Herbicide / safener combinations based on herbicides from the class of chiral n-(1,3,4-oxadiazol-2-yl)phenyl carboxylic acid amides and the salts thereof

Abstract

The invention relates to combinations containing one or more components (A) which are effective as safeners and one or more herbicidally active compounds (component (B)), wherein component (B) represents one or more compounds of the general formula (I) or the agrochemically acceptable salts thereof.

Description

[0001] Herbicide / safener combinations based on herbicides from the class of chiral N-(l,3,4-oxadiazol-2-yl)phenylcarboxamides and their salts

[0002] Description

[0003] The invention lies in the technical field of plant protection agents which can be used against undesired plant growth in cultivated land, for seed preparation or in plant cultures and which contain a combination of at least one safener (A) and at least one herbicide (B) from the class of chiral N-(l,3,4-oxadiazol-2-yl)phenylcarboxamides and salts thereof.

[0004] The effectiveness of known herbicides against weeds is at a high level, but generally depends on the application rate, the respective preparation form, the weed spectrum, the weeds to be controlled, the climatic and soil conditions, etc., but above all on the crop tolerance.

[0005] One way to improve the application profile of a herbicide may be to combine a safener with one or more herbicidal active ingredients that contribute the desired additional properties. However, the combined use of several active ingredients often results in phenomena of physical and biological incompatibility, e.g., instability in a co-formulation, decomposition of an active ingredient, or antagonism between the active ingredients. The safeners may also have a limited range of activity, protecting the crop only against one herbicide but not against all components in the case of combined applications of several herbicides.

[0006] Safeners, also called antidotes, of various chemical structures have been known for approximately 70 years. It is also known that they differ significantly in their protective functions, meaning their application is limited to selected herbicides and / or the crop to be protected. In addition, it is required that a selected herbicide / safener combination does not negatively affect herbicidal efficacy with respect to the weeds to be controlled.

[0007] Herbicide / safener combinations containing certain racemic herbicides from the class of N-(l,3,4-oxadiazol-2-yl)phenylcarboxamides are known, for example, from WO 2015 / 049225.

[0008] It has now been found that certain safeners are extremely effective in protecting different

[0009] Crops can be used when applying one or more herbicides from the class of chiral N-(l,3,4-oxadiazol-2-yl)phenylcarboxamides of formula (I).

[0010] Compounds of formula (I) are known from WO 2022 / 189495.

[0011] Particularly suitable safeners for use in this invention are mefenpyr diethyl, isoxadifen ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet mexyl, fluxofenim, and furilazole. These are known from "The Pesticide Manual," 12th edition 2000, or 13th edition 2003, or 14th edition 2006 / 2007.

[0012] The present invention thus relates to safener / herbicide combinations containing

[0013] (A) one or more components (A) active as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and

[0014] (B) one or more herbicidally active compounds of formula (I) as component (B), wherein

[0015] R is hydrogen or methyl,

[0016] X means CI or methyl,

[0017] R' is methyl or c-Pr, Z is CF3 or CHF2, and wherein the compounds of formula (I) have the absolute configuration indicated above.

[0018] In the following, only the neutral compound is mentioned and thus includes all existing forms as listed, unless a specific form of the active ingredient is relevant in a particular context, such as in the table examples below for biological activity.

[0019] The herbicide / safener combinations according to the invention may contain further components, e.g., other active ingredients against harmful organisms such as weeds, plant-harming animals, or plant-harming fungi, in particular active ingredients from the group of herbicides other than the herbicides listed under B, fungicides, insecticides, acaricides, nematicides, and miticides and related substances, or also other types of crop protection active ingredients (e.g., resistance inducers), crop-protective active ingredients (safeners, antidotes, other than component (A)), plant growth regulators, and / or additives and / or formulation aids customary in crop protection. The components can be formulated and applied together (ready-to-use formulation), or they can be formulated separately and applied together, e.g., in a tank mix or in sequential application.

[0020] In preferred embodiments, the herbicides (B), as defined in connection with the present invention, are the only herbicidally active ingredients in the herbicide / safener combinations according to the invention.

[0021] In other preferred embodiments, the safeners (A) and the herbicides (B), as defined in connection with the present invention, are the only safeners and the only herbicidally active ingredients in the herbicide / safener combinations according to the invention.

