Pyridazine mixture as a herbicidal composition

Abstract

This invention relates to compositions comprising a compound having formula (I) or an agriculturally chemically acceptable salt thereof (wherein R...). 1 The composition comprises (A) a compound (H or methyl) and at least one compound or an agrochemically acceptable salt thereof as component (B), selected from the group consisting of B-I, B-II, B-III, B-IV, B-V, B-VI, B-VII, B-VIII, and B-IX, and relates to the use of said composition in controlling or inhibiting plant growth.

Description

[0001] This invention relates to novel weed control combinations and their use in controlling or inhibiting plant growth.

[0002] According to a first aspect of the invention, a composition is provided comprising a compound having formula (I) or an agrochemically acceptable salt thereof as component (A):

[0003]

[0004] Where R 1 It is H or methyl;

[0005] And, at least one compound selected from the group consisting of, or an agrochemically acceptable salt thereof, is selected as component (B):

[0006]

[0007] In a second aspect, the present invention provides the use of the compositions of the present invention as herbicides.

[0008] In a third aspect, the present invention provides (i) methods for inhibiting plant growth and (ii) methods for controlling plants, said methods comprising applying a herbicidal amount of the composition of the present invention to the plants, parts thereof or sites thereof.

[0009] In a fourth aspect, the present invention provides a method for selectively controlling weeds and / or weeds in crops containing useful plants, the method comprising applying a herbicidal amount of the composition of the present invention to these useful plants, parts thereof, or their locations or to the cultivated area.

[0010] In a fifth aspect, the present invention provides a formulation comprising the composition of the present invention, said formulation comprising, by weight, 0.01% to 90% of an active agent, 0% to 25% of an agriculturally acceptable surfactant, and 10% to 99.9% of a solid or liquid formulation inert agent and one or more adjuvants.

[0011] In a sixth aspect, the present invention provides a concentrated composition for dilution by a user, the concentrated composition comprising the composition of the present invention, the concentrated composition comprising, by weight, from 2% to 80%, preferably between about 5% and 70% of an active agent.

[0012] When active ingredients are combined, for any given combination of active ingredients, the expected effect E follows the so-called Colby formula and can be calculated as follows (Colby, SR, “Calculating synergistic and antagonistic responses of herbicide combination”, Weeds, Vol. 15, pp. 20-22; 1967):

[0013] ppm = milligrams of active ingredient (AI) per liter

[0014] X = % effect of active ingredient (based on the first active ingredient) using p ppm.

[0015] Y = % effect of the active ingredient in q ppm as the second active ingredient.

[0016] According to Colby, using active ingredients at p+q ppm, the expected effect of active ingredient A+B is expressed by the following formula:

[0017]

[0018] If the observed effect (O) is greater than the expected effect (E), then the combined effect is superadditive, i.e., a synergistic effect exists. Mathematically, a synergistic effect corresponds to a positive value of the difference (OE). In the case of purely complementary addition of the active ingredient (expected activity), the difference (OE) is zero. A negative value of the difference (OE) indicates a loss of activity compared to the expected activity.

[0019] Compounds having formula (I) and compounds having formulas BI to B-IX are all effective herbicides.

[0020] Compounds having formula (I) are described in WO 2020 / 069057 and WO 2015 / 168010.

[0021] Compound B1 is described in US 2012 / 019055. Compound B-II is described in WO 2013 / 176282. Compound B-III is described in WO 2016 / 196593. Compound B-IV is described in WO 2010 / 126989. Compound BV is described in EP 1 122 244. Compounds B-VI and B-VII are described in US 2014 / 274695. Compounds B-VIII and B-IX are described in WO 2018 / 208582.

[0022] Therefore, the combination of the present invention utilizes any superimposed herbicidal activity, and some embodiments may even exhibit synergistic effects. This synergistic effect occurs whenever the combined effect of the active ingredients exceeds the sum of the effects of the individual components.

[0023] The combination of the present invention can also provide an expanded activity spectrum compared to the activity obtained by each individual component, and / or allow for the use of lower ratios of the individual components when used in combination compared to when used alone, in order to modulate effective herbicidal activity.

[0024] Furthermore, the compositions of the present invention can also exhibit increased crop tolerance when compared to the effects of individual components (A) or (B). This occurs when the combined effect of the active ingredients causes less damage to the beneficial crop than the effect of any single active ingredient.

[0025] The presence of one or more possible asymmetric carbon atoms in the compounds of components (A) and (B) means that the compounds can exist in chiral isomers, i.e., enantiomers or diastereomers. As a result of restricted rotation around single bonds, trans-isomers may also exist. Formulas (I) and BI to B-IX are intended to include all such possible isomers and mixtures thereof. This invention includes all such possible isomers and mixtures thereof. Similarly, the above formulas are intended to include all possible tautomers (including lactam-lactamimide tautomers and keto-enol tautomers) (where present). This invention includes all possible tautomers of the compounds. This invention includes all such possible isomers and mixtures thereof.

