An herbicidal formulation comprising saflufenacil and fluroxypyr

Abstract

The present invention provides suspoemulsion formulations comprising: (i) a continuous aqueous phase comprising saflufenacil which is suspended in said continuous aqueous phase; (ii) a liquid organic phase comprising fluroxypyr or a salt, an ester, or a combination thereof, and a water-immiscible solvent; and (iii) a surfactant. Such formulations are useful in controlling weed.

Description

AN HERBICIDAL FORMULATION COMPRISING SAFLUFENACIL AND FLUROXYPYRTECHNICAL FIELD

[0001] The present invention provides a suspoemulsion formulation comprising saflufenacil and fluroxypyr. The formulations of the invention are useful in controlling weed.BACKGROUND ART

[0002] A suspoemulsion (SE) is typically a conventional type of formulation in the field of the agrochemical formulations and is used to combine two active ingredients with very different physical properties into one formulation.

[0003] The suspoemulsion usually comprises a continuous aqueous phase, a dispersed oil phase, and a suspended solid phase. The oil phase usually comprises a water-immiscible solvent and a first pesticide, which is dissolved in the water-immiscible solvent. The oil phase usually forms droplets within the aqueous phase. The solid phase usually comprises a second pesticide, which is suspended in a continuous aqueous phase as solid particles. SE formulations are conventionally diluted with a carrier, such as water, when making up the spray mixture.

[0004] Suspoemulsions can be prepared by first preparing separately a concentrated oil-in- water emulsion (EW) formulation and a suspension concentrate (SC) formulation, and then combining them. Creating stable emulsions that additionally contain at least one solid active ingredient, that is, suspo-emulsions (or suspoemulsions), presents significant challenges to the formulation chemist such as aggregation of the solid particles, crystal growth or coalescence of the emulsion droplets, mainly due to Ostwald ripening, or heteroflocculation. For instance, when a conventional suspoemulsion is stored under severe environment at high temperature or low temperature, oil droplets and particles (dispersoids) dispersed in water may sometimes cause particle growth, separation of an aqueous layer and formation of a hard cake due to aggregation and precipitation of dispersoids, or a change in appearance such as creaming of the formulation.

[0005] Saflufenacil (2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-l- (2H)pyrimidinyl]-4-fluoro-N-[[methyl(l-methylethyl)amino]sulfonyl]benzamide) is a herbicide belonging to the group of protoporphyrinogen oxidase (PPO) inhibitors, more specifically a pyrimidinedione-based PPO inhibitor. Saflufenacil has been described in WO01 / 083459. Further processes for its preparation are described in WO 03 / 097589, WO 05 / 054208, WO 06 / 097589, WO 06 / 125746, WO 08 / 043835, and WO 08 / 043836. Saflufenacil is particularly useful for preplant applications and selective pre-emergence weed control in multiple crops. In particular, it is useful as a foliar contact and residual broadleaved weed herbicide. It is absorbed by foliage and roots with translocation in the apoplast and limited movement in the phloem. Saflufenacil is applied to foliage and is used for residual control of broad-leaved weeds, including glyphosate- and ALS-resistant biotypes. Saflufenacil is applied pre-emergence in corn and sorghum, at 50-125 gram / hectare (g / ha); preplant for rapid foliar burn-down in soybeans, cereals, cotton, legumes; and post-directed in tree fruit and nuts, at 18-25 g / ha, and in sugarcane at 24.5-96 g / ha.

[0006] Like many herbicides, salfufenacil is only sparingly soluble in water and mixtures of water with water-miscible solvents such as Ci-C4-alkanols, C2-C4-alkandiols and C2-C4- alkantriols, and such aqueous dilutions may become instable. The solubility of saflufenacil in water, at 20°C, is 0.0025 g / 100 mL and 0.21 g / 100 mL, at pH 5 and 7, respectively. In methanol, isopropyl alcohol, and octanol, saflufenacil has a solubility of 2.98 g / 100 mL, 0.25 g / 100 mL, and <0.01 g / 100 mL, respectively, at 20°C (Pesticide Fact Sheet (saflufenacil); United States Environmental Protection Agency, Office of Prevention, Pesticides and Toxic Substances, August 2009; https: / / www3.epa.gov / pesticides / chem search / reg actions / registration / fs PC-118203 01- Aug-09.pdf). Moreover, the saflufenacil-based aqueous dilutions sometimes show fluctuations in herbicidal efficiency.

[0007] When trying to formulate saflufenacil one faces several problems. Saflufenacil carries a N-amino-sulfonylcarboxamide side chain that might undergo hydrolysis at basic pH values (Roskamp et al. , 2013). Apart from that, saflufenacil exists in different crystalline and non-crystalline modifications, i.e., amorphous forms, crystalline hydrates and a crystalline anhydrate, which may undergo uncontrolled interconversion. This interconversion may lead to coarsening of the saflufenacil particles, in particular when formulated as suspension concentrate. These factors might result in a reduced chemical and physical stability of the formulations, an effect that is particularly pronounced when the formulations are stored over prolonged periods of time and / or at elevated temperatures. Said factors may also lead to poor dilution properties as the coarse saflufenacil particles are prone to separate from the diluted formulation.