[0022] The herbicide / safener combinations according to the invention contain at least one herbicidally active compound of the formula (I) as component (B), which has the above-specified absolute (S) configuration, wherein the corresponding (R)-enantiomer, if present in the herbicide / safener combination, makes up less than 20 wt. %, based on the total amount of the two enantiomers. The proportion of the enantiomer of the above-specified absolute configuration of the formula (I) as component (B) in herbicide / safener combinations according to the invention is preferably more than 85 wt. %, preferably more than 90 wt. %, and more preferably more than 95 wt. %, in each case based on the total amount of the two enantiomers. In other words, if the corresponding (R)-enantiomer is present in the herbicide / safener combinations, the compound of the formula (I) as component (B), which has the absolute configuration indicated in formula (I), is in a high orpreferably very high enantiomer excess.

[0023] The individual safeners contained as component (A) are also referred to below as compounds (A), active ingredients (A), components (A), or safeners (A). Accordingly, the individual herbicidal active ingredients contained as component (B) are also referred to below as compounds (B), active ingredients (B), components (B), herbicides (B), or compounds of formula (I).

[0024] An advantageous property of the combination of safeners (A) and herbicides (B) according to the invention is that safeners (A) and herbicides (B) are compatible with each other, ie they can be used together without significant chemical incompatibilities of the safener (A) and / or the herbicides (B) occurring, which lead to decomposition of the safener (A) or the herbicide(s) (B).

[0025] This favorable compatibility also extends to the biological properties of the active ingredients when used in combination. Antagonistic effects are generally not observed when controlling weeds with the herbicide / safener combinations according to the invention.

[0026] The results of our own biological experiments have shown that herbicide / safener combinations according to the invention exhibit significantly increased crop tolerance.

[0027] In these experiments, the damage to the crop caused by the respective herbicide (component (B)) (= herbicide damage without safener) could be significantly reduced by adding a safener (component (A)).

[0028] Depending on the nature of the substituents defined above, the compounds of formula (I) exhibit acidic properties and can form salts, optionally also internal salts or adducts, with inorganic or organic bases or with metal ions. These salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or ammonium salts, salts with organic amines, or quaternary ammonium salts, for example with cations of the formula [NRR'R "R '] + , wherein R to R ' each independently represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl. Alkylsulfonium and alkylsulfoxonium salts, such as (C1-C4)-trialkylsulfonium and (C1-C4)-trialkylsulfoxonium salts, are also suitable.

[0029] Preferred, particularly preferred, and very particularly preferred meanings for the individual safeners (A) and herbicides (B) are described below. In a first embodiment of the present invention, the herbicide / safener combination according to the invention preferably contains, in addition to at least one component (A) as defined above, a compound [component B] of the general formula (I) or its agronomically acceptable salts according to Table 1:

[0030] Table 1 In a second embodiment of the present invention, the herbicide / safener combination according to the invention contains, in addition to at least one component (A) as defined above, preferably a compound [component B] of the general formula (I) or its agronomically acceptable salts according to Table 2: Table 2 In a third embodiment of the present invention, the herbicide / safener combination according to the invention contains, in addition to at least one component (A) as defined above, preferably a compound [component B] of the general formula (I) or its agronomically acceptable salts according to Table 3:

[0031] Table 3

[0032] Particularly preferred are the herbicide / safener combinations according to the invention containing

[0033] (1) Isoxadifen-ethyl and

[0034] 2-Chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfmyl]-4-(trifluoromethyl)benzamide (compound of formula 1-4),

[0035] (2) Isoxadifen-ethyl and

[0036] 2-Chloro-N-(5-methyl-1, 3, 4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl] -4-(trifluoromethyl)benzamide (compound of formula 1-5),

[0037] (3) Cyprosulfamide and

[0038] 2-Chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfmyl]-4-(trifluoromethyl)benzamide (compound of formula 1-4),

[0039] (4) Cyprosulfamide and

[0040] 2-Chloro-N-(5-methyl-1, 3, 4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl] -4-(trifluoromethyl)benzamide (compound of formula 1-5).

[0041] The application rates of the herbicides (B) are in the range from 20 to 400 g of active ingredient per hectare (hereinafter g ai / ha), preferably 40 to 200 g ai / ha, in particular 40 to 100 g ai / ha), and those of the safeners (A) are in the range from 1 to 1000 g ai / ha, preferably from 10 to 500 g ai / ha, in particular from 20 to 200 g / ha of active ingredient. The application rates of the herbicides (B) are preferably in the range from 50 to 200 g ai / ha, and those of the safeners (A) are in the range from 20 to 200 g ai / ha.

[0042] The application rates of the herbicides (B) are further preferably in the range of 50 to 200 g ai / ha, and those of the safeners (A) in the range of 50 to 150 g ai / ha.

