMDS, DMPA, DNOC, dodemorph, dodicin, dodine, dofenapyn, doguadine, dominicalure, doramectin, DPC, drazoxolon, DSMA, d-trans-allethrin, d-trans-resmethrin, dufulin, dymron, EBEP, EBP, ebufos, ecdysterone, echlomezol, EDB, EDC, EDDP, edifenphos, eglinazine, emamectin, EMPC, empenthrin, enadenine, endosulfan, endothal, endothall, endothion, endrin, enestroburin, enilconazole, enoxastrobin, ephirsulfonate, EPN, epocholeone, epofenonane, epoxiconazole, eprinomectin, epronaz, epsilon-metofluthrin, epsilon-momfluorothrin, EPTC, epyrifenacil, erbon, ergocalciferol, erlujixiancaoan, esdepallethrine, esfenval erate, ESP, esprocarb, etacelasil, etaconazole, etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron, ethaprochlor, ethephon, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl, ethobenzanid, ethofumesate, ethohexadiol, ethoprop, ethoprophos, ethoxyfen, ethoxyquin, ethoxysulfuron, ethychlozate, ethyl formate, ethyl pyrophosphate, ethylan, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, ethylicin, ethylmercury 2,3 -dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etinofen, ETM, etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos, etrimphos, eugenol, EXD, famoxadone, famphur, fenac, fenamidone, fenaminosulf, fenaminstrobin, fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorphos, fenclofos, fenclorim, feneptamidoquin, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenidin, fenitropan, fenitrothion, fenizon, fenjuntong, fenmezoditiaz,fenobucarb, fenolovo, fenoprop, fenopyramid, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenoxycarb, fenpiclonil, fenpicoxamid, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyrazone, fenpyroximate, fenquinotrione, fenridazon, fenson, fensulfothion, fenteracol, fenthiaprop, fenthion, fenthion- ethyl, fentiaprop, fentin, fentrazamide, fentrifanil, fenuron, fenuron-TCA, fenvalerate, feproxydim, ferbam, ferimzone, ferric phosphate, ferrous sulfate, fipronil, flamprop, flamprop- M, flazasulfuron, flocoumafen, flometoquin, flonicamid, florasulam, florpyrauxifen, florylpicoxamid, fluacrypyrim, fluazaindolizine, fluazifop, fluazifop-P, fluazinam, fluazolate, fluazuron, flubendiamide, flubeneteram, flubenzimine, flubrocythrinate, flucarbazone, flucetosulfuron, fluchloralin, fluchloraminopyr, fluchlordiniliprole, flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluenethyl, fluenetil, fluensulfone, flufenacet, flufenerim, flufenican, flufenoxadiazam, flufenoximacil, flufenoxuron, flufenoxystrobin, flufenprox, flufenpyr, flufenzine, flufiprole, fluhexafon, fluindapyr, flumethrin, flumetnicam, flumetover, flumetralin, flumetsulam, flumetyl sulforim, flumezin, flumiclorac, flumioxazin, flumipropyn, flumorph, fluometuron, fluopicolide, fluopimomide, fluopyram, fluorbenside, fluoridamid, fluoroacetamide, fluoroacetic acid, fluorochloridone, fluorodifen, fluoroglycofen, fluoroimide, fluoromide, fluoromidine, fluoronitrofen, fluoroxypyr, fluothiuron, fluotrimazole, fluoxapiprolin, fluoxastrobin, fluoxytioconazole, flupentiofenox, flupoxam, flupropacil, flupropadine, flupropanate, flupyradifurone, flupyrimin, flupyroxystrobin, flupyrsulfuron, fluquinconazole, fluquinometoate, fluralaner, flurazole, flurecol, flurenol, fluridone, flurochloridone, fluromidine, fluroxypyr, flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide, flusulfmam, flutenzine, fluthiacet, fluthiamide, flutianil, flutolanil, flutriafol, fluvalinate, fluxametamide, fluxapyroxad, fluxofenim, folpel, folpet, fomesafen, fonofos, foramsulfuron, for chlorfenuron, formaldehyde, formetanate, formothion, formparanate, fosamine, fosetyl, fosmethilan, fospirate, fosthiazate, fosthietan, frontalin, fthalide, fuberidazole, fucaojing, fucaomi, fujunmanzhi, fulumi, fumarin, funaihecaoling, fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr, furan tebufenozide, furathiocarb, furcarbanil, furconazole, furconazole-c / .s, furethrin, furfural, furilazole, furmecyclox, furophanate, furyloxyfen, galquin, gamma-BHC, gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellin A3, gibberellins, gliftor, glitor, glucochloralose, glufosinate, glufosinate-P, glyodin, glyoxime, glyphosate, glyphosine, gossyplure, grandlure, griseofulvin, guanoctine, guazatine, halacrinate, halauxifen, halfenprox, halofenozide, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, haloxyfop-R, HCA, HCB, HCH, hemel, hempa, HEOD, heptachlor, heptafluthrin, heptenophos, heptopargil, herbimycin, herbimycinA, heterophos, hexachlor, hexachloran, hexachloroacetone, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumuron, hexafluoramin, hexaflurate, hexalure, hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf, homobrassinolide, huancaiwo, huanchongjing, huangcaoling, huanjunzuo, hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanamide, hydrogen cyanide, hydroprene, hydroxyisoxazole, hymexazol, hyquincarb, IAA, IBA, IBP, icafolin, icaridin, imazalil, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, imibenconazole, imicyafos, imidacloprid, imidaclothiz, iminoctadine, imiprothrin, inabenfide, indanofan, indazapyroxamet, indaziflam, indolauxipyr, indoxacarb, inezin, infusorial earth, inpyrfluxam, iodobonil, iodocarb, iodofenphos, iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, IPC, ipconazole, ipfencarbazone, ipfentrifluconazole, ipflufenoquin, iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, iptriazopyrid, IPX, isamidofos, isazofos, isobenzan, isocarbamid, isocarbamide, isocarbophos, isocil, isocycloseram, isodrin, isofenphos, isofenphos-methyl, isofetamid, isoflualanam, isoflucypram, isolan, isomethiozin, isonoruron, isopamphos, isopolinate, isoprocarb, isoprocil, isopropalin, isopropazol, isoprothiolane, isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxaflutole, isoxapyrifop, isoxathion, isuron, ivermectin, ixoxaben, izopamfos, izopamphos, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan, jiecaoxi, Jinganmycin A, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kadethrin, A / / y / -bifenthrin, A / / y / -tefluthrin, karbutilate, karetazan, kasugamycin, kejunlin, kelevan, ketospiradox, kieselguhr, kinetin, kinoprene, kiralaxyl, kresoxim-methyl, kuicaoxi, lactofen, / r / a-cyhalothrin, lancotrione, latilure, lead arsenate, ledprona, lenacil, lepimectin, leptophos, lianbenjingzhi, lime sulfur, lindane, lineatin, linuron, lirimfos, litlure, looplure, lotilaner, lufenuron, liifuqingchongxianan, liixiancaolin, Ivdingjunzhi, Ivfumijvzhi, Ivxiancaolin, lythidathion, M-74, M-81, MAA, magnesium phosphide, malathion, maldison, maleic hydrazide, malonoben, maltodextrin, MAMA, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, matrine, mazidox, MCC, MCP, MCPA, MCPA-thioethyl, MCPB, MCPP, mebenil, mecarbam, mecarbinzid, mecarphon, mecoprop, mecoprop-P, medimeform, medinoterb, medlure, mefenacet, mefenoxam, mefenpyr, mefentrifluconazole, mefluidide, megatomoic acid, melissyl alcohol, melitoxin, MEMC, menazon, MEP, mepanipyrim, meperfluthrin, mephenate, mephosfolan, mepiquat, mepronil, meptyldinocap, mercaptodimethur, mercaptophos, mercaptophos thiol, mercaptothion, mercuric chloride, mercuric oxide, mercurous chloride, merphos, merphosoxide, mesoprazine, mesosulfuron, mesotrione, mesulfen, mesulfenfos, mesulphen, metacresol, metaflumizone, metalaxyl, metalaxyl-M, metaldehyde, metam, metamifop, metamitron, metaphos, metarylpicoxamid, metaxon, metazachlor, metazosulfuron, metazoxolon, metcamifen, metconazole, metepa, metflurazon, methabenzthiazuron, methacrifos, methalpropalin, metham, methamidophos, methasulfocarb, methazole, methfuroxam, methibenzuron, methidathion, methiobencarb, methiocarb, methiopyrisulfuron, methiotepa, methiozolin, methiuron, methocrotophos, metholcarb, methometon, methomyl, methoprene, methoprotryn, methoprotryne, methoquin-butyl, methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methyl apholate, methyl bromide, methyl eugenol, methyl iodide, methyl isothiocyanate, methyl parathion, methyl acetophos, methylchloroform, methyldithiocarbamic acid, methyldymron, methylene chloride, methyl-isofenphos, methylmercaptophos, methylmercaptophos oxide, methylmercaptophos thiol, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, methylneodecanamide, methylnitrophos, methyltriazothion, metiozolin, metiram, metiram- zinc, metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb, metometuron, metominostrobin, metosulam, metoxadiazone, metoxuron, metproxybicyclone, metrafenone, metriam, metribuzin, metrifonate, metriphonate, metsulfovax, metsulfuron, metyltetraprole, mevinphos, mexacarbate, miechuwei, mieshuan, miewenjuzhi, milbemectin, milbemycin oxime, milneb, mimanan, mipafox, MIPC, mirex, mivorilaner, MNAF, modoflaner, moguchun, molinate, molosultap, momfluorothrin, monalide, monisuron, monoamitraz, monochloroacetic acid, monocrotophos, monolinuron, monomehypo, monosulfiram, monosulfuron, monosultap, monuron, monuron-TCA, morfamquat, moroxydine, morphothion, morzid, moxidectin, MPMC, MSMA, MTMC, muscalure, myclobutanil, myclozolin, myricyl alcohol, A-(ethylmercury)- / ?-toluenesulphonanilide, NAA, NAAm, nabam, naftalofos, naled, naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthalophos, naphthoxyacetic acids, naphthyl acetic acids, naphthylindane- 1,3 -di ones, naphthyloxyacetic acids, naproanilide, napropamide, napropamide-M, naptalam, natamycin, NBPOS, neburea, neburon, nendrin, neonicotine, nichlorfos, niclofen, niclosamide, nicobifen, nicofluprole, nicosulfuron, nicotine, nicotine sulfate, nifluridide, nikkomycins, NIP, nipyraclofen, nipyralofen, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal- isopropyl, nobormide, nonanol, norbormide, norea, norflurazon, nomicotine, noruron, novaluron, noviflumuron, NPA, nuarimol, nuranone, OCH, octachlorodipropyl ether, octhilinone, o-di chlorobenzene, ofurace, omethoate, o-phenyl phenol, orbencarb, orfralure, orthobencarb, ortho- chlorobenzene, orthosulfamuron, oryctalure, orysastrobin, oryzalin,osthol, osthole, ostramone, ovatron, ovex, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon, oxapyrazone, oxasulfuron, oxathiapiprolin, oxaziclomefone, oxazosulfyl, oxine-copper, oxine-Cu, oxolinic acid, oxpoconazole, oxycarboxin, oxydemeton- methyl, oxydeprofos, oxy di sulfoton, oxyenadenine, oxyfluorfen, oxymatrine, oxytetracycline, oxythioquinox, PAC, paclobutrazol, paichongding, pallethrine, PAP, para- chlorobenzene, parafluron, paraquat, parathion, parathion-methyl, parinol, Paris green, PCNB, PCP, PCP-Na, / ?