EP4672962A1 - Liquid formulations comprising picolinamide fungicides and aldehyde-based solvents - Google Patents

Abstract

The present disclosure relates to stable liquid agricultural formulations containing picolinamide fungicides dissolved in liquids including aldehyde solvents. The present disclosure also relates to stable liquid agricultural formulations containing mixtures of fungicides that include picolinamide fungicides, where the mixture of fungicides is dissolved in liquids including aldehyde solvents. The present disclosure also relates to methods of using these stable liquid agricultural formulations containing the fungicides dissolved in the liquids comprising aldehyde solvents.

Description

Attorney Docket No. 112563-WO-SEC-1 LIQUID FORMULATIONS COMPRISING PICOLINAMIDE FUNGICIDES AND ALDEHYDE SOLVENTS CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 63/487,922, filed March 2, 2023, which is incorporated by reference herein in its entirety. FIELD The present disclosure relates to stable liquid agricultural formulations containing picolinamide fungicides dissolved in liquids comprising liquid aldehyde solvents. The present disclosure also relates to methods of using these stable liquid agricultural formulations containing the fungicides dissolved in liquids comprising liquid aldehyde solvents. BACKGROUND Agricultural formulations for crop protection may be prepared and sold in various physical states, such as solids, liquids, emulsions, gels, etc. The choice of the physical state in which an agricultural formulation is prepared and sold is determined by many factors, such as compatibility of the ingredients, ingredient solubility or suspensibility, stability of the ingredients during storage, ease of mixing by the end user, and the homogeneity and ease of application of the product by the end user, whether the agricultural formulation is diluted or used as-is. End users such as farmers tend to prefer liquid formulations for their ease of use in tank mixes. Liquid formulations, including concentrated liquid formulations, are particularly desirable, as they are easier and less expensive to transport, and use less packaging materials than less concentrated formulations. The end user may perceive highly concentrated liquid formulations as being a better value, as the end user is not paying for large amounts of diluents or other inert ingredients. However, some agricultural ingredients, such as some picolinamide fungicides, are insufficiently soluble in most solvents typically used for agricultural formulations. Also, some water-insoluble agricultural ingredients, such as some picolinamide fungicides, may be soluble in some organic solvents typically used for concentrated agricultural formulations; however, if the chosen organic solvent is then moderately or completely soluble in water, any water-insoluble agricultural ingredients may precipitate or crystallize when the concentrated agricultural formulation is tank-mixed with water. Therefore, there is an ongoing need to find stable liquid formulations, including stable concentrated formulations, containing fungicidal active ingredients, where the fungicidal active ingredients are soluble at a high concentration in the liquid formulation, and Attorney Docket No. 112563-WO-SEC-1 where the fungicidal active ingredients do not precipitate or crystallize when the liquid formulation is tank-mixed with water. SUMMARY Disclosed herein are liquid formulations that may be used as fungicides. The liquid formulations contain a picolinamide fungicide and liquid aldehyde solvent. In some aspects, the liquid formulation contains a liquid aldehyde solvent with a melting point from about -60 °C to about 0 °C and a boiling point from about 100 °C to about 300 °C at atmospheric pressure. In some aspects, the liquid aldehyde solvent in the formulation is liquid within the temperature range from about 0 °C to about 60 °C. In some aspects, the liquid aldehyde in the formulation is selected from the group consisting of benzaldehyde, p-anisaldehyde, 2-furaldehyde, trans-cinnamaldehyde, 3-(4-tert- butylphenyl)propionaldehyde, and 2,3-dihydro-2,2,6-trimethylbenzaldehyde. In some aspects, the picolinamide fungicide in the liquid formulation is selected from the group consisting of fenpicoxamid, florylpicoxamid, and metarylpicoxamid. In some aspects, the liquid formulation is an emulsifiable concentrate, an oil-in- water emulsion, a water-in-oil emulsion, or a micro-emulsion. Also disclosed herein are methods of preventing plant diseases by killing, inhibiting, or preventing the growth of fungi or spores that are parasitic on desirable vegetation, which comprises applying a liquid formulation contain a picolinamide fungicide and liquid aldehyde solvent to the vegetation, locus of the vegetation, or to the area where control of fungi or spores is desired. DETAILED DESCRIPTION 1. Definitions Terms used herein will have their customary meaning in the art unless specified otherwise. The singular forms "a," and "the" include plural references unless stated otherwise. To the extent that the term "or" is employed (e.g., A or B) it is intended to mean "A or B 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 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 C_n-C_m preceding a Attorney Docket No. 112563-WO-SEC-1 group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows. As used herein, the term “aldehyde” refers to organic compounds with the general structure of Formula (I): wherein the R group is an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, or alkynylaryl group. Exemplary R groups include but are not limited to methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, butyl, pentyl, cyclopentyl, hexyl, vinyl, propenyl, butenyl, pentenyl, propargyl, butynyl, pentynyl, phenyl, benzyl, naphthyl, and other hydrocarbon functional groups. The R groups may also include other substituents containing heteroatoms, including but not limited to halogens, amines, carbonyl groups, hydroxy groups, alkoxy groups, heterocyclic groups, and other heteroatom-containing functional groups. As used herein, the terms “liquid aldehyde” or “aldehyde solvent” refer to an aldehyde compound that is in the liquid state at most or all typical ambient outdoor temperatures, such as within the temperature range from about -10 °C to about 65 °C, about -5 °C to about 65 °C, about 0 °C to 60 °C, about 5 °C to about 55 °C, about 10 °C to about 50 °C, from about 12 °C to about 45 °C, from about 15 °C to about 45 °C, and from about 17 °C to about 40 °C, and at typical atmospheric pressures, such as from about 95 kPa to about 115 kPa. 