[0043] In a further preferred embodiment, the application rates of the herbicides (B) are more preferably in the range from 50 to 200 g ai / ha, and those of the safeners (A) are in the range from 75 to 125 g ai / ha.

[0044] Furthermore, the herbicide / safener combinations according to the invention can be used together with other active ingredients such as fungicides, insecticides, acaricides, etc., and / or plant growth regulators or adjuvants from the group of additives commonly used in crop protection, such as adjuvants and formulation aids. Their application forms, such as formulations or tank mixes, represent herbicidal compositions (compositions).

[0045] The invention therefore also relates to herbicide / safener combinations which contain additives commonly used in plant protection, such as adjuvants and formulation aids, and optionally other plant protection active ingredients.

[0046] The invention also relates to the use of or the application method using the herbicide / safener combinations according to the invention as herbicides and plant growth regulators, preferably as herbicides and plant growth regulators with a synergistically effective content of the herbicide combination contained in each case.

[0047] The ratios (A):(B) based on the weight are, depending on the effective application rates, generally in the range from 1:400 to 500:1, preferably in the range from 1:100 to 100:1, particularly preferably in the range from 1:40 to 20:1.

[0048] The ratios (A):(B) based on weight are therefore preferably in the range from 1:10 to 4:1, more preferably in the range from 1:5 to 3:1, particularly preferably in the range from 1:4 to 2:1.

[0049] In some embodiments, the proportions (A):(B) based on the weight are in the

[0050] Range from 1:2 to 2:1 or in the range from 1:2 to 1:1. The quantities specified are application rates (g ai / ha = grams of active ingredient per hectare) and thus also define the proportions in a co-formulation, a pre-mix, a tank mix, or a sequential application of the combined active ingredients.

[0051] The herbicide / safener combinations according to the invention are preferably suitable for controlling unwanted plant growth in economically important crops such as wheat (durum and soft wheat), maize, soybeans, sugar beet, sugar cane, cotton, rice, beans (such as, for example, bush beans and horse beans), flax, barley, oats, rye, triticale, potatoes and millet (sorghum), in particular maize and sugar cane.

[0052] For use, the herbicide / safener combinations according to the invention can be applied jointly or separately to the plants (e.g. harmful plants such as monocotyledonous or dicotyledonous weeds or undesirable crop plants), the seed (e.g. grains, seeds or vegetative propagating organs such as tubers or shoot parts with buds) or the area on which the plants grow (e.g. the cultivated area).

[0053] The herbicide / safener combinations can be applied pre-sowing (possibly also by incorporation into the soil), pre-emergence, or post-emergence. Application is preferably carried out using the early post-sowing pre-emergence method or post-emergence against weeds that have not yet emerged or have already emerged. The application can also be integrated into weed management systems with divided multiple applications (sequential applications).

[0054] In detail, some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the herbicide / safener combinations according to the invention are mentioned by way of example, without the mention being intended to imply a restriction to specific species.

[0055] On the side of the monocotyledonous weed species, for example Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Cynodon, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Imperata, Ischaemum, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum, Sphenoclea and Cyperus species are included in the annual group.

[0056] In the case of dicotyledonous weeds, the spectrum of action extends to species such as Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erodium, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Geranium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindemia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

[0057] If the herbicide / safener combinations according to the invention are applied to the soil surface before germination, the emergence of weed seedlings is either completely prevented or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.

[0058] When the herbicide / safener combination is applied post-emergence to the green parts of the plant, growth is halted after treatment, and the weeds remain at the growth stage present at the time of application or die completely after a certain period of time. This eliminates weed competition that is harmful to the crops very early and sustainably. The crops, however, are not or only slightly affected in their development by the application of the herbicide / safener combination.

[0059] The herbicide / safener combinations according to the invention are characterized by a rapid onset and long-lasting herbicidal effect. The rainfastness of the active ingredients in the combinations according to the invention is generally favorable. A particular advantage is that the effective dosages of components (A) and (B) used in the herbicide / safener combinations can be adjusted so low that their soil effect is optimally low. This not only makes their use in sensitive crops possible, but also virtually eliminates groundwater contamination.

[0060] Economically important crops for the application of the herbicide / safener combinations according to the invention are, for example, dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum and Zea.

[0061] Preferably, the herbicide / safener combinations according to the invention can also be used in transgenic

[0062] Crops are used which are resistant to growth promoters or to herbicides which inhibit essential plant enzymes, e.g. acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS), protoporphyrinogen IX oxidase (PPO), or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogous active substances.

