WO2025008812A1

WO2025008812A1 - Herbicidal mixtures comprising synthetic auxins and uses thereof

Info

Publication number: WO2025008812A1
Application number: PCT/IL2024/050641
Authority: WO
Inventors: Caroline ROYER; Pierre-Yves KERGOAT; Eti SHARON; Lorenzo CAMPIONI; Ehud YOGEV
Original assignee: Adama Agan Ltd
Current assignee: Adama Agan Ltd
Priority date: 2023-07-03
Filing date: 2024-07-02
Publication date: 2025-01-09
Anticipated expiration: 2026-01-03

Abstract

The present invention provides herbicidal mixtures comprising at least two synthetic auxin herbicides and at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; compositions comprising said herbicidal mixtures; and methods for controlling weed utilizing said compositions.

Description

HERBICIDAL MIXTURES COMPRISING SYNTHETIC AUXINS AND USES THEREOF

TECHNICAL FIELD

[0001] The present invention relates to an herbicidal mixture comprising at least two synthetic auxin herbicides and at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; and a composition comprising said herbicidal mixture and an agriculturally acceptable carrier. Said compositions are useful in controlling weed.

BACKGROUND ART

[0002] Controlling weed or undesired vegetation is important to achieve high crop yield and quality. Often, crop cultures contain various undesired weeds and although herbicides can provide protection against a spectrum of weeds, they may not have any effect on certain type of weeds that might be present in the crop culture. Therefore, there is usually a strong need for using a mixture of herbicides.

[0003] Moreover, in crop protection, it is desirable to increase the specificity and the reliability of the action of active compounds, more particularly, to make sure said active compounds effectively control the harmful plants and, at the same time, are tolerated by the useful plants in question.

[0004] Mixtures of selected herbicides have several advantages over the use of a single herbicide including (a) an increase in the spectrum of weeds controlled or an extension of weed control over a longer period of time; (b) an improvement in crop safety and reduction in crop phytotoxicity by using minimum doses of selected herbicides applied in combination rather than a single high dose of one herbicide; and (c) a delay in the appearance of resistant weed species to selected herbicides. Yet, it is often difficult to predict the activity and selectivity of a specific herbicide mixture, considering that the behavior of a specific herbicide in the mixture may be affected by the presence of the other(s), and the activity of the mixture may considerably vary depending on the chemical characters of the herbicides in the mixture, the plant species, the growth stage, and the environmental conditions. Mostly, this practice results in reduced activity of the herbicides in the mixture. [0005] WO 2021/048862 discloses a synergistic herbicidal mixture which comprises aminopyralid and quinmerac, or an ester or salt of any of the foregoing, or a combination thereof, for controlling undesired vegetation.

[0006] EP 2 296 480 Bl covers herbicidal compositions comprising aminopyralid and an additional herbicide such as dimethenamid and metazachlor, for controlling undesired vegetation.

[0007] There is a need in the art to provide herbicidal mixtures having beneficial properties, e.g., enhanced weed control and reduced application rates.

SUMMARY OF INVENTION

[0008] In one aspect, the present invention relates to an herbicidal mixture comprising at least two synthetic auxin (auxin mimics) herbicides and at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide.

[0009] In certain embodiments, said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide.

[0010] In another aspect, the present invention relates to a composition comprising a herbicidal mixture comprising at least two synthetic auxin herbicides; at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; and an agriculturally acceptable carrier.

[0011] In certain embodiments, said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide.

[0012] In a further aspect, the present invention provides a method of controlling weed comprising applying to a locus an effective amount of a composition as defined above.

[0013] In yet another aspect, the present invention provides a kit comprising two compositions, wherein either: (i) one of said compositions comprises at least two synthetic auxin herbicides and the second composition comprises at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; or (ii) one of said compositions comprises at least one first synthetic auxin herbicide and the second composition comprises at least one second synthetic auxin herbicide together with at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide.

BRIEF DESCRIPTION OF DRAWINGS

[0014] Fig. 1 shows the efficacy (% control) at 14 days after application (DAA) of the triple mixtures comprising: (i) aminopyralid, (ii) quinmerac, and (iii) either metazachlor or dimethenamid; and the double mixtures: aminopyralid + quinmerac; aminopyralid + metazachlor; and aminopyralid + dimethenamid, at several application rates, in controlling Sinapis arvensis when applied pre-emergence.

DETAILED DESCRIPTION

[0015] In one aspect, the present invention relates to an herbicidal mixture comprising at least two, i.e., two, three, four, or more, synthetic auxin (auxin mimics) herbicides and at least one, i.e., one, two, three, or more, additional herbicide(s), wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide.

[0016] Many herbicide compounds are capable of existing in discernible, chemically different forms, including, e.g., an acid form, an ester form, or a salt form. In this regard, it should be noted that each one of the herbicides having, e.g., a carboxylic acid group, mentioned throughout this specification includes any agriculturally acceptable salt or ester thereof.

[0017] Synthetic auxin herbicides (Weed Science Society of America/ Herbicide Resistance Action Committee Group 4/O) are a class of herbicides that mimic the activity of indole-3 -acetic acid (IAA), an integral plant hormone affecting cell growth, development, and tropism. Structural variation in each herbicide molecule influences binding to receptor proteins and the degradation rate within the cell. Synthetic auxins are most commonly used to control broadleaf weeds in small grain cereals, fallow, and rangeland systems, although some are used to control grass and sedge species (Todd et al., 2020).

