WO2025176774A1 - Herbicidal compositions - Google Patents

Abstract

The invention relates to herbicidal compositions that contain an N-(1,3,4-oxadiazol-2-yl)arylcarboxylic acid amide and further herbicides

Description

Herbicidal compositions

Description

The present invention relates to agrochemically active herbicidal compositions, processes for their preparation and their use for controlling weeds.

WO2015/059187 A1 discloses herbicidal compositions containing

N-(l,3,4-oxadiazol-2-yl)arylcarboxylic acid amides. Herbicidal compositions containing 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-(methylsulfmyl)-4-(trifluoromethyl)benzamide in racemic form are also described therein as Example No. Al-14.

However, these herbicidal compositions known from WO2015/059187 Al often have an unfavorable profile with regard to their biological properties, such as herbicidal activity, compatibility with crops, toxicological and ecotoxicological properties.

The object of the present invention is to provide alternative herbicidally active compositions. This object is achieved by the herbicidal compositions according to the invention described below, comprising a specific N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide.

The present invention relates to herbicidal compositions containing

(A) the compound having the absolute configuration given in formula (1-5) (component A) or its salts, as well as

(B) one or more herbicides (component B) selected from groups B1 to B4:

Bl: Fenquinotrione and agronomically acceptable salts of fenquinotrione,

B2: Epyrifenacil and agronomically acceptable salts of epyrifenacil, B3: Salts of dicamba selected from the group consisting of tetrabutylamine salt of dicamba; dimethylamine salt of dicamba; isopropylamine salt of dicamba; diglycolamine salt of dicamba; N,N-bis-(3-aminopropyl)methylamine salt of dicamba; 3-(dimethylamino)propylamine salt of dicamba; choline salt of dicamba; monoethanolamine salt of dicamba; diethanolamine salt of dicamba; triethanolamine salt of dicamba; potassium salt of dicamba; and sodium salt of dicamba,

B4: Salts of 2,4-D selected from the group consisting of 2,4-D-ammonium; 2,4-D-choline (the choline salt of 2,4-D); 2,4-D-BAPMA (N,N-bis-(3-aminopropyl)methylamine salt of 2,4-D); 2,4-D-diethylammonium; 2,4-D-dodecylammonium; 2,4-D-heptylammonium; 2,4-D-lithium; 2,4-D-sodium; 2,4-D-tetradecylammonium; 2,4-D-triethylammonium; 2,4-D-DMAPA (3-(dimethylamino)propylamine salt of 2,4-D); 2,4-D-tris(2-hydroxypropyl)ammonium; and 2,4-D-monoethanolammonium (the monoethanolamine salt of 2,4-D).

In a further embodiment, these herbicidal compositions contain one or more safeners (component C) from the group consisting of

Benoxacor (Cl), Cloquintocet-mexyl (C2), Cyprosulfamide (C3), Dichlormide (C4), Fenclorim (C5), Fenchlorazole (C6), Furilazole (C7), Isoxadifen-ethyl (C8), Mefenpyr-diethyl (C9), 4-(Dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane of CAS 71526-07-3 (CIO), and 2,2,5-trimethyl-3-(dechloroacetyl)-l,3-oxazolidine of CAS 52836-31-4 (Cl 1).

In a further embodiment, these herbicidal compositions contain one or more safeners (component C) from the group consisting of

Cloquintocet-mexyl (C2), Cyprosulfamide (C3), Isoxadifen-ethyl (C8), Mefenpyr-diethyl (C9), 4-(Dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane of CAS 71526-07-3 (CIO), and 2,2,5-Trimethyl-3-(dechloroacetyl)-l,3-oxazolidine of CAS 52836-31-4 (Cl 1).

In a further embodiment, these herbicidal compositions contain one or more safeners (component C) from the group consisting of cyprosulfamide (C3) and isoxadifen-ethyl (C8).

Components (B) and (C) are known, for example, from "The Pesticide Manual", 19th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, and from the website http://www.alanwood.net/pesticides/. Fenquinotrione (CAS name: 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-l,3-cyclohexanedione; CAS 1342891-70-6) is known, for example, from US2010/0197674 Al. Epyrifenacil (CAS name: ethyl 2-[[3-[2-chloro-5-[3,6-dihydro-3-methyl- 2,6-dioxo-4-(trifluoromethyl)-l(227)-pyrimidinyl]-4-fluorophenoxy]-2-pyridinyl]oxy]acetate; CAS 353292-31-6) is known, for example, from US 6,537,948 B1.