-dichlorobenzene, PDJ, pebulate, pedinex, pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin, penfenate, penflufen, penfluron, penoxalin, penoxsulam, pentachlorophenol, pentachlorophenyl laurate, pentanochlor, penthiopyrad, pentmethrin, pentoxazone, perchlordecone, perfluidone, permethrin, pethoxamid, PHC, phenamacril, phenamacril-ethyl, phenaminosulf, phenazine oxide, phenetacarbe, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl, phenob enzur on, phenothiol, phenothrin, phenproxide, phenthoate, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phorate, phosacetim, phosalone, phosametine, phosazetim, phosazetin, phoscyclotin, phosdiphen, phosethyl, phosfolan, phosfolan-methyl, phosglycin, phosmet, phosnichlor, phosphamide, phosphamidon, phosphine, phosphinothricin, phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide, phthalophos, phthalthrin, picarbutrazox, picaridin, picloram, picolinafen, picoxystrobin, pimaricin, pindone, pinoxaden, pioxaniliprole, piperalin, piperazine, piperflanilide, piperonyl butoxide, piperonyl cyclonene, piperophos, piproctanly, piproctanyl, piprotal, pirimetaphos, pirimicarb, piriminil, pirimioxyphos, pirimiphos-ethyl, pirimiphos-methyl, pival, pivaldione, plifenate, PMA, PMP, polybutenes, polycarbamate, polychlorcamphene, polyethoxyquinoline, polyoxin D, polyoxins, polyoxorim, polythialan, potassium arsenite, potassium azide, potassium cyanate, potassium ethylxanthate, potassium naphthenate, potassium polysulfide, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, pretilachlor, primidophos, primisulfuron, probenazole, prochloraz, proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol, profluralin, profluthrin, profoxydim, profurite-aminium, proglinazine, prohexadione, prohydrojasmon, promacyl, promecarb, prometon, prometryn, prometryne, promurit, pronamide, pronitridine, propachlor, propafos, propamidine, propamocarb, propanil, propaphos, propaquizafop, propargite, proparthrin, propazine, propetamphos, propham, propiconazole, propidine, propineb, propisochlor, propoxur, propoxycarbazone, propyl isome, propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin, prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothioconazole, prothiofos, prothoate, protrifenbute, proxan, prymidophos,prynachlor, psoralen, psoralene, pydanon, pydiflumetofen, pyflubumide, pymetrozine, pyracarbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrapropoyne, pyraquinate, pyrasulfotole, pyraziflumid, pyrazolate, pyrazolynate, pyrazon, pyrazophos, pyrazosulfuron, pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz- propyl, pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridachlometyl, pyridafol, pyridalyl, pyridaphenthion, pyridaphenthione, pyridate, pyridinitril, pyrifenox, pyriflubenzoxim, pyrifluquinazon, pyriftalid, pyrimetaphos, pyrimethanil, pyrimicarbe, pyrimidifen, pyriminobac, pyriminostrobin, pyrimiphos-ethyl, pyrimiphos-methyl, pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxyfen, pyrisoxazole, pyrithiobac, pyrolan, pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur, qincaosuan, qingkuling, quassia, quinacetol, quinalphos, quinalphos-methyl, quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine, quinofumelin, quinomethionate, quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop, quizalofop-P, quwenzhi, quyingding, rabenzazole, rafoxanide, R-diniconazole, rebemide, reglone, renriduron, rescalure, resmethrin, rhodethanil, rhodojaponin-III, ribavirin, rimisoxafen, rimsulfuron, rizazole, R-metalaxyl, rodethanil, ronnel, rotenone, ryania, sabadilla, saflufenacil, saijunmao, saisentong, salicylanilide, salifluofen, sanguinarine, santonin, S- bioallethrin, schradan, scilliroside, seboctylamine, sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz, sesamex, sesamolin, sesone, sethoxydim, sevin, shuangjiaancaolin, shuangjianancaolin, S-hydroprene, siduron, sifumijvzhi, siglure, silafluofen, silatrane, silica aerogel, silica gel, silthiofam, silthiopham, silthiophan, silvex, simazine, simeconazole, simeton, simetryn, simetryne, sintofen, S-kinoprene, slaked lime, SMA, S-methoprene, S- metolachlor, sodium arsenite, sodium azide, sodium chlorate, sodium cyanide, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium o- phenylphenoxide, sodium orthophenylphenoxide, sodium pentachlorophenate, sodium pentachlorophenoxide, sodium polysulfide, sodium silicofluoride, sodium tetrathiocarbonate, sodium thiocyanate, solan, sophamide, spidoxamat, spinetoram, spinosad, spirobudifen, spirodiclofen, spiromesifen, spiropidion, spirotetramat, spiroxamine, stirofos, streptomycin, strychnine, sulcatol, sulcofuron, sulcotrione, sulfallate, sulfentrazone, sulfiflumin, sulfiram, sulfluramid, sulfodiazole, sulfometuron, sulfosate, sulfosulfuron, sulfotep, sulfotepp, sulfoxaflor, sulfoxamyl, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglycapin, sulphosate, sulprofos, sultropen, swep, toz -fluvalinate, tavron, tazimcarb, TBTO, TBZ, TCA, TCBA, TCMTB, TCNB, TDE, tebuconazole, tebufenozide, tebufenpyrad,tebufloquin, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tecoram, tedion, teflubenzuron, tefluthrin, tefuryltrione, tembotrione, temefos, temephos, tepa, TEPP, tepraloxydim, teproloxydim, terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuthylazine, terbutol, terbutryn, terbutryne, terraclor, terramicin, terramycin, tetcyclacis, tetflupyrolimet, tetrachlorantraniliprole, tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, tetradisul, tetrafluron, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetraniliprole, tetrapion, tetrasul, thallium sulfate, thallous sulfate, thenylchlor, theta- cypermethrin, thiabendazole, thiacloprid, thiadiazine, thiadifluor, thiamethoxam, thiameturon, thiapronil, thiazafluron, thiazfluron, thiazone, thiazopyr, thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone, thifensulfuron, thifluzamide, thimerosal, thimet, thiobencarb, thiocarboxime, thiochlorfenphim, thiochlorphenphime, thiocyanatodinitrobenzenes, thiocyclam, thiodan, thiodiazole-copper, thiodicarb, thiofanocarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon, thionazin, thiophanate, thiophanate-ethyl, thiophanate- methyl, thiophos, thioquinox, thiosemicarbazide, thiosultap, thiotepa, thioxamyl, thiram, thiuram, thuringiensin, tiabendazole, tiadinil, tiafenacil, tiaojiean, tiapyrachlor, TIB A, tifatol, tigolaner, tiocarbazil, tioclorim, tiorantraniliprole, tioxazafen, tioxymid, tirpate, TMTD, tolclofos-methyl, tolfenpyrad, tolprocarb, tolpyralate, tolyfluanid, tolylfluanid, tolylmercury acetate, tomarin, topramezone, toxaphene, TPN, tralkoxydim, tralocythrin, tralomethrin, tralopyril, transfluthrin, transpermethrin, tretamine, triacontanol, triadimefon, triadimenol, triafamone, triallate, tri-allate, triamiphos, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, triazbutil, triaziflam, triazophos, triazothion, triazoxide, tribasic copper chloride, tribasic copper sulfate, tribenuron, tribufos, tributyltin oxide, tricamba, trichlamide, trichlopyr, trichlorfon, trichlormetaphos-3, trichloronat, tri chi or onate, trichlorotrinitrobenzenes, trichlorphon, triclopyr, triclopyricarb, tricresol, tricyclazole, tricyclohexyltin hydroxide, tridemorph, tridiphane, trietazine, trifenmorph, trifenofos, trifloxystrobin, trifloxysulfuron, trifludimoxazin, trifluenfuronate, triflumezopyrim, triflumizole, triflumuron, trifluralin, triflusulfuron, trifop, trifopsime, triforine, trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac, triphenyltin, triprene, tripropindan, triptolide, tripyrasulfone, tritac, trithialan, triti conazole, tritosulfuron, trunc-call, tuoyelin, tyclopyrazoflor, umifoxolaner, uniconazole, uniconazole-P, urbacide, uredepa, vadescana, valerate, validamycin, validamycin A, valifenalate, valone, vamidothion, vangard, vaniliprole, vernolate, vinclozolin, vitamin D3, warfarin, xiaochongliulin, xinjunan, xiwojunan, xiwojunzhi, XMC, xylachlor, xylenols, xylylcarb, xymiazole, yishijing, zarilamid, zeatin, zengxiaoan, zengxiaolin, zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zinc thiozole, zinc tri chlorophenate, zinctrichlorophenoxide, zineb, ziram, zolaprofos, zoocoumarin, zoxamide, zuoanjunzhi, zuocaoan, zuojunzhi, zuomihuanglong, a-chlorohydrin, a-ecdysone, a-multistriatin, a- naphthaleneacetic acids, and P-ecdysone.
[0109] In some preferred aspects, the pesticidal formulation of the present disclosure can contain one or more additional fungicide as pre-mix, or being tank mixed with the one or more additional fungicides, or applied sequentially with the one or more additional fungicides. The additional fungicides may include In another aspect, the additional fungicides may include 2- (thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, acibenzolar-S-methyl, ametoctradin, aminopyrifen, amisulbrom, antimycin, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, bifem etstrobin, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroinconazide, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyclobutrifluram, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, feneptamidoquin, fenfuram, fenhexamid, fenopyramid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flubeneteram, fludioxonil, flufenoxadiazam, fluindapyr, flumetyl sulforim, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxapiprolin, fluoxastrobin, fluoxytioconazole, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), inpyrfluxam, iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamid, isoflucypram, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxium-methyl, laminarin, mancopper,mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metarylpicoxamid, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picarbutrazox, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propi conazole, propineb, proquinazid, prothioconazole, pydiflumetofen, pyrametostrobin, pyraoxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, quinoclamine, quinoxyfen, quintozene, seboctylamine, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, fungicidal sulfur derivatives, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate- methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triti conazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, (RS)-N-(3,5- dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-di chloropropane, 1,3 -di chi oro-1, 1,3,3- tetrafluoroacetone hydrate, 1 -chi oro-2, 4-dinitronaphthalene, l-chloro-2-nitropropane, 2-(2- heptadecyl-2-imidazolin- 1 -yl)ethanol, 2,3 -dihydro-5 -phenyl- 1 ,4-dithi-ine 1 , 1 ,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-l-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bi s(m ethylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chi obenthi azone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, coumoxystrobin, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlobentiazox, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipymetitrone, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, enoxastrobin, ESBP, etaconazole, etem, ethirim, fenaminstrobin, fenaminosulf, fenapanil, fenitropan,fenpicoxamid, florylpicoxamid, flufenoxystrobin, fluopimomide, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, ipfentrifluconazole, ipflufenoquin, isopamphos, isovaledione, mandestrobin, mebenil, mecarbinzid, mefentrifluconazole, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, metyltetraprole, milneb, mucochloric anhydride, myclozolin, 7V-3,5-dichlorophenyl-succinimide, N-3- nitrophenylitaconimide, natamycin, A-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyrapropoyne, pyridachlometyl, pyridinitril, pyrisoxazole, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, quinofumelin, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, triclopyricarb, triflumezopyrim, urbacid, and zarilamid.
