Herbicidal composition

Abstract

The present invention relates to a composition comprising a compound of formula (I) as component (A) or an agrochemically acceptable salt thereof and at least one compound selected from the group consisting of the following as component (B) or an agrochemically acceptable salt thereof, and its use in the control of plants or the inhibition of plant growth. JPEG2025524881000060.jpg40158

Description

Technical Field

[0001] The present invention relates to novel combinations of herbicides and their use in the control of plants or the inhibition of plant growth. Herbicidal isoxazolidinones are disclosed, for example, in US Patent No. 4,405,357.

Summary of the Invention

Means for Solving the Problems

[0002] In a first aspect of the present invention, a compound of formula (I):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0003] In a second aspect, the present invention provides the use of the composition of the present invention as a herbicide.

[0004] In a third aspect, the present invention provides a method for (i) inhibiting plant growth and (ii) controlling plants, the method comprising applying a herbicidally effective amount of the composition of the present invention to a plant, a part thereof, or a site thereof.

[0005] In a fourth aspect, the present invention provides a method for selectively controlling weeds and / or grasses in a crop of useful plants, which comprises applying a herbicidally effective amount of the composition of the present invention to the useful plants, a part or a site thereof, or a cultivation area, preferably excluding methods for treating the body of a human or animal by surgery or therapy and diagnostic methods practiced on the body of a human or animal.

[0006] In some examples of the method, components (A) and (B) are applied in an amount of 0.05 to 5000 g / ha, preferably 1 to 3000 g / ha, more preferably 5 to 1000 g / ha.

[0007] In some examples of the method, component (A) is applied in an amount of 10 to 1000 g / ha, and component (B) is applied in an amount of 1 to 4000 g / ha.

[0008] In a fifth aspect, the present invention provides a formulation comprising a composition of the present invention containing 0.01 to 90% by weight of an active agent, 0 to 25% of an agriculturally acceptable surfactant, and 10 to 99.9% of a solid or liquid formulation inert substance and adjuvant.

[0009] In a sixth aspect, the present invention provides a concentrated composition for dilution by the user, comprising a composition of the present invention containing 2 to 80% by weight, preferably about 5 to 70% by weight of an active agent.

[0010] In certain examples, components (A) and (B) are present in a weight ratio of 0.001:1 to 1000:1, 0.01:1 to 100:1, 0.1:1 to 10:1, 0.5:1 to 5:1, about 1:1, about 0.5:1 or about 0.1:1.

[0011] In certain examples, the compounds of formula (A) and (B) are the only herbicidally active compounds in the composition. Thus, in certain embodiments, the composition consists of components A and B, and optionally further comprises one or more agriculturally acceptable formulation adjuvants and / or pesticidally acceptable diluents or carriers.

[0012] When combining active ingredients, the activity (E) predicted for any given combination of active ingredients can be calculated as follows according to the so-called Colby's formula (Colby, S.R., Calculating synergistic and antagonistic responses of herbicide combination, Weeds, Vol. 15, pp. 20 - 22; 1967): ppm = mg / L of active ingredient (a.i.) X = % of action by the first active ingredient using p ppm of the active ingredient Y = % of action by the second active ingredient using q ppm of the active ingredient.

[0013] According to Colby, the predicted action of active ingredients A + B using p + q ppm of the active ingredient is represented by the following formula.

Equation

[0014] When the actually observed action (O) is greater than the predicted action E, the action of the combination is superadditive, i.e., there is a synergistic effect. Mathematically, the synergistic action corresponds to the positive value of the difference (O - E). In the case of a purely complementary addition of activities (predicted activity), the difference (O - E) is 0. A negative value of the difference (O - E) indicates a loss of activity compared to the predicted activity.

[0015] All of the compounds of Formula I and Formulas B - 1 to B - 20 are effective herbicidal compounds. The compounds of Formula I are known under the CAS number 2766607 - 82 - 1 and can be prepared by the methods described in French Patent No. 2483406 and US Patent No. 4405357.