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. As used herein, “oil” refers generally to an organic liquid that is hydrophobic and immiscible in water or aqueous liquids, unless otherwise specified. It should be understood that references to the sub-category of "oils” that are petroleum-based products (e.g., “diesel oil”) or triglyceride-based products (e.g., “olive oil” or “soybean oil”) will be specified or will be apparent by the context herein. As used herein, the terms “fungicide” and “fungicidal active ingredient” refer to an active ingredient that can prevent plant diseases by killing, inhibiting, or preventing the growth of fungi or spores that are parasitic on desirable vegetation, when applied in an appropriate amount. Most fungicides work by damaging the cell membrane of the fungus or spore, by Attorney Docket No. 112563-WO-SEC-1 inactivating critical enzymes within the fungus or spore, or by interfering with biochemical processes within the cells of the fungus or spore. As used herein, the term “fungicidal effect” is an adversely modifying effect of an active ingredient on fungi and spores, including, for example, killing, inhibiting, or preventing the growth of the fungi or spores. The term "fungicidal activity" refers generally to fungicidal effects of an active ingredient. As used herein, the terms “fungicidal formulation” or “formulation” may be understood to include mixtures 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, an adhesive, a chemical stabilizer, a physical stabilizer, a dye or colorant, or other such component. The additional component may be another fungicide or another agricultural chemical, such as an insecticide, a herbicide, a fertilizer, a nematocide, a miticide, a arthropodicide, a bactericide, a plant growth regulator, or combinations thereof that are compatible with the formulations of the present disclosure. As used herein, the terms “liquid formulation” or “liquid fungicidal formulation” may be understood to include formulations that are in the liquid state at most or all typical ambient outdoor temperatures, such as within the temperature range from about -10 °C to about 65 °C. As used herein, the terms “concentrate,” “concentrated formulation,” or “concentrated agricultural formulation” may be understood to refer to a mixture comprising an active ingredient, such as a fungicide, at a relatively high concentration, and also at least one other ingredient such as a solvent or carrier. Concentrated formulations are intended to be diluted with a liquid, such as water, by the end user, which reduces the concentration of the active ingredients to levels that are suitable for application to the area of interest. The diluted formulation may then be called a tank mix. In contrast, an “as-is” formulation is intended to be used by the end user without further dilution. As used herein, the term “tank mix” “may be understood to refer to a fungicidal mixture prepared from the liquid formulation by the end user. The end user prepares a tank mix by taking one or more actions, such as: diluting the liquid formulation with a diluting liquid, such as water, to a suitable concentration of the active ingredients; adding other ingredients or additives to the liquid formulation; mixing, dissolving, homogenizing or suspending the ingredients in the tank mix; or other such activities. The resulting tank mix is then suitable for application. The end user may then apply the tank mix, as-is or with other additives, to the area (e.g., cropland, pasture, orchard, etc.) where disease prevention is desired. In some aspects, the diluting liquid in a tank mix is water or other aqueous liquid. In some aspects, Attorney Docket No. 112563-WO-SEC-1 the diluting liquid may be water at ambient, often cold, outdoor temperatures, as may occur with agricultural usage in late winter, spring, or early summer. As used herein, the term “adjuvant” may be understood to include additives to the liquid 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 adhesives that help retain the fungicide on the surface of the crop. Adjuvants may be added to the liquid formulation, or adjuvants may be added to the tank mix by the end user prior to application of the tank mix. Adjuvants may also be included in the liquid fungicidal formulation, in which case the adjuvant may be referred to as a “built-in adjuvant.” As used herein, "applying" a fungicide or fungicidal formulation refers to delivering it directly to the crop or to the locus thereof where disease prevention is desired. Methods of application include, but are not limited to, pre-emergently contacting the soil or water where the crops are planted, applying a coating containing the fungicide to the seeds prior to planting the seeds, post-emergently contacting the crop, or contacting the area (soil or water) adjacent to the crop. 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. 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 cereals, legumes, vegetables, orchard and timber trees, grapevines, pasture grasses, etc. As used herein, "active ingredient" or "ai" refers to a chemical compound or formulation that has an effect on vegetation or a targeted pest, for example, a fungicidal effect on fungi or the spores thereof. 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, hydrates, or other chemical forms or derivatives of the chemical compound. As used herein, "acid equivalent" or "ae" refers to the amount of the acid form of an active ingredient that is calculated from the amount of a salt or ester form of that active ingredient. For example, if the acid form of an active ingredient "Z" has a molecular weight of 100 Dalton (“Da”), and the salt form of Z has a molecular weight of 120 Dalton, an Attorney Docket No. 112563-WO-SEC-1 application of 120 g ai/ha of the Z salt would be equal to applying 100 g ae/ha of the acid form of Z: 120 g ai/ha Z salt * (100 Da Z acid / 120 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, hydrates, etc. As used herein, “chemically stable” or “chemical stability” may be understood to refer to an active ingredient that experiences little or no chemical degradation or other form of loss when mixed with another substance, such as a solvent, a formulation, or another active ingredient, and stored for a given period of time under defined storage conditions. For the purpose of this disclosure, a formulation is considered chemically stable if the formulation loses less than about 6%, and preferably less than about 5% of the active ingredient(s) in the formulation. In many jurisdictions, an agricultural formulation is considered chemically stable if about 5% or less of the active ingredient in the formulation is lost after storage at 54 °C for two weeks As used herein, “physically stable” or “physical stability” refers to an active ingredient, formulation, or other composition that maintains its physical properties when stored for a given period of time under defined storage conditions. For example, a formulation that is a liquid solution is considered physically stable if the ingredients remain in solution during the storage period. In contrast, a liquid solution formulation that experiences gelling, solidification, crystallization or precipitation of some or all ingredients, phase separation, etc. would not be considered physically stable. 