[0063] The herbicide / safener combinations according to the invention can be present either as mixed formulations of components (A) and (B), optionally with further active ingredients, additives and / or customary formulation auxiliaries, which are then applied diluted with water in the customary manner, or as so-called tank mixes by joint dilution of the separately formulated or partially separately formulated components with water.

[0064] The herbicide / safener combinations according to the invention can be formulated in various ways, depending on the biological and / or chemical-physical parameters specified. General formulation options include, for example: wettable powders (WP), water-soluble powders (SP), emulsifiable concentrates (EC), water-soluble concentrates, aqueous solutions (SL), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, oil- or water-based dispersions, oil dispersions (ÖD), suspoemulsions, suspension concentrates (SC), oil-miscible solutions, capsule suspensions (CS), dusts (DP), seed dressings, granules for soil or broadcast application, granules (GR) in the form of micro-, spray-, lift- and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules or waxes.

[0065] The invention therefore also relates to herbicidal and plant growth regulating agents which contain the herbicide / safener combinations according to the invention.

[0066] The individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemische Technologie," Volume 7, C. Hanser Verlag Munich, 4th ed. 1986; van Valkenburg, "Pesticides Formulations," Marcel Dekker NY, 1973; K. Martens, "Spray Drying Handbook," 3rd ed. 1979, G. Goodwin Ltd. London.

[0067] The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; Hv Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY Marsden, "Solvents Guide", 2nd Ed., Interscience, NY 1963; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridegewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Ingredients", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Publishing Company, Stuttgart 1976, Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th Aull.

[0068] 1986.

[0069] On the basis of these formulations, combinations with other pesticidally active substances, such as other herbicides, fungicides, insecticides or other pesticides (e.g. acaricides, nematicides, molluscicides, rodenticides, aphicides, avicides, larvicides, ovicides, bactericides, virucides, etc.), as well as other safeners, fertilizers and / or growth regulators can also be produced, e.g. in the form of a ready-to-use formulation or as a tank mix.

[0070] Wettable powders are preparations that are evenly dispersible in water. In addition to the active ingredient, they contain a diluent or inert substance as well as ionic and / or non-ionic surfactants (wetting agents, dispersants), e.g., polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyltaurine. To produce the wettable powders, the herbicidal active ingredients are finely ground in conventional equipment such as hammer mills, fan mills, and air jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.

[0071] Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, e.g., butanol, cyclohexanone, dimethylformamide, xylene, or higher-boiling aromatics or hydrocarbons, or mixtures of organic solvents, with the addition of one or more ionic and / or non-ionic surfactants (emulsifiers). Examples of emulsifiers that can be used are: calcium alkylarylsulfonate salts such as calcium dodecylbenzenesulfonate or non-ionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, and sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan fatty acid esters.

[0072] Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

[0073] Suspension concentrates can be water- or oil-based. They can be produced, for example, by wet grinding using commercially available bead mills and, if necessary, with the addition of surfactants, such as those listed above for the other formulation types.

[0074] Emulsions, e.g. oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and, if appropriate, surfactants, such as those already listed above for the other formulation types.

[0075] Granules can be produced either by spraying the active ingredient onto adsorbent, granulated inert material or by applying active ingredient concentrates to the surface of carrier materials such as sand, kaolinite, or granulated inert material using adhesives such as polyvinyl alcohol, sodium polyacrylate, or mineral oils. Suitable active ingredients can also be granulated in the usual way for the production of fertilizer granules—if desired, mixed with fertilizers.

[0076] Water-dispersible granules are typically produced by processes such as spray drying, fluidized bed granulation, disc granulation, blending with high-speed mixers, and extrusion without solid inert material.

[0077] The agrochemical preparations generally contain 0.1 to 99% by weight (wt%), in particular 0.2 to 95% by weight, of active ingredients of components (A) and / or (B), the following concentrations being usual depending on the type of formulation:

[0078] In wettable powders, for example, the active ingredient concentration is approximately 10 to 95 wt.%, with the remainder (100 wt.%) consisting of conventional formulation ingredients. In emulsifiable concentrates, the active ingredient concentration can be approximately 1 to 90 wt.%, preferably 5 to 80 wt.%.

[0079] Dust-like formulations usually contain 5 to 20 wt.% of active ingredient, sprayable solutions contain about 0.05 to 80 wt.%, preferably 2 to 50 wt.% of active ingredient.

[0080] In granules such as dispersible granules, the active ingredient content depends partly on whether the active compound is liquid or solid and which granulation aids and fillers are used. Typically, the content for water-dispersible granules is between 1 and 95 wt.%, preferably between 10 and 80 wt.%.

