Formulation of emulsible concentrate (CE) with methyl carbazona

Description

1 / 39 “FORMULATION OF EMULSIFIABLE CONCENTRATE (EC) WITH THIENCARBAZONE-METHYL” TECHNICAL FIELD

[001] The present invention relates to the field of crop protection compositions. In particular, the invention relates to emulsifiable concentrate (EC) formulations comprising active herbicidal compounds from the sulfonylaminocarbonyltriazolinone group. BACKGROUND

[002] In general, active compounds for crop protection are not used in pure form. Depending on the area of ​​use and the type of use and the physical, chemical and biological parameters, the active compound is used as an active compound formulation in a mixture with usual auxiliaries and additives. Combinations with other active compounds are also known to broaden the spectrum of activity and / or to protect cultivated plants (e.g., by means of protectants, antidotes).

[003] Formulations of individual active compounds, and similar formulations of combinations of a plurality of active compounds for crop protection, should generally be easy to apply and easy to use and have broad biological action combined with high selectivity with respect to the active compounds used and, moreover, should be easy to formulate in the preparation process. Of particular importance in this document is the high chemical and physical stability (storage stability) of the formulation.

[004] Typical formulations in crop protection are concentrated suspensions (suspensions of active compounds) in which the particles of active compounds (discontinuous phase) are suspended in an external liquid phase (continuous phase). Depending on the nature of the external phase, suspensions are classified as suspension concentrates (SC), where the main component Petition 870250086134, dated 09 / 23 / 2025, page 7 / 53 Two-thirds of the external phase is water, or oil dispersions (OD), where the main component of the external phase is an organic solvent. The choice of the respective external phase is often determined by the stability of the active compounds in question. In general, active compounds that are unstable in water are formulated as OD, and active compounds that are unstable in organic solvents are formulated as CS.

[005] Sulfonylaminocarbonyltriazolinones are a class of highly effective and selective herbicides, described in documents WO 01 / 05788, WO 03 / 026426 and WO 03 / 026427. Thiencarbazone methyl (4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylate; CAS 317815-83-1) also belongs to this class of sulfonylaminocarbonyltriazolinones. These herbicides are normally formulated as oil dispersions, as described in document WO 2005 / 051082. Sulfonylaminocarbonyltriazolinone suspension concentrates are also known, for example, in document EP2170041.

[006] Although DO and CS formulations of sulfonylaminocarbonyltriazolinones have been shown to provide adequate storage stability and broad biological activity, these formulations are generally difficult to prepare and handle.

[007] Therefore, the objective of the present invention was to provide an improved formulation of crop protection agents, in particular sulfonylaminocarbonyltriazolinones, which has high chemical and physical stability and is easy to handle in terms of production and field application. SUMMARY

[008] This objective is achieved by the specific formulation of the emulsifiable concentrate (EC) of the present invention.

[009] Thus, the present invention relates to an emulsifiable concentrate (EC) formulation comprising Petition 870250086134, dated 09 / 23 / 2025, page 8 / 53 3 / 39 a) one or more active herbicidal compounds from the sulfonylaminocarbonyltriazolinone group, preferably thienocarbazone-methyl or an agrochemically acceptable salt, b) one or more organic solvents immiscible in water, c) one or more water-miscible organic solvents, d) one or more emulsifiers, (e) one or more organic bases, wherein the formulation exhibits a pH between pH 5.5 and pH 9.

[010] The pH of the formulation can be measured after diluting the emulsifiable concentrate formulation in distilled water to obtain a 10% w / w mixture.

[011] The pH of the formulation can be measured, in particular, by the following method: - Dilute the emulsifiable concentrate formulation in distilled water to obtain a 10% w / w mixture; - Stir the mixture with a magnetic stirrer at 1500 RPM for 10 minutes at 25 °C; and - Measure the pH of the stirred mixture at 25°C with a pH meter until the measured pH remains stable for 10 seconds.

[012] pH measurement can be performed with a Knick 766 pH meter (Calimatic, Knick SE 100N).

[013] The CE formulation may also include one or more of the following: f) one or more protection agents, g) one or more agrochemically active ingredients other than a) and f), h) other adjuvants compatible with agrochemical formulations, wetting agents and / or other additives.

[014] The term “emulsifiable concentrate” (abbreviated as “EC”) is known Petition 870250086134, dated 09 / 23 / 2025, p. 9 / 53 4 / 39 in the art. Emulsifiable concentrate (EC) formulations conventionally contain an active ingredient, one or more surfactants that act as emulsifiers after dilution of the EC with water, and a water-immiscible solvent.

[015] The term “miscible in water” means that the compound or solvent can have a solubility in water at 20 °C of at least 5 g / l, preferably at least 20 g / l, more preferably at least 50 g / l, in particular, at least 100 g / l.

[016] The term “immiscible in water” means that the compound or solvent can have a solubility in water at 20 °C of up to 100 g / l, preferably up to 50 g / l °C, more preferably up to 20 g / l, in particular, up to 5 g / l.

[017] Sulfonylaminocarbonyltriazolinones are described in document WO 01 / 05788. Sulfonylaminocarbonyltriazolinones have the general formula (I) PHN\ ' / so2(I) where Q1 represents O (oxygen) or S (sulfur). Q2 represents O (oxygen) or S (sulfur). R1 represents, in each case, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocycle or heterocycloalkyl, R2 represents hydrogen, cyano, nitro, halogen or represents, in each case, optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, alkynyl, alkenyloxy or alkynyloxy, R3 represents hydrogen, hydroxyl, mercapto, amino, cyano, halogenium or represents, in each case, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, Petition 870250086134, dated 09 / 23 / 2025, page. 10 / 53 5 / 39 alkylcarbonylamino, alkenyloxy, alkyloxy, alkyloxy, alkenylthio, alkynylthio, alkenylamino, alkynylamino, dialkylamino, dialkylamino, aziridine, pyrrolidine, piperidine, morpholine, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio, cycloalkylalkylamino, aryl, arylalkyl, aryloxy, arylalkoxy, arylthio, arylalkylthio, arylamino or arylalkylamino, and R4 represents hydrogen, hydroxyl, amino, cyano, represents alkylideneamino or represents, in each case, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylcarbonylamino, alkenyloxy, dialkylamino, cycloalkyl, cycloalkylamino, cycloalkylalkyl, optionally substituted aryl or arylalkyl, or R3 and R4 together represent optionally branched alkanodyls, and salts of the compounds of formula (I).

[018] Thienocarbazon-methyl (4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H1,2,4-triazol-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylate methyl; CAS No. 317815-83-1) is also described in document WO 01 / 05788. Thienocarbazon-methyl may be supplied in the form of its salt, preferably in the form of its sodium salt.

[019] Preferably, the CE formulation exhibits a pH between 6.0 and 8.5, more preferably between 6.5 and 8.0, and even more preferably between 6.8 and 7.7. The pH can be measured as described above.

[020] The pH of the CE is preferably adjusted by at least one or more organic bases.

[021] It has been found that EC formulations comprising sulfonylaminocarbonyltriazolinones, preferably thienocarbazone-methyl, require a specific pH to be chemically stable. When the pH is too acidic or too basic, the sulfonylaminocarbonyltriazolinone degrades by a significant percentage. With the use of an organic base, the pH can be adjusted. Petition 870250086134, dated 09 / 23 / 2025, page 11 / 53 6 / 39 appropriately to allow for a stable EC formulation for storage.

[022] In another embodiment, the emulsifiable concentrates according to the invention may comprise a) 0.01% to 5% by weight, preferably 0.1% to 2% by weight, even more preferably 0.3% to 1% by weight of one or more active herbicidal compounds from the sulfonylaminocarbonyltriazolinone group, preferably thienocarbazonamel or an agrochemically acceptable salt thereof; and / or b) 5 to 95% by weight, preferably 10 to 70% by weight, even more preferably 20 to 60% by weight of one or more water-immiscible organic solvents; and / or c) 5 to 95% by weight, preferably 10 to 60% by weight, even more preferably 20 to 40% by weight of one or more water-miscible organic solvents; and / or d) 0.1 to 30% by weight, preferably 1 to 25% by weight, even more preferably 5 to 20% by weight of one or more emulsifiers; and / or (e) 0.1 to 10% by weight, preferably 0.2 to 5% by weight, even more preferably 0.5 to 2% by weight of the organic base.