[0008] Fluroxypyr ([(4-Amino-3,5-dichloro-6-fluoropyridin-2-yl)oxy]acetic acid) is a pyridinoxy acid herbicide in the class of synthetic auxins and is used for control of a wide range of broadleaf weeds in, e.g., sugar cane, cereals, sweetcorn and olive trees. Fluroxypyr induces auxin-type responses in susceptible annual and perennial broadleaf weeds (auxin being a type of plant growth hormone).

[0009] It is usually commercialized as an ester called starane (fluroxypyr- 1 -methylheptyl ester), which is rapidly degraded to fluroxypyr acid. Its oral LD50 in rats is above 5000 mg / kg. It is classified by EPA as Toxicity Category II and as “not likely” human carcinogen. However, subchronic toxicity assays in rats showed nephrotoxicity, increased kidney weight, hispathological lesions and decreased renal function (Aramendia et al., 2005).

[0010] CN 102696613 B discloses herbicidal compositions for wheat fields. Specifically, a composition comprising saflufenacil, fluroxypyr-mepthyl, alkyl naphthalene sulfonate, sodium ligninsulfonate, synergist, stabilizer, and water was prepared.

[0011] There is a need to develop stable, high efficacy formulations comprising both saflufenacil and fluroxypyr as active ingredients.SUMMARY OF INVENTION

[0012] It has now been found, in accordance with the present invention, that a suspoemulsion formulation comprising saflufenacil and fluroxypyr showed superior efficacy in controlling weed as compared to an emulsifiable concentrate (EC) formulation comprising saflufenacil and fluroxypyr. This finding is highly important, as it enables to obtain high efficacy formulation comprising both saflufenacil and fluroxypyr and such an herbicidal composition is highly beneficial since the application thereof to a locus such as a field of crop would be much more convenient than applying each one of the herbicides, i.e., saflufenacil and fluroxypyr, from a separate composition.

[0013] In one aspect, the present invention thus provides a suspoemulsion formulation comprising: (i) a continuous aqueous phase comprising saflufenacil which is suspended in said continuous aqueous phase; (ii) a liquid organic phase comprising fluroxypyr or a salt, an ester, or a combination thereof, and a water-immiscible solvent; and (iii) a surfactant. In certain embodiments, the fluroxypyr comprised within said formulation is in the form of meptyl ester thereof.

[0014] In another aspect, the present invention relates to a method of controlling weed comprising applying to a locus an effective amount of said formulation.BRIEF DESCRIPTION OF DRAWINGS

[0015] Fig. 1 shows the efficacy (% control) at 28 days after application (DAA) of the suspoemulsion formulation comprising saflufenacil and fluroxypyr (SE), the emulsifiable concentrate formulation comprising saflufenacil and fluroxypyr (EC), and a tank mix of saflufenacil and fluroxypyr, in controlling the POROL weed when applied post-emergence at application rate (in gram of active ingredient per hectare; g ai / Ha) of 30 saflufenacil and 200 fluroxypyr (calculated on an acid equivalent base of fluroxypyr).DETAILED DESCRIPTION

[0016] In one aspect, disclosed herein is a suspoemulsion (SE) formulation comprising: (i) a continuous aqueous phase comprising saflufenacil which is suspended in said continuous aqueous phase; (ii) a liquid organic phase comprising fluroxypyr or a salt, an ester, or a combination thereof, and a water-immiscible solvent; and (iii) a surfactant.

[0017] In certain embodiments, the fluroxypyr comprised within the suspoemulsion formulation of the invention is in its acid free form rather than a salt form, i.e., wherein all its acid groups are in their free acid form.

[0018] In certain embodiments, the fluroxypyr comprised within the suspoemulsion formulation of the invention is in its salt form.

[0019] Non-limiting salts of fluroxypyr include alkali metal salts such as sodium salts and potassium salts; ammonium salts or substituted ammonium salts such as mono-, di- and tri- Ci-Cs-alkylammonium salts (e.g., methyl ammonium, dimethylammonium, and isopropylammonium); mono-, di- and tri-hydroxy-C2-Cs- alkylammonium salts such as hydroxy ethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts (e.g., monoethanolammonium and triisopropanolammonium salts); olamine salts; and diglycolamine salts.

[0020] In certain embodiments, the fluroxypyr comprised within the suspoemulsion formulation of the invention is in its ester form.

[0021] Non-limiting examples of esters of fluroxypyr include Ci-Cs-alkyl esters and C1-C4- alkoxy-C2-C4-alkyl esters, such as methyl esters, ethyl esters, isopropyl, butyl, hexyl, heptyl,isoheptyl, isooctyl, 2-ethylhexyl, methylheptyl (MHE; meptyl), butoxypropyl (butometyl), and butoxy ethyl esters; and aryl esters such as benzyl.

[0022] In particular such embodiments, the fluroxypyr comprised within the suspoemulsion formulation of the present invention is in its meptyl ester form.

[0023] In certain embodiments, the amount of fluroxypyr or a salt, an ester, or a combination thereof comprised within the suspoemulsion formulation of the invention according to any one of the embodiments above is at least about 8% by weight, e.g., from about 8% to about 35%, from about 8.5% to about 30%, from about 9% to about 25%, or from about 9.5% to about 20% (calculated on an acid equivalent base of fluroxypyr).