The following herbicides are preferred as component B:

Bl: Fenquinotrion,

B2: Epyrifenacil,

B3: Salts of dicamba selected from the group consisting of diglycolamine salt of dicamba; N,N-bis-(3-aminopropyl)methylamine salt of dicamba; 3-(dimethylamino)propylamine salt of dicamba; choline salt of dicamba; monoethanolamine salt of dicamba; and triethanolamine salt of dicamba,

B4: Salts of 2,4-D selected from the group consisting of 2,4-D-choline (the choline salt of 2,4-D); 2,4-D-BAPMA (N,N-bis-(3-aminopropyl)methylamine salt of 2,4-D); 2,4-D-DMAPA (3-(dimethylamino)propylamine salt of 2,4-D); 2,4-D-tris(2-hydroxypropyl)ammonium; and 2,4-D-monoethanolammonium (the monoethanolamine salt of 2,4-D).

The following herbicides are particularly preferred as component B:

Bl: Fenquinotrion,

B2: Epyrifenacil,

B3: Salts of dicamba selected from the group consisting of diglycolamine salt of dicamba; N,N-bis-(3-aminopropyl)methylamine salt of dicamba; 3-(dimethylamino)propylamine salt of dicamba; choline salt of dicamba; and monoethanolamine salt of dicamba,

B4: Salts of 2,4-D selected from the group consisting of 2,4-D-choline (the choline salt of 2,4-D); 2,4-D-BAPMA (N,N-bis-(3-aminopropyl)methylamine salt of 2,4-D); and 2,4-D DMAPA (3-(dimethylamino)propylamine salt of 2,4-D). The herbicidal compositions according to the invention containing as component (A) 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(trifluoromethyl)benzamide (compound of formula I-5, known from WO 2022/189495) generally showed a significantly higher herbicidal activity in direct comparison with corresponding compositions containing the racemic compound 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(RS)-methylsulfinyl]-4-(trifluoromethyl)benzamide (compound A1-14 from WO 2015/049225).

The combined use of herbicides (A) and (B) achieves performance characteristics that exceed what would be expected for their combination based on the known properties of the individual herbicides. For example, the herbicidal effects on a specific weed species exceed the expected value, as can be estimated using standard methods, e.g., according to Colby or other extrapolation methods.

A synergistic effect always occurs when the effect, in this case the herbicidal effect, of the active ingredient combination is greater than the sum of the effects of the individually applied active ingredients. The expected effect for a given combination of two active ingredients can be calculated according to S.R. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combination," Weeds 15 (1967), 20-22) (see below).

The synergistic effects therefore allow, for example, a reduction in the application rates of the individual active ingredients, a higher potency at the same application rate, the control of previously uncontrolled species of weeds (gaps), an increased residual effect, an increased long-term effect, an increased speed of action, an extension of the application period and/or a reduction in the number of necessary individual applications and - as a result for the user - economically and ecologically more advantageous weed control systems.

The herbicidal compositions according to the invention may contain additional further components, for example plant protection active ingredients of a different type and/or additives and/or formulation aids customary in plant protection, or may be used together with these.

The herbicides (A), (B) and optionally the safeners (C) can be applied in a known manner, for example jointly (for example as a co-formulation or as a tank mix) or also in quick succession (splitting), e.g. to the plants, plant parts, plant seeds or the area on which the plants are growing. It is possible, for example, to apply the individual active ingredients, the herbicidal compositions according to the invention or the herbicide-safener combination in several portions (sequential application), e.g. after pre-emergence applications, followed by post-emergence applications or after early post-emergence applications, followed by mid- or late post-emergence applications. Preference is given to joint or timely application. of the active ingredients of the respective combination. It is also possible to use the individual active ingredients or the herbicide-safener combination for seed treatment.

The application rate of component (A) in the herbicidal compositions according to the invention is preferably 0.01 to 200 g of active substance per hectare (hereinafter g a.i./ha), preferably 0.02 to 150 g a.i./ha, particularly preferably 0.05 to 120 g a.i./ha.

The application rate of component (A) in the herbicidal compositions according to the invention is preferably 0.1 to 120 g a.i./ha, preferably 0.25 to 100 g a.i./ha, particularly preferably 0.5 to 50 g a.i./ha.

The application rates of component (B) in the herbicidal compositions according to the invention are known in principle and are generally in the range from 0.1 to 2500 g a.i./ha, mostly in the range from 0.5 to 2000 g a.i./ha.

For the active ingredient of group B 1, the total application rate is preferably in the range of 0.1 to 250 g a.i./ha, preferably in the range of 1 to 150 a.i./ha, and more preferably in the range of 2 to 100 g a.i./ha.