[0016] Compound B-1 is described in European Patent Application Publication No. 2394141. Compound B-2 is described in European Patent Application Publication No. 2394141. Compound B-3 is described in British Patent Application Publication No. 917253. Compound B-4 is described in European Patent Application Publication No. 186118. Compound B-5 is described in US Patent No. 3244501. Compound B-6 is described in German Patent Application Publication No. 2232263. Compound B-7 is described in French Patent No. 1328112. Compound B-8 is described in German Patent Application Publication No. 19933260. Compound B-9 is described in International Publication No. 02062770. Compound B-10 is described in German Patent Application Publication No. 3422346. Compound B-11 is described in International Publication No. 0236595. Compound B-12 is described in US Patent No. 2655445. Compound B-13 is described in International Publication No. 9213845. Compound B-14 is described in German Patent Application Publication No. 4335297. Compound B-15 is described in British Patent Application Publication No. 2192877. Compound B-16 is described in European Patent Application Publication No. 0348737. Compound B-17 is described in German Patent Application Publication No. 2137992. Compound B-18 is described in European Patent Application Publication No. 0477808. Compound B-19 is described in European Patent Application Publication No. 0044808. Compound B-20 is described in European Patent Application Publication No. 0053011.

Mode for Carrying Out the Invention

[0017] Therefore, the combinations of the present invention utilize any additive herbicidal activity, and certain embodiments may even exhibit a synergistic effect. This always occurs when the action of the combination of active ingredients is greater than the sum of the actions of the individual components.

[0018] The combinations according to the invention can also provide an extended spectrum of activity for mediating effective herbicidal activity, compared to the activity obtained by each individual component, and / or can enable the use of a lower proportion of the individual components when used in combination than when used alone.

[0019] Furthermore, it is also possible that the compositions according to the invention exhibit increased crop tolerance when compared to the effects of component (A) or component (B) alone. This occurs when the action of the combination of active ingredients does not harm the crop, which is more useful than the action of one single active ingredient.

[0020] The presence of one or more possible asymmetric carbon atoms in the compounds of components (A) and (B) means that the compounds can occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. As a result of the restricted rotation around a single bond, atropisomers can also occur. Formulas (I) and B-1 to B-20 are intended to include all their possible isomeric forms and mixtures thereof. The present invention includes all possible isomeric forms and mixtures thereof. Similarly, formulas (I) and B-1 to B-20 are intended to include, where possible, all esters and mixtures thereof, such as methyl carboxylate, prop-2-propynyl carboxylate and cyanomethyl carboxylate esters and mixtures thereof. Similarly, the above formulas are 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 the compounds. The present invention includes all these possible isomeric forms and mixtures thereof.

[0021] The compounds of the compositions according to the invention are typically provided in the form of an agriculturally acceptable salt, zwitterion or salt of an agriculturally acceptable zwitterion. The present invention encompasses all such agriculturally acceptable salts, zwitterions and mixtures thereof in all proportions.

[0022] Suitable agriculturally acceptable salts for components (A) and (B) used in the present invention include, but are not limited to, chloride, bromide, iodide, fluoride, 2-naphthalenesulfonate, acetate, adipate, methoxide, ethoxide, propoxide, butoxide, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, butyl sulfate, butylsulfonate, butyrate, camphorate, cantharate, caprinate, caproate, caprylate, carbonate, citrate, diphosphate, edetate, edisylic acid salt, enanthate, ethanedisulfonic acid, ethanesulfonate, ethyl sulfate, formate, fumarate, gluceptate, gluconate, glucuronate, glutamate, glycerophosphate, heptadecanoate, hexadecanoate, bisulfate, hydroxide, hydroxynaphthoate, isethionate, lactate, lactobionate, laurate, malate, maleate, mandelate, mesylate, methanedisulfonate, methyl sulfate, mucate, myristate, napsylate, nitrate, nonadecanoate, octadecanoate, oxalate, pelargonate, pentadecanoate, pentafluoropropionate, perchlorate, phosphate, propionate, propyl sulfate, propylsulfonate, succinate, sulfate, tartrate, tosylate, tridecanoate, triflate, trifluoroacetate, undecylenate, and valerate. The anions are selected from these, and components (A) and (B) can be the same or different from each other.

[0023] Suitable cations include, but are not limited to, metals, conjugate acids of amines, and organic cations, and components (A) and (B) can be the same or different from each other. 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, benethamine, 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, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyl octylamine, 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, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, trihexylamine, triisobutylamine, 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, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium, and tripropylsulfoxonium.