[0024] In certain embodiments, the weight ratio between saflufenacil and fluroxypyr or a salt, an ester, or a combination thereof in the suspoemulsion formulation of the invention according to any one of the embodiments above is from about 1 :2 to about 1 :30, e.g., from about 1 :2.5 to about 1 :25, from about 1 :3 to about 1 :20, from about 1 :3.5 to about 1 : 15, from about 1 :4 to about 1 : 10, from about 1 :4.5 to about 1 :9, from about 1 :5 to about 1 :8, from about 1 :5.5 to about 1 :7, about 1 :6, about 1 :6.5, about 1 :7, or about 1 :7.5, respectively (calculated on an acid equivalent base of fluroxypyr).

[0025] In certain embodiments, the water-immiscible solvent comprised within the suspoemulsion formulation of the invention according to any one of the embodiments above is selected from a hydrocarbon-based solvent, an amide-based solvent, a lactam-based solvent, and a combination thereof.

[0026] Non-limiting examples of hydrocarbon-based solvents include aromatic hydrocarbon-based solvents such as toluene, xylene, alkylbenzene, phenylxylylethane, naphthalene, a mixture of C9-C16 aromatic hydrocarbons, and a mixture thereof; aliphatic hydrocarbon-based solvents such as paraffin, olefin, and a mixture thereof; alcohols; ketones; esters such as fatty acid ester; ethers; mineral oil; and vegetable oil such as soybean oil, olive oil, linseed oil, cotton seed oil, rapeseed oil, and castor oil.

[0027] Particular aromatic hydrocarbon-based solvents referred to herein are those comprising a mixture of C9-C16 aromatic hydrocarbons such as a solvent comprising a mixture of C10 aromatic hydrocarbons (e.g., Solgad 150 ULN which comprises hydrocarbons, C10, aromatics and <1% naphthalene), a solvent comprising a mixture of C10- C13 aromatic hydrocarbons (e.g., Solgad 200 ULN which comprises hydrocarbons, C10-C13, aromatics and <1% naphthalene), and a solvent comprising a mixture of C12 aromatichydrocarbons (e.g., Caromax® 28 LN which comprises C12 aromatic hydrocarbons having boiling points in the range of 247°C- 299°C and about 0.50% naphthalene).

[0028] Non-limiting examples of amide-based solvents include solvents having the formula (C?-C2o)alkyl-CO-N-(alkyl)2 such as 7V,7V-dimethyldecanamide (e.g., Rhodiasolv® ADMA 10).

[0029] The term "alkyl" typically means a linear or branched hydrocarbyl having, e.g., 1-8 carbon atoms and includes, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, and the like.

[0030] Non-limiting examples of lactam-based solvents include pyrrolidone-based solvents such as 7V-(Ci-Ci2)alkyl-2 -pyrrolidone (e.g., 7V-octyl-2-pyrrolidone).

[0031] Particular such embodiments are those wherein the water-immiscible solvent is a hydrocarbon-based solvent, preferably an aromatic hydrocarbon-based solvent such as a solvent comprising a mixture of C9-C16 aromatic hydrocarbons. More particular such embodiments are those wherein said aromatic hydrocarbon-based solvent is a solvent comprising a mixture of C10 aromatic hydrocarbons (e.g., Solgad 150 ULN which comprises hydrocarbons, CIO, aromatics and <1% naphthalene), a solvent comprising a mixture of C10- C13 aromatic hydrocarbons (e.g., Solgad 200 ULN which comprises hydrocarbons, C10- C13, aromatics and <1% naphthalene), or a solvent comprising a mixture of C12 aromatic hydrocarbons (e.g., Caromax® 28 LN which comprises C12 aromatic hydrocarbons having boiling points in the range of 247°C- 299°C and about 0.50% naphthalene).

[0032] Other particular such embodiments are those wherein the water-immiscible solvent is an amide-based solvent, preferably a solvent having the formula (C?-C2o)alkyl-CO-N- (alkyl)2 such as 7V,7V-dimethyldecanamide.

[0033] Yet other particular such embodiments are those wherein the water-immiscible solvent is a mixture of a hydrocarbon-based solvent, preferably an aromatic hydrocarbonbased solvent such as a solvent comprising a mixture of C9-C16 aromatic hydrocarbons; and an amide-based solvent, preferably a solvent having the formula (C?-C2o)alkyl-CO-N- (alkyl)2 such as 7V,7V-dimethyldecanamide.

[0034] In certain embodiments, the weight ratio between the water-immiscible solvent and fluroxypyr comprised within the suspoemulsion formulation of the invention according to any one of the embodiments above is from about 5: 1 to about 1 : 1, e.g., about 5: 1, about 4: 1, about 3: 1, about 2: 1, about 1.5: 1, or about 1 : 1, respectively (calculated on an acid equivalent base of fluroxypyr).

[0035] The term “surfactant” as used herein refers to any agriculturally acceptable material which decreases the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid; and imparts or improves emulsifiability, spreading, wetting, dispersibility, or other surface-modifying properties of a herbicidal formulation, and optionally stability of said formulation, e.g., by inhibiting crystal growth or avoiding particle agglomeration.

