Surfactant-stabilized cyclohexanedioxide oxime formulations

Abstract

To provide a stabilized cyclohexanedione oxime herbicide, a method for controlling weeds, and a method for preparing a stabilized herbicide composition.SOLUTION: There is provided a composition comprising: (±)-2-[(E)-l-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) (Clethodim), or an agriculturally acceptable salt thereof of 0.5 wt.% to 50 wt.%; an effective amount of a stabilizing surfactant comprising a mixture of alkylbenzenesulfonate and ethoxylated fatty acids; and a diluent being a nonpolar solvent. The nonpolar solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alkyl esters and does not contain at least epoxidized fatty acids and epoxidized esters of fatty acids. 15% or less of the Clethodim or the agriculturally acceptable salts thereof in the composition decomposes when stored at 54°C for two weeks.SELECTED DRAWING: None

Description

[Technical Field]

[0001]

[0003] Embodiments relate to formulations comprising a combination of an active herbicide, particularly a cyclohexanedione oxime herbicide, and a stabilizing surfactant. The formulations have, for example, improved stability.

[0004] Embodiments also relate to methods for controlling weeds.

[0005] Embodiments further provide methods for making surfactant-stabilized herbicide compositions. [Background technology]

[0002] An embodiment relates to a herbicidal composition having improved storage stability and comprising a cyclohexanedione oxime as an active compound and a stabilizing surfactant, wherein no epoxidized oil fatty acid or epoxidized ester of a fatty acid is present in the composition.

[0003] Certain cyclohexanedione oximes have herbicidal activity against a variety of post-emergence grass weeds. Examples of cyclohexanedione oximes include clethodim, sethoxydim, cycloxydim, alloxydim, tralkoxydim, tepraloxydim, clefoxydim, clefoxifim, butroxydim, and profoxydim.

[0004] The chemical structure of clethodim is shown below in Formula I. [ka]

[0005] Clethodim is an important commercial herbicide in the cyclohexanedione oxime class. It is a selective postemergence cyclohexenone herbicide used to control annual and perennial weeds in a wide variety of broadleaf crops, including soybean, cotton, flax, peanut, sunflower, sugar beet, potato, alfalfa, and most vegetables. However, environmental factors such as soil moisture, high temperature, UV light, and protic compounds cause clethodim to degrade. Water and protic compounds accelerate the degradation process. Protic compounds, such as HOCAL degradation products chloropropenol, O-(3-chloro-2-propenyl)hydroxylamine (an impurity of clethodim), and clethodim, accelerate degradation. Clethodim has a short lifespan due to its low persistence in most soils. Clethodim degradation is primarily caused by heat, i.e., sunlight and high temperature. The main degradation products in soil are sulfoxide, sulfone, and oxazole sulfone. Clethodim can also be rapidly degraded due to the formation of hydrochloric acid on the leaf surface in the presence of water through acid-catalyzed reactions and photolysis. Summary of the Invention

[0006] Embodiments herein provide, inter alia, a composition comprising cyclohexanedione oxime or an agriculturally acceptable salt thereof and an effective amount of a stabilizing surfactant, the composition being substantially free of epoxidized oil fatty acids or epoxidized esters of fatty acids. In one embodiment, the composition further comprises a diluent. In another embodiment, the composition further comprises one or more adjuvants. The adjuvants may include crop oils.

[0007] The diluent may be a non-polar solvent. In one embodiment, the non-polar solvent is an aliphatic hydrocarbon, an aromatic hydrocarbon, or an alkyl ester. In another embodiment, the non-polar solvent is an aromatic hydrocarbon. In a further embodiment, the aromatic hydrocarbon is benzene, toluene, xylene, substituted or unsubstituted naphthalene, a mono-alkylated aromatic, a poly-alkylated aromatic, or a mixture thereof. In yet another embodiment, the non-polar solvent is an alkyl ester. In a further embodiment, the alkyl ester is a methyl ester. In a further embodiment, the alkyl ester is a methyl ester of a vegetable oil. In a further embodiment, the vegetable oil is canola, linseed, safflower, soybean, or sunflower oil.

[0008] In one embodiment, the surfactant comprises an anionic surfactant, a nonionic surfactant, or a mixture thereof. Anionic surfactants include phosphoric acid mono- and di-esters of long-chain alcohols having 14 to 22 carbon atoms and their salts, phosphoric acid mono- and di-esters of alkylene oxide addition products of long-chain alcohols having 14 to 22 carbon atoms and their salts, alkyl sulfates having 14 to 22 carbon atoms, polyoxyethylene alkyl ether sulfates of alcohols having 14 to 22 carbon atoms, alkanesulfonates having 14 to 22 carbon atoms, or olefin sulfonates having 14 to 22 carbon atoms. Nonionic surfactants include, for example, ethoxylated fatty acids, alcohol ethoxylates, tristyrylphenol ethoxylates, ethoxylated sorbitan fatty acid esters, and mixtures thereof. In a further embodiment, the nonionic surfactant is an ethoxylated fatty acid. In a further embodiment, the ethoxylated fatty acid is castor oil ethoxylate.

[0009] Embodiments further provide compositions comprising 0.1% to 95% by weight of cyclohexanedione oxime or an agriculturally acceptable salt or metal complex thereof. In some embodiments, the composition comprises 0.1 to about 30% by weight of a surfactant.