2. Picolinamide Fungicides Picolinamide fungicides are C4 complex III fungicides. They have a fungicidal effect through mitochondrial electron transport inhibition by inhibiting ubiquinone reductase at the Qi (quinone inside) binding site on cytochrome bc₁. Examples of picolinamide fungicides include but are not limited to fenpicoxamid, florylpicoxamid, and metarylpicoxamid. A. Fenpicoxamid Formulations and methods of the present disclosure can include fenpicoxamid. Fenpicoxamid, shown below, is a systemic fungicide with contact and residual activity and translaminar plant mobility. Fenpicoxamid is a pro-pesticide that hydrolyzes to the 3- hydroxypyridine natural product, UK 2A, which is the biologically active species. Attorney Docket No. 112563-WO-SEC-1 Fenpicoxamid controls Septoria spp., yellow rust, brown rust, tan spot, and other diseases in cereal crops and bananas. Fenpicoxamid and its synthesis and fungicidal application via agricultural formulation or composition, is disclosed in patent application No. PCT/US2010/051598, which is herein incorporated in its entirety. Its fungicidal activity is described, for example, in The Pesticide Manual, Eighteenth Edition, 2023. Fenpicoxamid can be applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the growth of fungi or spores in an amount sufficient to induce a fungicidal effect. In some aspects, fenpicoxamid is applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount of 75 g ai/ha or more, such as 77.5 g ai/ha or more, 80 g ai/ha or more, 85 g ai/ha or more, 90 g ai/ha or more, 95 g ai/ha or more, 100 g ai/ha or more, 105 g ai/ha or more, 110 g ai/ha or more, 115 g ai/ha or more, 120 g ai/ha or more, 125 g ai/ha or more, or 130 g ai/ha or more; in an amount of 130 g ai/ha or less, such as 125 g ai/ha or less, 120 g ai/ha or less, 115 g ai/ha or less, 110 g ai/ha or less, 105 g ai/ha or less, 100 g ai/ha or less, 95 g ai/ha or less, 90 g ai/ha or less, 85 g ai/ha or less, 80 g ai/ha or less, 77.5 g ai/ha or less, or 75 g ai/ha or less; or in an amount ranging from any of the minimum values described above to any of the maximum values described above, such as 75–130 g ai/ha, 100-125 g ai/ha, 80-110 g ai/ha, 90-105 g ai/ha, 77.5-120 g ai/ha, 115–125 g ai/ha, 85-120 g ai/ha, 95-130 g ai/ha, or 80-100 g ai/ha. B. Florylpicoxamid Formulations and methods of the present disclosure can include florylpicoxamid. Florylpicoxamid, shown below, is a picolinamide fungicide that provides control of Septoria spp., Alternaria spp., Botrytis spp., Monilinia spp., powdery mildews, anthracnose, and scab, in cereals, grapes, fruit, nuts, and vegetables. Florylpicoxamid and its synthesis and fungicidal application via agricultural formulation or composition, is disclosed in patent application No. PCT/US2015/066760, which is herein incorporated in its entirety. Its herbicidal activity is described in The Pesticide Manual, Eighteenth Edition, 2023. Attorney Docket No. 112563-WO-SEC-1 Florylpicoxamid can be applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the growth of fungi or spores in an amount sufficient to induce a fungicidal effect. In some aspects, florylpicoxamid is applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount of 20 g ai/ha or more, such as 22.5 g ai/ha or more, 25 g ai/ha or more, 27.5 g ai/ha or more, 30 g ai/ha or more, 32.5 g ai/ha or more, 35 g ai/ha or more, 37.5 g ai/ha or more, 40 g ai/ha or more, 45 g ai/ha or more, 50 g ai/ha or more, 55 g ai/ha or more, 60 g ai/ha or more, 65 g ai/ha or more, 70 g ai/ha or more, 75 g ai/ha or more, 80 g ai/ha or more, 85 g ai/ha or more, 90 g ai/ha or more, 95 g ai/ha or more, 100 g ai/ha or more, 105 g ai/ha or more, 110 g ai/ha or more, 115 g ai/ha or more, 120 g ai/ha or more, 125 g ai/ha or more, 130 g ai/ha or more, 140 g ai/ha or more, 150 g ai/ha or more, 160 g ai/ha or more,170 g ai/ha or more, 175 g ai/ha or more, 180 g ai/ha or more, or 190 g ai/ha or more, ; in an amount of 200 g ai/ha or less, 190 g ai/ha or less, 180 g ai/ha or less, 175 g ai/ha or less, 170 g ai/ha or less, 160 g ai/ha or less, 150 g ai/ha or less, 140 g ai/ha or less, 130 g ai/ha or less, 125 g ai/ha or less, 120 g ai/ha or less, 115 g ai/ha or less, 110 g ai/ha or less, 105 g ai/ha or less, 100 g ai/ha or less, 95 g ai/ha or less, 90 g ai/ha or less, 85 g ai/ha or less, 80 g ai/ha or less, 75 g ai/ha or less, 70 g ai/ha or less, 65 g ai/ha or less, 60 g ai/ha or less, 55 g ai/ha or less, 50 g ai/ha or less, 45 g ai/ha or less, 40 g ai/ha or less, 37.5 g ai/ha or less, 35 g ai/ha or less, 32.5 g ai/ha or less, 30 g ai/ha or less, 27.5 g ai/ha or less, 25 g ai/ha or less, or 22.5 g ai/ha or less; or in an amount ranging from any of the minimum values described above to any of the maximum values described above, such as 20-200 g ai/ha, 50-180 g ai/ha, 110-150 g ai/ha, 27.5-85 g ai/ha, 32.5–60 g ai/ha, 20–40 g ai/ha, 120-175 g ai/ha, 160-200 g ai/ha, 40–100 g ai/ha, 30-125 g ai/ha, 30-75 g ai/ha, 90-125 g ai/ha, 60-100 g ai/ha, or 25-190 g ai/ha. Attorney Docket No. 112563-WO-SEC-1 C. Metarylpicoxamid Formulations and methods of the present disclosure can include metarylpicoxamid. Metarylpicoxamid, shown below, is a systemic picolinamide pro- fungicide with residual activity and translaminar plant mobility. Metarylpicoxamid hydrolyzes to the 3-hydroxypyridine natural product, which is the biologically active species. Metarylpicoxamid provides control of Asian soybean rust in soybeans. Metarylpicoxamid and its synthesis and fungicidal application via agricultural formulation or composition, is disclosed in patent application No. PCT/US2019/021263, which is herein incorporated in its entirety. Its herbicidal activity is described in The Pesticide Manual, Eighteenth Edition, 2023. Metarylpicoxamid can be applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the growth of fungi or spores in an amount sufficient to induce a fungicidal effect. In some aspects, metarylpicoxamid is applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount of 20 g ai/ha or more, such as 22.5 g ai/ha or more, 25 g ai/ha or more, 27.5 g ai/ha or more, 30 g ai/ha or more, 32.5 g ai/ha or more, 35 g ai/ha or more, 37.5 g ai/ha or more, 40 g ai/ha or more, 45 g ai/ha or more, 50 g ai/ha or more, 55 g ai/ha or more, 60 g ai/ha or more, 65 g ai/ha or more, 70 g ai/ha or more, 75 g ai/ha or more, 80 g ai/ha or more, 85 g ai/ha or more, 90 g ai/ha or more, 95 g ai/ha or more, 100 g ai/ha or more, 105 g ai/ha or more, 110 g ai/ha or more, 115 g ai/ha or more, 120 g ai/ha or more, 125 g ai/ha or more, 130 g ai/ha or more, 140 g ai/ha or more, 150 g ai/ha or more, 160 g ai/ha or more,170 g ai/ha or more, 175 g ai/ha or more, 180 g ai/ha or more, or 190 g ai/ha or more, ; in an amount of 200 g ai/ha or less, 190 g ai/ha or less, 180 g ai/ha or less, 175 g ai/ha or less, 170 g ai/ha or less, 160 g ai/ha or less, 150 g ai/ha or less, 140 g ai/ha or less, 130 g ai/ha or less, 125 g ai/ha or less, 120 g ai/ha or less, 115 g ai/ha or less, 110 g ai/ha or less, 105 g ai/ha or less, 100 g ai/ha or less, 95 g ai/ha or less, 90 g ai/ha or less, 85 g ai/ha or less, 80 g ai/ha or less, 75 g ai/ha or less, 70 g ai/ha or less, 65 g ai/ha or less, 60 g ai/ha or less, 55 g ai/ha or less, 50 g ai/ha or less, 45 g ai/ha or less, 40 g ai/ha or less, 37.5 g ai/ha or less, 35 g ai/ha or less, 32.5 