For the active ingredient of group B2, the total application rate is preferably in the range of 0.1 to 250 g a.i./ha, preferably in the range of 1 to 150 g a.i./ha, and more preferably in the range of 2 to 100 g a.i./ha.

For the active ingredient of group B2, the total application rate is preferably in the range of 0.25 to 150 g a.i./ha, preferably in the range of 0.5 to 100 g a.i./ha, and more preferably in the range of 0.5 to 50 g a.i./ha.

For the active ingredient from group B3, the total application rate is preferably in the range of 10 to 2000 g a.i./ha, preferably in the range of 25 to 1500 g a.i./ha, and more preferably in the range of 50 to 1000 g a.i./ha.

For the active ingredient from group B4, the total application rate is preferably in the range of 10 to 2000 g a.i./ha, preferably in the range of 25 to 1500 g a.i./ha, and more preferably in the range of 50 to 1000 g a.i./ha.

The above-mentioned respective application rates of components (A) and (B) in the herbicidal compositions according to the invention result in the corresponding respective preferably, preferentially or particularly preferably used or employed weight-related quantity ratios of the two components (A) and (B) to one another.

For example, the above-mentioned respective application rates mean that in one embodiment, preferably 0.01 to 200 g a.i./ha of component (A) and 0.1 to 250 g a.i./ha of the active ingredient of group B2 are applied or used in the herbicidal compositions according to the invention.

Analogously, for example, the above-mentioned respective application rates mean that in one embodiment, preferably 0.02 to 150 g a.i./ha of component (A) and 1 to 150 g a.i./ha of the active ingredient of group B2 are applied or used in the herbicidal compositions according to the invention.

Accordingly, for example, the above-mentioned respective application rates mean that in one embodiment, particularly preferably 0.05 to 120 g a.i./ha of component (A) and 2 to 100 g a.i./ha of the active ingredient of group B2 are applied or used in the herbicidal compositions according to the invention.

For example, the above-mentioned respective application rates mean that in one embodiment, preferably 0.1 to 120 g a.i./ha of component (A) and 0.25 to 150 g a.i./ha of the active ingredient of group B2 are applied or used in the herbicidal compositions according to the invention.

Analogously, for example, the above-mentioned respective application rates mean that in one embodiment, preferably 0.25 to 100 g a.i./ha of component (A) and 0.5 to 100 g a.i./ha of the active ingredient of group B2 are applied or used in the herbicidal compositions according to the invention.

Accordingly, for example, the above-mentioned respective application rates mean that in one embodiment, particularly preferably 0.5 to 50 g a.i./ha of component (A) and 0.5 to 50 g a.i./ha of the active ingredient of group B2 are applied or used in the herbicidal compositions according to the invention.

In a preferred embodiment, the weight ratio of the total amount of component (A) to the total amount of the active ingredient of group B2 in the herbicidal compositions according to the invention is in the range from 6:1 to 1:6. In a further preferred embodiment, the weight ratio of the total amount of component (A) to the total amount of the active ingredient of group B2 in the herbicidal compositions according to the invention is in the range from 4:1 to 1:4.

In other preferred embodiments, the weight ratio of the total amount of component (A) to the total amount of the active ingredient of group B2 in the herbicidal compositions according to the invention is in the range from 2:1 to 1:2.

In other preferred embodiments, the weight ratio of the total amount of component (A) to the total amount of the active ingredient of group B2 in the herbicidal compositions according to the invention is about 1:1 or exactly 1:1.

In the mixtures according to the invention, lower application rates of the respective active ingredient are generally required within the scope of the stated application rates compared to individual applications.

When the herbicidal compositions according to the invention are used pre- and post-emergence, a very broad spectrum of harmful plants is controlled, e.g. annual and perennial mono- or dicotyledonous weeds as well as unwanted crop plants.

