Weeding composition

Abstract

The present invention relates to compositions comprising as component (A) a compound of formula (I) or an agrochemically acceptable salt thereof, and as component (B) at least one compound selected from the group consisting of B-I, B-II, B-III, B-IV or an agrochemically acceptable salt thereof, and to the use of these compositions for controlling or inhibiting plant growth. # imgabs0 #

Description

[0001] The present invention relates to novel herbicidal combinations and their use in controlling plants or inhibiting plant growth. Herbicidal compounds and combinations are disclosed in, for example, CN 113105405A and CN 114431236A.

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

[0003]

[0004] And, at least one compound selected from the group consisting of the following or an agrochemically acceptable salt thereof as component (B):

[0005]

[0006] In a second aspect, the present invention provides the use of a composition of the present invention as a herbicide.

[0007] In a third aspect, the present invention provides a method of (i) inhibiting plant growth, and (ii) controlling plants, which method comprises applying to such plants, parts thereof, or the locus thereof, a herbicidally effective amount of a composition of the present invention.

[0008] In a fourth aspect, the present invention provides a method for selectively controlling grasses and / or weeds in crops of useful plants, which method comprises applying to the useful plants, parts thereof or the locus thereof or to the area under cultivation a herbicidally effective amount of a composition according to the invention, preferably in addition to methods of treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

[0009] In some examples of the method, component (A) and component (B) are applied in amounts from 0.05 to 4000 g / ha, preferably 0.5 to 1000 g / ha, preferably 0.5 to 500 g / ha.

[0010] In some examples of the method, component (A) is applied in an amount from 50 to 400 g / ha, and component (B) is applied in an amount from 50 to 250 g / ha.

[0011] In a fifth aspect, the present invention provides a formulation comprising a composition of the present invention, the formulation comprising by weight from 0.01% to 90% of an active agent, from 0 to 25% of an agriculturally acceptable surfactant and from 10% to 99.9% of a solid or liquid formulation inert and one or more adjuvants.

[0012] In a sixth aspect, the present invention provides a concentrate composition for dilution by a user, the concentrate composition comprising a composition of the present invention, the concentrate composition comprising from 2% to 80%, preferably between about 5% and 70% by weight of active agent.

[0013] In certain examples, components (A) and (B) are present in a weight ratio of from 8:1 to 1:8, from 8:1 to 1:5, about 2:1, about 1.6:1, or about 1:1.

[0014] In some instances, compounds of formula (I) and formula (II) are the only herbicidal active compounds in the composition. Accordingly, in some embodiments, the composition consists of component A and component B, optionally additionally consisting of one or more agriculturally acceptable formulation adjuvants and / or agrochemically acceptable diluents or carriers.

[0015] When active ingredients are combined, for any given combination of active ingredients, the expected effect (E) obeys 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):

[0016] ppm = milligrams of active ingredient (ai) per liter

[0017] X = % effect based on first active ingredient using p ppm of active ingredient

[0018] Y = % effect based on the second active ingredient using q ppm of active ingredient.

[0019] According to Colby, using p+q ppm of active ingredient, the expected effect of active ingredient A+B is expressed by the following formula:

[0020]

[0021] If the effect actually observed (O) is greater than the expected effect E, then the effect of the combination is superadditive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value of the difference (OE). In the case of purely complementary additions of actives (expected activity), the difference (OE) is zero. Negative values ​​of the difference (OE) indicate a loss of activity compared to the expected activity.

[0022] The compound of formula I and the compounds of formulae BI to B-IV are effective herbicidal compounds.

[0023] Compounds of formula I are described in WO 2021 / 139482 A1.

[0024] Compound BI is described in WO 1991 / 000278 A1. Compound B-II is described in WO 2010 / 038953 A2. Compound B-III is described in GB 785732 A. Compound B-IV is described in WO 2016 / 095768 A1.