[0110] In some more preferred aspects, the pesticidal formulation of the present disclosure comprises one or more additional fungicide selected from quinone inside inhibitor (Qil) fungicides. The quinone inside inhibitor (Qil) fungicides may be cyano-imidazole fungicides, sulfamoyl-triazole fungicides, and picolinamide fungicides. Nonlimiting examples of cyanoimidazole fungicides include cyazofamid. Nonlimiting examples of sulfamoyl-triazole fungicides include amisulbrom. Nonlimiting examples of picolinamide fungicides include fenpicoxamid, florylpicoxamid, and metarylpicoxamid. The preferred additional fungicides are picolinamide fungicides. The preferred picolinamide fungicide is florylpicoxamid.
[0111] In some aspects, the formulations of the present disclosure may include one or more fungicidal active ingredients in addition to the compound of Formula I or Formula I-B. In some aspects, the formulations do not include a fungicidal active ingredient in addition to the compound of Formula I or Formula I-B. In some aspects, the formulations may exclude one or more fungicidal active ingredients specified above. In some aspects, the formulations may include one or more fungicidal active ingredients in addition to the compound of Formula I or Formula I-B, but may exclude one or more fungicidal ingredients specified above.
[0112] In some most preferred aspects, the present disclosure provides fungicidal formulations with low moisture content that comprise the compound of Formula I and florylpicoxamid. Preferably, the moisture content in such fungicidal formulations is at no more than 1% in weight percent based on the total weight of the formulation. More preferably, themoisture content in such fungicidal formulations is at no more than 0.5% in weight percent based on the total weight of the formulation. Most preferably, the moisture content in such fungicidal formulations is at no more than 0.1% in weight percent based on the total weight of the formulation.
[0113] Surprisingly, the fungicidal formulations with low moisture content that comprise the compound of Formula I and florylpicoxamid show significantly improved stability when compared to the fungicidal formulations comprising the compound of Formula I and florylpicoxamid that contain higher moisture content.
[0114] In some alternatively most preferred aspects, the present disclosure provides fungicidal formulations that comprise the compound of Formula I, florylpicoxamid, and at least one dehydrating agent. Preferably, the at least one dehydrating agent is selected from molecular sieves. More preferably, the at least one dehydrating agent is molecular sieve 3 A.
[0115] In particularly preferred aspects, the present disclosure provides fungicidal formulations with low moisture content that comprises the compound of Formula I and florylpicoxamid, which is prepared by removing dehydrating agents from fungicidal formulations comprising the compound of Formula I, florylpicoxamid, and at least one dehydrating agent. Preferably, the at least one dehydrating agent is selected from molecular sieves. More preferably, the at least one dehydrating agent is molecular sieve 3 A.
[0116] In some aspects, the formulations comprise, in weight percent based on the total weight of the formulation, from about 0.1% to about 99% of the additional fungicide (e.g., about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, , 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 82.5%, 85%, 87.5%, 90%, 92.5%, or 95% of the additional fungicide, or within any range defined from any two of the forgoing values, such as from about 1% to about 95%, from about 10% to about 60%, from about 20% to about 45%, from about 55% to about 82.5%, or from about 12.5% to about 50% of the additional fungicide, by weight percent based on the total weight of the formulation. In some aspects, the formulations comprise, in grams active ingredient per liter (g ai / L) of the formulation, a concentration from about 1 g ai / L to about 850 g ai / L of the additional fungicide (e.g., about 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 12.5, 15, 17.5, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 110, 112, 115, 117, 120, 125, 130, 140, 150, 160, 170, 175, 180, 190, 200, 210, 215, 220, 225, 230, 240, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 800, or 850 g ai / Lof the additional fungicide, or within any range defined from any two of the forgoing values, such as from about 1 g ai / L to about 750 g ai / L, from about 1 g ai / L to about 600 g ai / L, from about 1 g ai / L to about 500 g ai / L, from about 1 g ai / L to about 450 g ai / L, from about 10 g ai / L to about 350 g ai / L, from about 20 g ai / L to about 150 g ai / L, or from about 112 g ai / L to about 250 g ai / L of the additional fungicide.3. Adjuvants
[0117] In some aspects, the additive includes an agriculturally acceptable adjuvant. Suitable adjuvants can enhance the biological performance of the formulation. Examples of adjuvants are any agents which promote solubility, stability, defoaming, compatibility of ingredients, and UV light protection of the pesticidal formulation; draft reduction and spray efficiency of the pesticidal formulation; and wetting, spreading, retention, deposition, adhesion, and penetration of the pesticidal formulation. The adjuvant as a component of the formulation refers to built-in adjuvant. Examples of suitable built-in adjuvants include, but not limited to, solvent and emulsifiers that are exemplified in previous context. Exemplary agriculturally acceptable adjuvants include, but are not limited to, solvents, co-solvents, antifreeze agents, antifoam agents, compatibilizing agents, sequestering agents, neutralizing agents and buffers, pH modifiers, corrosion inhibitors, colorants, odorants, penetration aids, wetting agents, spreading agents, dispersing agents, thickening agents, flow aids, anti-caking agents, crystallization inhibitors, antimicrobial agents, crop oil, adhesives (for instance, for use in seed formulations), surfactants, protective colloids, emulsifiers, tackifiers, UV absorbers or stabilizers, and mixtures thereof.
[0118] Exemplary agriculturally acceptable adjuvants include, but are not limited to, crop oil concentrates (e.g., 85% mineral oil + 15% emulsifiers); benzylcocoalkyldimethyl quaternary ammonium salts; nonylphenol ethoxylates; polyalkylene oxide alkyl ethers; blends of petroleum hydrocarbon, alkyl esters, organic acids, and anionic surfactants; C9-C11 alkylpolyglycoside; phosphate alcohol ethoxylates; natural primary alcohol (C12-C16) ethoxylate; di- ec-butylphenol EO-PO block copolymers; polysiloxane-methyl cap; nonylphenol ethoxy late+urea ammonium nitrates; emulsified methylated seed oils; tridecyl alcohol (synthetic) ethoxylates (e.g., 8 EO); tallow amine ethoxylates (e.g., 15 EO); and PEG(400) dioleate-99.
[0119] Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants, emulsifiers) include, but are not limited to: the alkali metal salts, alkaline earth metal salts and ammoniumsalts of fatty acids or of aromatic sulfonic acids (e.g., lignosulfonic acids, phenol sulfonic acids, naphthalenesulfonic acids, and dibutylnaphthalenesulfonic acid); alkyl- and alkylarylsulfonates; alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates; salts of sulfated hexa-, hepta- and octadecanols; salts of fatty alcohol glycol ethers; condensates of sulfonated naphthalene and its derivatives with formaldehyde; condensates of naphthalene or of the naphthalene sulfonic acids with phenol and formaldehyde; polyoxyethylene octylphenol ether; ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether; alkyl aryl polyether alcohols; isotridecyl alcohol; fatty alcohol / ethylene oxide condensates; ethoxylated castor oil; polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers; lauryl alcohol polyglycol ether acetate; sorbitol esters; lignosulfite waste liquors and proteins; denatured proteins, polysaccharides (e.g., methylcellulose); hydrophobically modified starches; and polyvinyl alcohol, polycarboxylates, polyalkoxylates, polyvinyl amine, polyethyleneimine, polyvinylpyrrolidone, and copolymers thereof.[01.20] Exemplary thickeners include, but are not limited to, polysaccharides (e.g., xanthan gum), organic and inorganic sheet minerals, and mixtures thereof.
[0121] Exemplary antifoam agents include, but are not limited to, silicone emulsions, long- chain alcohols, fatty acids, fatty acid salts, organofluorine compounds, and mixtures thereof.
[0122] Exemplary antimicrobial agents include, but are not limited to, bactericides based on dichlorophen and benzyl alcohol hemiformal; isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones; and mixtures thereof.
[0123] Exemplary antifreeze agents include, but are not limited to ethylene glycol, propylene glycol, urea, glycerol, and mixtures thereof.
[0124] Exemplary colorants include, but are not limited to, the dyes known under the names Rhodamine B, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108, and mixtures thereof.
[0125] Exemplary adhesives include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof.4. Carriers
[0126] In some aspects, the additive includes a carrier. In some aspects, the additive includes a liquid or solid carrier. In some aspects, the additive includes an organic or inorganic carrier. Exemplary liquid carriers include, but are not limited to: water; aqueous liquids; petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; fatty acid esters; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethyl hexyl stearate, / / -butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono, di and polycarboxylic acids and the like; toluene; xylene; petroleum naphtha; crop oil; acetone; methyl ethyl ketone; cyclohexanone; trichloroethylene; perchloroethylene; ethyl acetate; amyl acetate; butyl acetate; propylene glycol monomethyl ether and diethylene glycol monomethyl ether; methyl alcohol; ethyl alcohol; isopropyl alcohol; amyl alcohol; ethylene glycol; propylene glycol; glycerin; 7V-methyl-2-pyrrolidinone; 7V; / V-dimethyl alkylamides; dimethyl sulfoxide; and liquid fertilizers, as well as mixtures thereof. Exemplary solid carriers include, but are not limited to: silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, pyrophyllite clay, attapulgus clay, kieselguhr, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, and mixtures thereof.
[0127] Exemplary adhesives include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof.C. Packaging
[0128] In some aspects, the formulation can be in the form of a single package formulation containing the compound of Formula I or Formula I-B. In some aspects, the formulation can be in the form of a single package formulation containing the compound of Formula I or Formula I-B, and further including at least one additive. In some aspects, the formulation can be in the form of a multi-package formulation, such as a two-package formulation, whereinone package contains the compound of Formula I or Formula I-B, while the other package contains at least one additive. In some aspects of the two-package formulation, the formulation contains the compound of Formula I or Formula I-B, and the formulation including at least one additive are mixed before application and then applied simultaneously. In some aspects, the mixing is performed as a tank mix (e.g., the formulations are mixed immediately before or upon dilution with water). In some aspects, the formulation contains the compound of Formula1 or Formula I-B, and the formulation including at least one additive are not mixed as a tank mix, but rather are applied sequentially (in succession), for example, immediately or within 1 hour, within 2 hours, within 4 hours, within 8 hours, within 16 hours, within 24 hours, within2 days, or within 3 days, of each other.VI. Methods of Use
[0129] The pesticidal formulations disclosed herein can be applied in any known technique for applying pesticides or fungicides. Exemplary application techniques include, but are not limited to, spraying, atomizing, dusting, sprinkling, spreading, or direct application into water. The method of application can vary depending on the intended purpose. In some aspects, the method of application can be chosen to ensure the finest possible distribution of the formulations disclosed herein.