[0018] According to the literature, the candidate mechanisms of resistance to auxin herbicides can include target site modifications (auxin receptors or auxin-specific transporters) and non-target site mechanisms such as other transporters and enzymes that metabolize synthetic auxin herbicides. Target site resistance frequently arises from mutations in the active sites of the proteins to which the herbicide normally binds, rendering the protein insensitive to certain herbicides as non -native compounds; and a major nontarget-site resistance pathway involves resistance to auxin herbicides by metabolism, either by enhanced cytochrome P450 detoxification or by loss of pro-herbicide activation (Christoffoleti et al., 2015).

[0019] In certain embodiments, each one of the at least two synthetic auxin herbicides comprised within the mixture of the present invention is selected from a pyridine carboxylate, a pyridyloxy carboxylate, a benzoate, a quinoline carboxylate, a phenoxy carboxylate, aminocyclopyrachlor, and benazolin-ethyl.

[0020] Non-limiting examples of pyridine carboxylates include aminopyralid, clopyralid, halauxifen, florpyrauxifen, and picloram; non-limiting examples of pyridyloxy carboxylates include fluroxypyr and triclopyr; non-limiting examples of benzoates include chloramben and dicamba; non-limiting examples of quinoline carboxylates include quinclorac and quinmerac; and non-limiting examples of phenoxy carboxylates include dichlorprop, MCPA, MCPB, mecoprop, 2,4,5-T, 2,4-D, 2,4-DB, and clomeprop.

[0021] In certain embodiments, each one of the at least two synthetic auxin herbicides comprised within the mixture of the invention according to any one of the embodiments defined above is selected from a pyridine carboxylate such as aminopyralid, clopyralid, and halauxifen; and a quinoline carboxylate such as quinmerac. Particular such embodiments are those wherein said at least two synthetic auxin herbicides consist of two synthetic auxin herbicides selected from: (i) aminopyralid and quinmerac; (ii) aminopyralid and clopyralid; (iii) aminopyralid and halauxifen; (iv) quinmerac and clopyralid; and (v) quinmerac and halauxifen. More particular such embodiments are those wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac.

[0022] Very-long-chain fatty acids (VLCFAs) have more than 18 carbon atoms and fulfil essential functions in plants. VLCFAs are synthesized via sequential additions of C2 moi eties to Cl 8 fatty acids derived from fatty acid synthesis in the plastid. The elongation process occurs in the endoplasmic reticulum, and it is mediated by multiple complexes of four enzymes that catalyze sequential condensation, ketoacyl reduction, dehydration and enoyl reduction steps. VLCFAs are incorporated into major lipid pools such as triacylglycerols, waxes, phospholipids, and complex sphingolipids. For instance, phospholipids and sphingolipids are essential in cell division, polarity and differentiation, as well as being necessary in membrane trafficking and secretory pathways. VLCFAs are also important components of glycerolipids, waxes, cutin and suberin, depending on the tissue type and developmental stage, and insoluble wax -impregnated cutin (leaves) and suberin (roots) constitute an important barrier to the environment in the epidermal tissues of young seedlings.

[0023] Herbicides inhibiting the biosynthesis of VLCFAs (e.g. chloroacetamides (K3) and thiocarbamates (N)) have been used globally to control grass weed species in major crops such as com, rice, soybean, and wheat. These herbicides are applied in crop pre-emergence and provide a valuable option for controlling weed populations that have evolved stacked resistance to multiple (two or more) physiological modes of herbicide action (Busi, 2014).

[0024] In certain embodiments, the at least one additional herbicide comprised within the mixture of the invention according to any one of the embodiments above, each independently is selected from: (i) a VLCFA synthesis inhibitor such an a-chloroacetamide, an a- thioacetamide, an a-oxyacetamide, an oxirane, an isooxazoline, an azolyl-carboxamide, a benzofurane, and a thiocarbamate; and (ii) an amide-based herbicide such as napropamide, naproanilid, and diphenamid.

[0025] Non-limiting examples of a-chloroacetamides include dimethenamid, metazachlor, acetochlor, alachlor, butachlor, dimethachlor, metolachlor, pethoxamid, pretilachlor, propachlor, thenylchlor, and propisochlor; non-limiting examples of a-thioacetamides include anilofos and piperophos; non-limiting examples of a-oxyacetamides include mefenacet and flufenacet; non-limiting examples of oxiranes include indanofan and tridiphane; non-limiting examples of isooxazolines include fenoxasulfone and pyroxasulfone; non-limiting examples of azolyl-carboxamides include cafenstrole, fentrazamide, and ipfencarbazone; non-limiting examples of benzofuranes include benfuresate and ethofumesate; and non-limiting examples of thiocarbamates include thiobencarb (benthiocarb), vernolate, tri-allate, esprocarb, molinate, orbencarb, prosulfocarb, cycloate, dimepiperate, and EPTC.