[0010] In particular embodiments, the cyclohexanedione oxime or agriculturally acceptable salt thereof is selected from the group consisting of methyl (E)-(RS)-3-[1-(aroxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate), 5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-enone), (2-{1-[2-(4-chlorophenoxy)propoxyimino]butyl}-3-hydroxy-5-thian-3-ylcyclohex-2-enone), (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone), (±)-2-[1-( (Ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-enone), (±)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone), (EZ)-(RS)-2-{1-[(2E)-3-chloroallyloxy-imino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclo-hex-2-en-1-one), 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-enone), and 2-[1-[[2-(4-chlorophenoxy)propoxy]imino]butyl]-3-hydroxy-5-(tetrahydro-2H-thiopyran-3-yl)-2-cyclohexen-1-one. In one embodiment, the cyclohexanedione oxime or agriculturally acceptable salt thereof comprises (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) or a salt thereof. In certain embodiments, the composition comprises an emulsifiable concentrate, wettable powder, granule, pellet, dust, oil, or aerosol.

[0011] Embodiments provide methods for controlling weeds. In one embodiment, the method comprises applying to the weeds, crop, or locus a composition comprising cyclohexanedione oxime or an agriculturally acceptable salt thereof and an effective amount of a stabilizing surfactant. Compositions applicable in this manner may further comprise additional ingredients, such as a diluent and one or more adjuvants.

[0012] In certain embodiments, the method comprises the step of producing methyl (E)-(RS)-3-[1-(aroxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate), 5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-enone), (2-{1-[2-(4-chlorophenoxy)methyl]-4-methyl-2-propenyl ... (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone, (±)-2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-enone and applying a composition comprising a cyclohexanedione oxime or an agriculturally acceptable salt thereof selected from (±)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone), (EZ)-(RS)-2-{1-[(2E)-3-chloroallyloxy-imino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclo-hex-2-en-1-one), 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-enone), and 2-[1-[[2-(4-chlorophenoxy)propoxy]imino]butyl]-3-hydroxy-5-(tetrahydro-2H-thiopyran-3-yl)-2-cyclohexen-1-one. In certain embodiments, the method comprises applying a composition comprising (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) or a salt thereof.

[0013] The method includes controlling weeds, such as grasses. In certain embodiments, the grasses are barley, barnyard grass, corn, large crabgrass, seagrass, common millet, bromegrass, corn, large crabgrass, snowdrop, common corn, foxtail, cattail, goosegrass, sorghum, hornwort, barnyard grass, large crabgrass, hawkweed, oats, orchard grass, perennial grasses, quackgrass, and Persian rye. grasses, millet, weedy rice, western sorghum rhizome, rye, ryegrass, western sorghum seedlings, sorghum, northern crabgrass, narrow barley, brown rice, sorghum, wild oats, wild corn, wild canary seed, wild wheat, wheat, oats, wild millet, common millet, barley, brown rice, wild mousegrass, and golden foxtail.

[0014] The composition can be applied as a post-emergence or pre-emergence treatment. In one embodiment, the composition is applied to a crop that is in need of weed control or is at risk of undesirable weeds. Such crops may be, for example, canola, flax, pea, lentil, pulse, linola®, mustard, chickpea, sunflower, potato, alfalfa seedling, onion, and soybean.

[0015] Embodiments also provide methods of making a stabilized herbicide composition. In one embodiment, the method includes mixing cyclohexanedione oxime with one or more stabilizers to make the stabilized herbicide composition. In another embodiment, the method includes (a) mixing one or more stabilizers with a diluent to form a first mixture, (b) adding one or more adjuvants to the first mixture to form a second mixture, and (c) adding cyclohexanedione oxime to the second mixture to make the stabilized herbicide composition. DETAILED DESCRIPTION OF THE INVENTION

[0016] Embodiments specifically provide stabilized herbicide compositions. In one embodiment, the composition comprises a herbicide cyclohexanedione oxime or an agriculturally acceptable salt thereof and an effective amount of a stabilizing surfactant. The stabilizing surfactant is the primary component imparting stabilizing effects to the cyclohexanedione oxime. Thus, for example, it has been suggested that an epoxidized oil fatty acid or an epoxidized ester of a fatty acid could serve as a stabilizer. Such agents are specifically excluded from the compositions disclosed herein. Accordingly, some embodiments provide compositions comprising a herbicide cyclohexanedione oxime or an agriculturally acceptable salt thereof and an effective amount of a stabilizer consisting essentially of a stabilizing surfactant. Some embodiments provide compositions comprising a herbicide cyclohexanedione oxime or an agriculturally acceptable salt thereof and an effective amount of a stabilizer consisting essentially of a stabilizing surfactant. Some embodiments provide compositions comprising a herbicide cyclohexanedione oxime or an agriculturally acceptable salt thereof, an effective amount of a stabilizer consisting essentially of a stabilizing surfactant, and a second stabilizer that is not an epoxidized oil fatty acid or an epoxidized ester of a fatty acid. In some embodiments, there is provided a composition comprising the herbicide cyclohexanedione oxime or an agriculturally acceptable salt thereof and an effective amount of a stabilizing surfactant, wherein the composition is substantially free of epoxidized oil fatty acids or epoxidized esters of fatty acids.