The herbicidal compositions according to the invention are particularly suitable for use in crops such as cereals, maize, rice, soybeans, rapeseed, sugar beet, cotton, and sugar cane, as well as for use in permanent crops, plantations, and on non-cultivated land. They are also very suitable for use in transgenic crops of maize, cereals, sugar beet, rice, cotton, and Glycine max. (e.g., RR soybeans or LL soybeans and their crosses), Phaseolus, Pisum, Vicia, and Arachis, or vegetable crops from various botanical groups such as potatoes, leeks, cabbages, carrots, tomatoes, and onions, as well as permanent and plantation crops such as seed and stone fruit, soft fruit, vines, Hevea, bananas, sugar cane, coffee, tea, citrus, nut plantations, lawns, palm crops, and forestry crops. These crops are also preferred for the application of the herbicidal compositions (A)+(B) according to the invention, particular preference being given to use in cereals (e.g. wheat, barley, rye, oats), rice, maize, millet, sugar beet, sugar cane, sunflower, rapeseed and cotton. The herbicidal compositions (A)+(B) can also be used in tolerant and non-tolerant mutant crops and tolerant and non-tolerant transgenic crops, preferably of maize, rice, cereals, rapeseed, cotton, sugar beet and soybeans, e.g. those which are resistant to imidazolinone herbicides, atrazine, glufosinate, glyphosate, 2,4 D, dicamba and herbicides from the group of hydroxyphenylpyruvate dioxygenase inhibitors, such as sulcotrione, mesotrione, tembotrione, tefuryltrione, benzobicyclone, bicyclopyrone and ketospiradox. For the purposes of the invention, a herbicidally effective amount means an amount of one or more herbicides that is capable of adversely affecting plant growth. For the purposes of the invention, an antidotally effective amount means an amount of one or more safeners that is capable of reducing the phytotoxic effect of plant protection product active ingredients (e.g., herbicides) on crop plants.

Depending on their properties, the safeners (C) optionally and preferably present in the herbicidal compositions according to the invention can also be used to pretreat the seed of the crop (e.g., for seed dressing), or introduced into the seed beds prior to sowing, or applied together with the herbicide before or after plant emergence. Pre-emergence treatment includes both the treatment of the cultivated area (including any water present on the cultivated area, e.g., in rice applications) prior to sowing and the treatment of the sown but not yet overgrown cultivated areas. Joint application with the herbicide is preferred. Tank mixes or ready-to-use formulations can be used for this purpose.

In a preferred embodiment, the seed (e.g., grains, seeds, or vegetative propagation organs such as tubers or shoots with buds) or seedlings are pretreated with the safeners (C), optionally in combination with other agrochemical active ingredients. For seed pretreatment, the active ingredients can be applied to the seed, e.g., by dressing, or the active ingredients and the seed can be added to water or other solvents, and the active ingredients can be absorbed, e.g., by deposition or diffusion in the immersion process or by swelling or pre-germination. For seed pretreatment, the young plants can be brought into contact with the safeners, optionally in combination with other agrochemical active ingredients, e.g., by spraying, dipping, or watering, and then transplanted and, if appropriate, post-treated with the herbicides (A) and (B).

Seed or seedling treatment can be carried out with the safeners (C) alone or together with other agrochemical active ingredients—such as fungicides, insecticides, or agents for plant strengthening, fertilizing, or accelerating the swelling and germination processes. After pretreatment, the safeners can be applied again before, after, or together with the herbicide of formula (1-5) (A) and the herbicides (B), possibly also in combination with other known herbicides. Pretreating the seeds or seedlings can improve the long-term efficacy of the safeners.

The present invention therefore further relates to a method for controlling undesirable plants in plant crops, which is characterized in that the components (A), (B) and optionally (C) of the herbicidal compositions according to the invention are applied to the plants (e.g. harmful plants such as mono- or dicotyledonous weeds or undesired 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), e.g. together or separately. One or more safeners (C) can be applied to the plants, the seed or the area on which the plants grow (e.g. the cultivated area) before, after or simultaneously with the herbicide of the formula (1-5) (A) and the herbicides (B). In a preferred embodiment, the safeners (C) are used for seed treatment.

Unwanted plants are defined as all plants that grow in places where they are undesirable. These can include harmful plants (e.g., monocotyledonous or dicotyledonous weeds or undesirable crops), including those that are resistant to certain herbicidal active ingredients such as glyphosate, atrazine, glufosinate, or imidazolinone herbicides.

Monocotyledonous weeds come, for example, from the genera Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera. Dicotyledonous weeds come, for example, from the genera Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindemia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum, Euphorbia.

When the herbicidal compositions according to the invention are used, a very broad spectrum of weeds is controlled, such as, for example, Amaranthus tuberculatus, Erigeron bonariensis, Polygonum convolvulus, Solanum nigrum, Sorghum halepense and Xanthium strumarium (see biological examples below).

The invention also relates to the use of the herbicidal compositions according to the invention for controlling undesirable plant growth, preferably in plant crops.

