MXPA97005996A - Herbicide composition and method to control hier - Google Patents

Abstract

A herbicidal composition, comprising at least one compound of the formula I, wherein R 1 is: R 2 is methyl, methoxy, or -OCHF 2, R 3 is methyl or -OCHF 2, and E is = CH-or = N-, where E is = N- when R2 is methoxy or an agrochemically acceptable salt of at least one of the compounds of the formula I, and a compound of the formula II, and / or of the formula III, or an agrochemically acceptable salt of the compound of the formula II and / or III, mixed with others

Description

HERBICIDE COMPOSITION AND METHOD FOR CONTROLLING HERBS The present invention relates to a novel herbicidal composition comprising a combination of herbicidal active ingredients which is suitable for the selective control of herbs in crops of useful plants, for example in cereal crops, rapeseed, sweet beet, sugar cane, crops of plantation, rice, cotton, and especially corn and soybeans. The invention also relates to a method for controlling herbs in crops of useful plants, and to the use of the novel composition for that purpose. The compounds of the formula I: in don -CH2CH2CF3, R2 is methyl, methoxy, or -OCHF2, R3 is methyl or -0CHF2, and E is = CH- or = N-, where E = N- when R2 is methoxy, and the salts thereof, have herbicidal action This is described, for example, in European Patents Nos. EP-A-84,020, EP-A-496,701, and EP-A-120, 814. The following compounds of formulas II and III: OR CH3-P-CH2CH2-CH-COOH (ü) OH NH, OR HO-P-CH2NHCH2-COOH (III) OH and their agrochemically acceptable salts, especially the alkali metal, ammonium and amine salts, are likewise known as herbicides (glufosinates and glyphosates), for example in the "The Pesticide Manual", Tenth Edition 1994, Crop Protection Publications , and they are also commercially available. It has now been surprisingly discovered that a combination of variable proportions of at least one of the compounds of the formula I with one of the above-mentioned compounds of the formula II and / or III, produces a herbicidal action which can control the greater part of the herbs that occur especially in crops of useful plants, before emergence, and especially also after emergence, without significant damage to the useful plant. Accordingly, in accordance with the present invention, a novel composition is proposed for the selective control of herbs which, in addition to the customary formulation aids, comprises as an active ingredient, - at least one compound of the formula I: where Rj is, -C02CH3 or - CH2CH2CF3, R2 is methyl, methoxy, or -0CHF2, R3 is methyl or -0CHF2, and E is = CH- or = N-, where E = N- when R2 is methoxy, or an agrochemically acceptable salt of at least one of the compounds of the formula I, and a compound of the formula II: OR CH3-P-CH2CH2-CH-COOH (II) I I OH NH2 and / or of formula III: or II HO-P-CH2NHCH2-COOH (III), OH or an agrochemically acceptable salt of the compound of formula II and / or III, in admixture with one another. Examples of the agrochemically acceptable salts of the compound of the formula I are given in the abovementioned European Patent Numbers EP-A-84, 020, EP-A-496, 701, and EP-A-120,814, in each case on page 4. The amines described therein, and also the alkali metal hydroxides and the ammonium hydroxide, are likewise examples of suitable salt forming agents for the compounds of the formulas II and III. The herbicidal mixture according to the invention can be used against a large number of agronomically important herbs, such as Veronica, Galium, Ppapver, Solanum, Chenopodium, Amaranthus, Xanthium, Abutilon, Ambrosia, Sagittarius, Ipomoea, Cassiastora, Datura stramonium, Sesbania. exaltata and AIDS spinosa, in crops of useful plants, especially in crops of corn and soybeans. The compositions according to the invention are suitable for all methods and applications customary in agriculture, for example application before emergence, application after emergence, which is preferred, and seed coating. The herbicidal mixture according to the invention is especially suitable for controlling herbs in crops of useful plants, such as cereals, rapeseed, sweet beets, sugarcane, plantation crops, rice, cotton, especially corn and soybeans. Crops should be understood to include those crops that have become tolerant to herbicides or classes of herbicides, for example to glyphosates or glufosinates, by conventional breeding methods or genetic technology. The combination of active ingredients according to the invention comprises the compound or compounds of the formula I and the compound of the formula II and / or III in any desired mixing ratio, generally with an excess of one component over the other. The preferred mixing ratios between the compounds of the formula I and the mixing partner of the formula II and / or III, are in general 1:20 to 1: 5. The compositions according to the invention preferably comprise, as the compound of the formula I, a compound of the formula la: of the formula Ib: and / or of the formula you: Other preferred compositions comprise a compound of the formula la, Ib, or le, and the compound of the formula II and / or III. Of these, compositions comprising a compound of the formula la, Ib, or le and the compound of the formula II or III are especially suitable. The application concentration can vary within wide limits, and depends on the nature of the soil, the type of use (before or after emergence, seed coating, application to the seed furrow, - application without cultivation work, etc.) , of the crop plant, of the grass to be controlled, of the prevailing climatic conditions, and of other factors determined by the type of use, the time of use and the objective crop. In general, the mixture of active ingredients according to the invention can be applied at an application concentration of 250 to 2,500 grams, especially 500 to 1,000 grams of active ingredient mixture per hectare. In the composition according to the invention, the compound or compounds of the formula I are present in a weight ratio of 1: 100 to 1: 0.001 with respect to the compound of the formula II and / or III. Mixtures of the compound or compounds of the formula I with the compound of the formula II and / or III can be used in an unmodified form, ie, as obtained in the synthesis, but are preferably formulated from the customary manner together with the auxiliaries employed by custom in the technology of the formulation, for example in directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dry powders, granules, or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomizing, dusting, wetting, dispersing, or watering, are selected in accordance with the intended objectives and the prevailing circumstances. The formulations, i.e., the compositions, preparations, or mixtures comprising the compounds (active ingredients) of the formulas I and II and / or III, and where appropriate, one or more solid formulation auxiliaries or liquids, are prepared in a manner known per se, for example, by homogeneous mixing and / or milling of the active ingredients with the formulation aids, for example solvents or solid carriers. It is also possible to use surface-active compounds (surfactants) in the preparation of the formulations. Suitable solvents are: aromatic hydrocarbons, preferably fractions containing from 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, for example mixtures of xylene or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons, such as paraffins, cyclohexane, or tetrahydronaphthalene; alcohols, such as ethanol, propanol, or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether; ketones, such as cyclohexanone, isophorone, or diacetone alcohol; strongly polar solvents, such as N-methyl 2-pyrrolidone, dimethyl sulfoxide, or water, - vegetable oils and esters thereof, such as rapeseed oil, castor oil, or soybean oil; and where appropriate, also silicone oils. The solid carriers used, for example, for dry powders and dispersible powders, are normally natural mineral fillers, such as calcite, talc, kaolin, montmori-lonita, or attapulgite. In order to improve physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granular absorbent carriers are porous types, for example pumice, broken septum, sepiolite, or benthicone, and suitable non-sorbent carriers are, for example, calcite or sand. In addition, a large number of previously granulated materials of an inorganic or organic nature can be used, for example, especially dolomite or pulverized plant residues. Depending on the nature of the compound of formula I to be formulated, suitable surface active compounds are nonionic, cationic, and / or anionic surfactants having good emulsifying, dispersing, and wetting properties. The term "surfactants" will also be understood to comprise mixtures of surfactants.