[0026] The compounds in the compositions of the present invention are typically provided in the form of agronomically acceptable salts, zwitterions, or salts of agronomically acceptable zwitterions. The present invention covers all such agronomically acceptable salts, zwitterions, and mixtures thereof in all proportions.

[0027] As used in this invention, suitable agronomically acceptable salts for components (A) and (B) include anions selected from, but not limited to, chlorides, bromides, iodides, fluorides, 2-naphthalenesulfonates, acetates, adipates, methanols, ethanols, propoxides, butanols, aspartates, benzenesulfonates, benzoates, bicarbonates, bisulfates, tartrates, butyl sulfates, butyl sulfonates, butyrates, camphorates, camphor sulfonates, decanoates, hexanoates, octanoates, carbonates, citrates, diphosphates, edetates, ethanedisulfonates, heptanoates, ethanedisulfonates, ethanesulfonates, ethyl sulfates, formates, fumarates, glucono-p-ethylates, gluconates, glucuronates. Glutamate, glycerol phosphate, heptadecanate, hexadecanoate, hydrogen sulfate, hydroxide, hydroxynaphthyl carboxylate, hydroxyethanesulfonate, lactate, lactobionate, laurate, malate, maleate, mandelate, methanesulfonate, dimethyl sulfonate, methyl sulfate, mucilage, myristate, naphthalene sulfonate, nitrate, nonadecanate, octadecanoate, oxalate, nonanoate, pentadecanoate, pentafluoropropionate, perchlorate, phosphate, propionate, propyl sulfate, propyl sulfonate, succinate, sulfate, tartrate, toluenesulfonate, tridecanoate, trifluoromethanesulfonate, trifluoroacetate, undecanoate, and valerate; and each of components (A) and (B) may be the same or may be different.

[0028] Suitable cations include, but are not limited to, metals, conjugate acids of amines, and organic cations, and may be the same or different for each of components (A) and (B). Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc. Examples of suitable amines include allylamine, ammonia, pentanylamine, arginine, phenethylbenzylamine, benzathine penicillin, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, dipentylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisopentylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, diacetylacetylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecanolamine, heptylamine, hexadecyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isopentylamine, isobutanolamine, isobutylamine, isopropanolamine, and isopropylamine. Lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonamine, methyloctadecylamine, methylpentadecanamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, methylpyridine, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearamide, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tri(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfonium oxide, triethylsulfonium, triethylsulfonium oxide, trimethylsulfonium, trimethylsulfonium oxide, tripropylsulfonium, and tripropylsulfonium oxide.

[0029] The herbicides of components (A) and (B) are well known in the art and can be commercially available or manufactured using methods available in the art.

[0030] Formula (I) defines compounds having formulas AI and A-II:

[0031]

[0032] Table 1 below describes specific combinations of components (A) and (B) according to the present invention.

[0033] Table 1 - Compositions of the present invention comprising a compound having formula AI or A-II as component (A) and a herbicide selected from the group consisting of compounds having formulas BI to B-IX as component (B).

[0034]

[0035]

[0036] Throughout this document, the term "composition" should be interpreted as meaning different mixtures or combinations of components (A) and (B), such as in a single "ready-to-use with water" form, in a combined spray mixture (which consists of a single formulation of a single active ingredient, such as a "tank mix"), and when these single active ingredients are used in combination in a sequential manner (i.e., one after the other, for a moderately short period of time, such as hours or days). For the purposes of this invention, the order in which components (A) and (B) are applied is not important.

[0037] As used herein, the term "herbicide" refers to a compound that controls or alters plant growth. The term "effective herbicidal dose" refers to the amount of this compound or a combination of such compounds that can produce a controlling or altering effect on plant growth. Controlling or altering effects include all deviations from natural development, such as killing, inhibiting, leaf scorching, albinism, dwarfing, etc.

[0038] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds, and seedlings, along with the established vegetation.

[0039] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0040] The term "plant propagation material" refers to all reproductive parts of a plant, such as seeds or vegetative parts like cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and other parts of the plant.

[0041] As used in this article, the term "safety agent" refers to a chemical that, when used in combination with a herbicide, reduces the undesirable effects of the herbicide on non-target organisms. For example, a safety agent protects crops from damage caused by herbicide resistance, but does not prevent the herbicide from killing weeds.