[0025] Thus, the combinations of the present invention take advantage of any additive herbicidal activities, and certain embodiments may even exhibit synergistic effects.A synergistic effect exists whenever the effect of the active ingredient combination is greater than the sum of the effects of the individual components.

[0026] The combinations of the invention may also provide an expanded spectrum of activity compared to the activity obtained with each individual component and / or allow the use of lower amounts of the individual components when used in combination compared to when used individually in order to modulate effective herbicidal activity.

[0027] Furthermore, the compositions of the invention may also show increased crop tolerance when compared to the action of component (A) or component (B) alone. This occurs when the action of the active ingredient combination is less damaging to useful crops than the action of one of the active ingredients alone.

[0028] The presence of one or more possible asymmetric carbon atoms in the compound of components (A) and (B) means that the compound can exist in the form of chiral isomers, i.e., enantiomers or diastereomers. As a result of restricted rotation around a single bond, atropisomers may also exist. Formula (I) and BI to B-IV are intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof. Similarly, formula (I) and BI to B-IV are intended to include (where possible) all esters and mixtures thereof, such as carboxylic acid methyl esters, carboxylic acid prop-2-propynyl esters and carboxylic acid cyanomethyl esters and mixtures thereof. Similarly, the above formula is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) (when present). The present invention includes all possible tautomeric forms of compounds. The present invention includes all these possible isomeric forms and mixtures thereof.

[0029] The compounds of the compositions of the invention will typically be provided in the form of an agronomically acceptable salt, zwitterion, or salt of an agronomically acceptable zwitterion. The invention encompasses all such agronomically acceptable salts, zwitterions, and mixtures thereof in all ratios.

[0030] As used in the present invention, suitable agronomically acceptable salts for components (A) and (B) include anions selected from, but not limited to, chloride, bromide, iodide, fluoride, 2-naphthalenesulfonate, acetate, adipate, methoxide, ethoxide, propoxide, butoxide, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, butylsulfate, butylsulfonate, butyrate, camphorate, camphorsulfonate, decanoate, hexanoate, octanoate, carbonate, citrate, diphosphate, edetate, edisylate, heptanoate, edisylate, ethanesulfonate, ethylsulfate, formate, fumarate, glucoheptonate, gluconate, glucuronate, glutathione ... The invention also includes but is not limited to the following salts: an amine salt, a glycerophosphate salt, a heptadecanoate salt, a hexadecanoate salt, a bisulfate salt, a hydroxide salt, a hydroxynaphthoate salt, an isethionate salt, a lactate salt, a lactobionate salt, a laurate salt, a malate salt, a maleate salt, a mandelate salt, a methanesulfonate salt, a methanedisulfonate salt, a methylsulfate salt, a mucate salt, a myristate salt, a naphthenate salt, a nitrate salt, a nonadecanoate salt, an octadecanoate salt, an oxalate salt, a nonadecanoate salt, a pentadecanoate salt, a pentafluoropropionate salt, a perchlorate salt, a phosphate salt, a propionate salt, a propylsulfate salt, a propylsulfonate salt, a succinate salt, a sulfate salt, a tartrate salt, a toluenesulfonate salt, a tridecanoate salt, a trifluoromethanesulfonate salt, a trifluoroacetate salt, an undecanoate salt, and a valerate salt; and may be the same or may be different for each of components (A) and (B).

[0031] 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, amylamine, arginine, phenethylbenzylamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecanamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine , lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearamide, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxide, triethylsulfonium, triethylsulfoxide, trimethylsulfonium, trimethylsulfoxide, tripropylsulfonium, and tripropylsulfoxide.

[0032] The herbicides of components (A) and (B) are well known in the art and can be obtained commercially or made using methods available in the art. Table 1 describes specific combinations of components (A) and (B) according to the present invention.