Both water-soluble soaps and synthetic water-soluble surface-active compounds are suitable anionic surfactants. Suitable soaps are the alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts of higher fatty acids (10 to 22 carbon atoms), for example, the sodium or potassium salts of oleic or stearic acid, or mixtures of natural fatty acids which can be obtained, for example, from coconut oil or tallow oil. Mention may also be made of the fatty acid methyl taurine salts. However, synthetic surfactants are more often used, especially fatty alcohol sulfonates, fatty alcohol sulfates, benzimidazole sulfonata-2 derivatives, or alkylaryl sulphonates. The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts, and contain an alkyl radical of 8 to 22 carbon atoms, which also includes the alkyl fraction of the acyl radicals, for example, the sodium or calcium salt of lignosulfonic acid of dodecyl sulfate, or of a mixture of fatty alcohol sulphates obtained from natural fatty acids. These compounds also comprise the salts of sulfonated and sulphonated fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and a fatty acid radical containing from 8 to 22 carbon atoms. Examples of the alkylaryl sulfonates are the sodium, calcium, or trietanolic amine salts of dodecylbenzenesulfonic acid, dibutyl naphthalenesulfonic acid, or a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are the corresponding phosphates, for example salts of the phosphoric acid ester of a p-nonylphenol adduct with 4 to 14 moles of ethylene oxide, or phospholipids. The nonionic surfactants are preferably derived from polyglycol ether of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids, and alkylphenols, these derivatives containing from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in the hydrocarbon fraction. (aliphatic), and from 6 to 18 carbon atoms in the alkyl fraction of alkylphenols. Other suitable nonionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylene diamine polypropylene glycol, and alkylpo-polypropylene glycol containing from 1 to 10 carbon atoms in the alkyl chain, whose adducts contain from 20 to 250 ethylene glycol ether groups, and from 10 to 100 propylene glycol ether groups. These compounds typically contain from 1 to 5 ethylene glycol units per unit of propylene glycol.