[0026] In particular such embodiments, said at least one additional herbicide is at least one of metazachlor, dimethenamide, and napropamide, i.e., said at least one additional herbicide is metazachlor, dimethenamide, napropamide, or a mixture thereof. More particular such embodiments are those wherein said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide. [0027] In certain embodiments, the at least two synthetic auxin herbicides comprised within the mixture of the invention according to any one of the embodiments defined above consist of two synthetic auxin herbicides selected from: (i) aminopyralid and quinmerac; (ii) aminopyralid and clopyralid; (iii) aminopyralid and halauxifen; (iv) quinmerac and clopyralid; and (v) quinmerac and halauxifen; and said at least one additional herbicide is metazachlor, dimethenamide, napropamide, or a mixture thereof. Particular such embodiments are those wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide. More particular such embodiments are those wherein the weight ratio between aminopyralid and quinmerac is in the range of from about 1 : 1 to about 1 : 100, e.g., from about 1 :2 to about 1 :80, from about 1 :5 to about 1 :60, from about 1: 10 to about 1 :50, or from about 1 :20 to about 1 :40. Other more particular such embodiments are those wherein the weight ratio between aminopyralid and said one additional herbicide is in the range of from about 1 :1 to about 1 :300, e.g., from about 1 :5 to about 1 :250, from about 1 : 10 to about 1 :200, from about 1 :20 to about 1 : 150, from about 1 :30 to about 1 : 120, from 1 :40 to about 1 : 100, from about 1 :50 to about 1 :90, or from about 1 :60 to about 1 :80. Still other more particular such embodiments are those wherein the weight ratio between aminopyralid and quinmerac is in the range of from about 1 : 1 to about 1 : 100, e.g., from about 1:2 to about 1:80, from about 1 :5 to about 1 :60, from about 1 : 10 to about 1 :50, or from about 1 :20 to about 1 :40; and the weight ratio between aminopyralid and said one additional herbicide is in the range of from about 1 : 1 to about 1 :300, e.g., from about 1 :5 to about 1 :250, from about 1 : 10 to about 1 :200, from about 1 :20 to about 1 :150, from about 1 :30 to about 1 :120, from 1 :40 to about 1 : 100, from about 1 :50 to about 1 :90, or from about 1 :60 to about 1 :80.

[0028] In another aspect, the present invention relates to a composition comprising: (i) an herbicidal mixture as defined herein according to any one of the embodiments above, i.e., a mixture comprising at least two synthetic auxin herbicides and at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a VLCFA synthesis inhibitor and an amide-based herbicide; and (ii) an agriculturally acceptable carrier.

[0029] The term “agriculturally acceptable carrier” as used herein refers to an inert substance which is known and accepted in the art for the formation of compositions for agricultural or horticultural use, and which facilitates the application of the active ingredients. The carrier may be in the form of a solid or a liquid.

[0030] Examples of solid carriers include, but are not limited to, mineral earths such as silica gels, silicates, talc, kaolin, sericite, attaclay, limestone, bentonite, lime, chalk, bole, mirabilite, loess, clay, dolomite, zeolite, diatomaceous earth, calcium carbonate, calcium sulfate, magnesium sulfate, magnesium oxide, sodium carbonate and bicarbonate, and sodium sulfate; ground synthetic materials; resins; waxes; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal, and nutshell meal; and cellulose powders.

[0031] Examples of liquid carriers include, but are not limited to, water; aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes; alcohols such as cyclohexanol, and decanol; ethylene glycol; polypropylene glycol; dipropropylene glycol; N,N- dimethylformamide; dimethylsulfoxide; dimethylacetamide; N-alkylpyrrolidones such as N-methyl-2-pyrrolidone; paraffins; various oils such as olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed, or coconut oil; fatty acid esters; and ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-pentanone.

[0032] In certain embodiments, the composition of the invention comprises at least two synthetic auxin herbicides; at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide, each as defined in any one of the embodiments above; an agriculturally acceptable carrier; and further comprises at least one, e.g., one, two, three, or more, agriculturally acceptable excipient(s) such as a surfactant. Particular such embodiments are those wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one of metazachlor, dimethenamide, and napropamide.

[0033] The term “agriculturally acceptable excipient” as used herein refers to an inert substance which is known and accepted in the art for the formation of compositions for agricultural or horticultural use, and that itself is not an active ingredient but is added to the formulation to improve one or more of its properties, such as stability, flowability, density, and the like. Examples of such excipients include, but are not limited to, solvents, pH modifiers (e.g., acids or bases), thickening agents (thickeners), sticking agents, surfactants, anti-oxidation agents, and anti-foaming agents. [0034] The term “surfactant” as used herein refers to any agriculturally acceptable material which imparts or improves emulsifiability, spreading, wetting, dispersibility, or other surface-modifying properties of a herbicidal formulation, and optionally stability of said formulation, e.g., by inhibiting crystal growth or avoiding particle agglomeration. Nonlimiting examples of surfactants include (i) nonionic surfactants such as fatty alcohol surfactants (e.g., cetyl alcohol), monoglyceride surfactants (e.g., glycerol monolaurate), polysorbate surfactants (e.g., Tween-20, Tween-40, Tween-60, Tween-65, Tween-80, and Tween-85), tri styrylphenol ethoxylate surfactants (e.g., Soprophor® TS/54), alkoxylated polyarylphenol phosphate esters such as an ethoxylated polyarylphenol phosphate salt, ethoxylated alkylphenol surfactants (e.g., a nonylphenol ethoxylate such as Tergitol NP- 9™), ethoxylated arylphenol surfactants, ethoxylated castor oil surfactants (e.g., Alkamuls® OR/36, Stepantex® CO-40, and Stepantex® CO-36), ethylene oxide- and propylene oxideblock copolymers (such as a (Ci-Cs)-alkyl alcohol ethylene oxide-propylene oxide copolymer), and polyvinyl alcohol-vinyl acetate copolymers; (ii) anionic surfactants such as fatty acid sulfonates (e.g., lauryl sulfonate); (iii) cationic surfactants such as quaternary ammonium surfactants (e.g., cetylpyridinium chloride and dimethyldioctadecylammonium chloride); and (iv) ampholytic surfactants such as cocamidopropyl betaine and (3-[(3- Cholamidopropyl) dimethylammonio]-l-propanesulfonate).