[0024] The herbicides of components (A) and (B) are well-known in the art and can be obtained commercially or can be manufactured using methods available in the art. Table 1 describes specific combinations of components (A) and (B) according to the present invention.

[0025] [Table 1]

[0026] Throughout this specification, the expression "composition" is to be interpreted as meaning various mixtures or combinations of components (A) and (B), including continuously, i.e., when applied successively over a moderately short period such as several hours or days, for example, a combined spray mixture composed of separate formulations of a single active ingredient in a single "ready mix" form, "tank mix", etc., and the combined use of a single active ingredient. The order of applying components (A) and (B) is not essential for carrying out the present invention.

[0027] As used herein, the term "herbicide" means a compound that suppresses or modifies plant growth. The term "herbicidally effective amount" means an amount of such a compound or a combination of such compounds that can produce a suppressive or modifying effect on plant growth. Suppressing or modifying the effect includes all deviations from natural occurrence, such as death, delay, leaf burn, albinism, atrophy, etc.

[0028] As used herein, the term "site" means a field in which a plant is growing, or in which seeds of a cultivated plant are sown, or in which seeds will be placed in the soil. This includes the soil, seeds and seedlings, as well as established vegetation.

[0029] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, petioles, leaves and fruits.

[0030] The term "plant propagation material" refers to all reproductive parts of a plant, such as seeds, or vegetative parts of a plant, such as cuttings and tubers. This includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes and parts of plants.

[0031] As used herein, the term "toxicity mitigator" means a chemical substance that, when used in combination with a herbicide, reduces the undesirable effects of the herbicide on non-target organisms. For example, a toxicity mitigator protects the crop from damage by the herbicide, but does not prevent the herbicide from killing weeds.

[0032] Useful plant crops for which the composition according to the invention can be used include perennial and annual crops, such as berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, corn (maize), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; agricultural crops, such as sugar and fodder beets, coffee, hops, mustard, canola, poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears and plums; grasses, such as Bermuda grass, bluegrass, bentgrass, crabgrass, fescue, ryegrass, St. Augustine grass and miscanthus; herbs, such as basil, borage, chives, coriander, lavender, lamb's lettuce, mint, oregano, parsley, rosemary, sage, thyme; legumes, such as beans, lentils, peas and soybeans; nuts, such as almonds, cashew nuts, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms, such as oil palm; ornamental plants, such as flowers, shrubs and trees; other trees, such as cocoa, coconuts, olives and rubber; vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, marrow, melons, okra, onions, peppers, potatoes, pumpkins, turnips, spinach and tomatoes; and grapes, such as wine grapes.

[0033] It should be understood that the crops are those that occur naturally, those obtained by conventional breeding methods or those obtained by genetic engineering. They include crops that include so-called output traits (such as improved storage stability, higher nutritional value and improved flavor).

[0034] Crops are understood to include crops that have been made resistant to herbicides or classes of herbicides (e.g., ALS inhibitors, GS inhibitors, EPSPS inhibitors, PPO inhibitors, ACCase inhibitors, and HPPD inhibitors) by conventional breeding methods or genetic engineering. An example of a crop made resistant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer canola. Examples of crops made resistant to herbicides by genetic engineering methods include, for example, glyphosate-resistant and glufosinate-resistant corn varieties commercially available under the trade names RoundupReady® and LibertyLink®.

[0035] It should also be understood that the crops are those that have become resistant to harmful insects by genetic engineering methods, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the cotton bollworm), and Bt potato (resistant to the Colorado potato beetle). An example of Bt corn is the Bt 176 corn hybrid of NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in European Patent Application Publication No. 451 878, European Patent Application Publication No. 374 753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, International Publication No. 03 / 052073, and European Patent Application Publication No. 427 529. Examples of transgenic plants containing one or more genes encoding insect resistance and expressing one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Plant crops or their seed materials can be resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic events). For example, the seeds can be resistant to glyphosate while having the ability to express the insecticidal Cry3 protein.

[0036] The compositions of the present invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, and Lolium rigidum (Lolium spp.), Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include, for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica, and Xanthium strumarium.