[0130] In some aspects, the present disclosure provides a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented with any of the formulations disclosed herein.
[0131] In some aspects, the present disclosure provides a method for the control or prevention of fungal attack on a plant, the method including the steps of applying any of the formulations disclosed herein to at least one of the fungus, a seed, the plant, and an area adjacent to the plant.
[0132] In some aspects, the present disclosure provides a method for the control or prevention of fungal attack on a plant, the method comprising contacting an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, foliage of the plant, and a growth medium adapted to grow a plant or a seed, with any of the formulations disclosed herein.
[0133] In some aspects, the present disclosure provides a method for the control or prevention of fungal attack on a plant, the method including the steps of applying any of the formulations disclosed herein to a growth medium adapted to grow a plant or a seed.
[0134] In some aspects, the present disclosure provides a use of the formulations disclosed herein, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of any of the formulations disclosed herein to soil, a plant, a part of a plant, foliage, and / or roots.
[0135] In some aspects, the formulations disclosed herein are applied to an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, foliage of the plant, and a growth medium adapted to grow a plant or a seed, by spraying (e.g., foliar spraying). In some aspects, the spraying techniques use, for example, water as carrier and spray volume rates of from 2 liters per hectare (L / ha) to 2000 L / ha (e.g., from 10-1000 L / ha or from 50-500 L / ha). In some aspects, the formulations disclosed herein are applied by the low-volume or the ultra- low-volume method, wherein the application is in the form of micro granules. In some aspects, the formulations disclosed herein can be applied as dry formulations (e.g., granules, water dispersible granules (WDG), powders, or dusts).
[0136] In some aspects, fungicidal activity is exhibited by the compounds of the mixture when they are applied directly to the plant or to the locus of the plant at any stage of fungal diseases or before infestation. The effect observed can depend upon the type of fungal pathogen and disease to be controlled, the stage of the fungal disease, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. In some aspects, these and other factors can be adjusted to promote non-selective or selective fungicidal action.
[0137] The formulations and methods disclosed herein can be used to control fungal pathogens or diseases from fungal pathogens in a variety of applications. The formulations and methods disclosed herein can be used for controlling fungal pathogens or diseases from fungal pathogens in areas including, but not limited to, farmland, turfgrass, pastures, grasslands, rangelands, fallow land, rights-of-way, aquatic settings, tree and vine, wildlife management areas, or rangeland. In some aspects, the fungal pathogen or disease is controlled in a row crop. Exemplary crops include, but are not limited to, wheat, barley, triticale, rye, teff, oats, maize,cotton, soy, sorghum, rice, millet, sugarcane and range land (e.g., pasture grasses). In some aspects, the formulations and methods disclosed herein can be used for controlling fungal pathogens or diseases from fungal pathogens in maize, wheat, barley, rice, sorghum, millet, oats, or a combination thereof. In some aspects, the formulations and methods disclosed herein can be used for controlling fungal pathogens or diseases from fungal pathogens in broadleaf crops. In some aspects, the formulations and methods disclosed herein can be used for controlling fungal pathogens or diseases from fungal pathogens in canola, flax, sunflower, soy, or cotton. In some aspects, the formulations and methods disclosed herein can be used to control fungal pathogens or diseases from fungal pathogens in conservation reserve program lands (CRP), trees, vines, grasslands, and grasses grown for seeds. In some aspects, the formulations and methods disclosed herein can be used on lawns e.g., residential, industrial, and institutional), golf courses, parks, cemeteries, athletic fields, and sod farms.
[0138] The compositions and methods disclosed herein can also be used in crop plants that are resistant to, for instance, herbicides, insecticides, fungicides, pathogens, insects, or combinations thereof. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more herbicides because of genetic engineering or breeding. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more pathogens such as plant pathogenic fungi owing to genetic engineering or breeding. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to attack by insects owing to genetic engineering or breeding. In some aspects, the compositions described herein and other complementary fungicides are applied at the same time, either as a combination composition or as a tank mix, or as sequential applications. The compositions and methods may be used in controlling fungal pathogens or diseases from fungal pathogens in crops possessing agronomic stress tolerance (including but not limited to drought, cold, heat, salt, water, nutrient, fertility, pH), pest tolerance (including but not limited to insects, fungi, and pathogens), and crop improvement traits (including but not limited to yield; protein, carbohydrate, or oil content; protein, carbohydrate, or oil composition; plant stature and plant architecture).
[0139] The formulation described herein may be used to control fungal pathogens that may include, but are not limited to:
[0140] On cucurbits: powdery mildew (Erysiphe cichoracearum, Sphaerotheca fuliginea, Podosphaera xanthii), ring spot (Mycosphaerella brassicicola), blackleg (Plenodomus lingam), anthracnose (Colletotrichum higginsianum, Colletotrichum obiculare, Colletotrichumspp., Glomerella lagenarium), gummy stem blight (Mycosphaerella melonis, Didymella bryoniae, Stagonosporopsis cucurbilacearum Altemaria leaf spot and blight (Alternaria cucumerina, Alternaria alternata f. sp. cucurbitae, Alternaria spp.), Cercospora leaf spot (Cercospora citrullina, Cercospora spp.), Fusarium wilt (Fusarium oxysporum), belly rot (Rhizoctonia solani), Corynespora blight / target spot (Corynespora cassiicola). scab (Cladosporium cucumerinum). Verticillium wilt (Verticillium dahliae, Verticillium albo- alrum), black root rot (Thielaviopsis basicola), blue mold rot (Penicillium spp.), charcoal rot (Macrophomina phaseolina , and crater rot (fruit) (Myrothecium roridurriy,
[0141] On tomato: powdery mildew (Leveillula laurica), Septoria leaf spot (Septoria lycopersici), white mold (Sclerotinia sclerotiorum, Sclerotinia minor), target spot (Corynespora cassiicola), southern blight (Sclerotium rolfsii), gray mold (Botrytis cinerea), gray leaf spot (Stemphylium spp.), Fusarium wilt, Fusarium crown and root rot (Fusarium oxysporum , anthracnose (Colletotrichum coccodes, Colletotrichum dematium, Colletotrichum gloeosporioides, Glomerella cingulate), Altemaria stem canker and black mold (Alternaria alternata), black root rot (Chalara elegans), Cercospora leaf mold (Cercospora fuligena), charcoal rot (Macrophomina phaseolina), corky root rot (Pyrenochaeta lycopersici), Didymella stem rot (Didymella lycopersici), early blight (Alternaria solani), leaf mold (Passalora fulva, Mycovellosiella fulva), phoma rot (Phoma destructiva), and sour rot (Geotrichum candidum),'
[0142] On leafy vegetables: Cercospora leaf spot (Cercospora longissimi, Cercospora spp.), gray mold / Botrytis rot (Botrytis cinerea), Altemaria leaf spot and blight (Alternaria sonchi, Alternaria spp.), powdery mildew (Erysiphe cichor acearum, Golovinomyces cichor acearum, Uncinula spp.), rust (Puccinia dioicae), Septoria leaf spot (Septoria lactucae, Septoria spp.), southern blight (Sclerotium rolfsii), basal rot Phoma exigua), Rhizoctonia bottom rot (Rhizoctonia solani), Sclerotinia drop (Sclerotinia minor, Sclerotinia sclerotiorum), and Stemphylium leaf spot (Stemphylium botryosum),'
[0143] On potato: anthracnose or black dot (Colletotrichum coccodes), brown spot and black pit (Alternaria alternata), Cercospora leaf blotch (Cercospora concors), charcoal rot (Macrophomina phaseolina), common rust (Puccinia pittieriana), deforming rust (Aecidium cantensis), early blight (Alternaria solani), Fusarium dry rot and Fusarium wilt (Fusarium spp.), gangrene Phoma exigua f. sp. foveata), gray mold (Botrytis cinerea), black blight or Phoma leaf spot (Stagonosporopsis andigena, Phoma andigena var. andinai), powdery mildew (Erysiphe cichoracearum), Rhizoctonia canker and black scurf Rhizoctonia solani), Roselliniablack rot (Rosellinia spp), Septoria leaf spot (Septoria lycopersici var. malagutil), silver scurf (Helminthosporium solani), skin spot (Polyscytalum pustulans), stem rot (Sclerotium rolfsii), Thecaphora smut (Thecaphora solani), Ulocladium blight (Ulocladium alrum), Verticillium wilt (Verticillium albo-alrum), and white mold (Sclerotinia sderoliorum)
[0144] On peppers: southern blight (Sclerotium rolfsii), powdery mildew (Leveillula laurica), anthracnose (Colletotrichum capsici, Colletorichum acutalum, Colletorichum spp.), Cercospora (frogeye) leaf spot (Cercospora capsici, Cercospora spp.), charcoal rot (Macrophomina phaseo na), damping-off and root rot (Rhizoctonia solani), Fusarium stem rot (Fusarium solani), Fusarium wilt (Fusarium oxysporum f. sp. capsici), gray leaf spot (Stemphylium spp.), gray mold (Botrytis cinerea), Verticillium wilt (Verticillium albo-alrum), and white mold (Sclerotinia sderoliorum
[0015] On cole crops: Altemaria leaf spot and blight (Alternaria brassicicola, Alternaria spp.), Anthracnose (Colletotrichum spp.), black leg (Leptosphaeria maculans, Phoma lingam), Cercospora leaf spot (Cercopsora spp.), Fusarium yellows and other diseases (Fusarium spp.), gray mold / Botrytis blight (Botrytis cinerea), powdery mildew (Erysiphe polygoni), Rhizoctonia rot and blight (Rhizoctonia solani), ring spot (Mycosphaerella brassicicola , Sclerotinia rot (Sclerotinia spp.), white leaf spot (Pseudocercosporella capsellae).