The herbicidal compositions according to the invention can be prepared by known processes, e.g. as mixed formulations of the individual components, optionally with further active ingredients, additives and/or customary formulation auxiliaries, which are then applied diluted with water in the usual way, or as so-called tank mixes by joint dilution of the separately formulated or partially separately formulated individual components with water. The staggered application (split application) of the Separately formulated or partially separately formulated individual components. It is also possible to apply the individual components or the herbicidal compositions in several portions (sequential application), e.g., after pre-emergence applications followed by post-emergence applications, or after early post-emergence applications followed by mid- or late post-emergence applications. The joint or timely application of the active ingredients of the respective combination is preferred.

The herbicidal compositions according to the invention can also be used to control harmful plants in crops of known or yet to be developed genetically modified plants.

Transgenic plants are generally characterized by particularly advantageous traits, such as resistance to certain pesticides, especially certain herbicides; resistance to plant diseases or pathogens that cause plant diseases, such as certain insects or microorganisms such as fungi, bacteria, or viruses. Other special traits affect the harvested crop in terms of quantity, quality, storability, composition, and specific ingredients. Transgenic plants with increased starch content or altered starch quality, or those with a different fatty acid composition of the harvested crop, are known. Other special traits may include tolerance or resistance to abiotic stressors, such as heat, cold, drought, salt, and ultraviolet radiation.

The herbicidal compositions according to the invention are preferably used in economically important transgenic crops of useful and ornamental plants, e.g. cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize or also crops of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetables.

Conventional approaches to producing new plants with modified traits compared to existing plants include classical breeding methods and the creation of mutants. Alternatively, new plants with modified traits can be created using genetic engineering techniques (see, for example, EP-A-0221044, EP-A-0131624). For example, several cases have been described of genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806), transgenic crop plants which are resistant to certain herbicides of the glufosinate type (cf. e.g. EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or sulfonylureas (EP-A-0257993, US-A-5013659), transgenic crop plants, for example cotton, with the ability to Bacillus thuringiensis- To produce toxins (Bt toxins) which

Making plants resistant to specific pests (EP-A-0142924, EP-A-0193259). Transgenic crops with modified fatty acid composition (WO 91/13972). Genetically modified crops with new constituents or secondary substances, e.g., new phytoalexins, that cause increased disease resistance (EPA 309862, EPA0464461). Genetically modified plants with reduced photorespiration that exhibit higher yields and greater stress tolerance (EPA 0305398).

Transgenic crops that produce pharmaceutically or diagnostically important proteins (“molecular pharming”); transgenic crops that are characterized by higher yields or better quality; transgenic crops that are characterized by a combination of, for example, the above-mentioned new traits (“gene stacking”)

Numerous molecular biological techniques for producing new transgenic plants with altered traits are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christen, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic manipulations, nucleic acid molecules can be introduced into plasmids, allowing mutagenesis or sequence modification through recombination of DNA sequences. Using standard procedures, base exchanges can be performed, partial sequences can be removed, or natural or synthetic sequences can be added. Adapters or linkers can be attached to the DNA fragments to connect them together, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker, "Genes and Clones," VCH Weinheim, 2nd ed., 1996.

The production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme that specifically cleaves transcripts of the above-mentioned gene product.

For this purpose, DNA molecules can be used that contain the entire coding sequence of a gene product, including any flanking sequences that may be present, or DNA molecules that contain only parts of the coding sequence, whereby these parts must be long enough to produce an antisense effect in the cells. It is also possible to use DNA Sequences that show a high degree of homology to the coding sequences of a gene product, but are not completely identical.

When nucleic acid molecules are expressed in plants, the synthesized protein can be localized in any compartment of the plant cell. However, to achieve localization in a specific compartment, the coding region can be linked to DNA sequences that ensure localization in a specific compartment. Such sequences are known to Bachmann (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Expression of nucleic acid molecules can also occur in the organelles of plant cells.

The transgenic plant cells can be regenerated into whole plants using known techniques. The transgenic plants can, in principle, be plants of any plant species, i.e., both monocotyledonous and dicotyledonous.

Transgenic plants are available that exhibit altered properties through overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

The compositions according to the invention can preferably be used in transgenic crops which are resistant to growth promoters, such as dicamba, or to herbicides which inhibit essential plant enzymes, e.g. acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoyl isoxazoles and analogous active ingredients.

When the compositions according to the invention are used in transgenic crops, in addition to the effects on weeds observed in other crops, effects often occur which are specific to the application in the respective transgenic crop, for example a modified or specifically expanded weed spectrum which can be controlled, modified application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influence on the growth and yield of the transgenic crops.