[0037] In all aspects of the present invention, in any particular embodiment, for example, the weeds to be controlled and / or growth inhibited can be monocotyledonous or dicotyledonous weeds that are resistant or tolerant to one or more other herbicides, such as HPPD inhibitor herbicides like mesotrione, PSII inhibitor herbicides like atrazine, ACCase inhibitor herbicides, or EPSPS inhibitor herbicides like glyphosate. Such weeds include, but are not limited to, resistant Amaranthus biotypes. In one embodiment, such weeds include grasses that are tolerant to ACCase inhibitor herbicides.

[0038] The compositions of the present invention can also be mixed with one or more additional pesticides including herbicides different from the herbicide of formula (I) and the herbicide of component (B), fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, chemical sterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, or other biologically active compounds to form multi-component pesticides that provide a broader range of agricultural protection.

[0039] Similarly, the compositions of the present invention (including those containing one or more additional pesticides described in the previous paragraph) may further contain one or more toxicity mitigators. Specifically, the following toxicity mitigators are particularly preferred: AD 67 (MON 4660), benoxacor, cloquintocet - mexyl, cymetrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole - ethyl, fenchlorine, flurazole, fluxofenim, furilazole, furilazone, isoxadifen - ethyl, mefenpyr - diethyl, mefenate, oxabetrinil, naphthalic 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 toxicity mitigators may also be used in the form of esters or salts, for example, as described in The Pesticide Manual, 15th Ed. (BCPC), 2009. Thus, a reference to cloquintocet - mexyl also applies to cloquintocet and its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts as disclosed in WO 02 / 34048, and a reference to fenchlorazole - ethyl also applies to fenchlorazole and the like.

[0040] The compositions of the present invention can be applied before or after planting of the crop, before the weeds appear (pre - emergence application) or after the weeds have appeared (post - emergence application). When a toxicity mitigator is combined with the mixture of the present invention, the mixing ratio of the compound of formula (I) to the toxicity mitigator is preferably from 100:1 to 1:10, particularly from 20:1 to 1:1.

[0041] It is possible to simultaneously apply the toxicity mitigator and the composition of the present invention. For example, the toxicity mitigator and the composition of the present invention can be applied to a pre-emergence site or to a post-emergence crop. It is also possible to apply the toxicity mitigator and the composition of the present invention sequentially. For example, the toxicity mitigator can be applied as a seed treatment before sowing the seeds, or the composition of the present invention can be applied to a pre-emergence site or to a post-emergence crop.

[0042] However, those skilled in the art will understand that the composition of the present invention is particularly useful for non-selective burn-down applications and can therefore also be used to control volunteer plants or avoid crop plants. In such situations, it is clear that there is no need to include a toxicity mitigator in the composition of the present invention.

[0043] Generally, the mixing ratio (by weight) of the compound of formula (I) to the compound of component B is from 0.001:1 to 1000:1, preferably from 0.001:1 to 500:1, more preferably from 0.01:1 to 50:1, and even more preferably from 0.1:1 to 5:1. An exemplary range of A:B ratios of preferred compositions 1.001 to 1.020 of the present invention is shown in Table 2 below.

[0044] [Table 2]

[0045] A person skilled in the art will fully understand that for any one of Composition Numbers 1.001 to 1.020 described in Table 2 above, the most preferred ratio range of A:B is 1:1000 to 5:1, and each of Composition Numbers 1.001 to 1.020 described in Table 2 can be used at any one of the following individualized ratios: 1:1000, 1:50, 1:100, 1:50, 1:30, 1:15, 1:10, 1:8, 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, and 8:1.

[0046] In some embodiments, component (B) is selected from B-4, B-6, B-7, B-9, B-16, and B-20.

[0047] In some embodiments, the weight ratio of the compound of formula (I) to component (B) is in the range of about 1:8 to 8:1, preferably about 1:8, 1:6, 1:4, 1:2, 1:1, 2:1, 4:1, 6:1, or 8:1.

[0048] In one embodiment, Composition Number 1.004 is used for controlling Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria faberi, Amaranthus retroflexus, Abutilon theophrasti, Chenopodium album, Lolium perenne, and / or Ipomoea hederacea. In one embodiment, the range of the ratio of A:B to Composition Number 1.004 is 4:1 to 1:1, such as about 4:1, 3:1, 2:1, or 1:1, preferably 4:1 to 2:1.