[023] The CE formulation may also include one or more of the following: f) 0 to 10% by weight, preferably 1 to 8% by weight, even more preferably 2 to 6% by weight of one or more protective agents; and / or g) 0 to 40% by weight, preferably 5 to 30% by weight, even more preferably 10 to 25% by weight of one or more agrochemically active ingredients other than a) ef); and / or h) 0 to 40% by weight, preferably 5 to 30% by weight, even more preferably 10 to 20% by weight of other adjuvants compatible with agrochemical formulations, wetting agents and / or other additives. Petition 870250086134, dated 09 / 23 / 2025, page 12 / 53 7 / 39

[024] In this document and throughout the description, the term “% by weight” refers to the relative weight of the component in question based on the total weight of the formulation, unless otherwise defined.

[025] The water-immiscible organic solvent b) may be a hydrocarbon, which may be unsubstituted or substituted.

[026] Examples of water-immiscible organic solvents b) are aromatic hydrocarbons, for example, benzenes substituted with mono- or polyalkyl groups, such as toluene, xylenes, mesitene, ethylbenzene or naphthalenes substituted with mono- or polyalkyl groups, such as 1-methylnaphthalene, 2-methylnaphthalene or dimethylnaphthalene, or other aromatic hydrocarbons derived from benzene, such as indane or Tetralin®, or mixtures thereof; aliphatic hydrocarbons, for example, linear or branched chain aliphatics, for example, of the formula CnH2n+2, such as pentane, hexane, octane, 2-methylbutane or 2,2,4-trimethylpentane, or cyclic aliphatics, optionally substituted with alkyl, such as cyclohexane or methylcyclopentane, or mixtures thereof, such as solvents of the Exxsol® D, Isopar® or Bayol® series, for example, Bayol® 82 (ExxonMobil Chemicals), or the Isane® IP or Hydroseal® G series (TotalFinaElf);Mixtures of aromatic and aliphatic hydrocarbons, such as solvents from the Solvesso® series, for example, Solvesso® 100, Solvesso® 150 or Solvesso® 200 (ExxonMobil Chemicals), from the Solvarex® / Solvaro® series (TotalFinaElf) or from the Caromax® series, for example, Caromax® 28 (Petrochem Carless); or halogenated hydrocarbons, such as halogenated aromatic and aliphatic hydrocarbons, such as chlorobenzene or methylene chloride.

[027] Alternatively, the water-immiscible organic solvent b) may be selected from fatty acid esters, for example, of natural origin, for example, natural oils, such as animal or vegetable oils, or of synthetic origin, for example, the Edenor® series, for example, Edenor® MEPa or Edenor® MESU, or the Agnique®ME series or the Agnique®AE series (Cognis), the Salim®ME series (Salim), the series Petition 870250086134, dated 09 / 23 / 2025, page 13 / 53 8 / 39 Radia®, for example, Radia® 30167 (ICI), the Prilube® series, for example, Prilube® 1530 (Petrofina), the Stepan® C series (Stepan) or the Witconol® 23 series (Witco). Fatty acid esters are preferably C10-C22 esters, with preference for C12C20. C10-C22 fatty acid esters are, for example, unsaturated or saturated C10-C22 fatty acid esters, in particular those with an even number of carbon atoms, such as, for example, erucic acid, lauric acid, palmitic acid and, in particular, C18 fatty acids, such as stearic acid, oleic acid, linoleic acid or linolenic acid.Examples of fatty acid esters, such as C10-C22 fatty acid esters, are glycerol and glycol esters of fatty acids, such as C10-C22 fatty acids, or their transesterification products, for example, alkyl esters of fatty acids, such as C1-C20 alkyl esters of C10-C22 fatty acids, which can be obtained, for example, by transesterification of the aforementioned glycerol or glycol fatty acid esters, such as C10-C22 fatty acid esters, with C1-C20 alcohols (e.g., methanol, ethanol, propanol, or butanol). Transesterification can be carried out by known methods, as described, for example, in Roempp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart. Preferred fatty acid alkyl esters, such as C1-C20 alkyl esters of C10-C22 fatty acids, include methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters, and dodecyl esters.Preferred glycol and glycerol fatty acid esters, such as C10-C22 fatty acid esters, are uniform or mixed glycol and glycerol esters of C10-C22 fatty acids, in particular fatty acids with an even number of carbon atoms, such as erucic acid, lauric acid, palmitic acid, and in particular C18 fatty acids, such as stearic acid, oleic acid, linoleic acid or linolenic acid.

[028] Animal oils are generally known and commercially available. For the purposes of this invention, the term “animal oils” shall be Petition 870250086134, dated 09 / 23 / 2025, p. 14 / 53 9 / 39 understood to mean, for example, oils of animal origin, such as whale oil, cod liver oil, musk oil or marten oil.

[029] Vegetable oils are generally known and commercially available. For the purposes of the present invention, the term “vegetable oils” shall be understood to mean, for example, oils from oilseed plant species, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, arachis oil, olive oil or castor oil, in particular rapeseed oil, wherein vegetable oils also include their transesterification products, for example, alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester.

[030] Vegetable oils are preferably C10-C22 fatty acid esters, preferably C12-C20. C10-C22 fatty acid esters are, for example, unsaturated or saturated C10-C22 fatty acid esters with an even number of carbon atoms, for example, erucic acid, lauric acid, palmitic acid and, in particular, C18 fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.

[031] Examples of vegetable oils are C10-C22 fatty acid esters of glycerol or glycol with C10-C22 fatty acids or C1-C20 alkyl esters of C10-C22 fatty acids which can be obtained, for example, by transesterification of the C10-C22 fatty acid esters of glycerol or glycol mentioned above with C1-C20 alcohols (e.g., methanol, ethanol, propanol or butanol). Transesterification can be carried out by known methods, as described, for example, in Roempp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart.

[032] Vegetable oils may be contained in the adjuvants according to the invention, for example, in the form of commercially available vegetable oils, in particular rapeseed oils, such as rapeseed oil methyl ester, for example, Phytorob® Petition 870250086134, dated 09 / 23 / 2025, p. 15 / 53 10 / 39 B (Novance, France), Edenor® MESU and the Agnique® ME series (Cognis, Germany), the Radia® series (ICI), the Prilube® series (Petrofina), or biodiesel or in the form of commercially available vegetable oil-containing formulation additives, in particular those based on rapeseed oils, such as rapeseed oil methyl esters, for example, Hasten® (Victorian Chemical Company, Australia, hereinafter referred to as Hasten, main ingredient: rapeseed oil ethyl ester), Actirob® B (Novance, France, hereinafter referred to as ActirobB, main ingredient: rapeseed oil methyl ester), Rako-Binol® (Bayer AG, Germany, hereinafter referred to as Rako-Binol, main ingredient: rapeseed oil), Renol® (Stefes, Germany, hereinafter referred to as Renol, vegetable oil ingredient: rapeseed oil methyl ester) or Stefes Mero® (Stefes, Germany, hereinafter referred to as Mero, main ingredient: rapeseed oil methyl ester).

[033] Examples of synthetic fatty acid esters are, for example, those derived from fatty acids with an odd number of carbon atoms, such as C11-C21 fatty acid esters.

[034] Preferred water-immiscible organic solvents b) are aromatic hydrocarbons and / or aliphatic hydrocarbons.

[035] The water-immiscible organic solvent b) may be present alone or in a mixture of different water-immiscible solvents.

[036] The water-miscible organic solvent (c) is preferably a linear or cyclic alkyl carbonate, in particular methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, propylene carbonate, glycerol-1,2 carbonate and butylene carbonate, or a mixture thereof.

[037] Furthermore, preferably, the water-miscible organic solvent c) is propylene carbonate and / or glycerol-1,2-carbonate, and even more preferably propylene carbonate. Petition 870250086134, dated 09 / 23 / 2025, page 16 / 53 11 / 39

[038] Surprisingly, sulfonylaminocarbonyltriazolinones, preferably thienocarbazone-methyl, have been found to be chemically stabilized significantly in a biphasic solvent system comprising a water-immiscible solvent and a water-miscible solvent, wherein the latter is a linear or cyclic carbonate. These carbonates, in combination with a suitable pH between 5.5 and 9, preferably between 6 and 8.5, preferably between 6.5 and 8.0, and even more preferably between 6.8 and 7.7, effectively prevent chemical degradation of the ai over time.

[039] The EC formulation according to the invention also comprises, as an additional essential component d), at least one suitable emulsifying component, comprising forming an oil-in-water emulsion when the EC formulation of the invention is added to water.

[040] The emulsifier may be an ionic (cationic or anionic), amphoteric or non-ionic surfactant, such as an ionic, non-ionic or amphoteric emulsifier, or a mixture thereof, including standard surfactants present in formulations of agrochemically active ingredients.