[0081] In addition, the active ingredient formulations mentioned may contain the usual adhesives, wetting agents, dispersing agents, emulsifying agents, penetrating agents, preservatives, antifreeze agents and solvents, fillers, colorants and carriers, defoamers, evaporation inhibitors and agents that influence the pH value or viscosity.

[0082] For application, the formulations available in commercial form are diluted, if necessary, in the usual way, e.g., with water in the case of wettable powders, emulsifiable concentrates, dispersions, and water-dispersible granules. Dust-like preparations, soil or broadcast granules, and sprayable solutions are not usually diluted with other inert substances prior to application. The herbicide / safener combinations according to the invention can be applied to the plants, plant parts, plant seeds, or the cultivated area (arable soil), preferably to the green plants and plant parts and, if appropriate, also to the arable soil.

[0083] One possible application is the joint application of the herbicide / safener combinations in the form of tank mixtures, whereby the optimally formulated concentrated formulations of the individual active ingredients are mixed together with water in the tank and the resulting spray mixture is applied.

[0084] A joint formulation of the herbicide / safener combinations according to the invention has the advantage of easier application because the amounts of the components are already adjusted in the correct ratio. Furthermore, the adjuvants can be optimally matched to each other in the formulation, whereas a tank mix of different formulations can result in undesirable combinations of adjuvants.

[0085] A. General formulation examples a) A dust is obtained by mixing 10 parts by weight (= parts by weight) of a component (A) or (B) or of a component mixture (A) + (B) (and optionally further components) and / or their salts and 90 parts by weight of talc as an inert substance and grinding the mixture in a hammer mill. b) A wettable powder which is easily dispersible in water is obtained by mixing 25 parts by weight of a component or of a component mixture, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurine as wetting and dispersing agent and grinding the mixture in a pin mill. c) A dispersion concentrate which is easily dispersible in water is obtained by mixing 20 parts by weight of a component or a mixture of components with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight.-parts of paraffinic mineral oil (boiling range, for example, approx. 255 to 277 °C) and ground in a ball mill to a fineness of less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of a component or a mixture of components, 75 parts by weight of cyclohexanone as solvent, and 10 parts by weight of ethoxylated nonylphenol as emulsifier. e) Water-dispersible granules are obtained by

[0086] 75 parts by weight of a component of a component mixture,

[0087] 10 parts by weight of calcium ligninsulfonate,

[0088] 5 parts by weight of sodium lauryl sulfate,

[0089] 3 parts by weight of polyvinyl alcohol and

[0090] 7 parts by weight of kaolin are mixed, ground on a pin mill and the powder is granulated in a fluidized bed by spraying water as a granulating liquid.

[0091] 1) A water-dispersible granulate is also obtained by

[0092] 25 parts by weight of a component of a component mixture,

[0093] 5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium,

[0094] 2 parts by weight of oleoylmethyltaurine sodium,

[0095] 1 part by weight polyvinyl alcohol,

[0096] 17 parts by weight of calcium carbonate and

[0097] 50 parts by weight of water are homogenized and pre-crushed on a colloid mill, then ground on a bead mill and the resulting suspension is atomized and dried in a spray tower using a single-component nozzle.

[0098] BIOLOGICAL EXAMPLES

[0099] Effect of selected herbicide / safener combinations according to the invention using the example of pest reduction on maize:

[0100] The seeds of the crops to be treated were placed in soil in plastic pots (approximately 8 cm in diameter), covered with soil, and grown in a greenhouse under favorable conditions for germination and growth. The test plants were treated at the early leaf stage (BBCH11 - BBCH12; the first and second leaves had unfolded, respectively).

[0101] The test compounds were formulated as wettable powders (WPs), which were then suspended in water. The herbicide-safener mixtures indicated were prepared from these suspensions.

[0102] The spray application to the above-ground parts of the plants was carried out according to the respective

[0103] Test doses were sprayed onto the above-ground parts of the plants with a water application rate corresponding to 300 l / ha and with the addition of a commercially available wetting agent (Mero®, based on rapeseed oil methyl ester, Bayer) (1.5 l / ha) and ammonium sulfate (2 kg / ha).

[0104] After application, the plants were cultivated in a greenhouse under favorable growth conditions. Ten days after application, a visual assessment of herbicide damage was performed. The appearance of the treated plants was compared with that of the untreated controls, and the damage to the treated plants was rated on a scale of 0% to 100%.