[0036] In certain embodiments, the surfactant comprised within the suspoemulsion formulation of the invention according to any one of the embodiments above is selected from (i) nonionic surfactants such as fatty alcohol surfactants (e.g., cetyl alcohol), monoglyceride surfactants (e.g., glycerol monolaurate), polysorbate surfactants (e.g., Tween-20, Tween-40, Tween-60, Tween-65, Tween-80, and Tween-85), tri styrylphenol ethoxylate surfactants (e.g., Soprophor® TS / 54), ethoxylated alkylphenol surfactants (e.g., a nonylphenol ethoxylate such as Tergitol NP-9™), ethoxylated arylphenol surfactants, ethoxylated vegetable oil surfactants (e.g., Alkamuls® OR / 36, Stepantex® CO-40, Emulsogen® EL 200 / 300 / 360 / 400, and Stepantex® CO-36), ethylene oxide- and propylene oxide-block copolymers, acrylic copolymers (e.g., Atlox™ 4913-LQ- (MV)), and polyvinyl alcohol- vinyl acetate copolymers; (ii) anionic surfactants such as fatty acid sulfonates (e.g., lauryl sulfonate), (Cs-C2o)-benzene sulfonates such as calcium dodecylbenzene sulfonate and isopropylamine dodecylbenzene sulfonate (e.g., Libramul® IP A), and a polymer-based anionic surfactant such as a di-block co-polymer-based surfactant (e.g., Geropon® MAI which includes a di-block co-polymer made from an anchoring hydrophobic block of ethylacrylate and a stabilizing hydrophilic block of 2-acrylamido-2-methylpropane sulfonic acid); (iii) cationic surfactants such as quaternary ammonium surfactants (e.g., cetylpyridinium chloride and dimethyldioctadecylammonium chloride); and (iv) ampholytic surfactants such as cocamidopropyl betaine and (3-[(3-Cholamidopropyl) dimethylammonio]-l-propanesulfonate).

[0037] In certain embodiments, the suspoemulsion formulation of the invention according to any one of the embodiments above further comprises an anti-freeze agent, a defoamer, a PH modifier, a thickener, a wetting agent, a preservative, or a combination thereof.

[0038] The term “anti-freeze agent” as used herein refers to an additive which lowers the freezing point of a water-based liquid.

[0039] Non-limiting examples of anti-freeze agents include propylene glycol; ethylene glycol; urea; glycerine; and an inorganic salt such as sodium chloride, magnesium chloride,calcium chloride, potassium acetate, sodium acetate, ammonium phosphate, ammonium nitrate, and ammonium sulphate.

[0040] The terms “anti-foaming agent” or “defoamer” are used herein interchangeably and refer to a chemical agent that is added to a composition so as to prevent, attenuate, or counter foam generation in the composition. Generally, such agents have surface active properties, are insoluble in the foaming medium, easily spreadable on the foamy surface, possess affinity to the air-liquid surface, and destabilize the foam lamellas which rupture the air bubbles and break down the surface foam.

[0041] Non-limiting examples of anti-foaming agents include siloxane-based antifoams such as organopolysiloxanes, e.g., polydimethylsiloxane-based compounds (e.g., SAG™ 1572); a mixture of alkenes, C11-C12, hydroformylation products, low boiling, or a commercially available product comprising it such as Geronol AF 80; a mineral oil-based defoamer or a commercially available product comprising it such as Lucrafoam® PDT; a blend of special wax, hydrophobic silica, and mineral oil or a commercially available product comprising it such as DEE FO® 3010E / 50; a silicon emulsion or a commercially available product comprising it such as Silfoam® SE 47, Silfoam® SRE, Silcolapse® RG 12, and SAG 10E; and a silicone-based compound or a commercially available product comprising it such as Silcolapse™ 910 and Xiameter® ACP-1000.

[0042] The terms “pH modifier” and “pH adjuster” are used here interchangeably and refer to an agriculturally acceptable excipient which include acidic and alkaline agents.

[0043] Non-limiting examples of pH modifiers include acidic agents such as organic acids and inorganic acids, e.g., acetic acid, citric acid, tartaric acid, alpha-hydroxy acids, betahydroxy acids, salicylic acid, lactic acid, glycolic acid, and natural fruit acids, or inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof; and alkaline agents such as inorganic bases, e.g., alkali metal hydroxides (e.g., sodium, potassium, and ammonium), and alkali metal salts of inorganic acids (e.g., sodium borate (borax), sodium phosphate, and sodium pyrophosphate) and organic bases, e.g., triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol, dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L-arginine, aminomethyl propanol, tromethamine(2-amino 2-hydroxymethyl-l,3-propanediol), and PEG-15 cocamine.

[0044] The terms “thickening agent” or “thickener” are used here interchangeably and refer to an additive that is added to an agrochemical formulation to increase its viscosity andprevent sedimentation of the active ingredient(s), thereby conferring greater stability and allowing storage thereof for a longer period.

[0045] Non-limiting examples of thickening agents include starch, dextrin, cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl starch, pullulan, sodium alginate, ammonium alginate, propylene glycol alginate, guar gum, locust bean gum, Arabic gum, xanthan gum, diutan gum, gelatin, casein, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, a block polymer of ethylene and propylene, sodium polyacrylate, polyvinyl pyrrolidone, and carrageenan.

[0046] The terms “wetting agent” or “wetter” are used here interchangeably and refer to a surfactant which lowers the surface tension of water allowing it to spread and penetrate. Wetting agents do this by weakening water’s cohesive properties and strengthening its adhesive properties.