[041] The emulsifier may be at least one nonionic surfactant selected from the group of alkoxylated alcohols, ethoxylated alcohols, ethopropoxylated alcohols, alkylphenol ethoxylates, tristyrylphenol alkoxylateds, tributylphenol alkoxylateds, alkylamine ethoxylates, ethoxylated vegetable oils, including their hydrogenated forms, ethylene oxide and propylene oxide polyadducts (e.g., polyoxyethylene-polyethylene-polyethylene). For example, polyoxyethylene-polyoxypropylene block copolymers (and their derivatives), ethoxylated fatty acids, nonionic polymeric surfactants (e.g., polyvinyl alcohol, polyvinylpyrrolidone, polymethacrylates and their derivatives), sorbitan esters and their ethoxylates, sorbitol esters, propylene glycol esters of fatty acids and polyglyceroles.

[042] Examples of preferred nonionic surfactants are ethoxylated alcohols Petition 870250086134, dated 09 / 23 / 2025, page 17 / 53 12 / 39 (e.g., Brij 020-SO-(MV), Croda), ethoxylated alcohols (e.g., Agnique KE 3551, BASF), alkoxylated tristyrylphenols, ethoxylated tristyrylphenols (e.g., Soprophor TS / 16, Rhodia), ethoxylated tristyrylphenols (e.g., Soprophor 796 / P, Rhodia) and ethoxylated vegetable oils (e.g., Tanemul® KS, Tanatex Chemicals).

[043] Examples of suitable anionic surfactants include, but are not limited to, polyacrylic acid salts, polymer salts of acrylic acid / acrylate ester mixtures, polymer salts of acrylic acid / styrene mixtures, lignosulfonic acid salts (such as sodium lignosulfonate), phenolsulfonic acid salts, salts of condensation products of phenolsulfonic acid and formaldehyde, naphthalenesulfonic acid salts, naphthalenesulfonic acid salts and formaldehyde condensation products, salts of condensed naphthalene sulfonates or alkyl naphthalenes, salts of dodecyl and tridecylbenzene sulfonates, salts of sulfosuccinic esters or sulfosuccinates, alkyl sulfate salts, polyethylated and / or polypropoxylated alkyl sulfate salts, salts of paraffin sulfonates, alkyl sulfonate salts, polyethoxylated and / or polypropoxylated alkyl sulfonate salts, aryl sulfate salts, polyethoxylated and / or polypropoxylated aryl sulfate salts,aryl sulfonate salts, polyethoxylated and / or polypropoxylated aryl sulfonate salts, alkylaryl sulfate salts, polyethoxylated and / or polypropoxylated alkylaryl sulfate salts, alkylaryl sulfonate salts, polyethoxylated and / or polypropoxylated alkylaryl sulfonate salts, diphenyl sulfonate and diphenyl oxide sulfonate salts, alpha-olefin sulfonate salts, fatty acid and oil sulfonate salts, alpha-sulfonated methyl ester salts, taurine derivative salts (preferably alkyl taurates), isethionate salts, alkylphosphoric ester salts, arylphosphoric ester salts, ester salts alkylaryl phosphoric acids, phosphoric ester salts of linear or branched aliphatic alcohols polyethoxylated and / or polypropoxylated, phosphoric ester salts of aryl alcohols polyethoxylated and / or Petition 870250086134, dated 09 / 23 / 2025, page 18 / 53 13 / 39 polypropoxylates, protein hydrolysates, lignosulfite residues, polystyrene sulfonic acid salts, polyvinyl sulfonic acid salts, carboxylate salts, ether carboxylate salts.

[044] Examples of such surfactants or emulsifiers are: Ether carboxylates, sulfonates, sulfates and phosphates, and their inorganic salts (e.g., alkali metal, alkaline earth metal or ammonium salts) and organic salts (e.g., amine or alkanolamine-based salts), such as Genapol®LRO, Sandopan® products, Clariant's Hostaphat / Hordaphos® products, Elementis' Servoxyl® products, Agnique® SLS products (Cognis);Salts of aliphatic, cycloaliphatic and olefinic carboxylic acids and polycarboxylic acids, as well as alpha-sulfo fatty acid esters obtained from Cognis, sulfosuccinates, alkanesulfonates, paraffinsulfonates and olefinsulfonates and their inorganic (e.g., alkali metal and alkaline earth metal) and organic (e.g., amine or alkanolamine-based) salts, such as Netzer IS®, Hoe® S1728, Hostapur® OS, Hostapur® SAS from Clariant, Triton® GR7ME and GR5 from Dow, Empimin® products from Huntsman, Marlon®-PS65 from Condea, sulfosuccinamates, such as Aerosol® products from Cytec or Empimin® products from Huntsman, polyacrylic and polymethacrylic surfactant derivatives, such as Sokalan® products from BASF.;

[045] Preferred anionic emulsifiers are: phosphated or sulfated (poly)alkylphenol alkoxylates, phosphated or sulfated poly(arylalkyl)phenol alkoxylates, (poly)alkyl- and poly(arylalkyl)benzenesulfonates in acid or salt form and sulfosuccinates.

[046] The most preferred anionic emulsifiers are emulsifiers based on the calcium salt of dodecylbenzenesulfonic acid, such as Rhodacal® 60 BE (Rhodia) or Calsogen® 4814 (Clariant), Atlox® 4838B X-MSU (Croda), Ninate® 60E XMSU (Stepan) or Nansa® EVM 70 / 2E (Huntsman).

[047] One or more organic bases e) can be selected from Petition 870250086134, dated 09 / 23 / 2025, page 19 / 53 14 / 39 amine-based organic compounds, preferably selected from alkylamines, amino alcohols, alkylamino alcohols, aromatic amines, (poly)ethoxylated amines and (poly)ethoxylated / propoxylated amines.

[048] The organic base is used to adjust the pH of the formulation. By adjusting the pH in a range between 5.5 and 9, preferably between 6.0 and 8.5 and, even more preferably, between 6.5 and 8.0, the ai is chemically stabilized.

[049] The organic base, in particular the amine-based organic compound, is preferentially soluble in the two-phase solvent system of the water-immiscible solvent and the water-miscible solvent, in particular in the concentration ranges given.

[050] An alkylamine can be, for example, triethylamine, and an aromatic amine can be, for example, pyridine. An amino alcohol can be, for example, triethanolamine.

[051] Preferably, the organic base is an (poly)ethoxylated amine, such as a fatty amine ethoxylate of the following formula (II) „3' rJ' R D2'R(II) with R1' being a linear or branched chain alkyl, preferably an unsubstituted C2-24 linear chain alkyl, R2' being -(CH2-CH2-O)xH, and R3' being -(CH2-CH2-O)yH with x+y between 2 and 20. Examples are stearylamine with 8 mol of EO (e.g., Clariant's Genamin S080) and a coconut fatty amine-based ethoxylate (e.g., Clariant's Genamin C050).

[052] In another embodiment, one or more organic bases are selected from amine-based organic bases and one or more water-miscible organic solvents are selected from methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, propylene carbonate, glycerol-1,2-carbonate and butylene carbonate. Preferably, one or more organic bases are ethoxylated amines and one Petition 870250086134, dated 09 / 23 / 2025, page 20 / 53 15 / 39 The water-miscible organic solvent is propylene carbonate.

[053] The emulsifiable concentrates according to the invention may comprise, as component f), protective agents that are suitable for reducing or preventing damage to the cultivated plant. Suitable protective agents are known, for example, from document WO-A-96 / 14747 and the literature cited therein. In the organic solvent, the protective agents are present in dissolved form.