[0042] The compositions according to the invention can be used in useful plant crops including perennial and annual crops, such as berry plants, such as blackberries, blueberries, cranberries, raspberries, and strawberries; cereals, such as barley, corn, millet, oats, rice, rye, sorghum, triticale, and wheat; fiber plants, such as cotton, flax, hemp, jute, and sisal; field crops, such as sugar beets and forage beets, coffee beans, hops, mustard, rapeseed (canola), poppies, sugarcane, sunflowers, tea, and tobacco; fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears, and plums; and grasses, such as Bermuda grass, bluegrass, benjamin grass, centipede grass, yew grass, ryegrass, and sage grass. Stinging grass and zoysia grass; herbs such as basil, borage, chives, coriander, lavender, angelica, mint, oregano, parsley, rosemary, sage, and thyme; legumes such as kidney beans, lentils, peas, and soybeans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palm trees such as oil palms; ornamental plants such as flowers, shrubs, and trees; other trees such as cacao, coconut, olive, and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melons, okra, onions, peppers, potatoes, squash, rhubarb, spinach, and tomatoes; and grapevines such as grapes.

[0043] Crops should be understood as those that exist naturally, are obtained through conventional breeding methods, or are obtained through genetic engineering. These include crops that possess so-called output traits (such as improved storage stability, higher nutritional value, and improved flavor).

[0044] Crops should be understood to also include those crops that have been conferred tolerance to herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACC enzyme-inhibitors, and HPPD-inhibitors) through conventional breeding methods or through genetic engineering. Examples of crops conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods are... Summer rapeseed (canola). Examples of crops that have been conferred herbicide tolerance through genetic engineering include, for example, maize varieties resistant to glyphosate and glufosinate. and The trademark is available for purchase.

[0045] Crops should also be understood as those crops that have been genetically engineered to be resistant to harmful insects, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the boll weevil), and Bt potato (resistant to the Colorado beetle). An example of Bt corn is... The Bt 176 maize hybrid (Syngenta Seeds). Bt toxin is a protein naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073, and EP-A-427 529. Examples of transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are... Yield (corn), (cotton), (cotton), (potato), as well as Plant crops or their seed material can be both herbicide-resistant and insect-resistant (“cumulative” transgenic results). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0046] The compositions of the present invention are typically used to control a variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can be controlled typically include Alopecurus myosuroides, Avenafatua, Brachiaria plantaginea, Bromos tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perennium, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include: Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Spatholobus suberectus, Galium aparine, Ipomoea quamoclit, Kochia scoparia, Polygonum aviculare, Rapeseed simonii, Solanum nigrum, Stellaria media, Veronica persica, and Xanthium sibiricum.

[0047] In all aspects of the invention, in any particular embodiment, the weeds to be controlled and / or suppressed may be monocotyledonous or dicotyledonous weeds tolerant to or resistant to one or more other herbicides, such as HPPD inhibitor herbicides like nitrofurazone, PSII inhibitor herbicides like atrazine, or EPSPS inhibitors like glyphosate. Such weeds include, but are not limited to, resistant amaranth biotypes.

[0048] The compositions of the present invention may also be mixed with one or more other pest control agents, including herbicides, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, chemical sterilizers, chemical pheromones, insect repellents, attractants, pheromones, feeding stimulants, or other bioactive compounds different from those having formula (I) and component (B) to form a multi-component pest control agent that provides broader-spectrum agricultural protection.

[0049] Similarly, the compositions of the present invention (including those comprising one or more other biocides as described above) may further comprise one or more safeners. In particular, the following safeners are especially preferred: AD 67 (MON4660), glyphosate, quinalazine, glyphosate nitrile, propanesulfonamide, dichloropropeneamine, dicyclonon, synergist, glyphosate sulfadiazine, glyphosate nitrile, fluroxypyr, glyphosate oxychloride, furilazome, bis(oxazolyl)sulfonate, pyrazolyl glyphosate, mephenate, glyphosate nitrile, naphthalenecarboxylic anhydride (CAS RN 81-84-5), TI-35, N-isopropyl-4-(2-methoxybenzoylaminosulfonyl)-benzamide (CAS RN 221668-34-4), and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Such safeners can also be in the form of esters or salts, as mentioned in The Pesticide Manual (15th edition (BCPC), 2009). Therefore, the mention of methyl methoxyquin also applies to methoxyquin and a lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or its phosphonium salt (as disclosed in WO 02 / 34048), and the mention of ethyl methoxyquin also applies to methoxyquin, etc.

[0050] The compositions of the present invention can be applied before or after crop planting, before weeds appear (pre-emergence application) or after weeds appear (post-emergence application). When the safener is combined with the mixture of the present invention, it is preferred that the mixing ratio of the compound having formula (I) to the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0051] The safety agent and composition of the present invention can be applied simultaneously. For example, the safety agent and composition of the present invention can be applied to the site before emergence or applied to the crop after emergence. The safety agent and composition of the present invention can also be applied sequentially. For example, the safety agent can be applied as a seed treatment before sowing, and the composition of the present invention can be applied to the site before emergence or applied to the crop after emergence.

[0052] However, those skilled in the art will understand that the compositions of the present invention are particularly suitable for non-selective burn-down applications, and therefore also for controlling volunteer or escape crop plants. In this case, it is clearly unnecessary to include a safener in the compositions of the present invention.