[0017] As used herein, "substantially free" means that the composition may contain trace amounts of epoxidized oil fatty acids or epoxidized esters of fatty acids (e.g., less than 1%, or less than 0.5%, or less than 0.25%), but the amount of epoxidized oil fatty acids or epoxidized esters of fatty acids present in the composition in such trace amounts does not have a significant effect on the performance and stability of the composition. Such substantially free compositions may be free of, i.e., absent, epoxidized oil fatty acids or epoxidized esters of fatty acids.

[0018] In various embodiments, the herbicide cyclohexanedione oxime or agriculturally acceptable salt thereof is selected from the group consisting of alloxydim (methyl (E)-(RS)-3-[1-(aroxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate) or a salt thereof, butroxydim (5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-enone) or a salt thereof, or its salts, clethodim ((±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) also known as BAS625H or its salts, clethodim ((±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) or its salts, cycloxydim ((±)- 2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-enone) or its salt, propyloxydim 2-[1-[[2-(4-chlorophenoxy)propoxy]imino]butyl]-3-hydroxy-5-(tetrahydro-2H-thiopyran-3-yl)-2-cyclohexen-1-one or its salt, sethoxydim ((±)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl] tepraloxydim ((EZ)-(RS)-2-{1-[(2E)-3-chloroallyloxy-imino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one) or a salt thereof, and tralkoxydim (2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-enone) or a salt thereof.

[0019] Cyclohexanedione oximes are commercially available, for example, clethodim is provided by Valent USA Corporation and Arysta LifeScience North America, sethoxydim and alloxydim are manufactured by Nippon Soda Co., Ltd. or BASF Corporation, cycloxydim and profoxydim are manufactured by BASF Corporation, and butroxydim is manufactured by CropCare Australia.

[0020] The concentration of cyclohexanedione oxime in the formulation can be expressed in units of percent or grams per liter. The weight percent (or "wt %") of cyclohexanedione oxime in the formulation can vary. In certain embodiments, the weight percent of cyclohexanedione oxime in the formulation is 0.1 wt % to 95 wt %. In other embodiments, the weight percent of cyclohexanedione oxime in the formulation is 0.5 wt % to 90 wt %. In further embodiments, the weight percent of cyclohexanedione oxime in the formulation is 10 wt % to 70 wt %. In further embodiments, the weight percent of cyclohexanedione oxime in the formulation is 10 wt % to 60 wt %. In yet other embodiments, the weight percent of cyclohexanedione oxime in the formulation is 10 wt % to 50 wt %. In further embodiments, the weight percent of cyclohexanedione oxime in the formulation is 20 wt % to 50 wt %. In further embodiments, the weight percent of cyclohexanedione oxime in the formulation is 30 wt % to 40 wt %. Similarly, the grams per liter of cyclohexanedione oxime in the formulation can range from 20 g / L to 800 g / L or from 100 g / L to 400 g / L.

[0021] The weight percent of the stabilizing surfactant in the formulation can be about 0.1% to about 15% by weight, about 1% to about 12% by weight, or about 1% to about 10% by weight. Typically, the amount of stabilizer (e.g., by weight) will be less than the amount of herbicidal active ingredient. However, the amount may be determined based on the specific stabilizer and active ingredient, optionally combined with other ingredients such as solvents / diluents / and adjuvants. Typically, a formulation with 3% to 8% adjuvant may contain 1% to 5% stabilizer, a formulation with 8% to 16% adjuvant may contain 1% to 10% stabilizer, and a formulation with 17% to 30% adjuvant may contain 1% to 15% stabilizer.

[0022] As used herein, the terms "stabilized" or "stabilized" refer to a herbicide composition that exhibits increased chemical and / or physical stability or reduced degradation compared to an unstabilized herbicide composition. The degree of stabilization can be measured by herbicidal activity or the amount of active (undegraded) herbicide. For example, a stabilized herbicide exhibits greater activity against one or more weeds than an unstabilized herbicide after a period of storage exposed to heat, light, moisture (water), or other conditions that degrade the herbicide, thereby reducing its activity. In certain embodiments, the cyclohexanedione oxime contained in the formulation is degraded by no more than about 25% within 24 months. In other embodiments, the cyclohexanedione oxime contained in the formulation is degraded by no more than about 15% within 24 months. In further embodiments, the cyclohexanedione oxime contained in the formulation is degraded by no more than about 10% within 24 months. In yet other embodiments, the cyclohexanedione oxime contained in the formulation is degraded by no more than about 5% within 24 months. In a further embodiment, the cyclohexanedione oxime contained in the formulation degrades by no more than about 3% within 24 months.

[0023] As used herein, the term "effective amount," when used in reference to a stabilizer, refers to the amount of stabilizer required to inhibit, reduce, or prevent the decomposition of an active ingredient (e.g., a herbicide) in a composition due to exposure to one or more external environmental effects, such as sunlight (UV), moisture (e.g., humidity, water), and heat. Typically, an effective amount of stabilizer results in no more than 25% decomposition of the active ingredient due to exposure to UV, moisture, or heat within an extended period of time, e.g., two years. In other embodiments, an effective amount of stabilizer results in no more than about 15%, or no more than about 10%, or no more than about 5% decomposition of the active ingredient due to exposure to UV, moisture (e.g., humidity, water), or heat within two years.