[054] S1) Compounds of the heterocyclic carboxylic acid derivative group (formula S1) (Ra1U (S1) where the symbols and indices are defined as follows: πα is an integer value in the range of 0 to 5, preferably 0 to 3; Ra1 is halogen, alkyl (C1-C4), alkoxy (C1-C4), nitro or haloalkyl (C1-C4); Wa is a divalent heterocyclic moiety, unsubstituted or substituted, selected from the group of five-membered, partially unsaturated or aromatic heterocycles, with 1 to 3 hetero-ring atoms selected from the nitrogen (N) and oxygen (O) groups, and with at least one N atom and no more than one O atom in the ring, preferably a five-membered heterocyclic moiety selected from the (Wa1) to (Wa4) groups. (WA1) (WA2) (Wa3) (Wa4) (Wa5) mA is 0 or 1; Ra2 is ORa3, SRa3 or NRa3Ra4 or a saturated or unsaturated heterocycle of 3 to 7 members containing at least one N atom and up to 3 heteroatoms, preferably combined with other heteroatoms of the O (oxygen) and S groups. Petition 870250086134, dated 09 / 23 / 2025, page 21 / 53 16 / 39 (sulfur), and which is linked to the carbonyl group at (S1) via a nitrogen atom, and which is unsubstituted or substituted by molecules selected from the (C1-C4) alkyl, (C1-C4) alkoxy or possibly substituted phenyl group, preferably ORa3, NHRa4 or N(CH3)2, particularly ORa3; Ra3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon moiety, preferably containing from 1 to 18 carbon atoms; Ra4 is hydrogen, alkyl (C1-C6), alkoxy (C1-C6) or phenyl, substituted or unsubstituted; Ra5 is hydrogen, alkyl (C1-C8), haloalkyl (C1-C8), alkoxy (C1-C4)-alkyl (C1Cs), cyano or COORa9, where Ra9 is hydrogen, alkyl (C1-C8), haloalkyl (C1-C8), alkoxy (C1-C4)-alkyl (C1-C4), hydroxyalkyl (C1-C6), cycloalkyl (C3-C12) or trisalkylsyl (C1-C4); Ra6, Ra7, Ra8 are independently substituted or unsubstituted hydrogen, alkyl (C1-C8), haloalkyl (C1-C8), cycloalkyl (C3-C12), or phenyl; Ra10 is hydrogen, cycloalkyl (C3-C12), substituted or unsubstituted phenyl, or substituted or unsubstituted heteroaryl.

[055] S1a) Dichlorophenylpyrazoline-3-carboxylic acid type compounds (S1a), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate ethyl (S1-1) (“mefenpyr-diethyl”) and related compounds, as described in WO-A-91 / 07874.

[056] S1b) Dichlorophenylpyrazolecarboxylic acid derivatives (S1b), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4) and compounds as described in documents EP—A—333131 and EP-A-269806.

[057] S1c) 1,5-diphenylpyrazole-3-carboxylic acid derivatives (S1c), Petition 870250086134, dated 09 / 23 / 2025, page 22 / 53 17 / 39 preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related compounds, as described, for example, in document EP-A-268554.

[058] S1d) Triazolecarboxylic acid type compounds (S1d), preferably compounds like chloro(-ethyl ester), i.e., ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl1H-1,2,4-triazol-3-carboxylate (S1-7), and related compounds, as described in documents EP-A-174562 and EP-A-346620.

[059] S1e) Compounds of 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type (S1e), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds, as described in WO-A-91 / 08202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-11) (“isoxadiphen-ethyl”) or n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13), as described in patent application WO-A-95 / 07897.

[060] S1f) compounds of the triazolyloxyacetic acid type (S1f), preferably compounds such as methyl-{[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate (S1-14) or {[1,5-Bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S115) or methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate (S1-16) or acid {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic (S1-17) or methyl-{[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)1H-1,2,4-triazol-3-yl]oxy}acetate (S1-18) or {[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S1-19), as described in patent application WO2021105101.

[061] S2) Compounds of the 8-quinolinoxy derivative group (S2):

[062] S2a) 8-quinolineoxyacetic acid type compounds (S2a), Petition 870250086134, dated 09 / 23 / 2025, page 23 / 53 18 / 39 preferably 1-methylhexyl acetate (5-chloro-8-quinolinoxy) (“cloquintocetmexyl”) (S2-1), 1,3-dimethylbut-1-yl acetate (5-chloro-8-quinolinoxy) (S2-2), 4-allyloxybutyl acetate (5-chloro-8-quinolinoxy) (S2-3), 4-allyloxybutyl acetate (5-chloro-8-quinolinoxy) (S2-3), 1-allyloxyprop-2-yl (5-chloro8-quinolinoxy) (S2-4), ethyl acetate (5-chloro-8-quinolinoxy) (S2-5), methyl acetate (5-chloro-8-quinolinoxy) (S2-6), allyl acetate (5-chloro-8-quinolinoxy) (S2-7), (5-chloro8-quinolinoxy)acetate 2-(2-propylideneiminoxy)-1-ethyl (S2-8), 2-oxopropyl-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9) and related compounds, as described in documents EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0 492 366, and also (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts, for example, lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in document WO-A2002 / 34048.

[063] S2b) (5-chloro-8-quinolinexy)malonic acid type compounds (S2b), preferably compounds such as diethyl (5-chloro-8-quinolinexy)malonate, diallyl (5-chloro-8-quinolinexy)malonate, methyl (5-chloro-8-quinolinexy)malonate and methyl (5-chloro-8-quinolinexy)malonate and related compounds, as described in document EP-A-0 582 198.

[064] S3) Active ingredients of the dichloroacetamide type (S3), which are frequently used as pre-emergence protectants (protectants that act in the soil), for example, “diclormide” (N,N-diallyl-2,2-dichloroacetamide) (S3-1), “R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), “R-28725” (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3), “benoxacor” (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), “PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5), “DKA-24” (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide), from SagroPetição 870250086134, dated 23 / 09 / 2025, page 24 / 53 19 / 39 Chem (S3-6), “AD-67” or “MON 4660” (3-dichloroacetyl-1-oxa-3-azaaspiro[4,5]decane) from Nitrokemia or Monsanto (S3-7), “TI-35” (1-dichloroacetylazepane), from TRI-Chemical RT (S3-8), “diclonon” (dicyclonon) or “BAS145138” or “LAB145138” (S3-9) ((RS )-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) from BASF, “furilazol” or “MON 13900” ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), and its isomer (R) (S3-11).

[065] S4) Acylsulfonamide class compounds (S4):

[066] S4a) N-Acylsulfonamides of formula (S4a) and their salts, as described in document WO-A-97 / 45016, in what Ra1é alkyl (C1-C4), cycloalkyl (C5-C4), where the last 2 radicals are replaced by substituents va of the halogen group, alkoxy (C1-C4), haloalkoxy (C1-C4) and alkylthio (C1-C4) and, in the case of cyclic radicals, also by alkyl (C1-C4) and haloalkyl (C1-C4); Ra2e halogen, alkyl (C1-C4), alkoxy (C1-C4), CF3; mA is 1 or 2; va is 0, 1, 2 or 3;

[067] S4b) 4-(benzoylsulfamoyl)benzamide type compounds of formula (S4b) and their salts, as described in document WO-A-99 / 16744, Petition 870250086134, dated 09 / 23 / 2025, p. 25 / 53 20 / 39 in which Rb1, Rb2 are, independently, hydrogen, alkyl (Ci-Ce), cycloalkyl (CsCe), alkenyl (Cs-Ce), alkynyl (Cs-Ce), Rb3 is halogen, alkyl (C1-C4), haloalkyl (C1-C4) or alkoxy (C1-C4) and mB is 1 or 2, for example, those in which Rb1 = cyclopropyl, Rb2 = hydrogen and (Rb3) = 2-OMe (“cyprosulfamide”, S4-1), Rb1= cyclopropyl, Rb2= hydrogen and (Rb3) = 5-CI-2-OMe (S4-2), Rb1 = ethyl, Rb2 = hydrogen and (Rb3) = 2-OMe (S4-3), Rb1= isopropyl, Rb2= hydrogen and (Rb3) = 5-CI-2-OMe (S4-4) and Rb1 = isopropyl, Rb2 = hydrogen and (Rb3) = 2-OMe (S4-5);

[068] S4C) Benzoylsulfamoylphenylurea class compounds of formula (S4C), as described in document EP-A-365484, in what Rc1, Rc2 are independently hydrogen, alkyl (Ci-Cs), cycloalkyl (CsCs), alkenyl (Cs-Ce), alkynyl (Cs-Ce), Rc3 is halogen, alkyl (C1-C4), alkoxy (C1-C4), CFs, and mc is 1 or 2; for example, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea;

[069] S4d) N-phenylsulfonyl terephthalamide type compounds of formula (S4d) and their salts, known, for example, from CN document 101838227, Petition 870250086134, dated 09 / 23 / 2025, page 26 / 53 21 / 39 in what Rd4 is halogen, alkyl (C1-C4), alkoxy (C1-C4), CF3; mo is 1 or 2; Rd5 is hydrogen, alkyl (Ci-Ce), cycloalkyl (Cs-Ce), alkenyl (C2-C6), alkynyl (C2-C6), cycloalkenyl (Cs-Ce).

[070] S5) Active ingredients from the class of hydroxyaromatics and derivatives of aromatic-aliphatic carboxylic acids (S5), for example, ethyl 3,4,5triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, acid 2hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A2004 / 084631, WO-A-2005 / 015994, WO-A-2005 / 016001.