[0053] In general, the mixing ratio (by weight) of the compound having formula (I) to the compound of component B is from 0.01:1 to 100:1, more preferably from 0.025:1 to 20:1, and even more preferably from 1:30 to 20:1. Therefore, the preferred ratio range of the preferred compositions of the present invention is given in Table 2 below.

[0054] Table 2: Exemplary ratio ranges of specific compositions of the present invention

[0055]

[0056] Those skilled in the art will understand that the most preferred A:B ratio range for any of the compositions numbered 1.001 to 1.009 and 2.001 to 2.009 described in Table 2 above is from 1:30 to 20:1, and each of the compositions numbered 1.001 to 1.009 and 2.001 to 2.009 described in Table 2 can be used in any of the following individual ratios: 1:30, 1:15, 2:15, ... 3:20, 1:6, 1:5, 1:4, 4:15, 3:10, 1:3, 5:14, 3:8, 2:5, 8:15, 3:5, 5:7, 3:4, 4:5, 1:2, 1:1, 16:15, 6:5, 4:3, 10:7, 3:2, 8:5, 5:3, 2:1, 12:5, 8:3, 20:7, 16:5, 10:3, 4:1, 8:1, 12:1, and 16:1.

[0057] When used in the compositions of the present invention, component (A) is typically applied at a ratio of 50 to 2000 g / ha, more particularly 50, 75, 100, 125, 150, 200, 250, 300, 400, 500, 750, 800, 1000, 1250, 1500, 1800, or 2000 g / ha. Such ratios of component (A) are typically used in combination with component (B) at a ratio of 5 to 2000 g / ha, and more specifically in combination with component (B) at a ratio of 5, 10, 15, 20, 25, 50, 75, 100, 125, 140, 150, 200, 250, 300, 400, 500, 750, 1000, 1250, 1500, 1800, or 2000 g / ha. The examples described herein illustrate, but are not limited, the range of application rates of components (A) and (B) that can be used in this invention.

[0058] The amount of the composition according to the invention to be applied will depend on various factors, such as the compound used; the object being treated, such as plants, soil, or seeds; the type of treatment, such as spraying, dusting, or seed dressing; or the timing of application. In agricultural practice, the application rate of the composition according to the invention depends on the type of effect desired and is typically in the range of 55 to 4000 g, and more generally between 55 and 2000 g / ha of total composition per hectare. Application is usually made by spraying, typically using a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or drenching can also be used.

[0059] The compositions of the present invention can be advantageously used in formulations in which the “active ingredient” refers to a corresponding mixture of a compound having formula (I) and a compound of component B, or, when a safener is also used, a corresponding mixture of a compound having formula (I) and a compound of component B and a safener.

[0060] Individual components of the compositions of the present invention can be used as the technically active ingredients produced. However, more typically, the compositions according to the invention can be formulated in a variety of ways using formulation adjuvants (such as carriers, solvents, and surfactants). These formulations can be in various physical forms, for example, as powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspensions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films, or in other known forms, such as those known from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. It can be diluted with, for example, water, liquid fertilizer, micronutrients, biological organisms, oil or solvents.

[0061] These formulations can be prepared, for example, by mixing the active ingredients with formulation aids to obtain compositions in the form of finely dispersed solids, particles, solutions, dispersions, or emulsions. These active ingredients can also be formulated with other aids, such as finely dispersed solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surfactants, or combinations thereof.

[0062] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredient within a porous carrier. This allows the active ingredient to be released into the environment in a controlled amount (e.g., slow release). Microcapsules typically have a diameter from 0.1 to 500 micrometers. The amount of active ingredient they contain is approximately 25% to 95% by weight of the capsule. These active ingredients can be in the form of a monolithic solid, fine particles in a solid or liquid dispersion, or in a solution-suitable form. The encapsulating membrane can contain, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, or chemically modified polymers, as well as starch xanthates, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely dispersed particles within a solid matrix of a base substance, but these microcapsules themselves are not encapsulated.

[0063] Suitable formulation aids for preparing compositions according to the invention are known in themselves. As liquid carriers, the following can be used: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butenyl carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl... Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, deca-acetate, etc. Hexadecane, hexanediol, isopentyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, isopropyl acetone, methoxypropanol, methyl isopentyl ketone, methyl isobutyl ketone, methyl lauryl ketone, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleyleneamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate Propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols with higher molecular weights, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0064] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0065] Many surfactants can be advantageously used in both solid and liquid formulations, especially those that can be diluted with a carrier before use. Surfactants can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates, such as diethanolammonium dodecyl sulfate; salts of alkyl aryl sulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / olefin oxide addition products, such as ethoxylated nonylphenol; alcohol / olefin oxide addition products, such as ethoxylated tridecyl alcohol; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates; and other substances, such as those described in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing. Corp.), Ridgewood, New Jersey (1981).