[0035] The compositions of the present invention may be employed or prepared in any conventional form, for example, as wettable powders (WP), emulsion concentrates (EC), microemulsion concentrates (MEC), water-soluble powders (SP), water-soluble concentrates (SL), suspoemulsion (SE), oil dispersions (OD), concentrated emulsions (BW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, capsule suspensions (CS), suspension concentrates (SC), suspension concentrates, dusts (DP), oil- miscible solutions (OL), seed-dressing products, granules (GR) in the form of microgranules, spray granules, coated granules and absorption granules, granules for soil application or broadcasting, water-soluble granules (SG), water-dispersible granules (WDG), ULV formulations, microcapsules or waxes. These individual formulation types are known in the art.

[0036] In a further aspect, the present invention relates to various agricultural uses, e.g., pre- and/or post-emergence weed control, in which a composition as defined in any one of the embodiments above is utilized. [0037] In one particular such aspect, disclosed herein is a method of controlling weed, also referred to herein as undesired vegetation, comprising applying to a locus an effective amount of a composition as defined herein, in any one of the embodiments above.

[0038] The term “locus” as used herein refers not only to areas where the weed may already be developed, but also to areas where weeds have yet to emerge, and to areas under cultivation. Locus includes the crop and propagation material of the crop (all the generative parts of the crop such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant). Examples of propagation material of the crop include seeds, tubers, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, buds and other parts of plants, including seedlings and young plants, which could be transplanted after germination or after emergence from soil. Locus also includes the area surrounding the crop and the growing media of the crop, such as soil and crop field.

[0039] In certain embodiments, the locus is a field of crop. The term “crop” (or “plant”) as used herein refers to whole plants, plant organs (e.g., leaves, stems, twigs, roots, trunks, limbs, shoots, fruits, etc.), plant cells, or plant seeds. Non-limiting examples of crops are plants of the genus Brassica, specifically Brassica napus, sunflower, com, soybean, wheat, barley, oats, chickpeas, fruit trees, nut trees, lentils, sugar beet, and grain sorghum. Yet, it should be clear that the list of crops provided herein is general, and the particular crop(s) treatable according to the method of the invention will depend on the specific herbicides comprised within the composition applied to the locus. The specific herbicides composing said composition may also affect the decision whether the composition is to be applied to the locus treated pre- or post-emergence of weeds.

[0040] Weeds that can be controlled by the method of the present invention include any weed, e.g., an annual or perennial grass or broad-leaved weed, that is sensitive to at least one of the herbicides comprised within the composition applied, i.e., to either one or more of the at least two synthetic auxin herbicides or at least one of the additional one or more herbicide(s) comprised within the composition, and thus could be controlled by either pre- or post-emergence application of said herbicide.

[0041] Non-limiting examples of weeds that can be controlled by the method of the present invention include Matricaria, Aethusa cynapium, Anthemis arvensis, Capsella bursa- pastoris, Centaurea cineraria, Centaurea cyanus, Chenopodium album, Daucus carota, Descurainia Sophia, Fumaria officinalis, Geranium dissectum, Geranium pusilium, Lamium amplexicaule, Lamium purpureum, Tripleurospermum inodorum, Mercurialis annua, Myosotis arvensis, Papaver rhoeas, Fallopia convolvulus, Senecio vulgaris, Sinapis arvensis, Solanum nigrum, Sonchus arvensis, Spergula arvensis, Sisymbrium officinale, Thlaspi arvense, Veronica arvensis, Veronica hederifolia, Viola, Papaver, Lolium, Alopecurus, Apera, Sinapis, Stellaria, Galium, Lamium, Myosotis, and Veronica.

[0042] In certain embodiments, the at least two synthetic auxin herbicides and the at least one additional herbicide, utilized according to the method of the invention according to any one of the embodiments defined above, are applied from a sole composition, e.g., in the form of a “ready mix” (“ready-for-use”) composition, which is optionally diluted with water before use.