[071] S6) Active ingredients from the class of 1,2-dihydroquinoxalin-2-ones (S6), for example, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)1,2-dihydroquinoxaline-2-thione, hydrochloride 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2one, as described in WO-A-2005 / 112630.

[072] S7) Compounds of the class of diphenylmethoxyacetic acid derivatives (S7), for example, methyl diphenylmethoxyacetate (CAS Reg. N241858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in document WO-A-98 / 38856.

[073] S8) Compounds of formula (S8), as described in document WO-A98 / 27049, Rd20 (Ro'U —θΓί °' ° Petition 870250086134, dated 09 / 23 / 2025, page 27 / 53 22 / 39 where the symbols and indices are defined as follows: Rd1 is halogen, alkyl (C1-C4), haloalkyl (C1-C4), alkoxy (C1-C4), haloalkoxy (C1-C4), Rd2 is hydrogen or alkyl (C1-C4). Rd3 is hydrogen, alkyl (C1-C5), alkenyl (C2-C4), alkynyl (C2-C4) or aryl, wherein each of the carbon-containing radicals mentioned above is unsubstituted or substituted by one or more, preferably up to three, identical or different radicals from the halogen and alkoxy group; or their salts, where is an integer from 0 to 2.

[074] S9) Active ingredients of the 3-(5-tetrazolylcarbonyl)-2-quinolone class (S9), for example, 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. N2219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. N295855-00-8), as described in document WO-A-1999 / 000020.

[075] S10) Compounds of formulas (S10a) or (S10b), as described in documents WO-A-2007 / 023719 and WO-A-2007 / 023764 in what Re1 is halogen, alkyl (C1-C4), methoxy, nitro, cyano, CF3, OCF3, Ye and Ze are independently 0 or S, πε is an integer from 0 to 4, Re2 is alkyl (C1-C16), alkenyl (C2-C6), cycloalkyl (Cs-Ce), aryl; benzyl, halobenzyl, Re3 is hydrogen or alkyl (Ci-Ce). Petition 870250086134, dated 09 / 23 / 2025, page 28 / 53 23 / 39

[076] S11) Active ingredients of the oxy-imino compound type (S11), which are known as seed treatment agents, for example, “oxabetrinil” ((Z)-1,3-dioxolan-2-ylmethoxy-imino(phenyl)acetonitrile) (S11-1), which is known as a seed protection agent for millet / sorghum against damage caused by metolachlor, “fluxofenim” [1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)-oxime] (S11-2), known as a seed protection agent for millet / sorghum against damage caused by metolachlor, and “ciometrinil” or “CGA-43089” ((Z)-cyanomethoxy-imino(phenyl)acetonitrile) (S113), known as a seed protectant for Millet / sorghum against damage caused by metolachlor.

[077] S12) Active ingredients of the isothiochromanones class (S12), for example, [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]methyl acetate (CAS Reg. No 205121-04-6) (S12-1) and compounds as described in document WO-A1998 / 13361.

[078] S13) One or more compounds from the (S13) group: “Naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a corn seed protectant against damage caused by thiocarbamate herbicides, “fenchlorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), known as a pretylachlor protectant in sown rice, “flurazole” (2-chloro-4-trifluoromethyl-1,3-thiazol-5-benzyl carboxylate) (S13-3), known as a millet / sorghum seed protectant against damage caused by alachlor and metolachlor, “CL 304415” (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, known as a protectant for corn against damage caused by Petition 870250086134, dated 09 / 23 / 2025, page 29 / 53 24 / 39 imidazolinones, “MG 191” (CAS Reg. No 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a protectant for corn, “MG 838” (CAS Reg. No 133993-74-5) (1-oxa-4-azaespiro[4,5]decane-4-carbodithioate of 2-propenyl) (S13-6) from Nitrokemia “disulfotonium” (O,O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7), “dietolate” (O,O-diethyl O-phenyl phosphorodithioate) (S13-8), “mefenate” (4-chlorophenylmethylcarbamate) (S13-9).

[079] S14) Active ingredients that, in addition to herbicidal action against weeds, also have a protective action on cultivated plants, such as rice, for example, “dimepiperate” or “MY-93” (S-1-methyl 1-phenylethylpiperidine-1-carbothioate), which is known as a protectant for rice against damage caused by the herbicide molinate, “daimuron” or “SK 23” (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), known as a protectant for rice against damage caused by the herbicide imazosulfuron, “cumiluron” = “JC-940” (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see document JP-A-60087254), which is known as a protectant for rice against damage caused by some herbicides, “methoxyphenone” or “NK 049” (3,3'-dimethyl-4-methoxybenzophenone), known as a rice protector against damage caused by some herbicides, “CSB” (1-bromo-4-(chloromethylsulfonyl)benzene) from Kumiai, (CAS Reg. No 54091-06-4), known as a protector against damage caused by some herbicides in rice.

[080] S15) Compounds of formula (S15) or their tautomers Petition 870250086134, dated 09 / 23 / 2025, page 30 / 53 25 / 39 as described in documents WO-A-2008 / 131861 and WO-A-2008 / 131860 where Rh1 is a haloalkyl (C1-C1) radical and Rh2 is hydrogen or halogen and Rh3 and Rh4 are independently hydrogen, alkyl (C1-C16), alkenyl (C2C16) or alkynyl (C2-C16), where each of the last 3 radicals is unsubstituted or is substituted by one or more radicals of the halogen group, hydroxyl, cyano, alkoxy (C1C4), haloalkoxy (C1-C4), alkylthio (C1-C4), alkylamino (C1-C4), di[alkyl (C1-C4)]amino, [alkoxy (C1-C4)]carbonyl, [haloalkoxy (C1-C4)]carbonyl, unsubstituted or substituted cycloalkyl (Cs-Ce), unsubstituted or substituted phenyl and unsubstituted or substituted heterocycle, or cycloalkyl (Cs-Ce), cycloalkenyl (C4-Ce), cycloalkyl (Cs-Ce) fused on one side of the ring to a saturated carbocyclic ring or unsaturated 4- to 6-membered, or cycloalkenyl (C4-Ce) group fused on one side of the ring to a saturated or unsaturated 4- to 6-membered carbocyclic ring, wherein each of the last 4 radicals is unsubstituted or substituted by one or more radicals from the halogen, hydroxyl, cyano, alkyl (C1-C4), haloalkyl (C1-C4), or alkoxy (C1-C4) group.haloalkoxy (C1-C4), alkylthio (C1-C4), alkylamino (C1-C4), di[alkyl (C1-C4)]amino, [alkoxy (C1-C4)]carbonyl, [haloalkoxy (C1-C4)]carbonyl, unsubstituted or substituted cycloalkyl (C1-C1), unsubstituted or substituted phenyl, and unsubstituted or substituted heterocycle, or, Rh3 is alkoxy (C1-C4), alkenyloxy (C2-C4), alkynyloxy (C2-C6) or haloalkoxy (C2C4) and Petition 870250086134, dated 09 / 23 / 2025, p. 31 / 53 26 / 39 Rh4 is hydrogen or alkyl (C1-C4) or Rh3 and Rh4, together with the directly bonded nitrogen atom, represent a four- to eight-membered heterocyclic ring that, like the nitrogen atom, may also contain other ring heteroatoms, preferably up to two ring heteroatoms from the N, O, and S groups, and which is unsubstituted or substituted by one or more radicals from the halogen, cyano, nitro, alkyl (C1-C4), haloalkyl (C1-C4), alkoxy (C1-C4), haloalkoxy (C1-C4), and alkylthio (C1-C4) groups.

[081] S16) Active ingredients that are used primarily as herbicides, but also have a protective action on cultivated plants, for example, (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-chloro-o-tolyloxy)acetic acid (MCPA), 4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1-(Ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloroethyl).

[082] Preferred protectants in combination with the herbicide combinations of the invention are: cloquintocet-mexil, cyprosulfamide, fenchlorazole ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenchlorim, cumiluron, S4-1 and S4-5, and particularly preferred protectants are: cloquintocet-mexil, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.