[0033] Table 1 - Compositions according to the invention comprising as component (A) a compound of formula (I) and as component (B) a herbicide selected from the group consisting of compounds of formulae BI to B-IV

[0034]

[0035] Throughout this document, the expression "composition" should be interpreted as meaning different mixtures or combinations of components (A) and (B), for example in a single "ready-to-use" form, in a combined spray mixture (which consists of separate formulations of the single active ingredients, such as a "tank mix"), as well as the combined use of these single active ingredients when applied in a sequential manner (i.e., one after the other, in a reasonably short period of time, such as a few hours or days). For the implementation of the present invention, the order in which components (A) and (B) are applied is not important.

[0036] As used herein, the term "herbicide" means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means an amount of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on plant growth. Controlling or modifying effects include all deviations from natural development, for example, killing, retardation, leaf burn, albinism, dwarfing, etc.

[0037] As used herein, the term "locus" means a place in or on which plants grow, or where seeds of cultivated plants are sown, or where seeds are to be placed in the soil. It includes soil, seeds and seedlings, as well as established vegetation.

[0038] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0039] The term "plant propagation material" means all reproductive parts of a plant, for example seeds or vegetative parts such as cuttings and tubers of a plant. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes and plant parts.

[0040] As used herein, the term "safener" means a chemical that, when used in combination with a herbicide, reduces the undesirable effects of the herbicide on non-target organisms, e.g., a safener protects crops from damage by resistant herbicides but does not prevent the herbicide from killing weeds.

[0041] Crops of useful plants in which the compositions according to the invention can be used include perennial and annual crops, such as berry plants, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar and fodder beets, coffee beans, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears and plums; grasses, for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and zoysia grass; herbs such as basil, borage, chives, cilantro, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; legumes such as beans, lentils, peas, and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palm plants such as oil palms; ornamental plants such as flowers, shrubs, and trees; other trees such as cocoa, coconut, olive, and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, okra, onions, peppers, potatoes, squash, rhubarb, spinach, and tomatoes; and vines such as grapes.

[0042] Crops are to be understood as those which occur naturally, are obtained by conventional breeding methods or are obtained by genetic engineering. They include crops with so-called output traits, such as improved storage stability, higher nutritional value and improved flavor.

[0043] Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACCase-inhibitors and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones (e.g. imazamox) by conventional methods of breeding are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, maize varieties resistant to glyphosate and glufosinate, which are marketed under the trade names Roundup and and It is commercially available.

[0044] Crops are also to be understood as those crops which have been rendered resistant to harmful insects by genetic engineering methods, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the boll weevil) and also Bt potato (resistant to the Colorado beetle). An example of Bt maize is Bt 176 corn hybrid (Syngenta Seeds). Bt toxins are proteins naturally produced 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 comprising one or more genes encoding insecticide resistance and expressing one or more toxins are (Corn), Yield (corn), (cotton), (cotton), (potato), as well as Plant crops or their seed material can both be resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic events). For example, seeds can have the ability to express an insecticidal Cry3 protein while being tolerant to glyphosate.

[0045] The compositions of the present invention are typically useful for controlling a variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that are typically controlled include Alopecurus myosuroides, Avenafatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, 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, Bidenspilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis sarvensis, Solanum nigrum, Stellaria media, eronica persica, and Xanthium strumarium.

[0046] In all aspects of the invention, in any particular embodiment, for example, the weeds to be controlled and / or growth inhibited may be monocotyledonous or dicotyledonous weeds that tolerate or are resistant to one or more other herbicides, for example, HPPD inhibitor herbicides such as mesotrione, PSII inhibitor herbicides such as atrazine or EPSPS inhibitors such as glyphosate. Such weeds include, but are not limited to, resistant Amaranthus biotypes.

[0047] The compositions of the present invention may also be mixed with one or more additional pesticides including herbicides (other than those of the herbicide of formula (I) and component (B)), fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form multi-component pesticides giving even broader spectrum agricultural protection.