[0043] In certain embodiments, the at least two synthetic auxin herbicides and the at least one additional herbicide, utilized according to the method of the invention according to any one of the embodiments defined above, are applied from two separate compositions (i.e., one of said compositions comprises said at least two synthetic auxin herbicides, and the second composition comprises said at least one additional herbicide), either: (i) concurrently (simultaneously), e.g., in the form of a “tank mix”, or (ii) sequentially in any order, e.g., after diluting each one said compositions with water.

[0044] In certain embodiments, the at least two synthetic auxin herbicides consist of two synthetic auxin herbicides; and one of said synthetic auxin herbicides is applied from one composition and the second synthetic auxin herbicide together with said at least one additional herbicide are applied from another composition, wherein said compositions are applied either concurrently, e.g., in the form of a “tank mix”, or sequentially in any order, e.g., after diluting each one said compositions with water.

[0045] The composition(s) applied according to the method of the invention according to any one of the embodiments defined above, each independently may be of any type known in the art, e.g., a soluble liquid, suspension concentrate, emulsifiable concentrate, or concentrated aqueous emulsion.

[0046] In certain embodiments, the composition applied according to the method of the invention according to any one of the embodiments defined above comprises: (i) two synthetic auxin herbicides, as said at least two synthetic auxin herbicides, selected from aminopyralid and quinmerac; aminopyralid and clopyralid; aminopyralid and halauxifen; quinmerac and clopyralid; and quinmerac and halauxifen; and (ii) at least one of metazachlor, dimethenamide, and napropamide, as said at least one additional herbicide. Particular such embodiments are those wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide. More particular such embodiments are those wherein aminopyralid is applied at a rate in the range of from about 1 to about 50 gram/hectare (g/ha), e.g., from about 2 to about 30 g/ha, from about 3 to about 15 g/ha, or from about 5 to 7.5 g/ha; quinmerac is applied at a rate in the range of from about 50 to about 800 g/ha, e.g., from about 75 to about 700 g/ha, from about 100 to about 600 g/ha, from about 125 to about 500 g/ha, from about 175 to about 400 g/ha, or from about 150 to 275 g/ha; and/or said one additional herbicide is applied at a rate in the range of from about 100 to about 3000 g/ha, e.g., from about 150 to about 2500 g/ha, from about 200 to about 2000 g/ha, or from about 250 to about 1125 g/ha. Still more particular such embodiments are those wherein the ratio between the application rate (g/ha) of aminopyralid and the application rate (g/ha) of quinmerac is from about 1 : 10 to about 1 : 100, e.g., from about 1 :20 to about 1 :90, or from about 1 :30 to about 1 :80, respectively; and/or the ratio between the application rate (g/ha) of aminopyralid and the application rate (g/ha) of said one additional herbicide is from about 1 :30 to about 1 :500, e.g., from about 1 :40 to about 1 :400, from about 1 :50 to about 1 :300, or from about 1 :60 to about 1 :200, respectively. [0047] In certain embodiments, the composition applied according to the method of the invention according to any one of the embodiments defined above comprises aminopyralid and quinmerac, as said at least two synthetic auxin herbicides; and metazachlor as said additional herbicide; and either (i) aminopyralid and quinmerac are applied from one composition (also referred to herein as “an aminopyralid-quinmerac-based composition") and metazachlor is applied from another composition (also referred to herein as “a metazachlor-based composition"), or (ii) aminopyralid is applied from one composition (also referred to herein as “an aminopyralid-based composition") and quinmerac together with metazachlor are applied from another composition (also referred to herein as “a quinmerac-metazachlor-based composition").

[0048] Specific such aminopyralid-quinmerac-based composition comprises aminopyralid in the form of a salt. Non-limiting examples of salts of aminopyralid include triisopropanolammonium salt (TIP A) salt and alkali metal ion salt such as potassium salt. More specific such aminopyralid-quinmerac-based compositions comprise aminopyralid in the form of a potassium salt, i.e., potassium 4-amino-3,6-dichloropyridine-2-carboxylate; and quinmerac in the form of a free acid, i.e., 7-chloro-3-methylquinoline-8-carboxylic acid. [0049] In a further aspect, the present invention relates to a kit comprising two compositions, wherein either: (i) one of said compositions comprises at least two synthetic auxin herbicides and the second composition comprises at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; or (ii) one of said compositions comprises at least one first synthetic auxin herbicide, and the second composition comprises at least one second synthetic auxin herbicide (wherein each one of the at least one first synthetic auxin herbicide comprised within the first composition is different from each one of the at least one second synthetic auxin herbicide comprised within the second composition) together with at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide.

[0050] In certain embodiments, each one of the synthetic auxin herbicides comprised within the kit of the present invention is selected from a pyridine carboxylate, a pyridyloxy carboxylate, a benzoate, a quinoline carboxylate, a phenoxy carboxylate, aminocyclopyrachlor, and benazolin-ethyl.