[0066] Other adjuvants that can be used in formulations for killing pests include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances that neutralize or change pH and buffer solutions, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, flow aids, lubricants, dispersants, thickeners, antifreeze agents, microbial agents, and liquid and solid fertilizers.

[0067] Formulations according to the invention may include additives comprising oils of vegetable or animal origin, mineral oils, alkyl esters of such oils, or mixtures of such oils with oil derivatives. The amount of oil additive in the composition according to the invention is typically from 0.01% to 10% of the mixture to be applied. For example, the oil additive may be added to the spray can at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or vegetable oils, such as rapeseed oil, olive oil, or sunflower oil; emulsified vegetable oils; alkyl esters of vegetable oils, such as methyl derivatives; or animal oils, such as fish oil or tallow. Preferred oil additives include C8C. 22 Alkyl esters of fatty acids, especially C 12 -C 18 Methyl derivatives of fatty acids, such as lauric acid, palmitic acid, and methyl esters of oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known in the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0068] These formulations typically contain, by weight, from 0.1% to 99%, particularly from 0.1% to 95% of compounds (A) and (B), and by weight, from 1% to 99.9% of formulation adjuvants, which preferably include from 0% to 25% by weight of surfactants. Commercial products may preferably be formulated as concentrates, while end users will typically use diluted formulations.

[0069] Application rates vary over a wide range and depend on soil properties, application method, crop species, pests to be controlled, primary climatic conditions, and other factors governed by application method, application time, and target crop. Generally, compounds can be applied at rates ranging from 1 l / ha to 2000 l / ha, particularly from 10 l / ha to 1000 l / ha.

[0070] Preferred formulations may have the following composition (wt%), wherein the term "active ingredient" refers to the total weight % of all active ingredients in the composition:

[0071] Emulsifiable concentrate :

[0072] Active ingredient: 1% to 95%, preferably 60% to 90%

[0073] Surfactant: 1% to 30%, preferably 5% to 20%

[0074] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0075] dust :

[0076] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0077] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%.

[0078] Suspension concentrate:

[0079] Active ingredient: 5% to 75%, preferably 10% to 50%

[0080] Water: 94% to 24%, preferably 88% to 30%

[0081] Surfactant: 1% to 40%, preferably 2% to 30%

[0082] wettable powder :

[0083] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0084] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0085] Solid carrier: 5% to 95%, preferably 15% to 90%

[0086] Granules:

[0087] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%.

[0088] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0089] Different aspects and embodiments of the invention will now be described in more detail by way of examples. It should be understood that modifications to the details may be made without departing from the scope of the invention.

[0090] Example

[0091] Examples of preparations

[0092] wettable powder a) b) c) Active ingredients 25％ 50％ 75％ Sodium lignosulfonate 5％ 5％ - Sodium lauryl sulfate 3％ - 5％ Sodium diisobutylnaphthalenesulfonate - 6％ 10％ Phenolic polyethylene glycol ether - 2％ - (7-8 mol of ethylene oxide) Highly dispersed silica 5％ 10％ 10％ Kaolin 62％ 27％ -

[0093] The combination is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0094] Powder for dry seed treatment a) b) c) Active ingredients 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silica 5％ 5％ - Kaolin 65％ 40％ - talc - 20

[0095] The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be used directly for seed treatment.

[0096]

[0097]

[0098] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0099] dust a) b) c) Active ingredients 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral packing - - 96％

[0100] A ready-to-use powder is obtained by mixing the mixture with a carrier and grinding the mixture in a suitable grinder. This type of powder can also be used for dry seed dressing.

[0101] Extruded granules Active ingredients 15％ Sodium lignosulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0102] Mix the combination with these additives and grind them, then wet the mixture with water.

[0103] The mixture is extruded and then dried in an air stream.

[0104] Coated granules Active ingredients 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0105] This finely ground mixture is applied evenly to kaolin moistened with polyethylene glycol in a mixer. This process yields dust-free coated granules.

[0106]

[0107]

[0108] The finely ground mixture is tightly blended with adjuvants to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension with any desired dilution. Using such dilutions, living plants along with their propagation material can be treated and protected against microbial infection by spraying, pouring, or immersion.

[0109] Flowable concentrate for seed treatment Active ingredients 40％ Propylene glycol 5％ Copolymer Butanol PO / EO 2％ Tristyrenephenol, with 10-20 moles of EO 2％ 1,2-Benzisothiazolin-3-one (in 20% aqueous solution) 0.5％ Monoazo-pigment calcium salts 5％ Silicone oil (in the form of a 75% water emulsion) 0.2％ water 45.3％

[0110] The finely ground mixture is tightly blended with adjuvants to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension with any desired dilution. Using such dilutions, living plants along with their propagation material can be treated and protected against microbial infection by spraying, pouring, or immersion.