[0047] Non-limiting examples of wetting agents include alkyl polysaccharides such as (Cs- Cio) alkylpolysaccharide (e.g., Multitrope™ 1620); alcohol ethoxylates such as polyoxyethylenated (POE) (10) isotridecanol (e.g., Imbentin™ -T / 65); and alkylphenol ethoxylates such as octyl phenol ethoxylate, nonyl phenol ethoxylate, and card phenol ethoxylate.

[0048] The term “preservative” as used herein refers to a chemical that is used in preventing spoilage and extending the shelflife of agriculture products, such as an antioxidant, biocide, and thermal stabilizer. According to the literature, without the addition or with an insufficient addition of preservatives, various problems result, mainly due to the growth of microorganisms; development of unpleasant odors; discolorations; pH changes, to which some pesticides are sensitive; changes in the viscosity caused by the degradation of polysaccharide-comprising thickeners; or phase separation / sedimentation of emulsions or suspensions as the result of microbial degradation of surfactants. Non-limiting examples of preservatives include isothiazolinone-based preservatives such as methyl-2H-isothiazol-3- one (MIT), l,2-benzisothiazol-3(2H)-one (BIT; e.g., Proxel® GXL), and chlor-2-methyl-2H- isothiazol-3-on (CMIT).

[0049] In certain embodiments, the furoxypyr comprised within the suspoemulsion formulation of the invention is in the form of a free acid or an ester thereof; the amount of fluroxypyr in said formulation is at least about 8% by weight (calculated on an acid equivalent base of fluroxypyr); the weight ratio between saflufenacil to fluroxypyr is from about 1 :2 to about 1 : 15, preferably from about 1 :5 to about 1 :8, respectively (calculated onan acid equivalent base of fluroxypyr); the water-immiscible solvent comprised within said formulation is selected from a hydrocarbon-based solvent, an amide-based solvent, a lactam- based solvent, and a combination thereof; and the surfactant comprised within said formulation is selected from (i) nonionic surfactants such as fatty alcohol surfactants (e.g., cetyl alcohol), monoglyceride surfactants (e.g., glycerol monolaurate), polysorbate surfactants (e.g., Tween-20, Tween-40, Tween-60, Tween-65, Tween-80, and Tween-85), tri styrylphenol ethoxylate surfactants (e.g., Soprophor® TS / 54), ethoxylated alkylphenol surfactants (e.g., a nonylphenol ethoxylate such as Tergitol NP-9™), ethoxylated arylphenol surfactants, ethoxylated vegetable oil surfactants (e.g., Alkamuls® OR / 36, Stepantex® CO- 40, Emulsogen® EL 200 / 300 / 360 / 400, and Stepantex® CO-36), ethylene oxide- and propylene oxide-block copolymers, acrylic copolymers (e.g., Atlox™ 4913-LQ- (MV)), and polyvinyl alcohol-vinyl acetate copolymers; (ii) anionic surfactants such as fatty acid sulfonates (e.g., lauryl sulfonate), (Cs-C2o)-benzene sulfonates such as calcium dodecylbenzene sulfonate and isopropylamine dodecylbenzene sulfonate (e.g., Libramul® IP A), and a polymer-based anionic surfactant such as a di-block co-polymer- based surfactant (e.g., Geropon® MAI which includes a di-block co-polymer made from an anchoring hydrophobic block of ethylacrylate and a stabilizing hydrophilic block of 2- acrylamido-2-methylpropane sulfonic acid); (iii) cationic surfactants such as quaternary ammonium surfactants (e.g., cetylpyridinium chloride and dimethyldioctadecylammonium chloride); (iv) ampholytic surfactants such as cocamidopropyl betaine and (3-[(3- Cholamidopropyl) dimethylammonio]-l-propanesulfonate); and (v) a mixture thereof (referred to herein as “saflufenacil-fluroxypyr-based formulations”).

[0050] In certain embodiments, the fluroxypyr comprised within the saflufenacil- fluroxypyr-based formulations of the present invention is in the form of meptyl ester thereof.

[0051] Particular such embodiments are those wherein the water-immiscible solvent comprised within the saflufenacil-fluroxypyr-based formulations of the present invention is a hydrocarbon-based solvent, preferably an aromatic hydrocarbon-based solvent such as a solvent comprising a mixture of C9-C16 aromatic hydrocarbons. More particular such embodiments are those wherein said aromatic hydrocarbon-based solvent is a solvent comprising a mixture of C10 aromatic hydrocarbons (e.g., Solgad 150 ULN which comprises hydrocarbons, CIO, aromatics and <1% naphthalene), a solvent comprising a mixture of C10- C13 aromatic hydrocarbons (e.g., Solgad 200 ULN which comprises hydrocarbons, C10- C13, aromatics and <1% naphthalene), or a solvent comprising a mixture of C12 aromatichydrocarbons (e.g., Caromax® 28 LN which comprises C12 aromatic hydrocarbons having boiling points in the range of 247°C- 299°C and about 0.50% naphthalene).

[0052] Other particular such embodiments are those wherein the water-immiscible solvent is an amide-based solvent, preferably a solvent having the formula (C?-C2o)alkyl-CO-N- (alkyl)2 such as 7V,7V-dimethyldecanamide.

[0053] Yet other particular such embodiments are those wherein the water-immiscible solvent is a mixture of a hydrocarbon-based solvent, preferably an aromatic hydrocarbonbased solvent such as a solvent comprising a mixture of C9-C16 aromatic hydrocarbons; and an amide-based solvent, preferably a solvent having the formula (C?-C2o)alkyl-CO-N- (alkyl)2 such as 7V,7V-dimethyldecanamide.