[0024] The formulation may contain one or more solvents. The amount of solvent in the formulation may range from 1% to 99% or from 30% to 80%. Suitable solvents include, for example, non-polar water-immiscible solvents or polar aprotic water-miscible organic solvents. Non-polar solvents include, for example, substituted or unsubstituted aliphatic or aromatic hydrocarbons, esters of vegetable oils, or mixtures thereof. Non-limiting examples of aromatic hydrocarbons include benzene or unsubstituted benzene derivatives, such as toluene, xylene, 1,2,4-trimethylbenzene, naphthalene, or mixtures thereof. In one embodiment, the solvent includes a mixture of naphthalene and 1,2,4-trimethylbenzene. In another embodiment, the solvent includes Aromatic 150, a high-boiling aromatic naphtha solvent containing <10% naphthalene and <1.7% 1,2,4-trimethylbenzene.

[0025] Alkyl esters can also be used as non-polar, water-immiscible solvents. Vegetable oils may be esterified with various alcohols to form vegetable oil alkyl esters. The fatty acids of these vegetable oils have 5 to 20 or 6 to 15 carbon atoms. Vegetable oil alkyl esters include, but are not limited to, methyl, ethyl, and butyl esters of canola (B. napus), flaxseed, safflower (Carthamus tinctorius L.), soybean, and sunflower oil. In one embodiment, the solvent is a mixture of methyl esters. A non-limiting example of a methyl ester is Agent 2416-21, manufactured by Stepan Company (22 W. Frontage Road, Northfield, Illinois).

[0026] Water-miscible polar aprotic solvents include, for example, alkyl lactate, isopropyl lactate, alkyl carbonate, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol, and polypropylene glycol alkyl ether, or mixtures thereof.

[0027] The composition may contain one or more adjuvants. Adjuvants may, for example, enhance or improve herbicide performance. Adjuvants may be added to the composition at the time of formulation or may be added to the mixture by an applicator prior to application. Adjuvants include, for example, surfactants (emulsifiers), crop oils, fertilizers, dispersants, compatibilizers, foam accelerators, foam suppressors, conditioners, and spray colorants (dyes). Adjuvants may be present in any desired amount. For example, the formulation may contain 0.1% to 3% adjuvant, 3% to 8% adjuvant, 8% to 16% adjuvant, 17% to 30% adjuvant, or 30% or more (e.g., 40% or more) adjuvant.

[0028] Surfactants can increase the solubility of the active ingredient in the solution. Surfactants can also affect spray retention, droplet spread, and drying rate. Surfactants can be anionic or nonionic. Examples of anionic surfactants include phosphoric acid mono- and diesters of long-chain alcohols having 14 to 22 carbon atoms and their salts, phosphoric acid mono- and diesters of alkylene oxide addition products of long-chain alcohols having 14 to 22 carbon atoms and their salts, alkyl sulfates having 14 to 22 carbon atoms, polyoxyethylene alkyl ether sulfates of alcohols having 14 to 22 carbon atoms, alkanesulfonates having 14 to 22 carbon atoms, and olefin sulfonates having 14 to 22 carbon atoms.

[0029] Suitable nonionic surfactants include, for example, alkyl end-capped surfactants, ethoxylated fatty acids, alcohol ethoxylates, tristyrylphenol ethoxylates, ethoxylated sorbitan fatty acid esters, or mixtures thereof. Ethoxylated fatty acids include castor oil or canola oil ethoxylates having at least 25, preferably 27 to 37, ethoxylated units, such as Sunaptol.RTM.CA350 (castor oil ethoxylate having 35 ethoxy units) from Uniqema (formerly ICI Surfactants), Mergital.RTM.EL33 (castor oil ethoxylate having 33 ethoxy units) from Henkel KGaA, Eumulgin.RTM.C03373 (canola oil ethoxylate having 30 ethoxy units) from Henkel KGaA, and Ukanil.RTM.2507 (castor oil ethoxylate) from Uniqema.

[0030] The surfactant may be present in any desired amount. For example, the surfactant may be present in the formulation in an amount of about 0.1 to about 30% by weight. In certain embodiments, the surfactant is present in the formulation in an amount of about 1 to about 20% by weight. In other embodiments, the surfactant is present in the formulation in an amount of about 5 to about 15% by weight.

[0031] Emulsifiers are a type of surfactant typically used to keep emulsions well-dispersed. Non-limiting examples of emulsifiers include Aerosol OT-100, Genapol XM 060, Synperonic A20, Soprophor BSU, Dehypon G2084, Rhodacal 70 / B, Atlox 4817B, Nansa EVM 70 / 2E, Phenyl Sulphonate CAL, Agent 2201-76E, Agent 2201-76, Agent 2416-20, Emulpon CO-360, T-Det C-40®, and Agnique™ SBO-10. Agent 2201-76 is manufactured by Stepan Company (22 W. Frontage Road, Northfield, Illinois) and is a blend of nonionic and anionic surfactants (82%). The ingredients in Agent 2201-76 are alkylbenzene sulfonates and fatty acid ethoxylates, aromatic petroleum hydrocarbons, 1-hexanol, and naphthalene. Agent 2416-20, also manufactured by Stepan Company (22 W. Frontage Road, Northfield, Illinois), is a blend of nonionic and anionic surfactants (35%-37%). Agent 2416-20 also contains aromatic petroleum hydrocarbons (57%-58%) and naphthalene (6%-7%). Emulpon CO-360, manufactured by Akzo Nobel Chemicals Ltd. (525 West Van Buren, Chicago, Illinois), contains ethoxylated castor oil (100% by weight) and oxirane (<0.001% by weight).T-Det C-40® is a nonionic emulsifier and a brand of ethoxylated (polyethoxylated) castor oil, available from Harcros Organics (5200 Speaker Road, PO Box 2930, Kansas City, Kansas) or Akzo Nobel Chemicals Ltd. (525 West Van Buren, Chicago, Illinois). Agnique™ SBO-10 is manufactured by Cognix GmbH, headquartered in Monheim, Germany, and contains alkoxylated triglycerides as ethoxylated soybean oil.