[083] One or more agrochemically active ingredients g) other than a) and f) may be selected from diflufenican, pyroxasulfone, metribuzin, mesotrione, aclonifene, bromoxynil, bromoxynil butyrate, potassium heptanoate and Petition 870250086134, dated 09 / 23 / 2025, page 32 / 53 27 / 39 octanoate, benzofenap, butachlor, 2,4-D, 2,4-D-butyl, -butyl, -dimethylammonium, diolamine, -ethyl, -2-ethylhexyl, -isobutyl, -iso-octyl, -isopropylammonium, -potassium, -triisopropanolammonium and -trolamine, diflufenican, dimethenamide, ethoxysulfuron, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, phenquinotrione, fentrazamide, florassulam, flufenacet, fluroxypyr, fluroxypyr-meptyl, foramsulfuron, iodosulfuron, iodosulfuron-methyl-sodium, isoproturon, isoxaflutole, mefenacet, mesosulfuron, mesosulfuron-methyl, metolachlor, S-metholachlor, metribuzin, metossulam, nicosulfuron, oxadiargila, oxadiazon, petoxamide, prosulfocarb, pyrasulfotole, piroxsulam, tefuryltrione, tembotrione, triafamonone, pendimethalin, propoxycarbazone, halauxifen-methyl, 2-methyl-4-chlorophenoxyacetic acid (MCPA).

[084] Preferably, the additional active agrochemical ingredient is fluroxypyr-meptyl.

[085] The formulation of the emulsifiable concentrate may also include adjuvants and additives commonly h) known in the art and compatible with agrochemical formulations. These additives may be, for example, stabilizers, such as antifreeze, preservatives, antioxidants, light stabilizers, in particular UV stabilizers, other agents that improve chemical and / or physical stability.

[086] Other additives are antifoaming agents, such as silicone and magnesium stearate antifoaming agents, - silicone oils, silicone oil preparations, especially non-ionic aqueous emulsions based on polydimethylsiloxane (dimethylsiloxanes and silicones, CAS No. 63148-62-9). Examples are Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, SAG 1572 and SAG 30 from Momentive.

[087] Other additives are penetration enhancers, such as ethoxylated linear and / or branched fatty alcohols (e.g., Clariant's Genapol® type X) with 2 to 20 EO units; ethoxylated linear and / or branched fatty alcohols with Petition 870250086134, dated 09 / 23 / 2025, p. 33 / 53 28 / 39 methyl end (e.g., Clariant's Genapol® type XM) comprising 2 to 20 EO units; ethoxylated coconut alcohols (e.g., Clariant's Genapol® type C) comprising 2 to 20 EO units; ethoxylated C12 / 15 alcohols (e.g., Croda's Synperonic® type A) comprising 2 to 20 EO units; branched or linear propoxy-ethoxylated alcohols, e.g., Solvay's Antarox® B / 82, Croda's Atlas® G5000, Levaco's Lucramul® HOT 5902, Evonik's Break-Thru Vibrant; propoxy-ethoxylated fatty acids, with Me end cap, e.g., Lion's Leofat® OC0503M; Alkyl ether citrate surfactants (e.g., Adsee CE line, Akzo Nobel); alkylpolysaccharides (e.g., Agnique® PG8107, PG8105 from BASF; Atplus® 438, AL-2559, AL-2575 from Croda); ethoxylated mono- or diesters of glycerin comprising fatty acids with 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g., Crovol® product line from Croda).For example, Croda's Crovol® product line; castor oil ethoxylates comprising an average of 5 to 40 EO units (e.g., Nouryon's Berol® line, Clariant's Emulsogen® EL line); block copolymer of polyethylene oxide and polypropylene oxide (e.g., BASF's Pluronic line).

[088] Other additives are wetting agents, spreading agents, retention agents, such as branched ethoxylated alcohols (e.g., Genapol®X type) with 2 to 20 EO units; branched ethoxylated alcohols with a methyl end (e.g., Genapol® XM type) comprising 2 to 20 EO units; propoxy-ethoxylated alcohols, branched or linear, e.g., Antarox® B / 848, Atlas® G5000, Lucramul® HOT 5902; organomodified polysiloxanes, e.g., BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwet 312, Silwett® 408, Silwet® 806; Mono- and diesters of sodium sulfosuccinate salts with branched or linear alcohols comprising 1 to 10 carbon atoms, for example, Geropon DOS; ethoxylated diacetylenic diols, for example, Surfynol® 4xx series.

[089] Suitable adjuvants, which normally function as Petition 870250086134, dated 09 / 23 / 2025, p. 34 / 53 29 / 39 absorption enhancers are oils, such as sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil; ethylhexyl oleate, ethylhexyl palmitate, ethylhexyl myristate / laurate, ethylhexyl laurate, ethylhexyl caprylate / caprate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate, rapeseed oil methyl ester, soybean oil methyl ester, rice bran oil methyl ester, mineral oils, for example, Exxsol® D100, Solvesso® 200ND. The adjuvant can also be selected from tris-alkyl phosphate esters, preferably tris(2-ethylhexyl) phosphate, for example, Disflamoll® TOF.

[090] The adjuvant may also be selected from the following group of compounds: ethoxylated branched alcohols (e.g., Genapol® X type) with 2 to 20 EO units; ethoxylated branched alcohols with a methyl end (e.g., Genapol® XM type) comprising 2 to 20 EO units; ethoxylated coco alcohols (e.g., Genapol® C type) comprising 2 to 20 EO units; ethoxylated C12 / 15 alcohols (e.g., Synperonic® A type) comprising 2 to 20 EO units; branched or linear propoxy-ethoxylated alcohols, e.g., Antarox® B / 848, Atlas® G5000, Lucramul® HOT 5902; propoxyethoxylated fatty acids, with a terminal cap Me, for example, Leofat®OC0503M; alkyl ether citrate surfactants (for example, Adsee® CE line, Akzo Nobel); I.Mono- or diester ethoxylates of glycerin comprising fatty acids with 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g., Crovol® line); castor oil ethoxylates comprising an average of 5 to 40 EO units (e.g., Berol® and Emmor® lines); ethoxylated oleic acid (e.g., Alkamuls® A and AP) comprising 2 to 20 EO units; ethoxylated sorbitan fatty acid esters comprising fatty acids with 8 to 18 carbon atoms and an average of 10 to 50 EO units (e.g., Arlatone® T, Tween line).

[091] The preferred absorption enhancers according to the present Petition 870250086134, dated 09 / 23 / 2025, p. 35 / 53 30 / 39 invention are tris-(2-ethylhexyl) phosphate, rapeseed oil methyl esters, ethoxylated coconut alcohols, propoxy-ethoxylated alcohols and mineral oils.

[092] The herbicide compositions have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous weeds. Even perennial weeds that produce shoots from rhizomes, rootstocks, or other perennial organs and that are difficult to control are well controlled. In this context, it does not matter whether the herbicide compositions are applied before sowing, in pre-emergence, or in post-emergence. Specific examples of some representatives of the monocotyledonous and dicotyledonous weed flora that can be controlled by the herbicide compositions can be mentioned, without the enumeration being a restriction to specific species.

[093] Examples of weed species on which herbicide compositions act efficiently are, among monocotyledonous weed species, Apera spica venti, Avena spp, Setaria spp. and Bromus spp., such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus, and annual Cyperus species and, among perennial species, Agropiron, Cynodon, Imperata and Sorghum and also perennial Cyperus species. In the case of dicotyledonous weed species, the spectrum of action extends to genera such as, for example, Abutilon spp, Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. Viola spp. and Xanthium spp. are among the annuals, while Convolvulus, Cirsium, Rumex, and Artemisia are among the perennial weeds.

[094] The herbicide compositions also act exceptionally efficiently on noxious plants found under the specific conditions of rice cultivation, such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus. Petition 870250086134, dated 09 / 23 / 2025, page 36 / 53 31 / 39

[095] If herbicide compositions are applied to the soil surface before germination, weed seedlings will be completely prevented from emerging, or else the weeds will grow until they reach the cotyledon stage, but then their growth will be interrupted and, finally, after three to four weeks, they will die completely.

[096] If herbicide compositions are applied post-emergence to the green parts of plants, growth is also drastically interrupted in a very short period after treatment, and weeds remain in the growth stage at the time of application or die completely after a certain time, so that weed competition, which is harmful to cultivated plants, is eliminated very early and in a sustained manner.

[097] The herbicidal compositions are distinguished by a rapid onset and long duration of herbicidal action. In general, the rain resistance of the active substances in the herbicidal compositions is advantageous. A specific advantage is that the dosages used in the herbicidal compositions and the effective dosages of the herbicidal compounds can be adjusted to such a low level that their action in the soil is optimally low. This not only allows them to be employed in sensitive crops first, but also practically avoids groundwater contamination. The combination of active compounds according to the invention allows the required application rate of the active substances to be considerably reduced.