[0048] Similarly, the compositions of the invention (including those comprising one or more additional pesticides as described in the preceding paragraph) may further comprise one or more safeners. In particular, the following safeners are particularly preferred: AD 67 (MON 4660), fenthiocarb, cloquintocet-mexyl, fenthiocarb, cyproconazole, dichloropropene, dicyclonon, fenthiocarb, fenthiocarb, fenthiocarb, fluazifop, fenthiocarb, furilazome, isoxadifen, mefenpyr, mephenate, fenthiocarb, naphthalene dicarboxylic anhydride (CAS RN 81-84-5), TI-35, N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Such safeners may also be in the form of esters or salts, as mentioned in The Pesticide Manual (15th edition (BCPC), 2009). Thus, a reference to clofosbuvir methyl also applies to clofosbuvir and a lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof (as disclosed in WO 02 / 34048), and a reference to fenthiocarb ethyl also applies to fenthiocarb, etc.

[0049] The composition of the invention can be applied before or after crop planting, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence application). When a safener is combined with the mixture of the invention, it is preferred that the mixing ratio of the compound of formula (I) to the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0050] The safener and composition of the present invention may be applied simultaneously. For example, the safener and composition of the present invention may be applied to the site before emergence or may be applied to the crop after emergence. The safener and composition of the present invention may also be applied sequentially. For example, the safener may be applied before sowing seeds as a seed treatment, and the composition of the present invention may be applied to the site before emergence or may be applied to the crop after emergence.

[0051] However, it will be appreciated by those skilled in the art that the compositions of the invention are particularly useful in non-selective burn-down applications and therefore may also be used to control volunteer or escape crop plants. In this case, it is obviously not necessary to include a safener in the compositions of the invention.

[0052] In general, the mixing ratio of the compound of formula (I) to the compound of component B (by weight) is from 0.001: 1 to 1000: 1, preferably from 0.01: 1 to 100: 1, more preferably from 0.025: 1 to 20: 1, even more preferably from 1: 30 to 20: 1. Therefore, the preferred ratio ranges of the preferred compositions of the present invention are given in Table 2 below.

[0053] Table 2: Exemplary ratio ranges for specific compositions of the invention

[0054]

[0055] The skilled person will appreciate that the most preferred ratio range of A:B for any one of the composition numbers 1.001 to 1.004 described in Table 2 above is from 1:20 to 10:1, and each of the composition numbers 1.001 to 1.004 described in Table 2 may be used in any of the following individual amounts: 1:1000, 1:500, 1:300, 1:250, 1:200, 1:100, 1:50, 1:40, 1:32, 1:30, 1:25, 1:20, 1:16, 1:15, 1:10, 1:8, 2:15, 3:20, 1:100. 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, 5:1, 8:1, 10:1, 12:1, 16:1, 20:1, 25:1, 30:1, 32:1, 50:1, 100:1, 200:1, 250:1, 500:1 and 1000:1.

[0056] When applied in the composition of the present invention, component (A) is typically applied in an amount of at least 0.01 g / ha or 0.05 g / ha, preferably at least 0.5 g / ha, more preferably at least 1 g / ha, still more preferably at least 5 g / ha, in particular in an amount of 50 to 2000 g / ha, more in particular 30, 50, 75, 100, 125, 150, 200, 250, 300, 400, 500, 750, 800, 1000, 1250, 1500, 1800, or 2000 g / ha. Such an amount of component (A) is typically applied in combination with at least 0.05 g / ha, preferably at least 0.5 g / ha, more preferably at least 1 g / ha of component B, typically 5 to 2000 g / ha of component B, and more specifically 5, 10, 15, 20, 25, 30, 50, 75, 100, 125, 140, 150, 200, 250, 300, 400, 500, 750, 1000, 1250, 1500, 1800 or 2000 g / ha of component (B). The examples described herein illustrate but do not limit the range of ratios of components (A) to (B) that can be used in the present invention.

[0057] Exemplary application rates (in g / ha) of preferred compositions of the invention are given in Table 3 below.