[0105] Examples:

[0106] 0% = no noticeable effect compared to the untreated plant

[0107] 20% = the treated plant population is compared to the untreated

[0108] Control population 20% damaged (e.g. growth height, leaf damage, etc.) 100% = treated plants completely damaged or dead.

[0109] The trials were conducted with commercially available maize seeds of the variety DKC3450 and the variety Johaninio.

[0110] In Table Bl below, the recorded damage values ​​are presented as averages from two replicates (= two pots per treatment). The following values ​​were also calculated from these:

[0111] Absolute damage reduction = damage value of herbicide control without safener - damage value of the combination of herbicide with safener

[0112] Relative damage reduction in relation to the damage value of the herbicide control = (Absolute damage reduction * 100) / Damage value of the herbicide control without safener

[0113] In a direct comparison of the two herbicidal compounds 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(RS)-methylsulfinyl]-4-(trifluoromethyl)benzamide (compound Al-14 from WO 2015 / 049225) and 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(trifluoromethyl)benzamide (compound of formula 1-5, known from WO 2022 / 189495), clear differences in crop plant tolerance in maize are observed.

[0114] In the herbicide / safener combinations containing 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(trifluoromethyl)benzamide (compound of formula 1-5, known from WO 2022 / 189495), a more significant effectiveness of the safener used was observed both with regard to the absolute reduction in damage and with regard to the relative reduction in damage, i.e. a significantly increased crop tolerance due to the use of the safener compared to the analogous experiments with the corresponding racemic 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(RS)-methylsulfinyl]-4-(trifluoromethyl)benzamide (compound Al-14 from WO 2015 / 049225).

[0115] Tables B1-B4 below present the results of the trials with the maize variety DKC3450. The herbicide damage was assessed 10 days after application of the respective herbicide alone or in combination with the safener cyprosulfamide.

[0116] Tables B5-B8 below present the results of trials with the maize variety Johaninio. Herbicide damage was assessed 10 days after application of the respective herbicide alone or in combination with the safener isoxadifen-ethyl.

[0117] The damage caused by the safeners cyprosulfamide and isoxadifen-ethyl to the maize varieties tested was negligible at the application rates of these safeners, ie the safeners alone caused a damage of 0% and practically 0%, respectively.

[0118] Table Bl: Maize variety DKC3450 - Assessment of herbicide damage 10 days after application

[0119] Table B2: Maize variety DKC3450 - Assessment of herbicide damage 10 days after application

[0120] Table B3: Maize variety DKC3450 - Assessment of herbicide damage 10 days after application

[0121] Table B4: Maize variety DKC3450 - Assessment of herbicide damage 10 days after application

[0122] Table B5: Maize variety Johaninio - Assessment of herbicide damage 10 days after application

[0123] Table B6: Maize variety Johaninio - Assessment of herbicide damage 10 days after application

[0124] Table B7: Maize variety Johaninio - Assessment of herbicide damage 10 days after application

[0125] Table B8: Maize variety Johaninio - Assessment of herbicide damage 10 days after application

[0126] Embodiments of the present invention are described below.

[0127] Form 1 relates to a safener / herbicide combination containing

[0128] (A) one or more components (A) active as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and

[0129] (B) one or more herbicidally active compounds of formula (I) as component (B), wherein

[0130] R is hydrogen or methyl,

[0131] X means CI or methyl,

[0132] R' means methyl or c-Pr,

[0133] Z represents CF3 or CHF2, and wherein the compounds of formula (I) have the absolute configuration indicated above.

[0134] Embodiment 2 relates to the safener / herbicide combination according to embodiment 1 containing

[0135] (A) one or more safener active components (A) selected from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and (B) one or more herbicidally active compounds of the formulas (1-1) to (1-16) as component (B), Embodiment 3 relates to the safener / herbicide combination according to embodiment 1 or 2 comprising (A) one or more components (A) active as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and (B) one or more herbicidally active compounds of the formulas (1-1) to (1-5) as

[0136] Component (B), Embodiment 4 relates to the safener / herbicide combination according to one of embodiments 1 to 3 comprising (A) one or more components (A) acting as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and

[0137] (B) one or more herbicidally active compounds of formulas (1-4) or (1-5) as component (B),

[0138] Embodiment 5 relates to the safener / herbicide combination according to one of embodiments 1 to 3 containing

[0139] (1) Isoxadifen-ethyl and

[0140] 2-Chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfmyl]-4-(trifluoromethyl)benzamide (compound of formula 1-4), or

[0141] (2) Isoxadifen-ethyl and

[0142] 2-Chloro-N-(5-methyl- 1, 3, 4-oxadiazol-2-yl)-3-[(S)-m ethylsulfinyl] -4-(trifluoromethyl)benzamide (compound of formula 1-5), or

[0143] (3) Cyprosulfamide and

[0144] 2-Chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfmyl]-4-(trifluoromethyl)benzamide (compound of formula 1-4), or

[0145] (4) Cyprosulfamide and

[0146] 2-Chloro-N-(5-methyl-1, 3, 4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl] -4-(trifluoromethyl)benzamide (compound of formula 1-5).