[0054] In certain embodiments, the weight ratio between the water-immiscible solvent and fluroxypyr comprised within the saflufenacil-fluroxypyr-based formulations of the present invention according to any one of the embodiments above is from about 5: 1 to about 1 : 1, e.g., about 5: 1, about 4: 1, about 3: 1, about 2: 1, about 1.5: 1, or about 1 : 1, respectively (calculated on an acid equivalent base of fluroxypyr).

[0055] In another aspect, the present invention relates to a method of controlling weed (undesired vegetation) comprising applying to a locus an effective amount of a formulation of the invention as defined in any one of the embodiments above.

[0056] The term "locus" as used herein refers not only to areas where the weed may already be developed, but also to areas where weeds have yet to emerge, and to areas under cultivation. Locus includes the crop and propagation material of the crop (all the generative parts of the crop such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant). Examples of propagation material of the crop include seeds, tubers, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, buds and other parts of plants, including seedlings and young plants, which could be transplanted after germination or after emergence from soil. Locus also includes the area surrounding the crop and the growing media of the crop, such as soil and crop field.

[0057] In certain embodiments, the locus is a field of crop. The term “crop” (or “plant”) as used herein refers to whole plants, plant organs (e.g., leaves, stems, twigs, roots, trunks, limbs, shoots, fruits, etc.), plant cells, or plant seeds. Non-limiting examples of crops are cotton, rice, banana, potato, coffee, sugar cane, citrus, beans, sunflower, apple, com, soybean, wheat, barley, oats, chickpeas, fruit trees, nut trees, lentils, peanut, and grain sorghum.

[0058] In certain embodiments, the weeds that can be controlled by the method of the present invention include Commelina benghalensis (COMBE), Alternanthera ficoidea (ALRFI), Sida rhombifolia (SIDRH), Portulaca oleracea (POROL), and Erigeron bonariensis (Conyza bonariensis,' ERIBO).

[0059] It should be noted that all numbers throughout this specification which refer to fluroxypyr, e.g., ratios and application rate, are calculated on an acid equivalent base of fluroxypyr. The term “acid equivalent” (a.e.) refers to the amount of the acid form of an active ingredient such as fluroxypyr 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, and the salt form of Z has a molecular weight of 130 Dalton, an application of 130 g ai / ha of the Z salt would be equal to applying 100 g ae / ha of the acid form of Z: 130 g ai / ha Z salt * (100 Da Z acid / 130 Da Z salt) = 100 g ae / ha Z acid. Specifically, 144 g of fluroxypyr in the form of meptyl-ester thereof (367 g / mol) equals to 100 g of fluroxypyr in the acid form thereof (255 g / mol).

[0060] Unless otherwise indicated, all numbers expressing, e.g., application rates or ratios between components, used in this specification, are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification are approximations that may vary by up to plus or minus 10% depending upon the desired properties to be obtained by the present invention.

[0061] The invention will now be illustrated by the following non-limiting Examples.EXAMPLESExample 1. Preparation of a suspoemulsion formulation comprising saflufenacil and fluroxypyr

[0062] A representative suspoemulsion formulation comprising saflufenacil and fluroxypyr was prepared by first preparing a solution comprising fluroxypyr-meptyl (about 15% w / w), emulsifires (a mixture of dodecylbenzene sulphonate isopropylamine and ethoxylated castor oil with 40 EO; about 5.5% w / w), and Solgad 150 ULN (about 34% w / w). Then, the obtained formulation was added to water (about 30%) during continues stirring. During agitation, about 3% of a formulation comprising saflufenacil was added: saflufenacil 53.84%, Poly Agro 1.92%, polyacrylic graft copolymer 1.92%, xanthan gum 0.13%, alcohol alkoxylate 1%, polydimethylsiloxane emulsion 0.17%, glycerin 2.92%, citric acid 0.1%, 1,2-benzisothiazolin-3-one 0.065% and water 22.3% (the preparation of the saflufenacil -based formulation is disclosed in WO 2023 / 095142). In the final step, the following mixture was added AG RH 23 (0.35% w / w), Proxel GXL (0.18% w / w), and water (13% w / w), and the stirring continued until homogeneity was obtained.Example 2. The efficacy of a suspoemulsion formulation comprising saflufenacil and fluroxypyr in controlling weeds

[0063] Objective. Evaluating the efficacy of the suspoemulsion formulation comprising saflufenacil and fluroxypyr-meptyl prepared in Example 1 as compared to an emulsifiable concentrate formulation comprising saflufenacil and fluroxypyr as detailed in Table 1, under field conditions in the control weeds.

[0064] Materials and methods. The trials were conducted under field conditions with natural infestations of the evaluated weeds, and foliar application was performed on the postemergence of the studied weeds. For the spray, a pressurized backpack sprayer with CO2 was used, equipped with an application boom containing six flat fan nozzles (110.02), spaced at 50 cm intervals. The pressure used was 40 PSI, providing a constant volume of 150 L / ha.