[0058] Table 3: Exemplary application rates of components of the compositions of the present invention

[0059]

[0060] The amount of the composition according to the invention to be applied will depend on various factors, such as the compound used; the object of treatment, such as, for example, plants, soil or seeds; the type of treatment, such as, for example, spraying, dusting or seed dressing; or the time of application. In agricultural practice, the application rate of the composition according to the invention depends on the type of action desired and is typically in the range of from 55 to 4000 g, and more typically between 55 and 2000 g / ha of total composition / hectare. Application is usually carried out by spraying the composition, typically by a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or immersion can also be used.

[0061] The compositions of the invention can advantageously be used in the following formulations (in this case, the "active ingredient" relates to the corresponding mixtures of the compound of formula (I) with the compounds of component B or, when a safener is also used, the corresponding mixtures of the compound of formula (I) with the compounds of component B and a safener).

[0062] The individual components of the composition of the present invention can be used as the technical active ingredient produced. However, more typically, the composition according to the present invention can be formulated in a variety of ways using formulation adjuvants (such as carriers, solvents and surface-active substances). These formulations can be in different physical forms, for example, in the form of dusting 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, suspoemulsions, 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, for example from Manual on Development and Use of FAO and WHO Specifications for Pesticides [Manual on the Development and Use of FAO and WHO Standards for Pesticides], United Nations, 1st edition, second revision (2010). Such formulations can be used directly or can be diluted before use. Dilution can be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0063] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surface-active substances or combinations thereof.

[0064] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) into the environment in a controlled amount. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredients they contain is about 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of an integral solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated film can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate 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 a solid matrix of a base material in the form of finely dispersed particles, but these microcapsules themselves are not wrapped.

[0065] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosin acid ester, 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, alkyl pyrrolidone, 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, acetic acid glyceryl, diacetic acid glyceryl, triacetin, decaglycerol Hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0066] Suitable solid carriers are, 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 materials.

[0067] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifying agents, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium dodecylsulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitan oleate; quaternary ammoniums, 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 also further substances, such as are described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company. Corp., Ridgewood New Jersey (1981).

[0068] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity regulators, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0069] The formulation according to the invention may include an additive comprising an oil of vegetable or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil with an oil derivative. The amount of the oil additive in the composition according to the invention is generally 0.01% to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oil of vegetable origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oil; alkyl esters of oil of vegetable origin, such as methyl derivatives; or oil of animal origin, such as fish oil or tallow. Preferred oil additives include C8C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0070] These formulations generally contain 0.1% to 99% by weight, especially 0.1% to 95% by weight, of compounds (A) and (B) and 1% to 99.9% by weight of formulation adjuvants, which preferably include 0 to 25% by weight of surface-active substances. Whereas commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0071] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. In general, the compound can be applied in an amount of from 1 l / ha to 2000 l / ha, especially from 10 l / ha to 1000 l / ha.

[0072] A preferred formulation may have the following composition (wt%), wherein the term "active ingredient" refers to the total wt% of the combination of all active ingredients in the composition:

[0073] Emulsifiable concentrates :

[0074] Active ingredient: 1% to 95%, preferably 60% to 90%

[0075] Surfactant: 1% to 30%, preferably 5% to 20%

[0076] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0077] powder :

[0078] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0079] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0080] Suspension concentrate:

[0081] Active ingredient: 5% to 75%, preferably 10% to 50%

[0082] Water: 94% to 24%, preferably 88% to 30%

[0083] Surfactant: 1% to 40%, preferably 2% to 30%

[0084] Wettable powder :

[0085] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0086] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0087] Solid carrier: 5% to 95%, preferably 15% to 90%

[0088] Granules:

[0089] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0090] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0091] Various aspects and embodiments of the invention will now be described in more detail by way of example. It will be appreciated that modifications of detail may be made without departing from the scope of the invention.