[0147] Embodiment 6 relates to the safener / herbicide combination according to one of embodiments 1 to 5, further comprising one or more additives customary in plant protection, preferably selected from the group of adjuvants and formulation aids.

[0148] Embodiment 7 relates to the safener / herbicide combination according to any one of embodiments 1 to 6, wherein the herbicides (B) are the only herbicidal active ingredients in the herbicide / safener combination.

[0149] Embodiment 8 relates to the safener / herbicide combination according to any one of embodiments 1 to 6, wherein the safeners (A) and the herbicides (B) are the only safeners and the only herbicidally active ingredients in the herbicide / safener combination. Embodiment 9 relates to the safener / herbicide combination according to any one of embodiments 1 to 8, wherein the compound of formula (I) is present as component (B), which has the absolute configuration indicated in formula (I), in an amount of at least 80 wt. %, based on the total amount of the two enantiomers.

[0150] Embodiment 10 relates to the safener / herbicide combination according to any one of embodiments 1 to 8, wherein the compound of formula (I) is present as component (B), which has the absolute configuration indicated in formula (I), in an amount of at least 85% by weight, based on the total amount of the two enantiomers.

[0151] Embodiment 11 relates to the safener / herbicide combination according to any one of embodiments 1 to 8, wherein the compound of formula (I) is present as component (B), which has the absolute configuration indicated in formula (I), in an amount of at least 90% by weight, based on the total amount of the two enantiomers.

[0152] Embodiment 12 relates to the safener / herbicide combination according to any one of embodiments 1 to 8, wherein the compound of formula (I) is present as component (B), which has the absolute configuration indicated in formula (I), in an amount of at least 95% by weight, based on the total amount of the two enantiomers.

[0153] Embodiment 13 relates to the safener / herbicide combination according to any one of embodiments 1 to 12, wherein the ratios (A):(B) by weight are in the range from 1:400 to 500:1.

[0154] Embodiment 14 relates to the safener / herbicide combination according to any one of embodiments 1 to 13, wherein the ratios (A):(B) by weight are in the range from 1:100 to 100:1.

[0155] Embodiment 15 relates to the safener / herbicide combination according to any one of embodiments 1 to 14, wherein the ratios (A):(B) by weight are in the range from 1:40 to 20:1.

[0156] Embodiment 16 relates to the safener / herbicide combination according to any one of embodiments 1 to 15, wherein the ratios (A):(B) by weight are in the range from 1:10 to 4:1.

[0157] Embodiment 17 relates to the safener / herbicide combination according to one of embodiments 1 to 16, wherein the ratios (A):(B) by weight are in the range from 1:5 to 3:1.

[0158] Embodiment 18 relates to the safener / herbicide combination according to any one of embodiments 1 to 17, wherein the ratios (A):(B) by weight are in the range from 1:4 to 2:1.

[0159] Embodiment 19 relates to the safener / herbicide combination according to one of embodiments 1 to 18, wherein the ratios (A):(B) by weight are in the range from 1:2 to 2:1.

[0160] Embodiment 20 relates to the safener / herbicide combination according to one of embodiments 1 to 19, wherein the ratios (A) : (B) by weight are in the range from 1 : 2 to 1 : 1.

[0161] Embodiment 21 relates to a method for protecting crop plants from phytotoxic side effects of a herbicide (B), characterized in that an effective amount of a safener (A) is applied to the plants, plant parts, plant seeds or the cultivation area before, after or simultaneously with the herbicide (B), wherein the combination of herbicide (B) and safener (A) is defined according to one of embodiments 1 to 20.

[0162] Embodiment 22 relates to a method according to embodiment 21, characterized in that the crops are maize or sugar cane.

[0163] Embodiment 23 relates to a method according to embodiment 21, characterized in that the crops are maize.

[0164] Embodiment 24 relates to a method according to one of embodiments 21 to 23, characterized in that the herbicides (B) are applied at an application rate of 20 to 400 g ai / ha.