[0065] Assessments. Each treatment was performed in 4 repetitions and an un-treated control was included for each weed species. The percentage of control of the weed infestations was assessed using a visual scale ranging from 0-100%, where 0% indicates the absence of symptoms, and 100% represents the death of the weeds [Brazilian Society of Weed Science — SBCPD (1995) Procedures for Installation, Evaluation and Analysis of Experiments with Herbicides, Londrina], These assessments were conducted at 28 days after application (DAA).

[0066] The tested weed used was Portulaca oleracea (POROL).

[0067] Table 2 summarizes the efficacy of the suspoemulsion formulation comprising saflufenacil and fluroxypyr-meptyl as prepared in Example 1 as compared to an emulsifiable concentrate formulation comprising saflufenacil and fluroxypyr shown in Table 1, on the tested weed at 28 days after application.Table 1Table 2g ai / Ha = gram active ingredient per hectare POROL - Portulacci oleraceci

[0068] Results. The efficacy at 28 days after application for the isolated active ingredients saflufenacil and fluroxypyr-meptyl showed 70% and 74.4%, respectively, control for the evaluated weed Portulaca oleraceae. The tested EC formulation obtained the control percent of 71.9 and the SE tested formulation obtained the control percent of 89.4, showing a superiority of the SE formulation when compared with the EC formulation.

[0069] The formulations of the SE type have the advantage of adapting very well to a mixture with active ingredients of very different physical properties, providing a possible increase in the activity of the actives and reducing the chance of incompatibility in the mixture, as it involves a combination of concentrated suspension (SC) and aqueous emulsion (EW) technologies.

Claims

CLAIMS1. A suspoemulsion formulation comprising: (i) a continuous aqueous phase comprising saflufenacil which is suspended in said continuous aqueous phase; (ii) a liquid organic phase comprising fluroxypyr or a salt, an ester, or a combination thereof, and a water-immiscible solvent; and (iii) a surfactant.

2. The suspoemulsion formulation of claim 1, wherein said fluroxypyr is in the form of a free acid or an ester thereof.

3. The suspoemulsion formulation of claim 2, wherein said fluroxypyr is in the form of meptyl ester thereof.

4. The suspoemulsion formulation of any one of claims 1-3, wherein the amount of fluroxypyr in said formulation is at least about 8% by weight (calculated on an acid equivalent base of fluroxypyr).

5. The suspoemulsion formulation of any one of claims 1-4, wherein the weight ratio between saflufenacil to fluroxypyr is from about 1 :2 to about 1 : 15, preferably from about 1 :5 to about 1 :8, respectively (calculated on an acid equivalent base of fluroxypyr).

6. The suspoemulsion formulation of any one of claims 1-5, wherein said water- immiscible solvent is selected from a hydrocarbon-based solvent, an amide-based solvent, a lactam-based solvent, and a combination thereof.

7. The suspoemulsion formulation of claim 6, wherein: (i) said hydrocarbon-based solvent is selected from an aromatic hydrocarbon-based solvent such as toluene, xylene, alkylbenzene, phenylxylyl ethane, naphthalene, a mixture of C9-C16 aromatic hydrocarbons, and a mixture thereof; an aliphatic hydrocarbon-based solvent such as paraffin, olefin, and a mixture thereof; alcohols; ketones; esters such as fatty acid ester; ethers; mineral oil; a vegetable oil such as soybean oil, olive oil, linseed oil, cotton seed oil, rapeseed oil, and castor oil, and a mixture thereof; (ii) said amide-based solvent is selected from a solvent having the formula (C?-C2o)alkyl-CO-N-(alkyl)2 such as MA-dimethyldecanamide (e.g., Rhodiasolv® ADMA 10); and / or (iii) said lactam -based solvent is selected from a pyrrolidone-based solvent such as A-(Ci-Cs)alkyl-2-pyrrolidone (e.g., A-octyl-2- pyrrolidone).

8. The suspoemulsion formulation of claim 6 or 7, wherein the weight ratio between said solvent and fluroxypyr is from about 5:1 to about 1 : 1, respectively (calculated on an acid equivalent base of fluroxypyr).

9. The suspoemulsion formulation of any one of claims 1-8, wherein said surfactant is selected from (i) nonionic surfactants such as fatty alcohol surfactants (e.g., cetyl alcohol), monoglyceride surfactants (e.g., glycerol monolaurate), polysorbate surfactants (e.g., Tween-20, Tween-40, Tween-60, Tween-65, Tween-80, and Tween-85), tri styrylphenol ethoxylate surfactants (e.g., Soprophor® TS / 54), ethoxylated alkylphenol surfactants (e.g., a nonylphenol ethoxylate such as Tergitol NP-9™), ethoxylated arylphenol surfactants, ethoxylated vegetable oil surfactants (e.g., Alkamuls® OR / 36, Stepantex® CO-40, Emulsogen® EL 200 / 300 / 360 / 400, and Stepantex® CO-36), ethylene oxide- and propylene oxide-block copolymers, acrylic copolymers (e.g., Atlox™ 4913-LQ- (MV)), and polyvinyl alcohol-vinyl acetate copolymers; (ii) anionic surfactants such as fatty acid sulfonates (e.g., lauryl sulfonate), (Cs-C2o)-benzene sulfonates such as calcium dodecylbenzene sulfonate and isopropylamine dodecylbenzene sulfonate (e.g., Libramul® IP A), and a polymer-based anionic surfactant such as a di-block co-polymer-based surfactant (e.g., Geropon® MAI which includes a di-block co-polymer made from an anchoring hydrophobic block of ethylacrylate and a stabilizing hydrophilic block of 2-acrylamido-2-methylpropane sulfonic acid); (iii) cationic surfactants such as quaternary ammonium surfactants (e.g., cetylpyridinium chloride and dimethyldioctadecylammonium chloride); (iv) ampholytic surfactants such as cocamidopropyl betaine and (3-[(3-Cholamidopropyl) dimethylammonio]-l-propanesulfonate); and (v) a mixture thereof.