g ai/ha or less, 30 g ai/ha or less, 27.5 g ai/ha or less, 25 g ai/ha or less, or 22.5 g ai/ha or less; or in an amount ranging from any of the minimum values Attorney Docket No. 112563-WO-SEC-1 described above to any of the maximum values described above, such as 20-200 g ai/ha, 50-180 g ai/ha, 110-150 g ai/ha, 27.5-85 g ai/ha, 32.5–60 g ai/ha, 20–40 g ai/ha, 120-175 g ai/ha, 160-200 g ai/ha, 40–100 g ai/ha, 30-125 g ai/ha, 30-75 g ai/ha, 90-125 g ai/ha, 60-100 g ai/ha, or 25-190 g ai/ha. 3. Aldehyde Solvents Aldehydes are organic compounds containing a carbonyl group with an attached hydrogen (e.g., --(C=O)H) at a terminal point of the molecule. The terminal carbonyl group of aldehydes is prone to nucleophilic addition reactions to the carbonyl carbon by Lewis bases, followed by electrophilic addition reactions to the carbonyl oxygen by Lewis acids. Aldehydes are typically more chemically reactive than other organic liquids, such as alcohols, ethers, and ketones, and therefore aldehydes are often not considered as possible solvents for reactive chemicals or in complex mixtures. It has been discovered, however, that some liquid aldehydes are excellent solvents for certain picolinamide fungicides that are otherwise known to be poorly soluble in typical solvents. In particular, the picolinamide fungicides fenpicoxamid, florylpicoxamid, and metarylpicoxamid surprisingly have been found to have increased solubility in liquid formulations containing liquid aldehydes as all or part of the solvent in the liquid formulation. Suitable liquid aldehydes have melting points from about -60 °C to about 0 °C and boiling points at atmospheric pressure from about 100 °C to about 300 °C, such that the liquid aldehydes are liquid at typical ambient outdoor temperatures. Preferably, the liquid aldehydes are liquid within the temperature range from about -10 °C to about 65 °C, about - 5 °C to about 65 °C, about 0 °C to 60 °C, about 5 °C to about 55 °C, about 10 °C to about 50 °C, from about 12 °C to about 45 °C, from about 15 °C to about 45 °C, and from about 17 °C to about 40 °C. It should also be understood that suitable liquid aldehydes may be liquid at temperatures outside these temperature ranges as well as within these ranges. Suitable liquid aldehydes may have molecular weights from about 80 Da to about 280 Da, preferably from about 85 Da to about 270 Da, from about 90 Da to about 260 Da, or from about 95 Da to about 250 Da. Examples of liquid aldehydes that are suitable for use as solvents for picolinamide fungicides include benzaldehyde, p-anisaldehyde, 2-furaldehyde (also called furfural), trans-cinnamaldehyde, 3-(4-tert-butylphenyl)-propionaldehyde (also called bourgeonal), and 2,3-dihydro-2,2,6-trimethylbenzaldehyde (also called safranal). The chemical structures and some properties of these solvents are shown in Table 1. Attorney Docket No. 112563-WO-SEC-1 Table 1. Structure and Properties of Select Liquid Aldehydes Concentrated agricultural formulations, such as emulsion concentrates or oil-in- water emulsions, may typically be diluted by the end user by adding a diluting liquid, such as water, and possibly other ingredients to prepare a tank mix. The tank mix is then ready for application to the area of interest (e.g., cropland, orchard, pasture, etc.). Sometimes organic solvents may be used to dissolve or disperse water-insoluble agricultural ingredients, such as some picolinamide fungicides, in the concentrated agricultural formulation. However, Attorney Docket No. 112563-WO-SEC-1 during preparation of a tank mix using water as the diluting liquid, if the chosen organic solvent in the concentrated agricultural formulation is moderately soluble or miscible in water, the organic solvent may dissolve into the diluting water instead of remaining as a separate phase (e.g., oil-in-water emulsion) in the tank mix. If this happens, water-insoluble agricultural ingredients in the concentrated agricultural formulation may precipitate or crystallize in the tank mix. This precipitation or crystallization is undesirable, because the solids formed in the precipitate or crystals may be difficult to homogeneously distribute in the tank mix, and the composition of the tank mix may be inconsistent while the tank mix is being applied to the area of interest. For instance, the amount of active ingredient (e.g., fungicide) may vary greatly during application if the tank mix is inhomogeneous. Solids that form in the tank mix may also clog the equipment used to apply the tank mix, such as tubing and spray nozzles in the applicator. This can result in reduced or no application of the tank mix, forces the end-user to clean out or replace the clogged equipment, and potentially exposes the end- user to contact with concentrated or solidified agricultural ingredients. It has been unexpectedly found that liquid aldehydes can be used as solvents in concentrated agricultural formulations to prevent or minimize the precipitation or crystallization of certain picolinamide fungicides in these formulations. Concentrated agricultural formulations containing a picolinamide fungicide dissolved in a liquid aldehyde can be diluted with water in tank mixes while forming little or no precipitation or crystallization of the fungicide. Liquid aldehydes typically have low or minimal solubility in water, particularly the cold water that is used in tank mixes. Instead, the liquid aldehydes remain as a separate phase when diluted with water, forming an oil-in-water emulsion instead. The picolinamide fungicide remains dissolved in the liquid aldehyde when the oil-in-water emulsion is formed in the tank mix, thus avoiding the formation of precipitates or crystals in the tank mix. 4. Formulations Fungicidal formulations may be prepared and sold in various physical states, such as solids, liquids, emulsions, gels, etc. The choice of the physical state in which a fungicidal formulation is prepared and sold is determined by many factors, such as compatibility of the ingredients, ingredient solubility or suspensibility, stability of the ingredients during storage, ease of mixing by the end user, or homogeneity and ease of application of the product by the end user, whether diluted or used as-is. End users such as farmers tend to prefer liquid formulations such as emulsifiable concentrates for their ease of use in tank mixes. Concentrated liquid formulations are particularly desirable, as they are easier and less expensive to transport, and use less packaging materials than less concentrated formulations. The end user may perceive Attorney Docket No. 112563-WO-SEC-1 concentrated liquid formulations as being a better value, as the end user is not paying for large amounts of diluents or other inert ingredients. Liquid formulations are often easier to dilute, emulsify, or homogenously suspend when prepared in tank mixes by the end user. This is particularly true when the tank mix is prepared with water at ambient, often cold, outdoor temperatures, as may occur with agricultural usage in late winter, spring, or early summer. A. Liquid Formulations In some aspects, the picolinamide fungicide may be present in a dissolved or emulsified form in a liquid formulation. Exemplary liquid formulations include, but are not limited to, emulsifiable concentrates, aqueous oil-in-water emulsions, organic-solvent-based water-in-oil emulsions, aqueous oil-in-water microemulsions, or aqueous oil-in-water suspo- emulsions. 