[0032] Crop oils or crop oil concentrates can be used to increase the effectiveness of herbicide formulations. Without being bound by theory, it is believed that crop oils retain moisture on the leaf surface longer than water, thereby increasing the time for herbicide penetration and the amount of herbicide that penetrates into the plant (e.g., weeds). Crop oils can improve herbicide uptake by plants (e.g., weeds). Thus, crop oils can improve, enhance, increase, or promote the efficacy or activity of herbicides. Crop oils can be present in the formulation at 1% to 40% by weight or 1% to 20% by weight. Crop oils can be derived from either petroleum-based oils or vegetable oils. Non-limiting examples of crop oils include soybean oil and petroleum-based oils.

[0033] The herbicide composition can be present in a conventional formulation. Non-limiting examples include solutions, emulsions, suspensions, wettable powders, powders, dusts, pastes, soluble powders, granules, pellets, emulsifiable concentrates, oil sprays, aerosols, natural and synthetic materials impregnated with the active compound, and very fine capsules (e.g., in polymeric substances). In certain embodiments, the composition is in the form of an emulsifiable concentrate, wettable powder, granules, dusts, oil sprays, or aerosols.

[0034] The formulation may optionally include an adhesive coating. Such coatings include those that promote adhesion of the active ingredient to the intended environment, e.g., weeds. Adhesive coatings include carboxymethylcellulose, natural and synthetic polymers in various forms (e.g., powder, granules, or latex). Other adhesive coatings include gum arabic, polyvinyl alcohol, and polyvinyl acetate. Phospholipids, such as cephalin and lecithin, and synthetic phospholipids are also examples of adhesive coatings. Further additives may be mineral oil and vegetable oil.

[0035] Colorants may also be included in the formulation, non-limiting examples being inorganic pigments such as iron oxide, titanium oxide, and Prussian blue, and organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc.

[0036] The herbicidal compositions may be applied in the form of a ready mix, or they may be formulated individually and mixed at the time of use, i.e., applied in the form of a tank mix.

[0037] The herbicide composition may be used as is or in the form of a formulation, and may also be used as a mixture with other herbicides, as a ready-mix, or as a tank mix. The herbicide composition may also be mixed with other active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, growth substances, plant nutrients, and agents for improving soil structure. For specific application purposes, particularly when applied after emergence, further additives may be included, such as plant-tolerant post-emergence formulations of mineral or vegetable oils (e.g., the commercially available product "Oleo DuPont 11E") or ammonium salts, such as ammonium sulfate or ammonium thiocyanate.

[0038] The herbicidal composition may also exclude any of the above, for example, other herbicides, fungicides, insecticides, miticides, nematicides, bird repellents, growth substances, plant nutrients, and agents that improve soil structure may be excluded or omitted from the composition.

[0039] The herbicidal compositions can be used as such, in the form of their formulation, or in a form prepared from a concentrated form by diluting said concentrated form, such as a ready-to-use liquid or concentrate, a solution, a suspension, an emulsion, or a solid (e.g., powder, paste, granule, and pellet), which is dispersed conventionally, for example, by watering, spraying, atomizing, dusting, or dusting.

[0040] The formulation can be prepared by mixing or suspending one or more stabilizers, active ingredients, and optionally adjuvants, diluents, or solvents. In certain embodiments, the formulation can be prepared, for example, by first mixing or suspending one or more stabilizers with a diluent or solvent. The resulting mixture containing the stabilizer is then combined with an appropriate amount of adjuvant. The active ingredient, cyclohexanedione oxime, can be added last and blended until the formulation is nearly or completely homogeneous.

[0041] In one embodiment, a method of making a stabilized herbicide composition includes mixing cyclohexanedione oxime with one or more stabilizers to form a stabilized composition. In another embodiment, the method includes a) mixing one or more stabilizers with a diluent to form a first mixture, b) adding one or more adjuvants to the first mixture to form a second mixture, and c) adding cyclohexanedione oxime to the second mixture to form the stabilized composition.

[0042] Desirable plants are generally referred to herein as "crops." As used herein, the term "crop" includes any edible or non-edible plant, including ornamental plant species having commercial value that are planted and cultivated for commercial use. Thus, crops include flowering and non-flowering plants, woody plants, vegetable plants, turf, and ground cover plants. Non-limiting examples of crops include canola, flax, peas, lentils, beans, Linola®, mustard, chickpeas, sunflowers, potatoes, alfalfa seedlings, onions, soybeans, and turfgrass. The term "plant" is meant to include germinated seeds, emerged seeds, and established vegetation, including roots and aboveground parts (e.g., leaves, petioles, flowers, fruits, twigs, branches, roots, etc.).