[0146] On sugar beets: Alternaria leaf spot (Alternaria alternate, Alternaria brassicae), anthracnose (Colletrotrichum dematium), Aphanomyces root rot (Aphanomyces cochlioides), Cercospora leaf spot (Cercospora beticola), charcoal rot (Macrophomina paseaolina), Choanephora rot (Choanephora cucurbitarum), damping-off, black leg, black root, and seedling blight (Aphanomyces cochlioides, Cylindrocladium spp., Fusarium spp., Phoma betae, Pleospora betae, Rhizoctonia solani, Thanatephorus cucumeris), Fusarium yellows (Fusarium oxysporum), leaf gall / beet tumor / crown wart (Physoderma leproides), phoma leaf spot and root rot Phoma betae), cotton root rot (Phymatotrichopsis omnivore), powdery mildew (Erysiphe polygoni, Erysiphe betae), Ramularia leaf spot (Ramularia beticola), Rhizoctonia foliar blight, crown rot, root rot (Rhizoctonia solani), Rhizopus root rot (Rhizopus arrhizus, Rhizopus stolonifera), rust (Uromyces betae), Sclerotinia crown and root rot (Sclerotinia sclerotiorum), seedling rust (Puccini subnitens), southern blight, Sclerotium root rot and stem rot (Sclerotium rolfsii), Stemphylium leaf spot (Stemphylium botryosum), storage rots (Botrytis cinerea, Penicillium spp., Phoma betae), Verticillium wilt (Verticillium albo- atrum) and violet root rot (Helicobasidium brebissonii),'
[0147] On rice: Seedling Diseases - Seedling Blight (Cochliobolus miyabeanus, Curvularia spp., Fusarium spp., Rhizoctonia solani, Sclerotium rolfsii, Athelia rolfsii and others); Seed Box Diseases - Cochliobolus miyabeanus, Gibberella fujikuroi (anam. Fusarium moniliforme), Phoma exigua, Fusarium ssp., Pythium ssp., Rhizopus spp., Tricoderma viride, Rhizoctonia solani, Sclerotium rolfsii,' Foliar Diseases - blast (Magnaporthe grisea), brown spot (Cochliobolus miyabeanus), leaf scald (Monographella albescens, Microdochium oryzae, Rhynchosporium oryzae), narrow brown leaf spot (Sphaerulina oryzina, Cercospora janseana, Cercospora oryzae), stackburn or Alternaria leaf spot (Alternaria padwickii), leaf smut (Eballistra oryzae, Entyloma oryzae), eyespot (Drechslera gigantea), white leaf streak (Mycovellosiella oryzae), collar rot (Phomopsis oryzae-sativae), rusts (Puccinia graminis f. sp. oryzae, Uromyces coronatus), Sheath and Culm Diseases - stem rot (Magnaporthe salvinii, Sclerotium oryzae [synanamorph]), sheath blight (Thanatephorus cucumeris, Rhizoctonia solani [anamorph]), sheath spot (Waitea circinata, Rhizoctonia oryzae [anamorph]), aggregate sheath spot (Thanetephorus cucumeris, Rhizoctonia solani [anamorph]), Waitea circinata, Rhizoctonia oryzae [anamorph]), Ceratobasidium oryzae sativae, Rhizoctonia oryzae-sativae [anamorph]), sheath net blotch (Cylindrocladium scoparium), sheath rot (Sarocladium oryzae), crown sheath rot (Gaeumannomyces graminis), Myrothecium blotch (Myrothecium verrucaria), sheath blotch (Pyrenochaeta oryzae),' Root and Crown Diseases - bakanae (Gibberella fujikuroi, Fusarium moniliforme [anamorph]), root rots (Fusarium spp.); Grain Diseases - false smut (Villosiclava virens), Udbatta (Balansia oryzae-sativae), glume blight (Epicoccum sorghi), black kernel (Cochliobolus lunatus), minute leaf and grain spot (Cochliobolus miyabeanus), red blotch of grains (Epicoccum nigrum), ear blight (Cochliobolus miyabeanus, Sphaerulina oryzina, Cochliobolus lunatus, Monographella nivalis, Fusarium spp., Phoma spp., Monographella albescens, Magnaporthe salvinii, Cladosporoium spp., Epicoccum sp., Nigrospora spp.);
[0148] On soybean: Alternaria leaf spot (Alternaria spp.), anthracnose (Colletotrichum truncatum, Colletotrichum dematium f truncatum, Glomerella glycines), black leaf blight (Arkoola nigra), black root rot (Thielaviopsis basicola, Chalara elegans), brown spot (Septoria glycines, Mycosphaerella usoenskajae), brown stem rot (Phialophora gregata, Cephalosporium gregatum), charcoal rot (Macrophomina phaseolina), Choanephora leaf blight (Choanephora infundibulifera, Choanephora trispora), damping-off, stem, root rot and aerial blight (Rhizoctonia solani, Thanatephorus cucumeris), Drechslera blight (Drechslera glycines), frogeye leaf spot (Cercospora sojina), Fusarium root rot (Fusarium spp.),Leptosphaerulina leaf spot (Leptosphaerulina trifolii), Mycoleptodiscus root rot (Mycoleptodiscus lerreslris . Neocosmospora stem rot (Neocosmospora vasinfecta, Acremonium spp.), Phomopsis seed decay (Phomopsis spp.), Phyllosticta leaf spot (Phyllosticta sojaecola), Phymatotrichum root rot, cotton root rot (Phymatotrichopsis omnivora, Phymatotrichum omnivorum), pod and stem blight (Diaporthe phaseolorum, Phomopsis sojae), powdery mildew (Microsphaera diffusa), purple seed stain (Cercospora kikuchii), Pyrenochaeta leaf spot (Pyrenochaeta glycines), red crown rot (Cylindrocladium crotalariae, Calonectria crotalariae), red leaf blotch, Dactuliophora leaf spot (Coniothyrium glycines, Dactuliochaeta glycines), rust (Phakopsora pachyrhizi), scab (Spaceloma glycines), Sclerotinia stem rot (Sclerotinia sclerotiorum), Southern blight, Sclerotium blight, damping- off and stem rot (Sclerotium rolfsii, Athelia rolfsii), stem canker (Diaporthe phaseolorum, Diaporthe phaseolorum var. caulivora, Phomopsis phaseoli), Stemphylium leaf blight (Stemphylium botryosum, Pleospora tarda), sudden death syndrome (Fusarium virguliforme, Fusarium solani f. sp. glycines), target spot (Corynespora cassiicola), white mold (Sclerotinia sclerotiorum), yeast spot (Nematospora coryli),'
[0149] On com: Anthracnose (Colletotrichum graminicola, Glomerella tucumanensis), Aspergillus ear and kernel rot (Aspergillus jlavus), banded leaf and sheath spot (Rhizoctonia solani, Rhizoctonia microsclerotia), black bundle disease (Acremonium strictum, Cephalosporium acremonium), black kernel rot (Marasmiellus spp.), brown spot, black spot, stalk rot (Physoderma maydis), Cephalosporium kernel rot (Acremonium strictum, Cephalosporium acremonium), charcoal rot (Macrophomina phaseolina), Corticium ear rot (Thanatephorus cucumeris, Corticium sasakii), Curvularia leaf spot (Curvularia spp.), Didymella leaf spot (Didymella exitalis), Diplodia ear rot, stalk rot, leaf spot, leaf streak (Diplodia spp.), dry ear rot, cob, kernel and stalk rot (Nigrospora oryzae), ear rots (Alternaria spp., Aspergillus spp., Botrytis cinerea, Fusarium culmorum, Cunninghamella spp., Curvularia pallescens, Rhizopus spp., Gonatobotrys simplex, Doratomyces stemonitis, Cephalotrichum stemonitis, Pithomyces maydicus, Scopulariopsis brumptii), ergot (Claviceps gigantea), eyespot (Aureobasidium zeae, Kabatiella zeae), Fusarium kernel, root and stalk rot, seed rot, stalk rot, ear rot, and seedling blight (Fusarium spp., Gibberella spp.), gray ear rot (Botryosphaeria zeae, Physalospora zeae), gray leaf spot, Cercospora leaf spot (Cercospora sorghi, Cercospora zeae-maydis), Helminthosporium root rot (Exserohilum pedicellatum, Helminthosporium pedicellatum), Cladosporium rot (Cladosporium spp.), leaf spots (Alternaria alternata, Ascochyta maydis, Ascochyta tritici, Ascochyta zeicola, Bipolarisvictoriae, Helminthosporium victoriae, Cochliobolus victoriae, Cochliobolus sativus, Bipolaris sorokiniana, Epicoccum nigrum, Exserohilum prolatum, Drechslera prolata, Graphium penicillioides, Leptosphaeria maydis, Leptothyrium zeae, Ophiosphaerella herpotricha, Paraphaeosphaeria michotii, Phoma spp., Septoria spp.), Northern corn leaf blight (Setosphaeria turcica), white blast, stalk rot, stripe (Exserohilum turcicum, Helminthosporium turcicum), Northern corn leaf spot (Cochliobolus carbonum , Helminthosporium ear rot (Bipolaris zeicola, Helminthosporium carbonum), Penicillium ear rot, blue eye, blue mold (Pennicillium spp.), Phaeocytostroma stalk rot and root rot (Phaeocytostroma ambiguum, Phaeocytosporella zeae), Phaeosphaeria leaf spot (Phaeosphaeria maydis, Sphaerulina maydis), Physalospora ear rot, Botryosphaeria ear rot (Botryosphaeria festucae, Physalospora zeicola), Pyrenochaeta stalk rot and root rot (Phoma terrestris, Pyrenochaeta terrestris), red kernel disease, ear mold, leaf and seed rot (Epicoccum nigrum), Rhizoctonia ear rot, root rot, stalk rot (Rhizoctonia spp.), root rots (Alternaria alternata, Cercospora sorghi, Dictochaeta fertilis, Fusarium spp., Gibberella spp., Microdochium bolleyi, Mucor spp., Periconia circinata, Rhizopus arrhizus) Rostratum leaf spot, Helminthosporium leaf disease, ear and stalk rot (Setosphaeria rostrata, Helminthosporium rostratum), rusts (Puccinia spp., Physopella spp.), brown rust of corn (Puccinia polysora), Sclerotium ear rot, Southern blight (Sclerotium rolfsii), seed rot-seedling blight (Bipolaris spp., Helminthosporium spp., Diplodia maydis, Exserohilum spp., Fusarium spp., Gibberella spp., Macrophomina phaseolina, Penicillium spp., Phomopsis spp., Rhizoctonia spp., Sclerotium rolfsii, Spicaria spp.), Selenophoma leaf spot (Selenophoma sp.), sheath rot (Gaeumannomyces graminis), shuck rot (Myrothecium gramineum), silage mold (Monascus spp.), smuts (Ustilago spp., Ustilaginoidea virens, Sphacelotheca reiliana, Sporisorium holci-sorghi), Southern corn leaf blight and stalk rot (Cochliobolus heterostrophus, Bipolaris maydis, Helminthosporium maydis), stalk rots (Cercospora sorghi, Fusarium spp., Nectria haematococca, Mariannaea elegans, Mucor spp., Rhopographus zeae, Spicaria spp.), storage rots (Aspergillus spp., Penicillium spp.), tar spot (Phyllachora maydis, Monographella maydis, Coniothyrium phyllachorae), Trichoderma ear rot and root rot (Trichoderma viride, Trichoderma lignorum, Hypocrea spp), white ear rot, root and stalk rot (Stenocarpella maydis, Diplodia zeae), yellow leaf blight (Ascochyta ischaemi, Phyllosticta maydis, Mycosphaerella zeae-maydis) and Zonate leaf spot (Gloeocercospora sorghi), '