[098] The properties and advantages mentioned above are necessary for the practice of weed control in order to keep agricultural crops free from unwanted competing plants and thus guarantee and / or increase yield levels from a qualitative and quantitative point of view. These new herbicide compositions significantly exceed the state of the art with respect to the properties described. Petition 870250086134, dated 09 / 23 / 2025, page 37 / 53 32 / 39

[099] Although herbicide compositions have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, economically important crop plants, for example, dicotyledonous crops such as soybeans, cotton, rapeseed, beet, or grass crops such as wheat, barley, rye, oats, millet, rice or corn, are damaged only to a small extent, if at all. This is why current herbicide compositions are highly suitable for the selective control of unwanted plant growth in agricultural or ornamental crop plantings.

[0100] Due to their herbicidal properties, herbicidal compositions can also be used to control weeds in genetically modified plant crops that are known or yet to be developed. In general, recombinant plants are distinguished by specific advantageous characteristics, for example, resistance to certain pesticides, particularly certain herbicides, resistance to plant diseases or to plant disease-causing organisms, such as insects or specific microorganisms, such as fungi, bacteria or viruses. Other specific characteristics refer, for example, to the harvested material in terms of quantity, quality, storage capacity, composition and specific constituents. Thus, for example, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition.

[0101] The use of herbicide compositions is preferable in economically important transgenic crops of useful and ornamental plants, for example, grass crops such as wheat, barley, rye, oats, millet, rice and maize, or crops of beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetables. Preferably, herbicide compositions may be used in useful plant crops that are resistant to the phytotoxic effects of herbicides or that Petition 870250086134, dated 09 / 23 / 2025, page 38 / 53 33 / 39 were made to resist these effects through recombinant techniques.

[0102] When using herbicide compositions in transgenic crops, effects are frequently observed, in addition to the effects against noxious plants to be observed in other crops, that are specific to the application in the transgenic crop in question, for example, a modified or specifically broadened spectrum of weeds that can be controlled, modified application rates that can be employed for application, preferably good combinability with other active herbicide compounds to which the transgenic crop is resistant, and an effect on the growth and yield level of the transgenic crop plants.

[0103] Therefore, the present invention also relates to a method of controlling unwanted vegetation (noxious plants), preferably in plant crops such as cereals (for example, wheat, barley, rye, oats, rice, corn and millet), sugar beet, sugar cane, rapeseed, cotton and soybean, especially preferably in monocotyledonous plants such as cereals, for example, wheat, barley, rye, oats and their hybrids, such as triticale, rice, corn and millet, wherein the formulations according to the invention or the herbicidal compositions that can be obtained from them are applied to the noxious plants, to parts of the plants, to the seeds of the plants or to the area where the plants grow, for example, the cultivated area, in an effective quantity.

[0104] Plants can also be genetically modified or obtained by mutation selection; preferably, they tolerate acetolactate synthase (ALS) inhibitors.

[0105] The plants treated according to the invention are, with respect to the use of herbicides, all types of noxious plants, such as weeds. With regard to the protection of cultivated plants by means of the application of, for example, fungicides and insecticides, use is preferable in economically important crops, Petition 870250086134, dated 09 / 23 / 2025, page 39 / 53 34 / 39 including, for example, transgenic crops, of useful and ornamental plants, for example, cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or crops of peanuts, beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other plant species.

[0106] The process for preparing the formulations according to the invention can be chosen from several known processes per se that describe the preparation of emulsifiable concentrates.

[0107] The formulations according to the invention have excellent chemical and physical stability during preparation and storage and are suitable, in particular, also for combinations of active compounds with different physicochemical properties. In general, the formulations according to the invention have the desired long-term storage stability and are not technically flawed. examples

[0108] The examples are intended to illustrate the invention and do not limit it to the processes and compounds described therein. Starting materials:

[0109] The compounds used in the examples are specified below in Table 1. Table 1: Chemicals used in the examples. Fluroxypyr-Meptyl (Bayer) Herbicide; CAS 81406-37-3 Thiencarbazone-methyl (Bayer) Herbicide; CAS 317815-83-1 Mefenpyr-Diethyl (Bayer) Safener; CAS 135590-91-9 Genamin S 080 (Clariant) Organic base; stearylamine ethoxylate (stearylamine with 8 mol ethylene oxide) Genamin C 050 (Clariant) Organic base; ethoxylated amine based on coconut fatty amine Triethanolamine Organic base; CAS 102-71-6 Propylene carbonate Water-miscible solvent; CAS 108-32-7 Dimethylformamide Water-miscible solvent; CAS 68-12-2 Dimethyl sulfoxide Water-miscible solvent; CAS 67-68-5 Glycerol-1,2-carbonate Water-miscible solvent; CAS 931-40-8 Petition 870250086134, dated 09 / 23 / 2025, pages 40 / 53 35 / 39 N-Methylpyrrolidone Water-miscible solvent; CAS 872-50-4 Steposol EA (Stepan) Water-miscible solvent; Acetamide, N[2-(acetyloxy)ethyl)]-N-methyl Rapeseed oil methyl ester (RME) Water-immiscible solvent Rhodacal 60 BE (Solvay) Anionic emulsifier; linear calcium dodecylbenzene sulfonate, 60% active Triton GR 7 ME (Dow) Anionic emulsifier; Sulfosuccinate Soprophor 796 / P (Solvay) Non-ionic emulsifier; Tristyrylphenol alkoxylate Emulsifier EL 400 (Clariant) Emulsifier; castor oil, ethoxylated (40 EO) Genapol X 090 (Clariant) Non-ionic emulsifier; Isotridecanol ethoxylate 9EO Solvesso 200 (Exxon) Aromatic superheavy solvent immiscible in water Example 1:

[0110] The emulsifiable concentrate formulations according to Table 2 below were prepared by first mixing all the liquid components and then adding the solid components to the mixture and finally heating it from 30 to 60 °C. In these formulations, different water-miscible organic solvents were tested, namely, propylene carbonate, glycerol-1,2-carbonate, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and acetamide, N-[2(acetyloxy)ethyl)]-N-methyl (Steposol EA).

[0111] The formulations were tested for stability at 54 °C after two weeks, measuring the thiencarbazone-methyl content by HPLC. The chemical degradation (%) in Table 2 below shows the relative loss of thiencarbazone-methyl compared to the initial amount (day 0). Table 2: Examples of CE formulation. Example No 1 No 2 No 3 No 4 No 5 No 6 Mefenpyr-Diethyl (% w / w) 2.78 2.78 2.78 2.78 2.78 2.78 Thiencarbazone-methyl (% w / w) 0.46 0.46 0.46 0.46 0.46 0.46 Rhodacal 60 BE (% w / w) 4 4 4 4 4 4 Soprophor 796 / P (% w / w) 4 4 4 4 4 4 Genapol p / p) 1 1 1 1 1 1 Propylene carbonate (% w / w) 25 - - - - - Petition 870250086134, dated 09 / 23 / 2025, pp. 41 / 53 36 / 39 Dimethylformamide (% w / w) - 25 - - - - Dimethyl sulfoxide (% w / w) - - 25 - - - Glycerol-1,2-carbonate (% w / w) - - - 25 - - N-Methylpyrrolidone (% w / w) - - - - 25 - Steposol EA (% w / w) - - - - - 25 Solvesso 200 (% w / w) 42.76 42.76 42.76 42.76 42.76 42.76 Chemical degradation (%) Thiencarbazone-methyl after 2 weeks at 54 °C -6.98 - 28.26 - 63.64 - 11.63 - 31.11 - 29.79

[0112] While propylene carbonate and glycerol-1,2-carbonate result in better formulation stability after two weeks of storage at 54 °C, in particular propylene carbonate with a degradation of only 6.98% (indicated as “-6.98”), the other polar aprotic solvents tested, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and Steposol EA (acetamide, N-[2(acetyloxy)ethyl)]-N-methyl) provide insufficient stability after 2 weeks of storage at 54 °C, with a loss of thiencarbazone-methyl of up to 63.64% compared to the initial thiencarbazone-methyl content measured directly after preparation of the formulation (= day 0). Example 2:

[0113] Other EC formulations were prepared as described above for Example 1, but with ingredients according to Table 3 below, and tested for the chemical stability of thiencarbazone-methyl as described in Example 1. ______Table 3: Other examples of EC formulations._____________________ Example # 7 0.46 0.46 0.46 0.46 0.46 0.46 MefenpyrDiethyl (% w / w) 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 Genamin S 080 (% w / w) 0 1 1 0 0 1 0 0 Petition 870250086134, dated 09 / 23 / 2025, pages 42 / 53 37 / 39 Genamin C 050 (%) Soprophor 796 / P (% w / w) 4 4 0 0 4 4 4 4 Castor Oil EO 40 (% w / w) 0 0 4 4 0 0 0 0 Syskem Rapeseed Oil Methyl Ester (% w / w) 10 10 10 10 10 10 10 10 Genapol X 090 (% p / p) 10 10 10 Propylene carbonate (% w / w) 28.85 28.85 28.85 28.85 28.85 28.85 28.85 28.85 Solvesso 200 (% w / w) 23.28 23.28 23.28 23.28 23.28 23.28 23.28 23.28 pH pH < 5 pH 6-8 pH 6-8 pH 6-8 pH 6-8 pH 6-8 pH 6-8 pH 6-8 Chemical degradation (%) Thiencarbazo methyl after 2 weeks at 54 °C High degradation (more than 10% loss) Low degradation (less than 10% loss) Low degradation (less than 10% loss) Low degradation (less than 10% loss) Low degradation (less than 10% loss) Low degradation (less than 10% loss) Low degradation (less than 10% loss) Low degradation (less than 10% loss) * Not in accordance with the present invention Petition 870250086134, dated 09 / 23 / 2025, pp. 43 / 53 38 / 39

[0114] As can be seen in the table above, formulation no. 7 with pH < 5 and no organic base offers insufficient stability after two weeks of storage at 54 °C, i.e., with chemical degradation of thiencarbazone-methyl of more than 10% compared to the initial thiencarbazone-methyl content measured directly after preparation of the formulation (= day 0), while the other formulations offer adequate storage stability with degradation below 10% (i.e., the loss of thiencarbazone-methyl is less than 10%). The pH of the respective formulations is measured after (i) diluting the formulation in distilled water to a 10% w / w formulation; (ii) stirring the mixture with a magnetic stirrer at 1,500 RPM for 10 minutes at 25 °C; (iii) measuring the pH of the stirred mixture at 25 °C with a pH meter until the measured pH remains stable for 10 s. pH is measured using a Knick 766 pH meter (Calimatic, Knick SE 100N). Example 3:

[0115] Other EC formulations were prepared according to the explanations in Example 1, with ingredients as per Table 4 below. The pH was determined as described in Example 2. Table 4: Other examples of CE formulations. Example No 15 (% w / w) No 16 (% w / w) No 17 (% w / w) Fluroxypyr-methyl 11.35 15.63 22.06 Thiencarbazone-methyl 0.48 0.46 0.93 Mefenpyr-diethyl 2.88 2.78 5.61 Genamin C 050 0.90 - 2.00 Genamin S 080 - 1.00 - Rhodacal 60 BE 4.00 4.00 4.00 Soprophor 796 / P 4.00 4.00 4.00 Rapeseed oil methyl ester 10.00 10.00 10.00 Genapol X 090 10.00 10.00 10.00 Propylene carbonate 28.85 28.85 28.04 Solvesso 200 27.54 23.28 13.36 pH 7.70 6 to 8 6 to 8 Chemical degradation (%) Thiencarbazone-methyl after 2 weeks at 54 °C -4.84 Low degradation (less than 10% loss) Low degradation (less than 10% loss) Petition 870250086134, dated 09 / 23 / 2025, pages 44 / 53 39 / 39

[0116] The formulations in Examples 15 to 17 provide excellent storage stability, as well as weed control after field application, such as against wild oats, green foxtail and yellow foxtail. Petition 870250086134, dated 09 / 23 / 2025, pp. 45 / 53

Claims

1 / 4 CLAIMS 1. Emulsifiable concentrate formulation comprising a) thiencarbazone-methyl or an agrochemically acceptable salt, b) one or more water-immiscible organic solvents, c) one or more water-miscible organic solvents selected from linear and cyclic carbonate esters, d) one or more emulsifiers, e) one or more organic bases, CHARACTERIZED in that the formulation exhibits a pH between pH 5.5 and pH 9.

2. Emulsifiable concentrate formulation, according to claim 1, CHARACTERIZED in that the formulation has a pH between pH 6.0 and 8.5, preferably between pH 6.5 and 8.0, and even more preferably between pH 6.8 and 7.

7.

3. Emulsifiable concentrate formulation, according to claim 1 or 2, CHARACTERIZED in that the pH is adjusted by means of one or more organic bases (e).

4. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that one or more organic bases is selected from amine-based organic bases.

5. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that one or more organic bases is an ethoxylated amine.

6. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that one or more water-immiscible organic solvents are selected from aromatic and / or aliphatic hydrocarbons. Petition 870250086134, dated 09 / 23 / 2025, page 46 / 53 2 / 4 7. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that one or more water-miscible organic solvents are selected from among methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, propylene carbonate, glycerol-1,2-carbonate and butylene carbonate, or mixtures thereof.

8. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that one or more water-miscible organic solvents is propylene carbonate.

9. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that one or more organic bases are selected from amine-based organic bases and one or more water-miscible organic solvents are selected from methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, propylene carbonate, glycerol-1,2-carbonate and butylene carbonate.

10. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that the organic base is an ethoxylated amine and the water-miscible organic solvent is propylene carbonate.

11. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that it further comprises one or more of the following: f) one or more protective agents, g) one or more active agrochemical ingredients other than a) and f), h) other adjuvants compatible with agrochemical formulations, wetting agents and / or other additives. Petition 870250086134, dated 09 / 23 / 2025, page 47 / 53 3 / 4 12. Emulsifiable concentrate formulation, according to claim 11, CHARACTERIZED in that the protectant is selected from cloquintocetmexil, cyprosulfamide, fenchlorazole ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumiluron; preferably in that the protectant is mefenpyr-diethyl.

13. Emulsifiable concentrate formulation, according to any one of the preceding claims 11 or 12, CHARACTERIZED in that one or more agrochemically active ingredients other than a) and f) are selected from diflufenican, pyroxasulfone, metribuzin, mesotrione, aclonifene, bromoxynil, bromoxynil-butyrate, potassium, heptanoate and octanoate, benzofenap, butachlor, 2,4-D, 2,4-D-butyl, butyl, dimethylammonium, diolamine, ethyl, 2-ethylhexyl, isobutyl, isooctyl, isopropylammonium, potassium, triisopropanolamine, and trolamine, diflufenican, dimethenamide, ethoxysulfuron, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, phenquinotrione, fentrazamide, florassulam, flufenacet, fluroxypyr, fluroxypyr-meptyl, foramsulfuron, iodosulfuron, iodosulfuron-methyl-sodium, isoproturon, isoxaflutole, mefenacet, mesosulfuron, mesosulfuron-methyl, metolachlor, S-metolachlor, metribuzin, metossulam, nicosulfuron, oxadiargil, oxadiazonepetoxamide, prosulfocarb, pyrasulfotol, piroxsulam, tefuryltrione, tembotrione, triafamone, pendimethalin, propoxycarbazone, halauxifene-methyl and 2-methyl-4-chlorophenoxyacetic acid (MCPA); preferably wherein the active agrochemical ingredient other than a) and f) is fluroxypyr-meptyl.

14. Emulsifiable concentrate formulation, according to any of the preceding claims, CHARACTERIZED in that it comprises a) 0.01% to 5% by weight, preferably 0.1% to 2% by weight, even more preferably a further 0.3% to 1% by weight of thienocarbazone-methyl or an agrochemically acceptable salt, b) 5% to 95% by weight, preferably 10% to 70% by weight, even more preferably 20% to 60% by weight of one or more immiscible organic solvents. Petition 870250086134, dated 09 / 23 / 2025, p.48 / 53 4 / 4 in water, c) 5 to 95% by weight, preferably 10 to 60% by weight, even more preferably 20 to 40% by weight of one or more water-miscible organic solvents, d) 0.1 to 30% by weight, preferably 1 to 25% by weight, even more preferably 5 to 20% by weight of one or more emulsifiers, e) 0.1 to 10% by weight, preferably 0.2 to 5% by weight, even more preferably 0.5 to 2% by weight of the organic base, f) 0 to 10% by weight, preferably 1 to 8% by weight, even more preferably 2 to 6% by weight of one or more protective agents, g) 0 to 40% by weight, preferably 5 to 30% by weight, even more preferably 10 to 25% by weight of one or more active agrochemical ingredients other than a) ef), h) 0 to 40% by weight, preferably 5 to 30% by weight, even more preferably 10 to 20% by weight of other adjuvants compatible with agrochemical formulations, wetting agents and / or other additives.

15. Method of combating unwanted plants in a leaf locus, CHARACTERIZED in that it comprises treating the leaf locus with a composition obtained from the emulsification of an emulsifiable concentrate formulation according to any one of claims 1 to 14 in water. Petition 870250086134, dated 09 / 23 / 2025, pp. 49 / 53