[0043] As used herein, the term "turf" refers to grasses, such as lawns, growing in a desired area or in an area that is purposefully planned and maintained. Turf also refers to turf soil, the surface layer of which is made up of grasses and grass roots.

[0044] The composition contains an active herbicide against one or more weeds. In the broadest sense, the term "weed" refers to a plant that grows in an undesirable location. In other words, a weed is a plant that is undesirable to a crop because it competes for water, nutrients, sunlight, soil, etc. Grass plants are an example of a weed.

[0045] Weeds can be controlled using the composition. An embodiment provides a method for controlling weeds. In one embodiment, the method comprises applying (contacting) a composition comprising cyclohexanedione oxime or an agriculturally acceptable salt thereof and a stabilizing surfactant to a locus or area of ​​weeds, crops, or plants. Such methods can be applied to plants, including, but not limited to, one or more weeds described herein.

[0046] The herbicidal composition may be applied before the weeds emerge (pre-emergence) or after the weeds emerge (post-emergence). The herbicidal composition may be applied to all or part of the weeds, crop or locus.

[0047] The weeds may be green plants or grass weeds. The grass plants being controlled are in the pre-emergence or post-emergence stage of growth at the time of application (contact) of the herbicidal composition.

[0048] In the methods, "management" and "managing" include any adverse change or deleterious effect, including any deviation from natural plant survival, growth, or proliferation. Non-limiting examples include inhibiting, reducing, or preventing the growth of all or any part of a weed (roots, stems, petioles, leaves, flowers, branches, etc.), weed germination, weed ripening, weed spread, or killing a weed.

[0049] The method can be used to manage one or more grass plants. Examples of grass species with which the compositions and methods can be used include, but are not limited to, barley (Hordeum vulgare), barnyardgrass (Echinochloa crusgalli), horsegrass (Cynodon dactylon), millet (Brachiaria platphylla), bromegrass species (Bromus species), corn (Zea mays), crabgrass species (Digitaria species), seagrass (Dactyloctenium aegyptium), common foxtail (Panicum dichotomiflorum), tall fescue (Festuca arundinacea), barnyardgrass (Hordeum jubatum), green foxtail (Setaria species), cattail, goosegrass (Eleusine indica), sorghum (Sorghum bicolor), hornwort (Rottboellia exaltata), barnyardgrass (Echinochloa colona), large crabgrass, hawkweed (Eragrostis cilanensis), oats (Avena sativa), orchardgrass (Dactylis glomerata), perennial grasses, quackgrass (Agropyron repens), Persian ryegrass, millet, weedy rice (Oryza sativa), corn rhizome (Sorghum halepense), rye (Secale cereale), Lolium species, corn seedlings (Sorghum halepense), corn (Sorghum bicolor), northern crabgrass, barnyard millet (Eriochlola gracillis), Leptochloa species, panicum (Panicum texanum), volunteer barley, volunteer oats, volunteer corn, volunteer canary seed, volunteer wheat, wheat (Triticum aestivum), wild oat (Avena fatua), wild millet (Panicum miliaceum), common corn (Panicumcapillare), narcosis (Eriochloa villosa), rat grass (Muhlenbergia frondisa), and golden foxtail.

[0050] Application rates vary depending, for example, on the crop or target weed. Typically, application rates are from 0.01 kg / ha to 5.00 kg / ha or from 0.03 kg / ha to 3.00 kg / ha of active ingredient. In some embodiments, application rates can be expressed as grams of active ingredient per hectare (g ai / ha), for example, from about 30 g ai / ha to about 300 g ai / ha.

[0051] The terms "composition" and "formulation" are interchangeable when used herein.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing, suitable methods and materials are described herein.

[0053] All applications, publications, patents, and other references and citations cited herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control.

[0054] As used herein, the singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise.

[0055] As used herein, the term "about" refers to a measurable value of a parameter, amount, duration, etc., and is meant to include a variation of + / - 15% or less from the specifically recited value, preferably a variation of + / - 10% or less, more preferably a variation of + / - 5% or less, even more preferably a variation of + / - 1% or less, and even more preferably a variation of + / - 0.1% or less, provided that such variations are appropriate for practicing the invention described herein. It should also be understood that the value referred to by the modifier "about" is itself specifically disclosed herein.

[0056] As used herein, all numerical values ​​or ranges of values ​​include integers within such ranges and fractions of said values ​​or integers within said ranges unless expressly stated otherwise. Thus, for example, a reference to a range of 90% to 100% includes 91%, 92%, 93%, 94%, 95%, 95%, 97%, etc., as well as 91.1%, 91.2%, 91.3%, 91.4%, 91.5%, etc., 92.1%, 92.2%, 92.3%, 92.4%, 92.5%, etc. A reference to a range of 90% to 100% includes 92.2% to 97.5%, 91.5 to 94.5%, etc. References to a series of overlapping ranges, for example, 0.1% to 15% and 1% to 10%, include the ranges 0.1% to 1%, 0.1% to 10%, 1% to 15%, and 10% to 15%.