[0051] Non-limiting examples of synthetic auxins include pyridine carboxylates (e.g., aminopyralid, clopyralid, halauxifen, florpyrauxifen, and picloram); pyridyloxy carboxylates (e.g., fluroxypyr and triclopyr); benzoates (e.g., chloramben and dicamba); quinoline carboxylates (e.g., quinclorac and quinmerac); phenoxy carboxylates (e.g., dichlorprop, MCPA, MCPB, mecoprop, 2,4, 5-T, 2,4-D, 2,4-DB, and clomeprop);

[0052] Non-limiting examples of VLCFA synthesis inhibitors include a-chloroacetamides (e.g., dimethenamid, metazachlor, acetochlor, alachlor, butachlor, dimethachlor, metolachlor, pethoxamid, pretilachlor, propachlor, thenylchlor, and propisochlor); a- thioacetamides (e.g., anilofos and piperophos); a-oxyacetamides (e.g., mefenacet and flufenacet); oxiranes (e.g., indanofan and tridiphane); isooxazolines (e.g., fenoxasulfone and pyroxasulfone); azolyl-carboxamides (e.g., cafenstrole, fentrazamide, and ipfencarbazone); benzofuranes (e.g., benfuresate and ethofumesate); and thiocarbamates (e.g., thiobencarb (benthiocarb), vernolate, tri-allate, esprocarb, molinate, orbencarb, prosulfocarb, cycloate, dimepiperate, and EPTC); and non-limiting examples of amide-based herbicides include napropamide, naproanilid, and diphenamid.

[0053] In certain embodiments, one of the compositions comprised within the kit of the invention comprises two synthetic auxin herbicides, as said at least two synthetic auxin herbicides, selected from: (i) aminopyralid and quinmerac; (ii) aminopyralid and clopyralid; (iii) aminopyralid and halauxifen; (iv) quinmerac and clopyralid; and (v) quinmerac and halauxifen; and the second composition comprised within the kit of the invention comprises at least one of metazachlor, dimethenamide, and napropamide, as said at least one additional herbicide. Particular such embodiments are those wherein said kit comprises an aminopyralid-quinmerac-based composition and a metazachlor-based composition, each as defined in any one of the embodiments above. More particular such embodiments are those wherein said aminopyralid-quinmerac-based composition comprises aminopyralid in the form of a salt such as triisopropanolammonium salt (TIP A) salt and alkali metal ion salt, e.g., potassium salt. Specific such aminopyralid-quinmerac-based compositions comprise aminopyralid in the form of a potassium salt, i.e., potassium 4-amino-3,6-dichloropyridine- 2-carboxylate; and quinmerac in the form of a free acid, i.e., 7-chl oro-3 -methylquinoline-8- carboxylic acid.

[0054] In certain embodiments, one of the compositions comprised within the kit of the invention comprises one first synthetic auxin herbicide; and the second composition comprised within the kit of the invention comprises one second synthetic auxin herbicide (wherein the first synthetic auxin herbicide comprised within the first composition is different from the second synthetic auxin herbicide comprised within the second composition) together with one of metazachlor, dimethenamide, and napropamide.

[0055] In particular such embodiments, the kit of the invention comprises an aminopyralidbased composition and quinmerac-metazachlor-based composition, each as defined in any one of the embodiments above. More particular such embodiments are those wherein said aminopyralid-based composition comprises aminopyralid in the form of a salt such as triisopropanolammonium salt (TIP A) salt and alkali metal ion salt, e.g., potassium salt. Still more particular such embodiments are those wherein said aminopyralid-based composition comprises aminopyralid in the form of a TIP A salt.

[0056] According to the invention, the kits of the invention may be utilized for various agricultural uses, e.g., pre- and/or post-emergence weed control, and applied according to any common practice. Recommended application methods of such kits may include the following steps: (i) filling a spraying tank with a certain amount of water, e.g., half or more of the spraying tank; (ii) adding one of the compositions comprised within the kit to the tank; (iii) adding the other composition; and (iv) adding of the remaining amount of water. To ensure thorough mixing of all the components, agitation (stirring/mixing), e.g., continuous stirring, may be required.

[0057] It should be noted that all numbers throughout this specification which refer to herbicides having a carboxylic acid group which may be present in an acid form, an ester form, or a salt form, such as ratios and application rates, are calculated on an acid equivalent base of said herbicides. The term “acid equivalent” (a.e.) refers to the amount of the acid form of an active ingredient that is calculated from the amount of a salt or ester form of that active ingredient. For example, if the acid form of an active ingredient "Z” has a molecular weight of 100 Dalton, and the salt form of Z has a molecular weight of 130 Dalton, an application of 130 g ai/ha of the Z salt would be equal to applying 100 g ae/ha of the acid form of Z: 130 g ai/ha Z salt * (100 Da Z acid / 130 Da Z salt) = 100 g ae/ha Z acid.

[0058] Unless otherwise indicated, all numbers expressing, e.g., application rates and ratios between components, used in this specification, are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification are approximations that may vary by up to plus or minus 10% depending upon the desired properties to be obtained by the present invention.

[0059] The invention will now be illustrated by the following non-limiting Examples.

EXAMPLES

Example 1. Evaluating the efficacy of mixtures comprising aminopyralid, quinmerac, and an additional herbicide selected from metazachlor and dimethenamid.

[0060] Objective. Evaluating the efficacy under greenhouse conditions of mixtures comprising aminopyralid, quinmerac, and an additional herbicide selected from metazachlor and dimethenamid, on the tested weed species applied pre-emergence.