10. The suspoemulsion formulation of any one of claims 1-9, further comprising an antifreeze agent, a defoamer, a PH modifier, a thickener, a wetting agent, a preservative agent, or a combination thereof.

11. The suspoemulsion formulation of claim 1, wherein: (i) said fluroxypyr is in the form of a free acid or an ester thereof; (ii) the amount of fluroxypyr in said formulation is at least about 8% by weight (calculated on an acid equivalent base of fluroxypyr); (iii) the weight ratio between saflufenacil to fluroxypyr is from about 1 :2 to about 1 : 15, preferably from about 1 :5 to about 1 :8, respectively (calculated on an acid equivalent base of fluroxypyr); (iv) said water-immiscible solvent is selected from a hydrocarbon-based solvent, an amide-based solvent, a lactam-based solvent, and a combination thereof; and (v) said surfactant is selected from (i) nonionic surfactants such as fatty alcohol surfactants (e.g., cetyl alcohol), monoglyceride surfactants (e.g., glycerol monolaurate), polysorbate surfactants (e.g., Tween-20, Tween-40, Tween-60, Tween-65, Tween-80, and Tween-85), tri styrylphenol ethoxylate surfactants (e.g., Soprophor® TS / 54), ethoxylated alkylphenol surfactants (e.g., a nonylphenol ethoxylate such as Tergitol NP-9™), ethoxylated arylphenol surfactants, ethoxylated vegetable oil surfactants (e.g., Alkamuls® OR / 36, Stepantex® CO-40, Emulsogen® EL 200 / 300 / 360 / 400, and Stepantex® CO-36), ethylene oxide- and propylene oxide-block copolymers, acrylic copolymers (e.g., Atlox™ 4913-LQ- (MV)), and polyvinyl alcohol-vinyl acetate copolymers; (ii) anionic surfactants such as fatty acid sulfonates (e.g., lauryl sulfonate), (Cs-C2o)-benzene sulfonates such as calcium dodecylbenzene sulfonate and isopropylamine dodecylbenzene sulfonate (e.g., Libramul® IP A), and a polymer-based anionic surfactant such as a di-block co-polymer-based surfactant (e.g., Geropon® MAI which includes a di-block co-polymer made from an anchoring hydrophobic block of ethylacrylate and a stabilizing hydrophilic block of 2-acrylamido-2-methylpropane sulfonic acid); (iii) cationic surfactants such as quaternary ammonium surfactants (e.g., cetylpyridinium chloride and dimethyldioctadecylammonium chloride); (iv) ampholytic surfactants such as cocamidopropyl betaine and (3-[(3-Cholamidopropyl) dimethylammonio]-l-propanesulfonate); and (v) a mixture thereof.

12. The suspoemulsion formulation of claim 11, wherein said fluroxypyr is in the form of meptyl ester thereof.

13. The suspoemulsion formulation of claim 11 or 12, wherein: (i) said hydrocarbonbased solvent is selected from an aromatic hydrocarbon-based solvent such as toluene, xylene, alkylbenzene, phenylxylyl ethane, naphthalene, a mixture of C9-C16 aromatic hydrocarbons, and a mixture thereof; an aliphatic hydrocarbon-based solvent such as paraffin, olefin, and a mixture thereof; alcohols; ketones; esters such as fatty acid ester; ethers; mineral oil; a vegetable oil such as soybean oil, olive oil, linseed oil, cotton seed oil, rapeseed oil, and castor oil, and a mixture thereof; (ii) said amide-based solvent is selected from a solvent having the formula (C?-C2o)alkyl-CO-N-(alkyl)2 such as N,N- dimethyldecanamide (e.g., Rhodiasolv® ADMA 10); and / or (iii) said lactam-based solventis selected from a pyrrolidone-based solvent such as 7V-(Ci-Cs)alkyl-2-pyrrolidone (e.g., N- octyl-2-pyrrolidone).

14. The suspoemulsion formulation of any one of claims 11-13, wherein the weight ratio between said solvent and fluroxypyr is from about 5: 1 to about 1 : 1, respectively (calculated on an acid equivalent base of fluroxypyr).

15. A method of controlling weed comprising applying to a locus an effective amount of a composition according to any one of claims 1-14.

16. The method of claim 15, wherein said locus is a field of crop.

17. The method of claim 16, wherein said crop is selected from cotton, rice, banana, potato, coffee, sugar cane, citrus, beans, sunflower, apple, corn, soybean, wheat, barley, oats, chickpeas, fruit trees, nut trees, lentils, peanut, and grain sorghum.

18. The method of claim 15, wherein said weed is selected from Commelina benghalensis (COMBE), Alternanthera ficoidea (ALRFI), Sidct rhombifolia (SIDR.H), Portulaca oleracea (POROL), and Erigeron bonariensis (Conyza bonariensis: ERIBO).

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