[0057] Embodiments are generally disclosed herein using affirmative language. The embodiments herein also specifically include embodiments in which certain subject matter, such as substances or materials, method steps and conditions, protocols, procedures, assays, or analyses, is excluded in whole or in part. Thus, even if an embodiment is not generally expressed herein, it is disclosed herein insofar as it does not include aspects not expressly included.

[0058] While a number of embodiments have been described, it will be understood that various modifications can be made without departing from the spirit and scope of the disclosed embodiments. Accordingly, the following examples are intended to illustrate, but not limit, the scope of the embodiments set forth in the claims.

[0059] Specific examples are set forth below to illustrate the embodiments herein. These examples are merely illustrative and should not be understood to limit the scope and underlying principles in any way. In addition to what has been shown and described herein, various modifications will become apparent to those skilled in the art from the following examples and the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. [Example]

[0060] In the following examples, exemplary herbicide formulations and other control herbicide formulations are tested for their storage stability, often in comparison with similar commercial herbicide formulations containing clethodim as the active ingredient.

[0061] In the following exemplary herbicide formulations of the present invention, similar commercial herbicide formulations containing clethodim as the active ingredient are prepared and tested for their storage stability at elevated temperature conditions. Formulation A-1 Clethodim 70% Generic Product (MUP) 51.4% Aerosol OT-100 (emulsifier) ​​10.0% Solvesso150 ND (solvent) 38.6% Formulation A-2 Clethodim 70% Generic Product (MUP) 51.4% Genapol XM 060 (emulsifier) ​​10.0% Solvesso150 ND (solvent) 38.6% Other formulations were prepared similarly, except that the surfactant was changed as outlined in the table below. Test Method Evaluation of the stability of stabilized clethodim formulations

[0062] All the above formulations were subjected to a 2-year stability study at 25°C. The formulations were stored at 54°C ± 2°C and evaluated at 7 and 14 days. A control formulation was also stored at -10°C ± 2°C and evaluated at 7 and 14 days. The weight percent of clethodim was determined at each time interval by high performance liquid chromatography (HPLC) analysis. The HPLC analysis was performed under the following conditions: Example 1

[0063] The formulations are summarized in Table 1. The moisture level, clethodim percentage (% AI), and percent clethodim remaining are also shown in Table 1. The percent remaining at -10°C is calculated when compared to the initial amount of clethodim present from the day 0 analysis. The percent remaining at 54°C is calculated when compared to either the initial amount from the day 0 analysis or an analysis at -10°C for the same time interval. Series A demonstrated improved chemical stability of clethodim formulations by selecting a stabilizing surfactant, while Series B showed significant clethodim degradation without a stabilizing surfactant at the same storage conditions. Example 2

[0064] Emulsion stability was tested according to standard protocol CIPAC MT 18.1.4. Table 2 shows formulations containing various ratios of nonionic and ionic surfactants and their emulsion stability in tap water aqueous media at 1 hour and 4 hours. The results show that the best emulsion performance was obtained when the ratio of nonionic surfactant to ionic surfactant was 7:3. Example 3

[0065] In Table 3, formulations were prepared using various ratios of Soprophor BSU to Aerosol OT-100 and tested for emulsion stability at 1 hour and 4 hours. A ratio of 7:3 was found to provide the best emulsion performance. Example 4

[0066] Table 4 shows the effect of ionic surfactants on emulsion stability by preparing formulations containing Soprophor BSU and various individual ionic surfactants. Example 5

[0067] Table 5 lists the emulsion test results by comparing various ionic surfactants in the presence of the nonionic surfactant Synperonic A20, while Table 6 shows the emulsion stability results for the control. Example 6

[0068] In Table 7, formulations were made using surfactants that showed a negative impact on the chemical stability of the clethodim EC formulation. Samples stored at 54°C for 2 weeks retained less than 77% of clethodim compared to those stored at -10°C for the same period. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

Claims

1. 0.5% to 50% by weight of (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) (clethodim), or an agriculturally acceptable salt thereof; an effective amount of a stabilizing surfactant which is a mixture of alkyl benzene sulfonate and ethoxylated fatty acid; a diluent that is a non-polar solvent; the non-polar solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alkyl esters; At least does not contain epoxidized oil fatty acids and epoxidized esters of fatty acids, A composition wherein 15% or less of the clethodim or agriculturally acceptable salt thereof decomposes when stored at 54°C for 2 weeks.

2. The composition of claim 1 further comprising one or more adjuvants.

3. 10. The composition of claim 1, wherein the non-polar solvent is an aromatic hydrocarbon.

4. 4. The composition of claim 3, wherein the aromatic hydrocarbon is benzene, toluene, xylene, substituted or unsubstituted naphthalene, mono-alkylated aromatic, poly-alkylated aromatic, or mixtures thereof.

5. 10. The composition of claim 1, wherein the non-polar solvent is an alkyl ester.

6. 6. The composition of claim 5, wherein the alkyl ester is a methyl ester.

7. 7. The composition of claim 6, wherein the alkyl ester is a methyl ester of a vegetable oil.

8. 8. The composition of claim 7, wherein the vegetable oil is canola, flaxseed, safflower, soybean, or sunflower oil.

9. 3. The composition of claim 2, wherein the one or more adjuvants comprises a crop oil.