The invention therefore also relates to the use of the compositions according to the invention for controlling harmful plants in transgenic crops. The use of the compositions according to the invention is preferred in economically important transgenic crops of useful and ornamental plants, for example cereals (e.g. wheat, barley, rye, oats), millet, rice, cassava and maize or also crops of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable crops.

The invention therefore also relates to the use of the compositions according to the invention for controlling harmful plants in transgenic crops or crops which exhibit tolerance through selective breeding.

The herbicides (A), (B), and optionally the safeners (C) can be converted together or separately into conventional formulations, e.g., for spraying, pouring, spraying, and seed dressing applications, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active ingredients, and microencapsulations in polymeric materials. The formulations may contain the usual excipients and additives.

These formulations are prepared in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurised liquefied gases and/or solid carriers, optionally using surface-active agents, i.e. emulsifiers and/or dispersants and/or foam-forming agents.

If water is used as an extender, organic solvents can also be used as co-solvents. The following are essentially suitable liquid solvents: aromatics such as xylene, toluene, alkylnaphthalenes; chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes, or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins, e.g., petroleum fractions, mineral and vegetable oils; alcohols such as butanol or glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; strongly polar solvents such as dimethylformamide or dimethyl sulfoxide; and water.

Suitable solid carriers are: e.g. ammonium salts and natural mineral flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral flours, such as highly dispersed silica, aluminum oxide and silicates; suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and Protein hydrolysates; suitable dispersants include, for example, lignin sulphate waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic, powdered, granular, or latex-like polymers such as gum arabic, polyvinyl alcohol, and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives may include mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight.

The herbicides (A), (B) and, where appropriate, the safeners (C) can be used as such or in their formulations, also in admixture with other agrochemical active ingredients, for controlling unwanted plant growth, e.g. for weed control or for controlling unwanted crop plants, whereby, for example, ready-made formulations or tank mixes are possible.

Mixtures with other known active ingredients such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil improvers are also possible, as are additives and formulation aids commonly used in plant protection.

The herbicides (A), (B), and optionally the safeners (C) can be applied as such, in the form of their formulations, or in the application forms prepared from them by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes, and granules. Application is typically carried out by, for example, watering, spraying, or spreading.

The active ingredients can be applied to the plants, plant parts, seeds, or the cultivated area (arable soil), preferably to the seeds or green plants and plant parts, and if necessary, also to the arable soil. One possible application is the joint application of the active ingredients in the form of tank mixes, in which 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. A joint formulation of the herbicidal compositions according to the invention with active ingredients (A), (B), and optionally (C) has the advantage of easier application because the amounts of the components can already be adjusted in the optimal ratio to one another. Furthermore, the auxiliaries in the formulation can be optimally coordinated with one another.

For use, the commercially available formulations may be diluted in the usual way, e.g., with water for wettable powders, emulsifiable concentrates, dispersions, and water-dispersible granules. Dust-like preparations, soil or

Granules for spreading and sprayable solutions are usually not diluted with other inert substances before use.

Biological examples:

The abbreviations used for the pests mean:

ABUTH: Abutilon theophrasti BRAPP: Brachiaria platyphylla

CYPIR: Cyperus iria EMEAU: Emex australis

EPHHL: Euphorbia heterophylla ERIBO: Erigeron bonariensis

PHBPU: Pharbitis purpurea POLCO: Polygonum convolvulus

SETVI: Setaria viridis SOLNI: Solanum nigrum

SORHA: Sorghum halepense XANST: Xanthium strumarium

Herbicidal activity against post-emergence weeds

Seeds of monocotyledonous or dicotyledonous weeds or cultivated plants are sown in wood fiber pots in sandy loam soil, covered with soil, and grown in a greenhouse under favorable growth conditions. Two to three weeks after sowing, the test plants are treated at the single-leaf stage. The compounds according to the invention, formulated as wettable powders (WP) or emulsion concentrates (EC), are then sprayed onto the green plant parts as an aqueous suspension or emulsion at a water application rate of the equivalent of 600 to 800 l/ha with the addition of 0.2% wetting agent. After approximately three weeks of the test plants being grown in the greenhouse under optimal growth conditions, the effectiveness of the preparations is visually assessed in comparison to untreated controls (herbicidal effectiveness in percent (%): 100% effectiveness = plants are dead, 0% effectiveness = same as control plants). Numerous compounds according to the invention demonstrated very good activity against a wide range of important weeds. The following tables show examples of the postemergence herbicidal activity of the compounds according to the invention, with the herbicidal activity expressed as a percentage.