[0111] Sustained-release capsule suspension

[0112] 28 parts of the mixture were combined with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water were added to this emulsion. The mixture was stirred until polymerization was complete. The resulting capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contained 28% of the active ingredient. The diameter of the medium capsule was 8-15 micrometers. The resulting formulation was applied to seeds as an aqueous suspension in a suitable apparatus for this purpose.

[0113] Biological examples

[0114] Sow the seeds of large foxtail grass (SETFA), barnyard grass (ECHCG), crabgrass (DIGSA), perennial ryegrass (LOLPE), large spike alfalfa (ALOMY), lambsquarters (CHEAL), bowl flower (IPOHE), chickweed (STEME), garland chrysanthemum (ABUTH), and amaranth (AMARE) in standard sterilized soil in a pot. After 8 days of cultivation under controlled conditions in a greenhouse (24°C / 19°C, day / night; 16 hours of light; no humidity control), the plants were sprayed with an aqueous spray solution at 500 l / Ha, as obtained below: The technically active ingredient was prepared in a mixture of a small amount of acetone and a solvent and emulsifier called IF50 (11.12% Emulsogen EL360™ + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50 g / L solution, which was then diluted with 0.2% Genapol XO80 (CAS No.: 9043-30-5) as a diluent to obtain the test compound at the desired final dosage.

[0115] When the active ingredients are applied as a mixture, an aqueous spray solution containing the two active ingredients is prepared as described above.

[0116] These test plants were then grown in a greenhouse under controlled conditions (24°C / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice daily. After 13 days, the test was visually assessed for percentage phytotoxicity of the plants compared to untreated control plants (where 100 = complete damage to the plant; 0 = no damage to the plant; and NC = no capture). In the randomized block design, each treatment was replicated two to four times.

[0117] Results for individual active ingredients are shown in Table B1 below, and results for combinations of the present invention are shown in Table B2 below.

[0118] Table B1 - Post-emergence control of individual compounds on weed species

[0119] Table B1.1 - Control of weed species by compound AI

[0120]

[0121] Table B1.2 - Control of weed species by compound BI

[0122]

[0123] Table B1.3 - Control of weed species by compound B-II

[0124]

[0125] Table B1.4 - Control of weed species by compound B-III

[0126]

[0127] Table B1.5 - Control of weed species by compound B-IV

[0128]

[0129] Table B1.6 - Control of weed species by compound BV

[0130]

[0131] Table B1.7 - Control of weed species by compound B-VI

[0132]

[0133] To determine whether the mixture of active ingredients has a synergistic effect on the percentage phytotoxicity of the test plants, the Colby formula was applied: SRColby (1967) "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 22, E = X + Y - (X * Y / 100), where

[0134] X = Average percentage of herbicide A when applied at a certain ratio; phytotoxicity.

[0135] Y = Average percentage of herbicide B when applied at a certain ratio; phytotoxicity.

[0136] E = The expected effect of the mixture of herbicides A and B, calculated according to the Colby formula.

[0137] Table B2 - Post-emergence herbicidal activity of the compounds of the present invention comprising a mixture of components (A) and (B) compared to the activity of individual components.

[0138] Herbicidal activity of 1.001g of the compositions in Table B2.1-Table 1

[0139] B2.1.1-SETFA

[0140] compound Application rate (g / ha) Observed Expected difference AI 2.5 13 - - BI 1.25 5 - - A-I+BI 2.5+1.25 65 17 48

[0141] B1.1.2-ECHCG

[0142]

[0143]

[0144] B2.1.3-DIGSA

[0145] compound Application rate (g / ha) Observed Expected difference AI 2.5 3 - - BI 1.25 8 - - BI 2.5 0 - - BI 5 0 - - A-I+BI 2.5+1.25 68 10 58 A-I+BI 2.5+2.5 13 3 10 A-I+BI 2.5+5 13 3 10

[0146] B2.1.4-LOLPE

[0147] compound Application rate (g / ha) Observed Expected difference AI 2.5 3 - - AI 5 28 - - BI 1.25 10 - - BI 2.5 0 - - BI 10 0 - - A-I+BI 2.5+1.25 50 12 38 A-I+BI 2.5+2.5 20 3 17 A-I+BI 5+10 40 28 12

[0148] B2.1.5-ALOMY

[0149] compound Application rate (g / ha) Observed Expected difference AI 2.5 0 - - BI 1.25 0 - - A-I+BI 2.5+1.25 58 0 58

[0150] Table B2.2-Table 1 composition 1.006 herbicidal activity B2.2.1-SETFA

[0151] compound Application rate (g / ha) Observed Expected difference AI 1.25 0 - - B-VI 1.25 0 - - A-I+B-VI 1.25+1.25 10 0 10

[0152] B2.2.2-ECHCG

[0153] compound Application rate (g / ha) actual Expected difference AI 1.25 0 - - B-VI 0.625 0 - - A-I+B-VI 1.25+0.625 10 0 10