10. 2. The composition of claim 1, comprising 10% to 50% by weight of said (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone), or an agriculturally acceptable salt thereof.

11. 2. The composition of claim 1, comprising 100 g / L to 500 g / L of said (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone), or an agriculturally acceptable salt thereof.

12. 10. The composition of claim 1 comprising from 0.1% to 30% by weight of said stabilizing surfactant.

13. 10. The composition of claim 1 comprising from 0.1% to 15% by weight of said stabilizing surfactant.

14. 10. The composition of claim 1 comprising from 1% to 99% by weight of said non-polar solvent.

15. 10. The composition of claim 1 comprising 10% to 80% by weight of said non-polar solvent.

16. 16. The composition of any of claims 1 to 15, comprising an emulsifiable concentrate including a microemulsion, a wettable powder, a granule, a pellet, a dust, an oil spray, an aerosol, a suspension concentrate, or a capsule.

17. 1. A method for controlling weeds, comprising: 0.5% to 50% by weight of (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) (clethodim), or an agriculturally acceptable salt thereof; an effective amount of a stabilizing surfactant which is a mixture of alkyl benzene sulfonate and ethoxylated fatty acid; a diluent which is a non-polar solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alkyl esters; applying to the weeds, crop, or locus a composition that is free of at least an epoxidized oil fatty acid and an epoxidized ester of a fatty acid; wherein no more than 15% of the clethodim or agriculturally acceptable salt in the composition decomposes when stored at 54°C for 2 weeks.

18. 20. The method of claim 17, wherein the composition further comprises one or more adjuvants.

19. 18. The method of claim 17, wherein the weeds are grasses.

20. The grass family plant is selected from the group consisting of barley, barnyard grass, corngrass, American millet, bromegrass, corn, large crabgrass, sea grass, common millet, giant fescue, narrow-leaved barley, green foxtail, cattail, goosegrass, sorghum, hornwort, barnyard grass, large crabgrass, hawkweed, oats, orchard grass, perennial grass, quackgrass, Persian ryegrass, millet, and weed grass.

20. The method of claim 19, wherein the plant is selected from the group consisting of rootstock, corn rhizome, rye, ryegrass, corn seedling, sorghum, northern crabgrass, narrow-leaved barley, brown barley, Korean brown grass, wild oat, wild corn, wild canary seed, wild wheat, wheat, oat, wild millet, common millet, barley grass, wild mousegrass, and golden foxtail.

21. 18. The method of claim 17, wherein the composition is applied as a post-emergence treatment.

22. 18. The method of claim 17, wherein the composition is applied to a crop in need of weed control or at risk of undesirable weeds.

23. 23. The method of claim 22, wherein the crop is any of canola, flax, pea, lentil, bean, linola®, mustard, chickpea, sunflower, potato, alfalfa seedling, onion, and soybean.

24. 1. A method of making a stabilized herbicide composition, comprising mixing 0.5% to 50% by weight of a cyclohexanedione oxime herbicide with one or more stabilizing surfactants and a diluent to make a stabilized composition; the cyclohexanedione oxime herbicide is (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) (clethodim); the stabilizing surfactant is a mixture of alkylbenzene sulfonate and ethoxylated fatty acid; the diluent is a non-polar solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alkyl esters; At least does not contain epoxidized oil fatty acids and epoxidized esters of fatty acids, 1. A method for making a stabilized herbicide composition, wherein no more than 15% of the clethodim or agriculturally acceptable salt in said composition decomposes when stored at 54°C for 2 weeks.

25. a) one or more stabilizing surfactants; b) one or more adjuvants, and c) 0.5% to 50% by weight of a cyclohexanedione oxime herbicide to the diluent in any order to form a stabilized composition; the cyclohexanedione oxime herbicide is (±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone) (clethodim); the stabilizing surfactant is a mixture of alkylbenzene sulfonate and ethoxylated fatty acid; the diluent is a non-polar solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alkyl esters; At least does not contain epoxidized oil fatty acids and epoxidized esters of fatty acids, 1. A method for making a stabilized herbicide composition, wherein no more than 15% of the clethodim or agriculturally acceptable salt in said composition decomposes when stored at 54°C for 2 weeks.

26. 2. The composition of claim 1, wherein the ethoxylated fatty acid is at least one selected from the group consisting of castor oil ethoxylate having 27 to 37 ethoxy units, canola oil ethoxylate having 27 to 37 ethoxy units, and ethoxylated soybean oil.

27. 18. The method of claim 17, wherein the ethoxylated fatty acid is at least one selected from the group consisting of castor oil ethoxylate having 27 to 37 ethoxy units, canola oil ethoxylate having 27 to 37 ethoxy units, and ethoxylated soybean oil.

28. 25. The method of making a stabilized herbicidal composition of claim 24, wherein the ethoxylated fatty acid is at least one selected from the group consisting of castor oil ethoxylate having from 27 to 37 ethoxy units, canola oil ethoxylate having from 27 to 37 ethoxy units, and ethoxylated soybean oil.

29. 26. The method of making a stabilized herbicide composition of claim 25, wherein the ethoxylated fatty acid is at least one selected from the group consisting of castor oil ethoxylate having 27 to 37 ethoxy units, canola oil ethoxylate having 27 to 37 ethoxy units, and ethoxylated soybean oil.

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