[0049] In one embodiment, Composition No. 1.006 is used for controlling Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria faberi, Amaranthus retroflexus, Abutilon theophrasti, Chenopodium album, Lolium perenne and / or Ipomoea hederacea. In one embodiment, the range of the ratio of A:B to Composition No. 1.006 is 4:1 to 1:1, about 4:1, 3:1, 2:1 or 1:1, etc.

[0050] In one embodiment, Composition No. 1.007 is used for controlling Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria faberi, Amaranthus retroflexus, Abutilon theophrasti, Chenopodium album, Lolium perenne and / or Ipomoea hederacea. In one embodiment, the range of the ratio of A:B to Composition No. 1.007 is 1:8 to 1:1, about 1:8, 1:6, 1:4, 1:2 or 1:1, etc.

[0051] In one embodiment, Composition No. 1.009 is used for controlling Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria faberi, Amaranthus retroflexus, Abutilon theophrasti, Chenopodium album, Lolium perenne and / or Ipomoea hederacea. In one embodiment, the range of the ratio of A:B for Composition No. 1.009 is 4:1 to 1:1, about 4:1, 3:1, 2:1 or 1:1, etc. In one embodiment, a composition containing Compound A and B-9 in a ratio of 1:1, 2:1 or 4:1 is used for controlling Lolium perenne. In one embodiment, the composition is applied before germination.

[0052] In one embodiment, Composition No. 1.016 is used for controlling Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria faberi, Amaranthus retroflexus, Abutilon theophrasti, Chenopodium album, Lolium perenne and / or Ipomoea hederacea. In one embodiment, the range of the ratio of A:B for Composition No. 1.016 is 8:1 to 1:1, about 8:1, 6:1, 4:1, 3:1, 2:1 or 1:1, etc.

[0053] In one embodiment, Composition No. 1.020 is used for controlling Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria faberi, Amaranthus retroflexus, Abutilon theophrasti, Chenopodium album, Lolium perenne and / or Ipomoea hederacea. In one embodiment, the range of the ratio of A:B for Composition No. 1.020 is 4:1 to 1:1, about 4:1, 3:1, 2:1 or 1:1, etc.

[0054] When applied with the composition of the present invention, component (A) is typically applied at a rate of at least 5 g / ha or at least 10 g / ha, preferably at least 20 g / ha, more preferably at least 50 g / ha, even more preferably at least 75 g / ha, particularly at a rate of 100 to 2500 g / ha, more particularly at a rate of 200, 250, 300, 400, 500, 600, 700, 750, 800, 1000, 1250, 1500, 1800 or 2000 g / ha. In an exemplary embodiment, component (A) is applied at a rate of 10 to 1000 g / ha, preferably at a rate of 50 to 500 g / ha, more preferably at a rate of 100 to 200 g / ha.

[0055] The proportion of such component (A) is typically related to at least 0.05 g / ha, preferably at least 0.1 g / ha, more preferably at least 1 g / ha of component B, typically 5 to 4000 g / ha of component B, and more specifically, it is applied in relation to 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 50, 75, 100, 125, 140, 150, 200, 250, 300, 400, 500, 750, 850, 1000, 1250, 1400, 1500, 1800, 2000, 2500, 3000, 3500, 4000 or 5000 g / ha of component (B). In an exemplary embodiment, component (B) is applied at a rate of 0.1 to 5000 g / ha, preferably at a rate of 1 to 500 g / ha, more preferably at a rate of 5 to 200 g / ha.

[0056] The examples described herein illustrate, but are not limited to, the ranges of the proportions of components (A) and (B) that can be used in the present invention.

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

[0058]

Table 3

[0059] The amount of the composition according to the present invention to be applied depends on various factors such as the compound used, the object to be treated, such as plants, soil or seeds, the type of treatment, such as spraying, spreading or seed dressing, or the application time. In agricultural practice, the application rate of the composition according to the present invention depends on the type of desired effect and is typically in the range of 10 to 4000 g of the total composition per hectare, more generally 55 to 2000 g / ha. Application is generally carried out by spraying the composition, typically over a large area by a sprayer attached to a tractor, but other methods, such as spreading (for powders), drip or drenching, can also be used.

[0060] The composition of the present invention can be advantageously used in the following formulations (in this case, the "active ingredient" relates to a mixture of each of the compound of formula (I) and the compound of component B, or, when a toxicity alleviating agent is also used, to a mixture of each of the compound of formula (I), the compound of component B, and the toxicity alleviating agent).