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-Revised-March-2017.pdf). The liquid formulation may be diluted with a diluting liquid, such as water, by the end user (e.g., as a tank mix), then applied by the end user as needed. Emulsifiable concentrates are liquid formulations where the active ingredient (e.g., fungicide) is dissolved at a relatively high concentration in an organic solvent. Emulsifiable concentrates become oil-in-water emulsions when diluted with water or an aqueous liquid by the end user. Typical organic solvents for forming emulsifiable concentrates often include alkyl amides, glycol ethers, methylated seed oils, fatty acid or triglyceride esters, phosphate triesters, alkyl lactates, alkylene carbonates, petroleum-based aromatic solvents, aliphatic or paraffinic oils, diamides, and ester amides. The emulsifiable concentrate formulation may also include other ingredients, such as a co-solvent, an emulsifier, an antifoam agent, or a built-in adjuvant. The emulsifiable concentrate is formulated to readily form a stable and homogeneous oil-in-water emulsion when diluted with water or other aqueous liquid before use. Emulsions are liquid mixtures containing two or more immiscible liquid phases, with droplets of one immiscible liquid dispersed in a continuous phase of the other immiscible liquid. There are several types of emulsions, including oil-in-water emulsions, water-in-oil emulsions, and microemulsions. More complex emulsion types, such as water-in-oil-in-water emulsions, are also known. “Conventional” emulsions include oil-in-water emulsions and water-in-oil emulsions, with larger droplets dispersed in the continuous phase. Oil-in-water emulsions are heterogeneous liquid formulations containing a hydrophobic organic liquid dispersed as Attorney Docket No. 112563-WO-SEC-1 droplets in a continuous water or aqueous liquid phase. In one aspect, the fungicide may be dissolved or dispersed in the hydrophobic 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 heterogeneous liquid formulations containing water or an aqueous liquid dispersed as droplets in a continuous hydrophobic organic liquid phase. In one aspect, the fungicide may be dissolved or dispersed in the continuous hydrophobic organic liquid phase of a water-in- oil emulsion. In another aspect, the fungicide may be dissolved or dispersed in the aqueous liquid droplets dispersed in a water-in-oil emulsion. The dispersed droplets in conventional emulsions are typically in the range of about 1 to 100 µm in diameter. This droplet size scatters light in such a way that the resulting conventional emulsion typically appears to be cloudy, milky, or opaque. Microemulsions are similar to conventional emulsions, but with some different physical properties. A microemulsion is a clear to opalescent liquid containing both organic liquid and water or an aqueous liquid, where the dispersed droplets are very small, typically less than 1 µm. 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 typically cloudy, milky, or opaque; and c) microemulsions are thermodynamically stable and remain dispersed, whereas conventional emulsions are kinetically stable but thermodynamically unstable, and may phase-separate unless mixing energy (e.g., high-shear mixing) is applied to maintain the emulsion droplets dispersed within the continuous liquid phase. A suspension is a heterogeneous liquid formulation containing a finely-divided solid, such as a powder, dispersed within a continuous liquid phase. A suspension concentrate is a suspension of finely-divided solid (e.g., powdered) active ingredients in water or an aqueous liquid as the continuous liquid phase, intended for dilution with water by the end user before use. An oil dispersion is a suspension of finely-divided solid (e.g., powdered) active ingredients in a hydrophobic organic liquid as the continuous liquid phase, intended for dilution with water by the end user before use. A suspo-emulsion is a heterogeneous liquid formulation combining both a suspension and an oil-in-water emulsion, in a continuous water or aqueous liquid phase. Oil- in-water emulsions and suspensions are described above. A suspo-emulsion concentrate is a suspo-emulsion intended for dilution with water by the end user before use. In some aspects, the liquid formulations comprise, in weight percent based on the total weight of the liquid formulation, from about 30 wt. % to about 85 wt. % of the liquid Attorney Docket No. 112563-WO-SEC-1 aldehyde (e.g., about 32.5%, 35%, 37.5%, 40%, 42.5%, 45%, 47.5%, 50%, 55%, 60%, 65%, 70%, 72.5%, 75%, 77.5%, 80%, 82.5%, or 85% by weight of the liquid aldehyde), or within any range defined from any two of the forgoing values, such as from about 30% to about 55%, from about 42.5% to about 75%, from about 35% to about 80%, from about 50% to about 80%, from about 40% to about 55%, from about 32.5% to about 82.5%, or from about 45% to about 65% of the liquid aldehyde, by weight percent based on the total weight of the liquid formulation. In some aspects, the liquid formulations comprise, in weight percent based on the total weight of the liquid formulation, from about 0.1% to about 70% of the picolinamide fungicide (e.g., about 0.15%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.75%, 0.8%, 0.9%, 1.0%,1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 7.5%, 8%, 9%, 10%, 11%, 12%, 12.5%, 13%, 14%, 15%, 16%, 17%, 17.5%, 18%, 19%, 20%, 22.5%, 25%, 27.5%, 30%, 32.5%, 35%, 37.5%, 40%, 45%, 50%, 55%, 60%, 65%, or 67.5% of the picolinamide fungicide), or within any range defined from any two of the forgoing values, such as from about 0.1% to about 70%, from about 0.1% to about 5%, from about 0.1% to about 3%, from about 0.5% to about 3%, from about 1% to about 5%, from about 4% to about 40%, from about 0.5% to about 7.5%, from about 17% to about 55%, from about 5% to about 15%, from about 8% to about 65%, from about 12.5% to about 25%, or from about 2% to about 10% of the picolinamide fungicide, by weight percent based on the total weight of the liquid formulation. In some aspects, the liquid formulations comprise, in grams active ingredient per liter (g ai/L) of the liquid formulation, a concentration from about 1 g ai/L to about 500 g ai/L of the picolinamide fungicide (e.g., about 1.5, 2, 2.5, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 11, 12, 12.5, 13, 14, 15, 16, 17, 17.5, 18, 19, 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 45, 50, 55, 60, 65, 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, or 475 g ai/L of the picolinamide fungicide), or within any range defined from any two of the forgoing values, such as from about 1 g ai/L to about 450 g ai/L, from about 50 to about 100 g ai/L, from about 100 g ai/L to about 350 g