[0150] On barley: Anthracnose (Colletotrichum cereale Manns), barley stripe (Pyrenophora graminea), common root rot, crown rot and seedling blight (Cochliobolussativus, Fusarium culmorum, Fusarium graminearum), dwarf bunt Tilletia controversa), ergot Claviceps purpurea), eyespot (Pseudocercosoporella herpotrichoides), halo spot (Pseudoseptoria donacis), kernel blight ( Alter naria spp., Arthrinium arundinis, Cochliobolus sativus, Fusarium spp.), Ascochyta leaf spot (Ascochyta spp.), net blotch (Drechslera teres, Pyrenophora teres), powdery mildew (Erysiphe graminis f.sp. hordei, Blumeria graminis), Rhizoctonia root rot (Rhizoctonia solani), crown rust (Puccinia coronata var. hordei), leaf rust (Puccinia hordei), stem rust (Puccinia graminis), stripe rust / yellow rust (Puccinia striiformis f. sp. hordei), scab / head blight (Fusarium spp.), Septoria speckled leaf blotch (Septoria passerinii, Stagonospora avenae f.sp. triticae), sharp eyespot (Rhizoctonia cerealis), covered smut (Ustilago hordei), false loose smut (Ustilago nigra), loose smut (Ustilago nuda), gray snow mold / Typhula blight (Typhula incarnata, Typhula ishikariensis), pink snow mold / Fusarium patch (Microdochium nivale), Ramularia leaf spot of barley (Ramularia collo- cygni), speckled snow mold (Typhula idahoensis), snow scald / Sclerotinia snow mold (Myriosclerotinia borealis, Sclerotinia borealis), southern blight (Sclerotium rolfsii), spot blotch (Cochliobolus sativus), Stagonospora blotch (Stagonospora avenae f.sp. triticae, Stagonospora nodorum, Septoria nodorum), take-all (Gaeumannomyces graminis var. tritici), tan spot (Pyrenophora tritici-repentis, Pyrenophora trichostoma) and Verticillium wilt (Verticillium dahliae),'
[0151] On wheat: Altemaria leaf blight (Alternaria triticina), anthracnose (Glomerella graminicola, Colletotrichum graminicola), Ascochyta leaf spot (Ascochyta tritici), Aureobasidium decay (Microdochium bolleyi, Aureobasidium bolleyi), black head molds, sooty molds (Alternaria spp., Cladosporium spp., Epicoccum spp., Sporobolomyces spp., Stemphylium spp.), black point, kernel smudge (Alternaria spp., Cochliobolus sativus, Cladosporium spp.), Cephalosporium stripe (Hymenula cerealis, Cephalosporium gramineum), common bunt = stinking smut (Tilletia spp.), common root rot (Cochliobolus sativus, Bipolaris sorokiniana, Helminthosporium sativum), cottony snow mold (Coprinus psychromorbidus), crown rot, foot rot, seedling blight, dryland root rot (Fusarium spp., Gibberella spp.), Dilophospora leaf spot, twist (Dilophospora alopecuri), dwarf bunt (Tilletia controversa), ergot (Claviceps purpurea, Sphacelia segetum), eyespot, foot rot, strawbreaker (Tapesia yallundae, Ramulispora herpotrichoides, Pseudocercosporella herpotrichoides, Tapesia acuformis, Ramulispora acuformis, Pseudocercosporella herpotrichoides var. acuformis), false eyespot (Gibellina cerealis), flag smut (Urocystis agropyri), halo spot (Pseudoseptoria donacis, Selenophoma donacis), karnal bunt, partial bunt (Tilletia indica,Neovossia indica), rusts Puccinia spp.), Leptosphaeria leaf spot (Phaeosphaeria herpotrichoides, Leptosphaeria herpotrichoides, Stagonospora), loose smut (Ustilago spp.), Microscopica leaf spot (Phaeosphaeria microscopica. Leptosphaeria microscopica), Phoma spot Phoma spp.), pink snow mold, Fusarium patch (Microdochium nivale, Fusarium nivale, Monographella nivalis), Platyspora leaf spot (Clathrospora pentamera, Platyspora pentamera), powdery mildew (Erysiphe graminis f.sp. tritici, Blumeria graminis, Erysiphe graminis, Oidium monilioides), Rhizoctonia root rot (Rhizoctonia solani, Thanatephorus cucumeris), scab, head blight, Fusarium head blight (FHB) (Fusarium spp., Gibberella spp., Microdochium nivale, Monographella nivalis), Sclerotinia snow mold, snow scald (Myriosclerotinia borealis, Sclerotinia borealis), Sclerotium wilt, Southern blight, Sclerotium base rot (Sclerotium rolfsii, Athelia rolfsii), Septoria blotch (Septoria tritici, Mycosphaerella graminicola), sharp eyespot (Rhizoctonia cerealis, Ceratobasidium cereale), speckled snow mold, gray snow mold, Typhula blight (Typhula spp.), spot blotch (Cochliobolus sativus, Bipolaris sorokiniana, Helminthosporium sativum), Stagonospora blotch (Phaeosphaeria spp., Stagonospora spp., Septoria spp.), storage molds (Aspergillus spp., Penicillium spp.), take-all (Gaeumannomyces graminis), tan spot, yellow leaf spot, red smudge (Pyrenophora tritici- repentis, Drechslera tritici-repentis), tar spot (Phyllachora graminis, Linochora graminis) and wheat blast (Magnaporthe grisedy,
[0152] On peanut: Alternaria leaf blight and leaf spot (Alternaria spp.), anthracnose (Colletotrichum spp.), Aspergillus crown rot (Aspergillus niger), blackhull (Thielaviopsis basicola), Botrytis blight (Botrytis cinerea), Charcoal rot and Macrophomina leaf spot (Macrophomina phaseolina), Choanephora leaf spot (Choanephora spp.), Collar rot (Lasiodiplodia theobromae), Cylindrocladium black rot and leaf spot Cylindr ocladium spp., Calonectria spp.), damping-off (Aspergillus spp., Fusarium spp., Rhizoctonia spp., Rhizopus spp.), Drechslera leaf spot (Bipolaris spicifera), Fusarium wilt and peg / root rot (Fusarium spp.), early leaf spot (Cercospora arachidicola), late leaf spot (Phaeoisariopsis personata, Cercosporidium personatum), melanosis (Stemphylium botryosum), Myrothecium leaf blight (Myrothecium roridum), Pepper spot and scorch (Leptosphaerulina crassiasca), Pestalotiopsis leaf spot (Pestalotiopsis arachidis), Phoma leaf blight Phoma microspore), Phomopsis foliar blight and leaf spot (Phomopsis spp.), Phyllosticta leaf spot (Phyllosticta spp.), Phymatotrichum root rot (Phymatotrichopsis omnivore, Fusarium scirpi), pod rot (Fusarium spp., Rhizoctonia spp.), powdery mildew Oidium arachidis), Rhizoctonia foliar blight, peg and root rot (Rhizoctonia solani), rust (Puccinia arachidis), scab (Sphaceloma arachidis),Sclerotinia blight (Sclerotinia spp.), stem rot / southern blight (Sclerotium rolfsii), Verticillium wilt (Verticillium spp.), web blotch / net blotch (Phoma arachidicola. Didymosphaeria arachidicola), yellow mold (Aspergiillus spp.), and zonate leaf spot (Cristulariella moricola
[0153] On other grain crops (including but not limited to rye, sorghum, oat, and triticale): Anthracnose (Colletotrichum spp.) black head molds (Alternaria spp., Cladosporium spp., Sporobolomyces spp., Stemphylium spp.), black point (Bipolaris spp., Fusarium spp.), bunt / stinking smut (Tilletia spp.), Cephalosporium stripe (Hymenula cerealis). Common root rot and seedling blight (Bipolaris sorokiniana . winter crown rot (Coprinus psychromorbidus), Dilophospora leaf spot (Dilophospora alopecuri), dwarf bunt (Tilletia conlroversa . ergot (Claviceps purpurea), Fusarium root rot (Fusarium culmorum), halo spot (Pseudoseptoria donacis), karnal bunt (Neovossia indica), leaf streak (Cercosporidium graminis), Leptosphaeria leaf spot (Phaeosphaeria herpotrichoides), loose smut (Ustilago tritici), pink snow mold (Fusarium spp.), powdery mildew (Erysiphe spp.), scab (Fusarium graminearum), Septoria leaf blotch and tritici blotch (Septoria spp.), sharp eyespot and Rhizoctonia root rot (Rhizoctonia cerealis), snow mold (Typhula spp.), spot blotch (Bipolaris sorokiniana), glume blotch (Septoria nodorum), stalk / stripe smut (Urocystis occulta), stem rust (Puccinia graminis), eyespot / foot rot (Pseudocercosporella herpotrichoides), stripe rust (Puccinia striiformis), take-all (Gaeumannomyces graminis), and tan spot (Pyrenophora tritici-repentis).[01.54] On stone and pome fruits: leaf spot (Mycosphaerella cer sella, Mycosphaerella pyri, Cercospora rubrotincta), anthracnose (Glomerella cingulata, Glomerella acutata), leaf spot of cherry (Blumeriella jaapii), powdery mildew (Podosphaeria leucotricha, Podosphaeria pannosa), Alternaria rot / black spot (Alternaria alternata, A. gaisen), gummosis (Botryosphaeria spp.), fruit rot (Botrytis cinerea), scab (Venturia inequalis, V. pirinia, V. carpophila, V. nashicola, Venturia spp.), southern blight (Sclerotium rolfsii), black rot (Botryosphaeria obtusa), Alternaria blotch and rot (Alternaria mali, Alternaria spp.), cedar apple rust (Gymnosporangium juniper -virginianae), American hawthorn rust (Gymnosporagium globosum), Japanese pear rust (Gymnosporangium asiaticum), European pear rust (Gymnosporangium sabinae), Kern’s pear rust (Gymnosporangium kernianum), pacific coast pear rust (Gymnosporangium libocedri), Rocky Mountain pear rust (Gymnosporangium nelsoni), bitter rot (Colletotrichum spp.), white rot (Botryosphaeria dothidea), black rot (Diplodia seriata), sooty blotch and flyspeck (pathogen complex including Dothideomycetes and Sordariomycetes), Fabraea leaf spot (Fabraea maculata, Diplocarpon mespili), brown spot (Stemphylium vesicarium), Brooks fruit spot (Mycosphaerella pomi),Phoma leaf and fruit spot (Phoma spp.), blotch (Phyllosticta sohlaria), black pox and blister canker (Ellisembia aslerinum). apple ring spot (Botryosphaeria spp.), calyx-end rot (Sclerotinia sclerotiorum), Monilinia leaf blight and brown rot (Monilinia spp.), Marssonina blotch (Diplocarpon mall), blue mold (Penicillium spp.), gray mold (Botrytis cinerea), and canker and wood rot diseases (Neonectria spp., Neofabraea spp., Diaporthe spp., Valsa spp., Botryosphaeria spp., Armilllaria spp., Chondrostereum spp., Schizophylum spp., Stereum spp., Trametes spp.);
[0155] On grapes: black rot (Guignardia bidwellii, Phyllosticta ampelicida), bitter rot (Greeneria uvicola), Eutypa dieback Eutypa lata), Botryosphaeria dieback and Macrophoma rot (Botryosphaeria spp. Botrytis bunch rot and blight (Botrytis cinerea), Phomopsis cane and leaf spot Phomopsis viticola, Cryptosporella viticola), Rotbrenner (Pseudopezicula tracheiphila, Pseudopeziza tracheiphila), anthracnose (Elsinoe ampehna), rust (Phakopsora ampelopsidis, Phakopsora euvilis), Septoria leaf spot (Septoria ampehna), leaf blight (Pseudocercospora vitis), leaf blotch (Briosia ampelophaga), powdery mildew (Erysiphe necator), white rot (Coniella diplodiella, Pilidiella diplodiella), ripe rot (Colletotrichum spp.), berry rots and molds (Alternaria spp., Cladosporium spp., Botrytis cinerea, Colletotrichum spp., Diplodia spp., Greeneria sp / z, Phomopsis spp., Aspergillus spp., Penicillium spp., Rhizopus spp., Fusarium spp., Stemphyilium spp., Ascochyta spp.);[01.56] On strawberries: Septoria hard rot and leaf spot Septoria spp.), powdery mildew (Sphaerotheca macular is, Podosphaera macularis), anthracnose (Colletotrichum spp.), common leaf spot (Mycosphaerella fragariae), Cercospora leaf spot (Cercospora spp.), leaf rust (Phragmidium potentillae, Frommeella tormentillae), Sclerotinia crown and fruit rot (Sclerotinia sclerotiorum), Alternaria fruit rot and black leaf spot (Alternaria spp.), anther and pistil blight / black root rot / hard brown rot (Rhizoctonia spp.), charcoal rot (Macrophomina phaseolina), Coniothyrium diseases (Coniothyrium fuckelii, Coniella fragariae), Dematophora crown and root rot / white root rot (Rosellinia necatrix), Diplodina rot / leaf and stalk rot Phoma lycopersici), fruit rots (Aspergillus niger, Cladosporium spp., Penicillium spp.), Byssochlamys rot (Byssochlamys fulva), Fruit blotch (Peronospora potentillae, Sphaeropsis malorum, Sclerotium rolfsii, Schizoparme slr minea), Gray mold leaf blight and dry crown rot (Botrytis cinerea), leaf scorch (Diplocarpon earlianum), Pestalotia fruit rot (Pestalotia sp.), Leaf blight (Phomopsis obscurans), Postharvest rots (Botrytis cinerea, Pichia spp., Saccharomyces spp.), southern blight (Sclerotium rolfsii)