[0154] B2.2.3-ALOMY

[0155] compound Application rate (g / ha) Observed Expected difference AI 2.5 0 - - B-VI 5 8 - - A-I+B-VI 2.5+5 18 8 10

[0156] Herbicidal activity of compositions B2.3-1-SETFA in Table 1 (1.005%)

[0157] compound Application rate (g / ha) Observed Expected difference AI 1.25 0 - - BV 0.08 0 - - A-I+BV 1.25+0.08 10 0 10

[0158] B2.3.2-DIGSA

[0159] compound Application rate (g / ha) Observed Expected difference AI 2.5 0 - - AI 0.625 1 - - BV 0.16 13 - - BV 0.08 0 - - A-I+BV 2.5+0.16 28 13 15 A-I+BV 0.625+0.08 15 1 14

[0160] B2.3.3-LOLPE

[0161] compound Application rate (g / ha) Observed Expected difference AI 2.5 1 - - AI 0.625 0 - - BV 0.16 5 - - BV 0.08 0 - - A-I+BV 2.5+0.16 28 6 22 A-I+BV 0.625+0.08 10 0 10

[0162] B2.3.4-ALOMY

[0163] compound Application rate (g / ha) Observed Expected difference AI 2.5 0 - - AI 5.0 0 - - BV 0.16 5 - - BV 0.625 55 - - A-I+BV 2.5+0.16 23 5 18 A-I+BV 5.0+0.625 65 55 10

[0164] B2.3.5-CHEAL

[0165] compound Application rate (g / ha) Observed Expected difference AI 1.25 21 - - AI 0.625 6 - - BV 0.08 8 - - A-I+BV 1.25+0.08 40 27 13 A-I+BV 0.625+0.08 43 13 30

[0166] Table B2.4-Table 1 composition 1.004 herbicidal activity B2.4.1-SETFA

[0167]

[0168]

[0169] B2.4.2-ECHCG

[0170] compound Application rate (g / ha) Observed Expected difference AI 1.25 0 - - B-IV 62.5 0 - - A-I+B-IV 1.25+62.5 18 0 18

[0171] B2.4.3-DIGSA

[0172] compound Application rate (g / ha) Observed Expected difference AI 10 8 - - B-IV 250 38 - - A-I+B-IV 10+250 53 42 10

[0173] B2.4.4-LOLPE

[0174]

[0175]

[0176] B2.4.5-ALOMY

[0177] compound Application rate (g / ha) Observed Expected difference AI 5 0 - - AI 0.625 0 - - B-IV 125 23 - - B-IV 31.25 0 - - B-IV 250 50 - - A-I+B-IV 5+125 63 23 40 A-I+B-IV 0.625+31.25 13 0 13 A-I+B-IV 5+250 63 50 13

[0178] B2.4.6-IPOHE

[0179] compound Application rate (g / ha) Observed Expected difference AI 2.5 48 - - AI 1.25 78 - - B-IV 62.5 35 - - A-I+B-IV 2.5+62.5 98 66 32 A-I+B-IV 1.25+62.5 98 85 13

[0180] B2.4.7-ABUTH

[0181] compound Application rate (g / ha) Observed Expected difference AI 5 55 - - AI 1.25 26 - - B-IV 125 13 - - A-I+B-IV 5+125 73 63 10 A-I+B-IV 1.25+125 50 36 14

[0182] B2.4.8-CHEAL

[0183] compound Application rate (g / ha) Observed Expected difference AI 5 26 - - AI 10 15 - - AI 2.5 16 - - B-IV 125 15 - - B-IV 250 20 A-I+B-IV 5+125 50 37 13 A-I+B-IV 10+250 73 32 41 A-I+B-IV 2.5+250 53 33 20

[0184] Herbicidal activity of composition B2.5-1-LOLPE in Table B2.5-Table 1 (1.003%)

[0185] compound Application rate (g / ha) Observed Expected difference AI 1.25 3 - - AI 0.625 3 - - B-III 6.25 43 - - B-III 12.5 55 - - A-I+B-III 1.25+6.25 60 44 16 A-I+B-III 0.625+12.5 68 56 12

[0186] B2.5.2-STEME

[0187] compound Application rate (g / ha) Observed Expected difference AI 1.25 58 - - B-III 12.5 14 - - A-I+B-III 1.25+12.5 80 63 17

[0188] B2.5.3-CHEAL

[0189] compound Application rate (g / ha) Observed Expected difference AI 1.25 13 - - B-III 12.5 14 - - A-I+B-III 1.25+12.5 43 25 18

[0190] Herbicidal activity of compositions B2.6-1-ECHCG in Table 1 (1.002g)

[0191] compound Application rate (g / ha) Observed Expected difference AI 2.5 8 - - AI 5 39 - - B-II 5 8 - - B-II 10 5 - - A-I+B-II 2.5+5 25 14 11 A-I+B-II 5+10 53 42 11