ai/L, from about 20 g ai/L to about 150 g ai/L, from about 2.5 to about 15 g ai/L, from about 1 to about 200 g ai/L, from about 5 to about 80 g ai/L, or from about 112 g ai/L to about 250 g ai/L of the picolinamide fungicide. In a liquid 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 can contain from about 0.005 to about 100 g ai/L of the picolinamide fungicide (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, 77.5, 80, 82.5, 85, 87.5, 90, 92.5, 95, Attorney Docket No. 112563-WO-SEC-1 or 97.5 g ai/L of picolinamide fungicide), 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 0.1 g ai/L to about 10 g ai/L, about 7.5 g ai/L to about 25 g ai/L, about 1 g ai/L to about 8 g ai/L, about 2 g ai/L to about 75 g ai/L, about 10 g ai/L to about 90 g ai/L, or about 0.25 g ai/L to about 5 g ai/L of the picolinamide fungicide in the tank mix. B. Additives The liquid formulations disclosed herein can also comprise one or more additives. The additive may be a solvent, a diluent, a carrier, an adjuvant, a surfactant, a dispersant, a chemical stabilizer, a physical stabilizer, a dye or colorant, or other such component. The additive may be another fungicide or another agricultural chemical, such as a safener, an insecticide, a fungicide, a fertilizer, a nematocide, a miticide, a arthropodicide, a bactericide, a plant growth regulator, or combinations thereof. In some aspects, the additive is premixed with the picolinamide fungicide. In some aspects, the additive is added to the liquid formulation in the tank mix. In some aspects, the additive is applied to vegetation or the locus thereof sequentially or simultaneously with the liquid formulation or tank mix. i. Other Pesticides In some aspects, the liquid formulations may include an additive comprising one or more additional pesticide active ingredients added to the liquid fungicidal formulations. These pesticide active ingredients may include one or more of an herbicide, an insecticide, a fungicide, a nematocide, a miticide, a arthropodicide, a bactericide, a plant growth regulator, or combinations thereof that are compatible with the liquid formulations of the present disclosure. In some aspects, the additive is an additional fungicide. The picolinamide fungicides of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. The liquid formulation can contain one or more additional herbicides, be tank mixed with the one or more additional herbicides, or applied sequentially with the one or more additional herbicides. Exemplary additional herbicides include, but are not limited to: 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, Attorney Docket No. 112563-WO-SEC-1 copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), coumoxystrobin, cuprous oxide, cyazofamid, 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, dipymetitrone, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, enoxastrobin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminostrobin, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, 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), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isofetamid, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl- M, metam, metam-ammonium, metam- potassium, metam-sodium, 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, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triazoxide, Attorney Docket No. 112563-WO-SEC-1 triclopyricarb, tricyclazole, tridemo h, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (i¾)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)- succinimide, 1,2- dichloropropane, 1,3-dichloro-l, 1, 3, 3-tetrafluoroacetone hydrate, l-chloro-2,4- dinitronaphthalene, l-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-l-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, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3- phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5- dichlorophenyl-succinimide, N-3- nitrophenylitaconimide, natamycin, N-ethylmercurio-4- toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb, prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof. In some aspects, the liquid formulations may include one or more fungicidal active ingredients in addition to the picolinamide fungicide. In some aspects, the liquid formulations do not include any fungicidal active ingredients in addition to the picolinamide fungicide. In some aspects, the liquid formulations may exclude one or more fungicidal active ingredients specified above. In some aspects, the liquid formulations may include one or more fungicidal active ingredients in addition to the picolinamide fungicide, but may exclude one or more fungicidal ingredients specified above. Attorney Docket No. 112563-WO-SEC-1 ii. Adjuvants In some aspects, the liquid formulations may include an additive comprising an agriculturally acceptable adjuvant. Exemplary agriculturally acceptable adjuvants include, but are not limited to, 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, surfactants, protective colloids, emulsifiers, tackifiers, and mixtures thereof. Exemplary agriculturally acceptable adjuvants include, but are not limited to, crop oil concentrates (e.g., 85% mineral oil + 15% emulsifiers); nonylphenol ethoxylates; benzylcocoalkyldimethyl quaternary ammonium salts; C₉-C₁₁ alkylpolyglycoside; phosphate alcohol ethoxylates; natural primary alcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrates; emulsified methylated seed oils; tridecyl alcohol ethoxylates (e.g., 8 EO); tallow amine ethoxylates (e.g., 15 EO); and PEG(400) dioleate-99. Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants, emulsifiers) include, but are not limited to: the alkali metal salts, alkaline earth metal salts and ammonium salts of fatty acids or of aromatic sulfonic acids (e.g., lignosulfonic acids, phenolsulfonic 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. Exemplary thickeners include, but are not limited to, polysaccharides (e.g., xanthan gum), organic and inorganic sheet minerals, and mixtures thereof. Exemplary antifoam agents include, but are not limited to, silicone emulsions, long-chain alcohols, fatty acids, fatty acid salts, organofluorine compounds, and mixtures thereof. Exemplary Attorney Docket No. 112563-WO-SEC-1 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. Exemplary antifreeze agents, include, but are not limited to ethylene glycol, propylene glycol, urea, glycerol, and mixtures thereof. 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. Exemplary adhesives include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof. 5. Methods The liquid formulations disclosed herein can be applied in any known technique for applying fungicides. Exemplary application techniques include, but are not limited to, spraying, atomizing, or direct application of the liquid formulation containing the fungicide onto soil or water. Other exemplary application techniques may include applying a coating containing the fungicidal formulation to seeds prior to planting the seeds. 