[0061] Materials and methods. The experiment included 500 pots, 5 repetitions for a treatment including non-treated control. The weed seeds were placed in plastic pots (300 cm' ³) filled with Newe Yaar soil (57% clay, 23% silt, and 20% sand, on a dry -weight basis and 2% organic matter). Treatments were applied using a motorized laboratory sprayer equipped with an EvenSpray 8001E flat fan nozzle (Spraying Systems Co., Wheaton, IL, USA) delivering 200 L ha'¹ at 245 kPa. The plants were seeded and kept in a greenhouse throughout the experiment.

[0062] Assessments. Weed control was assessed using a visual evaluation of 0-100 percentage scale, where 0 = no effect and 100 = complete control. An un-treated control was included for each weed species.

[0063] The tested weed was Sinapis arvensis.

[0064] Mixtures preparation. The utilized formulations were as follows: (i) aminopyralid 15 + quinmerac 470 SC; (ii) metazachlor 500 SC; (iii) aminopyralid 240 SL; and (iv) DMTA-P (dimethenamid) 720, and the application rates tested were 30%, 40% and 50% from the recommended application rate of 0.2 L/Ha. The tested mixtures were: (a) aminopyralid + quinmerac; (b) aminopyralid + metazachlor: (c) aminopyralid + dimethenamid; (d) aminopyralid + quinmerac + metazachlor: and (e) aminopyralid + quinmerac + dimethenamid.

[0065] The amounts of each active ingredient as used in the experiments (in gram active ingredient per hectare; g a.i./Ha) are summarized in Table 1. Table 1

[0066] Results. The efficacy of the tested mixtures (a)-(e) 14 days after application (DAA) to Sinapis arvensis pre-emergence is shown in Figure 1. As shown, the mixtures comprising aminopyralid + quinmerac and either metazachlor or dimethenamid had superior efficacy as compared to the mixtures comprising aminopyralid + quinmerac; (b) aminopyralid + metazachlor; and (c) aminopyralid + dimethenamid.

REFERENCES

Christoffoleti P. J., Figueiredo M R. A.D., Peres L.E.P., Nissen S., Gaines, T. Auxinic herbicides, mechanisms of action, and weed resistance: A look into recent plant science advances. Scientia Agricola, 2015, 72, 356-362

Todd O.E., Figueiredo M.R., Morran S., Soni N., Preston C., Kubes M.F., Napier R., Gaines T.A. Synthetic auxin herbicides: finding the lock and key to weed resistance. Plant Science, 2020, 300, 110631

Busi R. Resistance to herbicides inhibiting the biosynthesis of very-long-chain fatty acids. Pest management science, 2014, 70, 1378-1384

Claims

1. An herbicidal mixture comprising at least two synthetic auxin herbicides and at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide.

2. The herbicidal mixture of claim 1, wherein each one of said at least two synthetic auxin herbicides is selected from a pyridine carboxylate, a pyridyloxy carboxylate, a benzoate, a quinoline carboxylate, a phenoxy carboxylate, aminocyclopyrachlor, and benazolin-ethyl.

3. The herbicidal mixture of claim 2, wherein said pyridine carboxylate is aminopyralid, clopyralid, halauxifen, florpyrauxifen, or picloram; said pyridyloxy carboxylate is fluroxypyr or triclopyr; said benzoate is chloramben or dicamba; said quinoline carboxylate is quinclorac or quinmerac; and said phenoxy carboxylate is dichlorprop, MCPA, MCPB, mecoprop, 2,4, 5-T, 2,4-D, 2,4-DB, or clomeprop.

4. The herbicidal mixture according to any one of claims 1-3, wherein each one of said at least two synthetic auxin herbicides is selected from a pyridine carboxylate and a quinoline carboxylate.

5. The herbicidal mixture of claim 4, wherein said pyridine carboxylate is aminopyralid, clopyralid, or halauxifen; and said quinoline carboxylate is quinmerac.

6. The herbicidal mixture of claim 5, wherein said at least two synthetic auxin herbicides consist of two synthetic auxin herbicides selected from aminopyralid and quinmerac; aminopyralid and clopyralid; aminopyralid and halauxifen; quinmerac and clopyralid; and quinmerac and halauxifen.

7. The herbicidal mixture of claim 6, wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac.

8. The herbicidal mixture according to any one of claims 1-7, wherein said very long chain fatty acid (VLCFA) synthesis inhibitor is an a-chloroacetamide, an a-thioacetamide, an a-oxyacetamide, an oxirane, an isooxazoline, an azolyl-carboxamide, a benzofurane, or a thiocarbamate; and said amide-based herbicide is napropamide, naproanilid, or diphenamid.

9. The herbicidal mixture of claim 8, wherein said a-chloroacetamide is dimethenamid, metazachlor, acetochlor, alachlor, butachlor, dimethachlor, metolachlor, pethoxamid, pretilachlor, propachlor, thenylchlor, or propisochlor; said a-thioacetamide is anilofos or piperophos; said a-oxyacetamide is mefenacet or flufenacet; said oxirane is indanofan or tridiphane; said isooxazoline is fenoxasulfone or pyroxasulfone; said azolyl-carboxamide is cafenstrole, fentrazamide, or ipfencarbazone; said benzofurane is benfuresate or ethofumesate; and said thiocarbamate is thiobencarb (benthiocarb), vernolate, tri-allate, esprocarb, molinate, orbencarb, prosulfocarb, cycloate, dimepiperate, or EPTC.