[0092] Examples

[0093] Preparation Examples

[0094] Wettable powder a) b) c) Active ingredients 25％ 50％ 75％ Sodium lignin sulfonate 5％ 5％ - Sodium Lauryl Sulfate 3％ - 5％ Sodium diisobutylnaphthalene sulfonate - 6％ 10％ Phenol polyglycol ether - 2％ - (7-8 mol of ethylene oxide) Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0095] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0096] Powder for dry seed treatment a) b) c) Active ingredients 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silicic acid 5％ 5％ - Kaolin 65％ 40％ - talc - 20

[0097] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be used directly for seed treatment.

[0098] Emulsifiable concentrates Active ingredients 10％ Octylphenol Polyglycol Ether 3％ (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3％ Castor oil polyglycol ether (35 mol of ethylene oxide) 4％ Cyclohexanone 30％ Xylene mixture 50％

[0099] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0100] powder a) b) c) Active ingredients 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral fillers - - 96％

[0101] Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry seed dressing of seeds.

[0102] Extruded granules Active ingredients 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0103] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.

[0104] The mixture is extruded and then dried in a stream of air.

[0105] Coated granules Active ingredients 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0106] The finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0107] Suspension concentrates Active ingredients 40％ Propylene glycol 10％ Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6％ Sodium lignin sulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% emulsion in water) 1％ water 32％

[0108] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0109]

[0110] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0111] Extended-release capsule suspension

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

[0113] Biological Examples

[0114] Seeds of Amaranthus retroflexus (AMARE), Echinochloa crus-galli (ECHCG), Digitaria sanguinalis (DIGSA), Lolium perenne (LOLPE), Alopecurus myosuroides (ALOMY), Chenopodium album (CHEAL) and Ipomoea hederacea (IPOHE) were sown in standard sterilized soil in pots. After 8 days of cultivation under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with an aqueous spray solution obtained as follows at 500 l / Ha: the technical grade active ingredient was formulated in a small amount of acetone and a solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50 g / l solution, which was then diluted using 0.2% Genapol XO80 (CAS No.: 9043-30-5) as a diluent to obtain the desired final dose of the test compound. When the active ingredients are applied as a mixture, an aqueous spray solution containing the two active ingredients is prepared as above. These test plants are then grown under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the test was assessed visually for percent phytotoxicity of the plants when compared to untreated control plants (where 100 = complete damage to the plant; 0 = no damage to the plant). Two to four replications were performed for each treatment in a randomized block design.

[0115] To determine if a mixture of active ingredients is synergistic with respect to percent phytotoxicity to test plants, the Colby formula was applied: SR Colby (1967) "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, p. 22, E = X + Y - (X * Y / 100), where

[0116] X = average percent phytotoxicity of herbicide A when applied at a certain rate

[0117] Y = average percent phytotoxicity of herbicide B when applied at a certain rate

[0118] E = expected effect of a mixture of herbicides A and B calculated according to Colby's formula.

[0119] A+BI

[0120] ALOMY

[0121] Compound Quantity (g / ha) Observed Expected Difference A 0.039 0 - - A 0.313 3 - - BI 0.039 0 - - BI 0.625 8 - - A+BI 0.313+0.625 20 10 10 A+BI 0.039+0.039 10 0 10

[0122] LOLPE

[0123] Compound Quantity (g / ha) Observed Expected Difference A 0.078 3 - - A 0.313 5 - - BI 0.039 0 - - BI 0.313 5 - - BI 0.625 5 - - A+BI 0.313+0.625 20 10 10 A+BI 0.313+0.313 23 10 13 A+BI 0.078+0.039 13 3 10 A+B-1 0.313+0.156 15 5 10

[0124] DIGSA

[0125]

[0126]

[0127] ECHCG

[0128] Compound Quantity (g / ha) Observed Expected Difference A 0.313 1 - - BI 0.625 5 - - A+BI 0.313+0.625 30 6 24

[0129] AMARE

[0130] Compound Quantity (g / ha) Observed Expected Difference A 0.078 39 - - BI 0.078 33 - - A+BI 0.078+0.078 78 59 19