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 liquid formulations disclosed herein. In some aspects, a method of preventing plant diseases by killing, inhibiting, or preventing the growth of fungi or spores that are parasitic or disease-causing on desirable vegetation is disclosed herein. This method comprises contacting a liquid formulation comprising a picolinamide fungicide in a liquid aldehyde solvent to the desirable vegetation or the locus thereof, or applying the liquid formulation to the soil or water, to prevent the growth of fungi or spores that are parasitic or disease-causing on the desirable vegetation . The liquid formulations disclosed herein may be applied before the soil or vegetation is exposed to the fungus or spores thereof, to prevent disease from forming on the vegetation. The liquid formulations disclosed herein may be applied after the vegetation is exposed to the fungus or spores thereof, to stop the progression of the disease or to cure damage caused by the disease. When the liquid formulations are used in crops, the liquid formulations can be applied to the planted area after seeding and before or after the emergence of the crop plants. Attorney Docket No. 112563-WO-SEC-1 In some aspects, a coating containing the fungicide may be applied to the seeds of the crop plants prior to planting the seeds. In some aspects, the liquid formulations disclosed herein may show good crop tolerance even when the crop has already emerged and can be applied during or after the emergence of the crop plants. In some aspects, when the liquid formulations are used in crops, the liquid formulations can be applied to the area to be planted before seeding of the crop plants. In some aspects, the liquid formulations disclosed herein are applied to vegetation or an area adjacent the vegetation or applying to soil or water to preventing the growth of fungi or spores 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, wherein the vegetation is treated post-emergence, the liquid formulations disclosed herein are applied by foliar application. 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 growth or before planting or emergence. The effect observed can depend upon the type of fungus or spores thereof to be controlled, the application parameters of dilution and spray drop size, the environmental conditions at the time of use, the specific fungicide employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of liquid formulation applied. In some aspects, these and other factors can be adjusted to promote non-selective or selective fungicidal action. The liquid formulations and methods disclosed herein can be used to prevent plant diseases by killing, inhibiting, or preventing the growth of fungi or spores in a variety of applications. The liquid formulations and methods disclosed herein can be used for controlling fungi and spores thereof 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, plant 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, vegetables, fruits, and range land (e.g., pasture grasses). In some aspects, the liquid formulations and methods disclosed herein can be used for controlling plant disease in soy, vegetables, fruits, maize, wheat, barley, rice, sorghum, millet, oats, or a combination thereof. In some aspects, the liquid formulations and methods disclosed herein can be used for controlling plant disease in broadleaf crops. In some aspects, the liquid formulations and methods disclosed herein can be used for controlling plant disease in canola, flax, sunflower, soy, vegetables, fruits, or Attorney Docket No. 112563-WO-SEC-1 cotton. In some aspects, the liquid formulations and methods disclosed herein can be used in industrial vegetation management (IVM) or for utility, pipeline, roadside, and railroad rights−of−way applications. In some aspects, the liquid formulations and methods disclosed herein can also be used in forestry. In some aspects, the liquid formulations and methods disclosed herein can be used to control plant disease in conservation reserve program lands (CRP), trees, vines, grasslands, and grasses grown for seeds. In some aspects, the liquid 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. The liquid formulations and methods disclosed herein can also be used in crop plants that are resistant to, for instance, fungicides, pathogens, or insects. In some aspects, the liquid formulations and methods disclosed herein can be used in crop plants that are resistant to one or more fungicides because of genetic engineering or breeding. In some aspects, the liquid formulations 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 liquid formulations and methods disclosed herein can be used in crop plants that are resistant to attack by insects owing to genetic engineering or breeding. The liquid formulations described herein can be used to control fungicide resistant or tolerant plant diseases, fungi or spores thereof. 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. 6. Examples Example 1 - Solubility Testing The solubility of the picolinamide herbicide fenpicoxamid was tested in a variety of organic solvents. Mixtures of fenpicoxamid in the tested solvent were prepared as listed in Table 2. Solubility was determined by visual inspection at 20 °C. Among the solvents: p- anisaldehyde is a liquid aldehyde (see Table 1 above) (BASF); RHODIASOLV^® Green 25 is a water-soluble proprietary solvent blend for agriculture (Solvay); cyclohexanone is a ketone solvent that is slightly soluble in water; ARMID™ FMPC is a polar solvent blend of cationic and fatty amines, based on a morpholine derivative (Nouryon); Genagen NBP is a water- miscible n-butyl pyrrolidone solvent for agriculture (Clariant); benzyl acetate is an aromatic ester solvent; Rhodiasolv Polarclean is a water soluble polar solvent for agriculture (Solvay); Attorney Docket No. 112563-WO-SEC-1 and Hallcomid M-10 is a disubstituted capryl amide solvent (Stepan). Table 2 provides the solubility (measured as wt % of total solution) of fenpicoxamid in each of the tested solvents. Table 2. Solubility of Fenpicoxamid Across Diverse Solvent Chemistries. As can be seen in Table 2, fenpicoxamid is soluble at about 20 wt% in p- anisaldehyde. Fenpicoxamid is also soluble at greater than 15 wt% in Rhodiasolv Green 25, cyclohexanone, and Genagen NBP; however, the Rhodiasolv Green 25 and Genagen NBP are both water miscible and cyclohexanone is slightly soluble in water. Example 2 – Solubility Testing The solubilities of fenpicoxamid and another fungicide, prothioconazole, were tested in p-anisaldehyde at room temperature (RT) and also at -10 °C. Table 3 provides the solubility (measured as wt % of total solution) of each fungicide at both temperatures in the tested aldehyde solvent. Table 3. Solubility of Fenpicoxamid and Prothioconazole in p-Anisaldehyde The results of Table 3 show both fenpicoxamid and prothioconazole are soluble at 14 wt% or greater in p-anisaldehyde, even at -10 °C. Attorney Docket No. 112563-WO-SEC-1 Example 3 – Cold Temperature Physical Stability Concentrate formulations containing fenpicoxamid, prothioconazole, and suitable adjuvants were prepared in the solvent systems listed in Table 4.