10. The herbicidal mixture of claim 8 or 9, wherein said very long chain fatty acid (VLCFA) synthesis inhibitor is an a-chloroacetamide selected from metazachlor and dimethenamide; and said amide-based herbicide is napropamide.

11. The herbicidal mixture of claim 10, wherein said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide.

12. The herbicidal mixture according to claim 1, wherein said at least two synthetic auxin herbicides consist of two synthetic auxin herbicides selected from aminopyralid and quinmerac; aminopyralid and clopyralid; aminopyralid and halauxifen; quinmerac and clopyralid; and quinmerac and halauxifen; and said at least one additional herbicide is at least one of metazachlor, dimethenamide, or napropamide.

13. The herbicidal mixture according to claim 12, wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide.

14. The herbicidal mixture according to claim 13, wherein the weight ratio between aminopyralid and quinmerac is in the range of from about 1 : 1 to about 1 : 100, preferably from about 1 : 10 to about 1 :50; and/or the weight ratio between aminopyralid and said one additional herbicide is in the range of from about 1 : 1 to about 1 :300, preferably from about 1 :40 to about 1 : 100.

15. A composition comprising an herbicidal mixture comprising at least two synthetic auxin herbicides; at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; and an agriculturally acceptable carrier.

16. The composition of claim 15, further comprising at least one agriculturally acceptable excipient such as a surfactant.

17. A method of controlling weed comprising applying to a locus an effective amount of a composition according to claim 15 or 16.

18. The method of claim 17, wherein said locus is a field of crop.

19. The method of claim 18, wherein said crop is selected from plants of the genus Brassica, sunflower, corn, soybean, wheat, barley, oats, chickpeas, fruit trees, nut trees, lentils, sugar beet, and grain sorghum.

20. The method of claim 17, wherein said weed is Matricaria, Aethusa cynapium, Anthemis arvensis, Capsella bursa-pastor is, Centaurea cineraria, Centaurea cyanus, Chenopodium album, Daucus carota, Descurainia Sophia, Fumaria officinalis, Geranium dissectum, Geranium pusilium, Lamium amplexicaule, Lamium purpureum, Tripleurospermum inodorum, Mercurialis annua, Myosotis arvensis, Papaver rhoeas, Fallopia convolvulus, Senecio vulgaris, Sinapis arvensis, Solanum nigrum, Sonchus arvensis, Spergula arvensis, Sisymbrium officinale, Thlaspi arvense, Veronica arvensis, Veronica hederifolia, Viola, Papaver, Lolium, Alopecurus, Apera, Sinapis, Stellaria, Galium, Lamium, Myosotis, or Veronica.

21. The method according to any one of claims 17-20, wherein:

(i) said at least two synthetic auxin herbicides and said at least one additional herbicide are applied from a sole composition;

(ii) said at least two synthetic auxin herbicides are applied from one composition and said at least one additional herbicide is applied from another composition, either concurrently or sequentially in any order; or

(iii) said at least two synthetic auxin herbicides consist of two synthetic auxin herbicides; and one of said synthetic auxin herbicides is applied from one composition and the other synthetic auxin herbicide together with said at least one additional herbicide are applied from another composition, wherein said compositions are applied either concurrently or sequentially in any order.

22. The method of claim 21, wherein each one of said compositions is a soluble liquid composition, suspension concentrate, emulsifiable concentrate, or concentrated aqueous emulsion.

23. The method according to any one of claims 17-22, wherein said at least two synthetic auxin herbicides consist of two synthetic auxin herbicides selected from aminopyralid and quinmerac; aminopyralid and clopyralid; aminopyralid and halauxifen; quinmerac and clopyralid; and quinmerac and halauxifen; and said at least one additional herbicide is at least one of metazachlor, dimethenamide, or napropamide.

24. The method of claim 23, wherein said at least two herbicides consist of aminopyralid and quinmerac; and said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide.

25. The method according to any one of claims 17-24, wherein said at least two synthetic auxin herbicides consist of aminopyralid and quinmerac; said at least one additional herbicide is metazachlor; and either (i) aminopyralid and quinmerac are applied from one composition and metazachlor is applied from another composition; or (ii) aminopyralid is applied from one composition and quinmerac together with metazachlor are applied from another composition.

26. A kit comprising two compositions, wherein either: (i) one of said compositions comprises at least two synthetic auxin herbicides and the second composition comprises at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide; or (ii) one of said compositions comprises at least one first synthetic auxin herbicide and the second composition comprises at least one second synthetic auxin herbicide and at least one additional herbicide, wherein each of said at least one additional herbicide is independently selected from a very long chain fatty acid (VLCFA) synthesis inhibitor and an amide-based herbicide.

27. The kit of claim 26, wherein: (i) said at least two herbicides consist of aminopyralid and quinmerac; (ii) said at least one additional herbicide is one additional herbicide selected from metazachlor, dimethenamide, and napropamide; (iii) said at least one first synthetic auxin herbicide is aminopyralid; and/or (iv) said at least one second synthetic auxin herbicide is quinmerac.