When using the herbicidal compositions according to the invention, herbicidal effects on a weed species are frequently observed that exceed the formal sum of the effects of the herbicides contained therein when applied alone. Alternatively, in some cases, it can be observed that a lower application rate of the herbicidal compositions is required to achieve the same effect on a weed species compared to the individual preparations. Such increases in activity or effectiveness, or savings in application rate, are strong indications of a synergistic effect.

If the observed effect values already exceed the formal sum of the values for the trials with single applications, then they also exceed the expected value according to Colby, which is calculated according to the following formula and is also considered an indication of synergism (cf. SR Colby; in Weeds 15 (1967) pp. 20 to 22): E = A+B - (AB/100)

This means:

A = activity of the active ingredient (A) in % at an application rate of a [g a.i./ha];

B = activity of the active ingredient (B) in % at an application rate of b [g a.i./ha];

E = expected value of the effect of the combination (A)+(B) in % for the combined

Application rate a+b [g a.i./ha].

The observed values of the experiments show an effect of the herbicidal compositions at appropriate dosages that exceeds the expected values according to Colby (E) (A).

In the following tables, the abbreviations mean the following:

E: means the expected value according to the Colby formula.

A: means the difference between the actual and the expected value after the

Colby formula.

DAT : means days after treatment.

1-5 means the chiral (S -configured) compound of the formula:

The abbreviations used for the weeds in the following tables mean:

AMATU: Amaranthus tuberculatus

ERIBO: Erigeron bonariensis

POLCO: Polygonum convolvulus

SOLNI: Solanum nigrum

SORHA: Sorghum halepense

XANST: Xanthium strumarium

Herbicidal activity against post-emergence weeds: Seeds of monocotyledonous and dicotyledonous weeds are sown in plastic pots in sandy loam soil, covered with soil, and grown in a greenhouse under favorable growth conditions for between 13 and 30 days, depending on the species. After this cultivation phase, the test plants are in the early growth stage (BBCH 10-14), at which time the treatment is carried out. For this purpose, the active ingredients are formulated as wettable powders (WP) or emulsion concentrates (EC). From these, the specified mixtures are prepared as an aqueous suspension or emulsion and sprayed onto the plants at an application rate of the equivalent of 300 l/ha, with the addition of 1.5 l/ha of wetting agent (Mero) and 2 kg/ha of ammonium sulfate. After application, the plants are further stored in the greenhouse under favorable growth conditions. The efficacy of the mixtures is determined by visual assessment compared to untreated controls (herbicidal efficacy in percent (%): 100% efficacy = plants are dead, 0% efficacy = same as control plants). Depending on the rate of symptom development, visual assessment is performed 10 and/or 21 days after application (DAT), using two replicates per species and treatment.

The following tables show the herbicidal effects of the mixtures, with the herbicidal effect given in percent as the mean value of the two respective replicates.

A direct comparison of the herbicidal compounds 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(RS)-methylsulfmyl]-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 I-5, known from WO 2022/189495) in the respective combinations investigated showed significant differences in herbicidal efficacy.

Tables 1 - 16 show the results of the direct comparison of the herbicidal activity of epyrifenacil in combination with 2-chloro-N-(5-methyl-l,3,4-oxadiazol-2-yl)-3-[(RS)-methylsulfmyl]-4-(trifluoromethyl)benzamide (compound Al-14 from WO 2015/049225) or in combination with 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).

Table 1: Herbicidal activity [%] against AMATU 10 days after application (10 DAT)

Table 2: Herbicidal activity [%] against AMATU 21 days after application (21 DAT)

Table 3: Herbicidal activity [%] against ERIBO 10 days after application (10 DAT)

Table 4: Herbicidal activity [%] against ERIBO 21 days after application (21 DAT)

Table 5: Herbicidal activity [%] against POLCO 10 days after application (10 DAT) Table 6: Herbicidal activity [%] against POLCO 21 days after application (21 DAT)

Table 7: Herbicidal activity [%] against POLCO 10 days after application (10 DAT)

Table 8: Herbicidal activity [%] against POLCO 21 days after application (21 DAT)

Table 9: Herbicidal activity [%] against SOLNI 10 days after application (10 DAT)

Table 10: Herbicidal activity [%] against SOLNI 21 days after application (21 DAT) Table 11: Herbicidal activity [%] against SORHA 10 days after application (10 DAT)

Table 12: Herbicidal activity [%] against SORHA 21 days after application (21 DAT)

Table 13: Herbicidal activity [%] against XANST 10 days after application (10 DAT)