[0165] Embodiment 25 relates to a method according to one of embodiments 21 to 23, characterized in that the herbicides (B) are applied at an application rate of 40 to 200 g ai / ha.

[0166] Embodiment 26 relates to a method according to one of embodiments 21 to 23, characterized in that the herbicides (B) are applied at an application rate of 40 to 100 g ai / ha.

[0167] Embodiment 27 relates to a method according to one of embodiments 21 to 26, characterized in that the safeners (A) are applied at an application rate of 1 to 1000 g ai / ha.

[0168] Embodiment 28 relates to a method according to any one of embodiments 21 to 26, characterized in that the safeners (A) are applied at an application rate of 10 to 500 g ai / ha. 29 relates to a method according to any one of embodiments 21 to 26, characterized in that the safeners (A) are applied at an application rate of 20 to 200 g ai / ha. relates to a method according to one of embodiments 21 to 29, characterized in that the application rates of the herbicides (B) are in the range from 50 to 200 g ai / ha, and those of the safeners (A) are in the range from 20 to 200 g ai / ha. relates to a method according to one of embodiments 21 to 29, characterized in that the application rates of the herbicides (B) are in the range from 50 to 200 g ai / ha, and those of the safeners (A) are in the range from 50 to 150 g ai / ha.

[0169] 32 relates to a method according to one of embodiments 21 to 29, characterized in that the application rates of the herbicides (B) are in the range from 50 to 200 g ai / ha, and those of the safeners (A) are in the range from 75 to 125 g ai / ha.

[0170] 33 concerns the use of the safener / herbicide combination according to one of the

[0171] Forms 1 to 20 for controlling harmful plants or regulating plant growth.

Claims

Patent claims 1. Containing safener / herbicide combination (A) one or more components (A) active as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and (B) one or more herbicidally active compounds of formula (I) as component (B), wherein R is hydrogen or methyl, X means CI or methyl, R' means methyl or c-Pr, Z represents CF3 or CHF2, and wherein the compounds of formula (I) have the absolute configuration indicated above.

2. Safener / herbicide combination according to claim 1 containing (A) one or more components (A) active as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and (B) one or more herbicidally active compounds of formulas (1-1) to (1-16) as component (B), 3. Safener / herbicide combination according to one of claims 1 or 2, containing (A) one or more components (A) acting as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, Cloquintocet-mexyl, fluxofenim and furilazole, and (B) one or more herbicidally active compounds of formulas (1-1) to (1-5) as component (B), 4. Safener / herbicide combination according to one of claims 1 to 3, containing (C) one or more components (A) active as safeners from the group consisting of mefenpyr-diethyl, isoxadifen-ethyl, cyprosulfamide, fenchlorazole ethyl ester, benoxacor, cloquintocet-mexyl, fluxofenim and furilazole, and (D) one or more herbicidally active compounds of formulas (1-4) or (1-5) as component (B), 5. Safener / herbicide combination according to one of claims 1 to 3, containing (5) Isoxadifen-ethyl and 2-Chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfmyl]-4- (trifluoromethyl)benzamide (compound of formula 1-4), or (6) Isoxadifen-ethyl and 2-Chloro-N-(5-methyl- 1, 3, 4-oxadiazol-2-yl)-3-[(S)-m ethylsulfinyl] -4-(trifluoromethyl)benzamide (compound of formula 1-5), or (7) Cyprosulfamide and 2-Chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfmyl]-4- (trifluoromethyl)benzamide (compound of formula 1-4), or (8) Cyprosulfamide and 2-Chloro-N-(5-methyl-1, 3, 4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl] -4-(trifluoromethyl)benzamide (compound of formula 1-5).

6. Safener / herbicide combination according to one of claims 1 to 4, further comprising one or more additives customary in plant protection.

7. A method for protecting crop plants from phytotoxic side effects of a herbicide (B), characterized in that an effective amount of a safener (A) is applied to the plants, plant parts, plant seeds or the cultivated area before, after or simultaneously with the herbicide (B), the combination of herbicide (B) and safener (A) being defined according to any one of claims 1 to 5.

8. Process according to claim 7, characterized in that the crops are maize or sugar cane.

9. The method according to claim 7 or 8, characterized in that the herbicides (B) are applied at an application rate of 40 to 200 g / ha of active substance and in a weight ratio of safener (A) to herbicide (B) of 1:400 to 500:

1.

10. Use of the safener / herbicide combination according to any one of claims 1 to 5 for controlling weeds or regulating plant growth.

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