[0131] CHEAL

[0132] Compound Quantity (g / ha) Observed Expected Difference A 0.156 24 - - A 0.313 31 - - BI 0.156 20 - - BI 0.313 40 - - A+BI 0.156+0.156 55 39 16 A+BI 0.313+0.313 74 59 15

[0133] A+B-II LOLPE

[0134]

[0135]

[0136] DIGSA

[0137] Compound Quantity (g / ha) Observed Expected Difference A 0.313 9 - - B-II 0.313 8 - - A+B-II 0.313+0.313 28 16 12

[0138] AMARE

[0139] Compound Quantity (g / ha) Observed Expected Difference A 0.156 68 - - B-II 0.078 30 - - A+B-II 0.156+0.078 88 78 10

[0140] CHEAL

[0141] Compound Quantity (g / ha) Observed Expected Difference A 0.156 24 - - A 0.313 31 - - B-II 0.078 15 - - B-II 0.156 18 - - B-II 0.313 18 - - A+B-II 0.313+0.313 68 43 25 A+B-II 0.156+0.078 50 35 15 A+B-II 0.313+0.156 58 43 15

[0142] IPOHE

[0143] Compound Quantity (g / ha) Observed Expected Difference A 0.313 68 - - B-II 0.156 18 - - B-II 0.313 40 - - A+B-II 0.313+0.313 93 81 12 A+B-II 0.313+0.156 89 73 16

[0144] A+B-III AMARE

[0145] Compound Quantity (g / ha) Observed Expected Difference A 0.156 68 - - B-III 3.75 8 - - A+B-III 0.156+3.75 80 70 10

[0146] CANCEL

[0147] Compound Quantity (g / ha) Observed Expected Difference A 0.625 33 - - B-III 15 15 - - A+B-III 0.625+15 58 43 15

[0148] IPOHE

[0149] Compound Quantity (g / ha) Observed Expected Difference A 0.078 20 - - A 0.313 68 - - B-III 7.5 5 - - A+B-III 0.313+7.5 80 69 11 A+B-III 0.078+7.5 65 24 41

Claims

1. A composition comprising as component (A) a compound of formula (I) or an agrochemically acceptable salt thereof: and at least one compound selected from the group consisting of the following or an agrochemically acceptable salt thereof as component (B):

2. The composition according to claim 1, wherein The weight ratio of component (A) to component (B) is from 0.001:1 to 1000:1, 0.01:1 to 100:1; 0.025:1 to 20:1; or 1:30 to 20:

1.

3. The composition according to claim 2, wherein The weight ratio of A:B is from 8:1 to 1:8, from 8:1 to 1:5, about 2:1, about 1.6:1, or about 1:

1.

4. The composition according to any one of claims 1 to 3, wherein Component (A) and component (B) are applied in amounts of from 0.05 to 4000 g / ha.

5. An agrochemical composition comprising a herbicidally effective amount of a composition as defined in any one of claims 1 to 4.

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 comprises at least one additional pesticide.

8. The composition according to claim 7, wherein The additional pesticide is a herbicide or a herbicide safener.

9. A composition according to any one of claims 5 to 8, additionally comprising an agriculturally acceptable formulation adjuvant and / or an agrochemically acceptable diluent or carrier.

10. A method of controlling the growth of unwanted plants, the method comprising applying to the unwanted plants, parts thereof or the locus thereof a herbicidally effective amount of a composition according to any one of claims 1 to 9.

11. Use of a composition as defined in any one of claims 1 to 9 as a herbicide.

12. A formulation comprising a composition according to any one of claims 1 to 4, said formulation comprising by weight from 0.01% to 90% active agent, from 0 to 25% agriculturally acceptable surfactant and from 10% to 99.9% solid or liquid formulation inerts and one or more adjuvants.

13. A concentrated composition for dilution by a user comprising a composition according to any one of claims 1 to 4, said concentrated composition comprising from 2% to 80%, preferably between about 5% and 70% by weight of active agent.

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