Table 14: Herbicidal activity [%] against XANST 21 days after application (21 DAT)

Table 15: Herbicidal activity [%] against XANST 10 days after application (10 DAT) Table 16: Herbicidal activity [%] against XANST 21 days after application (21 DAT)

Claims

Patent claims 1. Herbicidal compositions containing (A) the compound having the absolute configuration given in formula (1-5) (component A) or its salts, as well as (B) one or more herbicides (component B) selected from groups B1 to B4: Bl: Fenquinotrione and agronomically acceptable salts of fenquinotrione, B2: Epyrifenacil and agronomically acceptable salts of epyrifenacil, B3: Salts of dicamba selected from the group consisting of tetrabutylamine salt of dicamba; dimethylamine salt of dicamba; isopropylamine salt of dicamba; diglycolamine salt of dicamba; N,N-bis-(3-aminopropyl)methylamine salt of dicamba; 3-(dimethylamino)propylamine salt of dicamba; choline salt of dicamba; monoethanolamine salt of dicamba; diethanolamine salt of dicamba; triethanolamine salt of dicamba; potassium salt of dicamba; and sodium salt of dicamba, B4: Salts of 2,4-D selected from the group consisting of 2,4-D-ammonium; 2,4-D-choline (the choline salt of 2,4-D); 2,4-D-BAPMA (N,N-bis-(3-aminopropyl)methylamine salt of 2,4-D); 2,4-D-diethylammonium; 2,4-D-dodecylammonium; 2,4-D-heptylammonium; 2,4-D-lithium; 2,4-D-sodium; 2,4-D-tetradecylammonium; 2,4-D-triethylammonium; 2,4-D-DMAPA (3-(dimethylamino)propylamine salt of 2,4-D); 2,4-D-tris(2-hydroxypropyl)ammonium; and 2,4-D-monoethanolammonium (the monoethanolamine salt of 2,4-D). 2. Herbicidal compositions according to claim 1, containing one or more herbicides (component B) selected from groups B1 to B4: Bl: Fenquinotrion, B2: Epyrifenacil, B3: Salts of dicamba selected from the group consisting of diglycolamine salt of dicamba; N,N-bis-(3-aminopropyl)methylamine salt of dicamba; 3-(dimethylamino)propylamine salt of dicamba; choline salt of dicamba; monoethanolamine salt of dicamba; and triethanolamine salt of dicamba, B4: Salts of 2,4-D selected from the group consisting of choline salt of 2,4-D; N,N-bis-(3-aminopropyl)methylamine salt of 2,4-D; 3-(dimethylamino)propylamine salt of 2,4-D; tris(2-hydroxypropyl)amine salt of 2,4-D; and monoethanolamine salt of 2,4-D. 3. Herbicidal compositions according to claim 1 or 2, containing one or more herbicides (component B) selected from groups B1 to B4: Bl: Fenquinotrion, B2: Epyrifenacil, B3: Salts of dicamba selected from the group consisting of diglycolamine salt of dicamba; N,N-bis-(3-aminopropyl)methylamine salt of dicamba; 3-(dimethylamino)propylamine salt of dicamba; choline salt of dicamba; and monoethanolamine salt of dicamba, B4: Salts of 2,4-D selected from the group consisting of choline salt of 2,4-D; N,N-bis-(3-aminopropyl)methylamine salt of 2,4-D; and 3-(dimethylamino)propylamine salt of 2,4-D. 4. Herbicidal compositions according to one of claims 1 to 3, additionally containing as component C one or more safeners from the group consisting of benoxacor, cloquintocet-mexyl, cyprosulfamide, dichlormid, fenclorim, fenchlorazole, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, 4-(dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane, and 2,2,5-trimethyl-3-(dechloroacetyl)-l,3-oxazolidine. 5. Herbicidal compositions according to any one of claims 1 to 4, containing the active ingredient of group B2 as the herbicide of component (B), wherein the weight ratio of the total amount of component (A) to the total amount of the active ingredient of group B2 is in the range from 6:1 to 1:6, preferably in the range from 4:1 to 1:4, in each case based on the total weight of the herbicidal compositions. 6. A method for controlling harmful plants in crops, characterized in that a herbicidally effective amount of a herbicidal composition according to one or more of claims 1 to 5 is applied to the harmful plants, plants, plant seeds or the area on which the plants grow. 7. Process according to claim 6, characterized in that the plants come from the group consisting of sugar cane, maize, wheat, rye, barley, oats, rice, sorghum, cotton and soybeans. 8. The method according to claim 6 or 7, characterized in that the plants are genetically modified.