[0061] The individual components of the composition of the present invention can be utilized as technically active ingredients during production. However, more typically, the composition according to the present invention can be formulated in various ways using formulation adjuvants such as carriers, solvents, and surfactants. The formulations can be in various physical forms, such as powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, foaming pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, water dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (using water or water-miscible organic solvents as carriers), impregnated polymer film forms, or other forms known, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. The dilution can be carried out, for example, using water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0062] The formulations can be prepared by mixing the active ingredient with formulation adjuvants, for example, to obtain a composition in the form of finely divided solids, granules, solutions, dispersions, or emulsions. The active ingredient 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, surfactants, or combinations thereof.

[0063] The active ingredient can also be included in very fine microcapsules. The microcapsules contain the active ingredient in a porous carrier. This enables the active ingredient to be released into the environment in a suppressed amount (e.g., sustained release). The microcapsules typically have a diameter of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient can be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulation membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, 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 and the active ingredient is included in the form of finely divided particles in a solid matrix of the base substance, but the microcapsules themselves are not encapsulated.

[0064] Formulation adjuvants suitable for the preparation of the composition according to the present invention are known per se. As the liquid carrier, water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, 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 amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, high molecular weight alcohols such as N-methyl-2-pyrrolidone may be used.,

[0065] 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 substances.,

[0066] Most surfactants can be advantageously used in both solid and liquid formulations, particularly those that can be diluted with a carrier before use. The surfactant can be anionic, cationic, nonionic or polymeric and can be used as an emulsifier, wetting agent or suspending agent or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium 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 di-alkyl phosphate esters; and further substances described, for example, in McCutcheon’s Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0067] Further adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, uptake promoters, micronutrients, plasticizers, lubricants, lubricants, dispersants, thickeners, antifreeze agents, bactericides and liquid and solid fertilizers.

[0068] The formulations according to the invention may contain additives comprising oils of plant or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils with oil derivatives. The amount of the oil additive in the composition according to the invention is generally from 0.01 to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or oils of plant origin, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of oils of plant origin, such as methyl derivatives, or oils of animal origin, such as fish oil or tallow. Preferred oil additives include alkyl esters of C8C 22 fatty acids, in particular C 12 ~C 18 methyl derivatives of fatty acids, such as methyl laurate, methyl palmitate and methyl oleate (methyl laurate, methyl palmitate and methyl oleate respectively). Many oil derivatives are known from Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0069] The formulations generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds (A) and (B) and from 1 to 99.9% by weight of formulation adjuvants, preferably from 0 to 25% by weight of surfactant. Commercial products may preferably be formulated as concentrates, but end-users usually use diluted formulations.

[0070] The application rates vary within a wide range and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied at a rate of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0071] Preferred formulations may have the following composition (% by weight), the term "active ingredient" referring to the total weight % of the combination of all active ingredients in the composition.

[0072] Emulsifiable concentrate: Active ingredient: 1 - 95%, preferably 60 - 90% Surfactant: 1 - 30%, preferably 5 - 20% Liquid carrier: 1 - 80%, preferably 1 - 35%

[0073] Dust: Active ingredient: 0.1 - 10%, preferably 0.1 - 5% Solid carrier: 99.9 - 90%, preferably 99.9 - 99%

[0074] Suspension concentrate: Active ingredient: 5 - 75%, preferably 10 - 50% Water: 94 - 24%, preferably 88 - 30% Surfactant: 1 - 40%, preferably 2 - 30%

[0075] Wettable powder: Active ingredient: 0.5 - 90%, preferably 1 - 80% Surfactant: 0.5 - 20%, preferably 1 - 15% Solid carrier: 5 - 95%, preferably 15 - 90%

[0076] Granule: Active ingredient: 0.1 - 30%, preferably 0.1 - 15% Solid carrier: 99.5 - 70%, preferably 97 - 85%

[0077] Here, various aspects and embodiments of the present invention will be described in more detail by way of example. It will be understood that changes in details can be made without departing from the scope of the present invention.