[0157] On bananas: Anthracnose (Colletotrichum musae, Armillaria corn rot (Ar millaria mellea, Armillaria tabescens), Black cross (Phyllachora musicola), Black root rot (Rosellinia bunodes), Black Sigatoka (Mycosphaerella fijiensis . Brown blotch (Pestalotiopsis leprogena), Brown spot (Cercospora hayi), Ceratocystis fruit rot (Ceratocystis paradoxa), Cigar-end (Verticillium theobromae, Trachysphaera frucligena), Cladosporium speckle (Cladosporium musae), Corm dry rot (Junghuhnia vincta), Cordana leaf spot (Cordana johnsionii, Cordana musae). Crown rot (Colletotrichum musae, Verticillium theobromae, Fusarium spp., Acremonium spp.), Cylindrocladium root rot (Cylindr ocladium spp.), Deightoniella fruit speckle, damping off, leaf spot and tip rot (Deightoniella torulosa), Diamond spot (Cercospora hayi, Fusarium spp.), Dwarf Cavendish tip rot (Nattrassia mangiferae), Eyespot (Drechslera giganteari), Fruit freckle (Guignardia musae), Fruit rot (Botryosphaeria ribis), Fungal root-rot (Fusarium spp., Rhizoctonia spp.), Fungal scald (Colletotrichum musae), Leaf rust (Uredo musae, Uromyces musae), Leaf speckle (Acrodontium simplex), Leaf spot (Curvularia eragrostidis, Drechslera musae-sapientum, Leptosphaeria musarum, Pestalotiopsis disseminata), Main stalk rot (Ceratocystis paradoxa), Malayan leaf spot (Haplobasidion musae), Marasmiellus rot (Marasmiellus inoderma), Panama disease (Fusarium oxysporum f. sp. cubense), Peduncle rot (Lasiodiplodia theobromae, Fusarium spp., Verticillium theobromae), Pestalotiopsis leaf spot (Pestalotiopsis palmarum), Phaeoseptoria leaf spot (Phaeoseptoria musae), Pitting (Pyricularia grisea), Pseudostem heart rot (Fusarium moniliforme), Root & rhizome rot Cylindr ocarpon musae), Sclerotinia fruit rot (Sclerotinia sclerotiorum), Septoria leaf spot (Septoria eumusae), Sheath rot (Nectria foliicola, Mycosphaerella musicola), Sooty mold (Limacinula tenuis), Speckle (Mycosphaerella musae), Black end disease (Nigrospora sphaerica), Stem-end rot (Colletotrichum musae), Tropical speckle (Ramichloridium musae), Verticillium tip rot (Verticillium theobromae), and Yellow Sigatoka (Mycosphaerella musicola).
[0158] On turfgrasses: Anthracnose (Glomerella graminicola, Colletotrichum graminicola), Ascochyta leaf blight (Ascochyta spp.), Brown and Large patch (Rhizoctonia solani), Brown ring patch (Waitea circinata), Copper spot (Gloeocercospora sorghi), Dead spot (Ophiosphaerella agrostis), Dollar spot (Sclerotinia homoeocarpa), Fairy ring (Agaricus spp., Lepiota spp., Marasmius oreades, Lycoperdon spp., Agrocybe pediades, etc.), Gray leaf spot (Pyricularia grisea), Gray snow mold (Typhula spp.), Leaf spot and Melting out (Drechslera spp., Bipolaris spp. / Leaf and sheath spot Waitea circinata var. zeae, Waitea circinata var. oryzae), Necrotic ring spot (Ophiosphaerella spp.), Pink patch (Limonomycesroseipellis), Pink snow mold (Microdochium nivale), Powdery mildew (Blumeria graminis), Pythium blight (Pythium spp.), Red leaf spot (Drechslera (Pyrenophord) erythrospild). Red thread (Laetisaria fuciformis), Rust diseases (Piicci iia spp.), Smut diseases (Ustilago spp.), Spring dead spot (Ophiosphaerella korrae, O. herpotrich, O. narmari). Summer patch (Magnaporthe poae), Take-all patch (Gaeumannomyces graminis), Yellow patch (Rhizoctonia cerealis), and Yellow tuft (Sclerophthora macrospord).VII. Methods of Preparation[01.59] The pesticidal formulations disclosed herein can be prepared in any known technique for preparing pesticidal formulations.
[0160] In some aspects, the pesticidal formulations disclosed herein may be prepared by adding dehydrating agents that are soluble in the pesticidal formulations at any step of the preparation process.
[0161] In some aspects, the pesticidal formulations disclosed herein may be prepared by adding dehydrating agents that are not soluble in the pesticidal formulations at any step of the preparation process. In some aspects, the undissolved dehydrating agents may be removed from the resulting pesticidal formulations before storage or transportation or the application in the field. In some aspects, the undissolved dehydrating agents may be removed from the resulting pesticidal formulations before transportation. In some aspects, the undissolved dehydrating agents may be removed from the resulting pesticidal formulations before the application in the field. In some preferred aspects, the undissolved dehydrating agents may be removed from the resulting pesticidal formulations before storage. In some aspects, the undissolved dehydrating agents may be removed from the pesticidal formulations by filtration. In some aspects, the removed dehydrating agents may be recycled.
[0162] By way of non-limiting illustration, examples of some aspects of the present disclosure are given below. Parts and percentages are on a per weight basis unless otherwise indicated.Examples
[0163] A list of formulations comprising the compound of Formula I or Formula I-B, were prepared for chemical and physical stability and other types of tests, as detailed herein below. Compounds of Formula I and Formula I-B were successfully prepared according to themethods disclosed in International Application No. PCT / US2024 / 027678. Compounds of Formula I and Formula I-B are observed to be solid.
[0164] Ingredients used in experiments herein are: A,A'-dicyclohexylcarbodiimide (DCC) (purchased from Sigma Aldrich, CAS no.: 538-75-0), A,A'-diisopropylcarbodiimide (DIC) (purchased from Sigma Aldrich, CAS no.: 693-13-0), bis(2,6-diisopropylphenyl)carbodiimide (BDC) (purchased from Sigma Aldrich, CAS no.: 2162-74-5), molecular sieve 3 A (purchased from ThermoFisher Sci, CAS no.: 308080-99-1), Plurafac LF 1300 (purchased from BASF SE, chemical name: Alcohols, Cl 6- 18, ethoxylated propoxylated), Agnique® CSO-25 (purchased from BASF, chemical name: ethoxylated castor oil, CAS no.: 61791-12-6), Aromatic 200ND (purchased from ExxonMobil, chemical name: Solvent naphtha petroleum, Heavy aromatic, naphthalene depleted, CAS no.: 64742-94-5), ATLAS® G-5002L (purchased from Croda, chemical name: Polyalkylene oxide block copolymer, CAS no. : 9038-95-3), Break-thru® S233 (purchased from Evonik, chemical name: polyether modified trisiloxane, CAS no.: 134180-76- 0), Hallcomid® M-10 (purchased from Stepan Company, chemical name: N, N- dimethyldecanamide, CAS no.: 14433-76-2), Genagen NBP (purchased from Clariant Corporation, chemical name: 2-Pyrrolidinone, 1 -butyl-, CAS no.: 3470-98-2).
[0165] Premix samples of the compounds of Formula I and Formula I-B with different mixing partners can also be prepared.Example 1
[0166] EC formulation and stability
[0167] Emulsifiable concentrates of the compound of Formula I were prepared with the solvents, surfactants and carbodiimides. The compound of Formula 1 was added and dissolved in the solvents listed in Table 1 and then the surfactants and carbodiimide were added sequentially under agitation for homogenization. The resulting samples were found to be transparent, light brown homogeneous solution with acceptable emulsion performance. Each sample was then split into four sub-samples, placing two sub-sample at -10°C, the third one at 54°C for one week, and the fourth one at 54°C for two weeks. Once the one-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed for the content of Compound of Formula I. Once the two-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed for content of Compound of Formula I.Table 1. Carbodiimides in Emulsifiable concentrate (EC) formulations of the Compound of Formula I.
[0168] As shown in Table 1, the EC formulation of the Compound of Formula I was stable (Sample 1, 94% compound of Formula I retention in two-week storage test) before water was added, and became less stable (Sample 2, 87% compound of Formula I retention in two-week storage test) after water was added. The addition of carbodiimides (Samples 3-9, the compound of Formula I retention is higher than 87% in each Samples 3-9) made the formulation stable again. It’s unexpected that in Samples 3-6, 8, and 9, the addition of carbodiimides stabilized the EC formulation even when the water content in the formulations far exceeded what the added carbodiimides could remove.
[0169] Emulsifiable concentrates of the compound of Formula I were prepared with the solvents, surfactants and other possible hydrating agents (including Molecular Sieve 3A, dibutylthiourea, and triethyl orthoacetate), as shown in Table 2. The compound of Formula 1 was added and dissolved in the solvents listed in Table 2 and then the surfactants and other hydrating agents were added sequentially under agitation for homogenization of liquid phase. The resulting samples were found to have transparent, light brown homogeneous liquid phase with acceptable emulsion performance. Each sample was then split into four sub-samples, placing two sub-sample at -10°C, the third one at 54°C for one week, and the fourth one at 54°C for two weeks. Once the one-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed for the content of Compound of Formula I. Once thetwo-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed for content of Compound of Formula I.Table 2. Molecular Sieves in Emulsifiable concentrate (EC) formulations with the Compound of Formula I.