Attorney Docket No. 112563-WO-SEC-1

Attorney Docket No. 112563-WO-SEC-1 For these liquid formulations, both fenpicoxamid and prothioconazole were completely dissolved in the solvent or solvent mixture. The concentrate formulations were stored for 2 weeks at a temperature of -5 °C or -10 °C. The formulations were evaluated for crystal formation after 1 week, and also at 2 weeks after being seeded with crystals. The results obtained after cold storage are given in Table 5 below. Table 5. Fenpicoxamid and Prothioconazole Cold Storage Physical Stability The results of Table 5 demonstrate that formulations containing fenpicoxamid and prothioconazole do not form crystals, except for Sample S7K-2-1, which uses a solvent system comprising Hallcomid® M-8-10 Ultra and benzyl acetate. Samples SK7-2-25 through SK7-2-61 do not form crystals, but incorporate the water-soluble solvents Genagen® NBP and Rhodiasolv Polarclean in the solvent systems. The remaining samples use solvent systems that contain p-anisaldehyde. Example 4 – Fungicide Storage Chemical Stability The concentrate formulations containing fenpicoxamid, prothioconazole, and the solvent systems listed in Table 4 were tested for chemical stability. The conditions Attorney Docket No. 112563-WO-SEC-1 (temperature: -10 °C, room temperature, or 54 °C; storage time: 2 weeks or 8 weeks) are reported in Table 6. After each storage interval, the remaining amount of prothioconazole and fenpicoxamid in each test solution was measured, and the fungicide loss (% of original amount) are presented in Table 6. Table 6. Prothioconazole and Fenpicoxamid Storage Stability The results of Table 6 demonstrate that formulations containing fenpicoxamid and prothioconazole in solvent systems including p-anisaldehyde (S7K-2-140-2 through S7K-14- 2-1) are chemically stable during storage at room temperature or 54 °C, showing less than about 6% loss of prothioconazole or fenpicoxamid. In contrast, the formulations containing fenpicoxamid and prothioconazole in solvent systems that did not contain p-anisaldehyde (S7K-2-25-1 through S7K-2-1-1) showed very little loss of prothioconazole, but significant loss of fenpicoxamid (greater than about 6%) when stored for two weeks at 54 °C. Attorney Docket No. 112563-WO-SEC-1 Example 5 – Example Concentrate Formulations Concentrate formulations containing fenpicoxamid, prothioconazole, an emulsifier and adjuvant package, and p-anisaldehyde as the solvent were prepared. The composition of these examples is given in Table 7. Table 7. Example Fungicide Concentrate Formulations As can be seen from the above examples and comparative data, the liquid fungicidal formulations comprising a picolinamide fungicide and a liquid aldehyde solvent allow for higher concentrated formulations, improved stability, and improved compatibility. The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions 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 compositions and method steps disclosed herein are specifically described, other combinations of the compositions 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 and are also disclosed. Other than in the examples, or where otherwise noted, all numbers Attorney Docket No. 112563-WO-SEC-1 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

Attorney Docket No. 112563-WO-SEC-1 What is claimed is: 1. A liquid fungicidal formulation comprising: a. a picolinamide fungicide; and b. a liquid aldehyde solvent. 2. The formulation of claim 1, wherein the aldehyde solvent, at atmospheric pressure, has a melting point from about -60 °C to about 0 °C and a boiling point from about 100 °C to about 300 °C. 3. The formulation of claim 1 or claim 2, wherein the liquid aldehyde solvent is liquid within the temperature range from about 0 °C to about 60 °C. 4. The formulation of any one of claims 1-3, wherein the liquid aldehyde is selected from the group consisting of benzaldehyde, p-anisaldehyde, 2- furaldehyde, trans-cinnamaldehyde, 3-(4-tert-butylphenyl)propionaldehyde, and 2,3- dihydro-2,2,6-trimethylbenzaldehyde. 5. The formulation of any one of claims 1-4, wherein the picolinamide fungicide is selected from the group consisting of fenpicoxamid, florylpicoxamid, metarylpicoxamid, and mixtures thereof. 6. The formulation according to any one of claims 1-5, further comprising an adjuvant. 7. The formulation according to any one of claims 1-6, comprising an admixture of the liquid aldehyde solvent with another solvent. 8. The formulation according to any one of claims 1-7, wherein the formulation is selected from the group consisting of an emulsifiable concentrate, an oil-in-water emulsion, a water-in-oil emulsion, a micro-emulsion, a suspension, and a suspo- emulsion. 9. The formulation according to any one of claims 1-8, further comprising a second fungicide. Attorney Docket No. 112563-WO-SEC-1 10. The formulation according to claim 9, wherein the second fungicide is an azole fungicide. 11. The formulation according to claim 9, wherein the second fungicide is a strobilurin fungicide. 12. A method of preventing plant diseases by killing, inhibiting, or preventing the growth of fungi or spores thereof that are parasitic on desirable vegetation, which comprises applying the formulation according to any one of claims 1-11 to the desirable vegetation, locus of the desirable vegetation, or to the area where control of the fungi or spores thereof is desired.