Examples

[0078] Formulation Examples

[0079]

Table 4

[0080] The combination is thoroughly mixed with the adjuvant, and the mixture is completely pulverized with a suitable mill, and then diluted with water to obtain a wettable powder that can be used directly for seed treatment.

[0081]

Table 5

[0082] The combination is thoroughly mixed with the adjuvant, and the mixture is completely pulverized with a suitable mill to obtain a powder that can be used directly for seed treatment.

[0083]

Table 6

[0084] Any necessary dilution emulsion that can be used for plant protection can be obtained by diluting this concentrate with water.

[0085]

Table 7

[0086] The immediately usable dust is obtained by mixing the combination with the carrier and pulverizing the mixture with a suitable mill. Such a powder can also be used for dry dressing of seeds.

[0087]

Table 8

[0088] The combination is mixed and pulverized with the adjuvant, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0089]

Table 9

[0090] The finely ground combination is uniformly applied in a mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0091]

Table 10

[0092] The finely ground combination is thoroughly mixed with an adjuvant to obtain a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water. Such dilutions can be used to treat living plants and plant propagation material by spraying, injection or immersion to protect against attack by microorganisms.

[0093]

Table 11

[0094] The finely ground combination is thoroughly mixed with an adjuvant to obtain a suspension concentrate, from which suspensions of any desired dilution can be obtained by diluting with water. Such dilutions can be used to treat living plants and plant propagation material by spraying, injection or immersion to protect against attack by microorganisms.

[0095] Sustained-release capsule suspension Mix 28 parts of the combination 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 part of an antifoaming agent and 51.6 parts of water until the desired particle size is achieved. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. 0.25 part of a thickening agent and 3 parts of a dispersing agent are added to the resulting capsule suspension to stabilize it. The capsule suspension formulation contains 28% active ingredient. The median capsule diameter is 8 - 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for the purpose.

[0096] Biological Examples Seeds of Amaranthus retroflexus (AMARE), Echinochloa crus-galli (ECHCG), Digitaria sanguinalis (DIGSA), Lolium perenne (LOLPE), Alopecurus myosuroides (ALOMY), Chenopodium album (CHEAL), Setaria faberi (SETFA), Abutilon theophrasti (ABUTH), Setaria viridis (SETVI) and Ipomoea hederacea (IPOHE) were sown in standard sterilized soil in pots. After culturing for 1 day under controlled conditions in a greenhouse (24 / 16 °C, day / night; 14-hour light; 65% humidity), the plants were sprayed with an aqueous spray solution (11.12% Emulsogen EL360 (trademark) + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) obtained from a formulation of the active ingredient in a solvent and emulsifier mixture called IF50 at 500 l / Ha to make a 50 g / l solution, which was then diluted using 0.2% Genapol XO80 (CAS number: 9043-30-5) as a diluent to obtain the test compound at the desired final dose.

[0097] When the active ingredients were applied as a mixture, an aqueous spray solution containing both active ingredients was prepared as described above.

[0098] The test plants were then grown under controlled conditions in a glass greenhouse (24 / 16 °C, day / night; 14-hour light; 65% humidity) and watered twice a day. After 13 days, the phytotoxicity rate for the plants (where 100 = total damage to the plant; 0 = no damage to the plant) was visually evaluated compared to the control untreated plants. Two to four replicate experiments were applied to each treatment in a randomized block test design.

[0099] To determine whether the mixture of active ingredients has a synergistic effect on the phytotoxicity rate of the test plants, Colby's formula was applied: S.R. Colby (1967) "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, p. 22., E = X + Y - (X * Y / 100), where X = the average percent phytotoxicity of herbicide A when applied at a certain rate Y = the average percent phytotoxicity using herbicide B when applied at a certain rate E = the predicted effect of the mixture of herbicides A and B calculated from Colby's formula.