[0170] As shown in Table 2, the EC formulation of the Compound of Formula I was stable (Sample 10) before water was added, and became less stable (Sample 11) after water was added. The addition of Molecular Sieve 3 A (Samples 12-13) made the formulation stable again. It was surprising that the final remaining water was not directly related to the stability of the EC formulation (for example, Sample 13 was more stable than Sample 15, despite Sample 13’ s higher remaining water content).Example 2
[0171] EW formulation and stability[0.172] Examples of EW solo formulation were successfully prepared with the Compound of Formula I in the following formulations. An organic solution was prepared by dissolving the Compound of Formula I in selected solvents in Table 3. A hydrophobic emulsifier was added into the organic solution while mixing. A homogeneous organic solution was prepared after mild agitation. An aqueous solution was prepared by dissolving a hydrophilic emulsifier. A homogeneous aqueous solution was prepared after mild agitation. Under continuous homogenization, the organic solution was slowly added into the aqueous phase. This was a crucial step to form a stable oil-in-water emulsion. The formed mixture was put under continuous homogenizing until the emulsion achieves uniform size and stable emulsion.
[0173] Each sample was then split into two sub-samples, placing one sub-sample at -10°C, and the other at 54°C for two weeks. Once the two-week storage period had ended, the sample stored at -10°C and the sample stored 54°C were analyzed for content of Compound of Formula I.Table 3. Carbodiimides in oil-in-water emulsion (EW) formulations of the Compound of Formula I.
[0174] As shown in Table 3, the EW formulation of the Compound of Formula I was not stable (Samples 17 and 18). Unexpectedly, the addition of carbodiimides (Samples 19-22) made the formulation much more stable, despite the high-water content (65 wt% in these samples) in EW formulations.
[0175] Further, an EW formulation (made from the ingredients: the compound of Formula I (19.3 wt%), Aromatic 200 ND (17.9 wt%), ATLAS G-5002L-LQ (5 wt%), Atlox 4912-SO (7.5 wt%), A,A’-dicyclohexylcarbodiimide (0.1%), and water (50.2 wt%)) was prepared. Two- week storage test (-10°C vs 54°C) was done to evaluate the stability. The two week retention of the compound of Formula I was at 95%.Example 3
[0176] Premix EC formulation with low moisture content and stability
[0177] The emulsifiable concentrate (Sample 23) of the compound of Formula I and florylpicoxamid was prepared by adding and dissolving the compound of Formula 1 and florylpicoxamid in the solvents and sequentially adding the surfactants under agitation for homogenization, according to the following weight percentages: 10% the compound of Formula I, 5% florylpicoxamid, 38.5% Hallcomid M-10, 28% Genagen NBP, 10% Tergitol ECO-30, 4% Atlas 1086, and 4% Atlas 5002L.
[0178] Sample 24 was prepared by adding molecular sieve 3 A into Sample 23 under adequate agitation, at the weight ratio of molecular sieve 3 A to Sample 23 of 1 :9, then filtering off the molecular sieve 3 A.
[0179] Sample 25 was prepared by adding molecular sieve 3A into Sample 23 under adequate agitation, at the weight ratio of molecular sieve 3 A to Sample 23 of 1 :9.
[0180] Sample 26 was prepared by adding water into Sample 23 under adequate agitation, at the weight ratio of water to Sample 23 of 25:975.
[0181] Sample 27 was prepared by adding water into Sample 24 under adequate agitation, at the weight ratio of water to Sample 24 of 25:975.
[0182] Each sample was then split into two sub-samples, placing one sub-sample at -10°C, and the second one at 54°C for two weeks. Once the two-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed by HPLC for content of the compound of Formula I and florylpicoxamid.
[0183] Sample 23 stored at -10 °C for two weeks was measured to have 0.324% moisture content. Sample 23 stored at 54 °C for two weeks was measured to have 0.235% moisture content. Other test results were as shown in Table 4.Table 4. Emulsifiable concentrate (EC) formulations of the Compound of Formula I and florylpicoxamid after stored at 54 °C for two weeks.
[0184] As shown in Table 4, the premix EC formulation of the Compound of Formula I and florylpicoxamid without further treatment (Sample 23) did not meet the industrial requirement of 90% Al retention in storage and transportation, as its florylpicoxamid content was 83%. The treatment by molecular sieve 3 A did reduce the final remaining water in Sample 24 (0.09%) and Sample 25 (0.032%), and significantly improved the Al retention (the compound of Formula I - 100% in both Samples 24 and 25; florypicoxamid - 96% in Sample 24 where molecular sieve 3 A was removed before the storage test; and florypicoxamid - 95% in Sample 24 where molecular sieve 3 A was not removed before the storage test), which met the industrial requirement. The water addition also significantly destabilized the formulation (Samples 26 and 27: the compound of Formula I - 67% and 79%, respectively; florypicoxamid - 16% and 42%, respectively). It was very surprising that the final remaining water content hadsuch an impact on the Al retention in premix EC formulations because Sample 11, 13, and 15 all had similar water content (2.68%, 1.69%, and 1.64%, respectively) but the retention of their compound of Formula I met the 90% retention industrial standard.Example 4
[0185] Premix EC formulation with low moisture content and stability
[0186] The emulsifiable concentrates (Samples 28-35) of the compound of Formula I and florylpicoxamid were prepared according to the Table 5.
[0187] Each sample was then split into two sub-samples, placing one sub-sample at -10°C, and the second one at 54°C for two weeks. Once the two-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed by HPLC for content of the compound of Formula I and florylpicoxamid.Table 5. Carbodiimides in emulsifiable concentrate (EC) formulations of the Compound of Formula I and florylpicoxamid.
[0188] As shown in Table 5, Samples 29-34, premix EC formulations of the compound of Formula I and florylpicoxamid with different levels of DCC, Morpho-CDI, or N,N-ditrityl CDI, showed increased retention for at least one active ingredient, when compared to similar formulation without carbodiimides (Sample 28). More specifically, Samples 29-33, containing various levels of DCC or Morpho-CDI, indicated that the presence of DCC or Morpho-CDI improved the chemical stability of both the compound of Formula I and florylpicoxamid in the EC formulation.Example 5
[0189] Premix EC formulation with low moisture content and stability[0.1 0] The emulsifiable concentrates (Samples 28 and 36-46) of the compound of Formula I and florylpicoxamid were prepared according to the Table 6. Each sample was then split into two sub-samples, placing one sub-sample at -10°C, and the second one at 54°C for two weeks. Once the two-week storage period had ended, a sample stored at -10°C and a sample stored 54°C were analyzed by HPLC for content of the compound of Formula I and florylpicoxamid.Table 6. Other dehydrating agents in emulsifiable concentrate (EC) formulations of the Compound of Formula I and florylpicoxamid.
[0191] As shown in Table 6, Samples 36-38, premix EC formulations of the compound of Formula I and florylpicoxamid with vinyltrimethoxy silane, tri ethyl Orthoacetate, or Triethoxyphenylsilane, showed increased retention for the compound of Formula I and florylpicoxamid, when compared to similar formulation without dehydrating agent (Sample 28).
[0192] The formulations and methods of the appended claims are not limited in scope by the specific formulations and methods described herein, which are intended as illustrations of a few aspects of the claims and any formulations and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the formulations and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative formulations and method steps disclosed herein are specifically described, other combinations of the formulations and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various aspects, the terms “consisting essentially of’ and “consisting of’ can be used in place of “comprising” and “including” to provide for more specific aspects of the disclosure and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood to be construed in light of the number of significant digits and ordinary rounding approaches, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims.
Claims
WHAT IS CLAIMED IS:
1. A Fungicidal formulation, comprising:(a) a fungicidal compound of Formula (I):Formula (I) or an acceptable salt, solvate, or hydrate thereof; and(b) at least one dehydrating agent.
2. The formulation of any of claims 1, wherein the acceptable salt of the fungicidal compound of Formula (I) is 4-(difluoromethoxy)benzyl 4- (((ethyl(methyl)amino)methylene)amino)-2,5-dimethylbenzoate hydrochloride (Formula I- B).
3. The formulation of any of claims 1-2, wherein the formulation is a liquid formulation and wherein the fungicidal compound of Formula (I) or an acceptable salt, solvate, or hydrate thereof is present in the liquid formulation at a concentration from 0.006 to 600 gram active ingredient per liter (g ai / L) of the liquid formulation.
4. The formulation of claim 3, wherein the liquid formulation is a soluble liquid concentrate, an aqueous solution, an oil solution, a suspension concentrate, an aqueous suspension, an aqueous dispersion, an aqueous emulsion, an aqueous microemulsion, an aqueous suspo-emulsion, an emulsifiable concentrate, an oil-in-water emulsion, an oil dispersion, an oil microemulsion, an oil suspo-emulsion, or a water-in-oil emulsion.
5. The formulation of claim 4, wherein the liquid formulation is an emulsifiable concentrate or an oil-in-water emulsion.
6. The formulation of claims 1-5, wherein the at least one dehydrating agent is selected from the group consisting of alkyl orthoesters, carbodiimides, molecular sieves, organosilanes, and mixtures therefore.
7. The formulation of claim 6, wherein the at least one dehydrating agent is selected from the group consisting of triethyl orthoacetate, 7-ethylbicyclooxazolidine, N,N'- di cyclohexylcarbodiimide, N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide methyl- / ?- toluenesulfonate, N,N-ditritylcarbodiimide, molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, vinyltrimethoxysilane, triethoxyphenylsilane, triethoxy(4- methoxyphenyl)silane, cyclohexyltrimethoxysilane, isooctyl trimethoxysilane, 3- (triethoxysilyl)propionitrile, 2-(2-(trimethoxysilyl)ethyl)pyridine, and mixtures thereof.
8. The formulation of claim 7, wherein the at least one dehydrating agent is selected from the group consisting of triethyl orthoacetate, N,N'-dicyclohexylcarbodiimide, molecular sieve 3A, molecular sieve 4A, vinyltrimethoxysilane, triethoxyphenylsilane, and mixtures thereof.
9. The formulation of any of claims 1-8, wherein the formulation further comprises one or more additional pesticide active ingredients.
10. A fungicidal formulation with low moisture content, comprising:(a) a fungicidal compound of Formula (I):Formula (I) or an acceptable salt, solvate, or hydrate thereof; and(b) one or more additional pesticide active ingredient.
11. The fungicidal formulation with low moisture content of claim 10, wherein the one or more additional pesticide active ingredient is quinone inside inhibitor (Qil) fungicides selected from the group consisting of cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid, and mixtures thereof.
12. The fungicidal formulation with low moisture content of any of claims 10 and 11, wherein the one or more additional pesticide active ingredients is florylpicoxamid.
13. A method of controlling fungal pathogens or diseases from fungal pathogens on a plant, comprising contacting an area adjacent to the plant, soil adapted to support growth of the plant, a root of the plant, foliage of the plant, and a growth medium adapted to grow a plant or a seed, with the formulation according to any one of claims 1-12.
14. Use of the formulation according to any one of claims 1-12 in control of fungal pathogens or diseases from fungal pathogens on a plant.
15. A method of preparing the fungicidal formulation with low moisture content of any of claims 10-12, comprising:(a) adding at least on hydrating agent during the preparation of the fungicidal formulation; and(b) removing the at least one hydrating agent before storage, transportation, or the application in the field.