[0192] B2.6.2-DIGSA

[0193] compound Application rate (g / ha) Observed Expected difference AI 5 21 - - AI 2.5 3 - - AI 1.25 0 - - B-II 2.5 0 - - B-II 5 10 - - B-II 10 3 - - A-I+B-II 5+2.5 38 21 17 A-I+B-II 2.5+2.5 20 3 17 A-I+B-II 5+5 43 29 14 A-I+B-II 1.25+2.5 10 0 10 A-I+B-II 2.5+5 33 12 21 A-I+B-II 5+10 53 23 30

[0194] B2.6.3-LOLPE

[0195]

[0196]

[0197] B2.6.4-ABUTH

[0198] compound Application rate (g / ha) Observed Expected difference AI 1.25 5 - - AI 2.5 21 - - AI 0.625 6 - - B-II 0.625 0 - - B-II 1.25 40 - - B-II 2.5 43 - - A-I+B-II 1.25+0.625 38 5 33 A-I+B-II 2.5+1.25 65 53 12 A-I+B-II 0.625+0.625 28 6 22 A-I+B-II 2.5+2.5 70 55 15

[0199] B2.6.5-CHEAL

[0200] compound Application rate (g / ha) Observed Expected difference AI 2.5 13 - - AI 1.25 1 - - B-II 1.25 15 - - B-II 2.5 30 - - A-I+B-II 2.5+1.25 53 26 27 A-I+B-II 2.5+2.5 53 39 14 A-I+B-II 1.25+2.5 43 31 12

[0201] B2.6.6-AMARE

[0202] compound Application rate (g / ha) Observed Expected difference AI 1.25 44 - - B-II 0.625 0 - - B-II 1.25 13 - - B-II 2.5 25 - - A-I+B-II 1.25+0.625 60 44 16 A-I+B-II 1.25+1.25 63 51 12 A-I+B-II 1.25+2.5 73 58 15

[0203] B2.6.7-STEME

[0204] compound Application rate (g / ha) Observed Expected difference AI 1.25 64 - - AI 2.5 66 - - AI 0.625 34 - - B-II 0.625 0 - - B-II 1.25 10 - - A-I+B-II 1.25+0.625 75 64 11 A-I+B-II 2.5+1.25 89 70 19 A-I+B-II 0.625+0.625 55 34 21 A-I+B-II 1.25+1.25 78 67 11

Claims

1. A composition comprising a compound having formula (I) or an agrochemically acceptable salt thereof as component (A): Where R 1 It is H or methyl; And at least one compound selected from the group consisting of, or an agriculturally chemically acceptable salt thereof, as component (B):

2. The composition according to claim 1, wherein, The weight ratio of component (A) to component (B) ranges from 0.01:1 to 100:

1.

3. The composition according to claim 1, wherein, The weight ratio of component (A) to component (B) ranges from 0.025:1 to 20:

1.

4. The composition according to any one of claims 1 to 3, wherein, The weight ratio of component (A) to component (B) ranges from 1:30 to 16:

1.

5. An agricultural chemical composition comprising a herbicidal amount of the composition as defined in any one of claims 1 to 4, wherein component (A) is applied at a ratio of 50 to 2000 g / ha to component B at a ratio of 5 to 2000 g / ha.

6. The composition according to claim 5, further comprising at least one additional active ingredient.

7. The composition according to claim 6, wherein, The at least one additional active ingredient includes at least one additional biocide.

8. The composition according to claim 7, wherein, The other pest control agent mentioned is a herbicide or a herbicide safener.

9. The composition according to any one of claims 5 to 8, further comprising an agriculturally acceptable formulation adjuvant.

10. The composition according to any one of claims 5 to 8, further comprising an agrochemically acceptable diluent or carrier.

11. A method for controlling unwanted plant growth, the method comprising applying to the unwanted plant, parts thereof, or site a herbicide-effective amount of the composition as described in any one of claims 1 to 10.

12. Use of the composition as a herbicide as defined in any one of claims 1 to 10.

13. A formulation comprising the composition according to any one of claims 1 to 4, said formulation comprising from 0.01% to 90% by weight of an active agent and from 0% to 25% by weight of an agriculturally acceptable surfactant.

14. The formulation according to claim 13, comprising from 10% to 99.9% of a solid or liquid formulation inert agent.

15. The formulation according to claim 13 or 14, comprising from 10% to 99.9% of one or more adjuvants.

16. A concentrated composition for dilution by a user, comprising the composition according to any one of claims 1 to 4, wherein the concentrated composition comprises an active agent of 2% to 80% by weight.

17. A concentrated composition for dilution by a user, comprising the composition according to any one of claims 1 to 4, wherein the concentrated composition comprises an active agent at a weight of between 5% and 70%.

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