[0100] A + B - 4

[0101] [Table 12]

[0102] [Table 13]

[0103] [Table 14]

[0104] [Table 15]

[0105] [Table 16]

[0106] [Table 17]

[0107] Table 18

[0108] A+B-6

[0109]

Table 19

[0110] Table 20

[0111] Table 21

[0112] Table 22

[0113] Table 23

[0114] Table 24

[0115] Table 25

[0116] A+B-7

[0117] Table 26

[0118] Table 27

[0119]

Table 28

[0120]

Table 29

[0121]

Table 30

[0122]

Table 31

[0123]

Table 32

[0124]

Table 33

[0125] A + B - 9

[0126]

Table 34

[0127]

Table 35

[0128]

Table 36

[0129]

Table 37

[0130]

Table 38

[0131] A + B - 16

[0132]

Table 39

[0133]

Table 40

[0134]

Table 41

[0135]

Table 42

[0136]

Table 43

[0137] A + B - 20

[0138]

Table 44

[0139]

Table 45

[0140]

Table 46

[0141]

Table 47

[0142]

Table 48

[0143]

Table 49

Claims

Claim 1 Compound of formula (I) as component (A): 【Chemical 1】 or an agriculturally acceptable salt thereof, and at least one compound selected from the group consisting of component (B): [Chemical 2] [Chemical Formula 3] 【Chemical Formula 4】 or an agriculturally acceptable salt thereof, a composition comprising. Claim 2 The weight ratio of component (A) to component (B) is from 0.001:1 to 1000:1, preferably from 0.001:1 to 500:1, more preferably from 0.01:1 to 50:1, even more preferably from 0.1:1 to 5:1, the composition according to claim 1. Claim 3 The weight ratio of component (A) to component (B) is about 1:1000, 1:50, 1:100, 1:50, 1:30, 1:15, 1:10, 1:8, 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, 6:1 or 8:1, the composition according to claim 2. Claim 4 Component (B) is selected from B-4, B-6, B-7, B-9, B-16 and B-20, the composition according to any one of claims 1 to 3. Claim 5 The weight ratio of the compound of formula (I) to component (B) is in the range of about 1:8 to 8:1, preferably about 1:8, 1:6, 1:4, 1:2, 1:1, 2:1, 4:1, 6:1 or 8:1, the composition according to any one of claims 1 to 4. Claim 6 Component (B) comprises compound B-9, preferably, the weight ratio of the compound of formula (I) to compound B-9 is about 4:1 to 1:1, about 4:1, 3:1, 2:1 or 1:1, etc., the composition according to any one of claims 1 to 5. Claim 7 An agrochemical composition comprising an herbicidally effective amount of the composition according to any one of claims 1 to 6. Claim 8 Further comprising at least one additional active ingredient, the composition according to claim 7. Claim 9 Said at least one additional active ingredient comprises at least one additional agrochemical, the composition according to claim 8. Claim 10 Said additional agrochemical is a herbicide or a herbicide toxicity mitigator, the composition according to claim 9. Claim 11 Further comprising an agriculturally acceptable formulation adjuvant and / or an agriculturally acceptable diluent or carrier, the composition according to any one of claims 6 to 10. Claim 12 A method for suppressing the growth of unwanted plants, comprising applying a herbicidally effective amount of the composition according to any one of claims 1 to 11 to the unwanted plants, a part thereof or a site thereof.

13. The method according to claim 12, wherein component (A) is applied at a rate of 10 to 1000 g / ha, preferably at a rate of 50 to 500 g / ha, more preferably at a rate of 100 to 200 g / ha.

14. The method according to claim 12 or 13, wherein component (B) is applied at a rate of 0.1 to 5000 g / ha, preferably at a rate of 1 to 500 g / ha, more preferably at a rate of 5 to 200 g / ha.

15. The method according to any one of claims 12 to 14, wherein component (B) comprises component B-9, and the method comprises the step of controlling species of the genus Lolium (Lolium spp.), preferably perennial ryegrass (Lolium perenne), Italian ryegrass (Lolium multiflorum) or rigid ryegrass (Lolium rigidum).

16. The method according to any one of claims 12 to 15, wherein the weight ratio of the compound of formula (I) to compound B-9 is about 4:1 to 1:

1.

17. The method according to any one of claims 12 to 16, wherein the composition is applied before germination.

18. Use of the composition according to any one of claims 1 to 11 as a herbicide.

19. A formulation comprising 0.01 to 90% by weight of an active agent, 0 to 25% of an agriculturally acceptable surfactant and 10 to 99.9% of a solid or liquid formulation inert substance and adjuvant, and comprising the composition according to any one of claims 1 to 6.

20. A concentrated composition for dilution by the user, comprising 2 to 80% by weight, preferably about 5 to 70% by weight of an active agent, and comprising the composition according to any one of claims 1 to 6.

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