Examples of the nonionic surfactants are nonylphenol polyethoxyethanols, polyglycolic castor oil ethers, polypropylene oxide / polyethylene adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol, and octylphenoxypolyethoxyethanol. The polyoxyethylene sorbitan fatty acid esters, for example, polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants. The cationic surfactants are preferably quaternary ammonium salts containing, as N substituent, at least one alkyl radical of 8 to 22 carbon atoms, and as other substituents, unsubstituted or halogenated radicals of lower alkyl, benzyl, or lower hydroxyalkyl. The salts are preferably in the form of halides, methyl sulfates, or ethyl sulfates, for example stearyltrimethyl ammonium chloride or ammonium benzyldi (2-chloroethyl) ethyl bromide. Surfactants customarily employed in the formulation technology, which can also be used in the compositions according to the invention, are described, inter alia, in "Me Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridge ood , New Jersey, 1981; Stache, H., "Tensid-Taschenbuch" (Handbook of Surfactants), Cari Hanser Verlag, Munich / Vienna 1981; and M. and J. Ash, "Encyclopedia of Surfactants," volumes I-III, Chemical Publishing Co., New York, 1980-1981.

The herbicidal compositions usually comprise from 0.1 to 99 percent, preferably from 0.1 to 95 percent of a mixture of active ingredients of the compounds of the formula I with the compound of the formula II and / or III, from 1 to 99 by percent of a solid or liquid auxiliary, and 0 to 25 percent, preferably 0.1 to 25 percent of a surfactant. Although the commercial products of preference will be formulated as concentrates, the end user will usually employ diluted formulations. The compositions may also comprise other auxiliaries, such as stabilizers, for example vegetable oils, or epoxidized vegetable oils (coconut oil, rapeseed oil, or epoxidized soy bean oil), defoamers, for example silicone oil, preservatives, regulators. of viscosity, binders, and viscosities, as well as fertilizers, or other active ingredients. Preferred formulations have especially the following composition (everywhere, the percentages are by weight): Emulsifiable concentrates: mixture of active ingredients: from 1 to 90 percent, preferably from 5 to 20 percent. surface activity agent: from 1 to 30 percent, preferably from 10 to 20 percent. liquid vehicle: from 5 to 94 percent, preferably from 70 to 85 percent.

Dry powders: mixture of active ingredients: from 0.1 to 10 percent, preferably from 0.1 to 5 percent. solid vehicle: from 99.9 to 90 percent, preferably from 99.9 to 99 percent.

Concentrates in suspension: mixture of active ingredients: from 5 to 75 percent, preferably from 10 to 50 percent. water: from 94 to 24 percent, preferably from 88 to 30 percent. surface activity agent from 1 to 40 percent, preferably from 2 to 30 percent.

Wettable powders: mixture of active ingredients: from 0.5 to 90 percent, preferably from 1 to 80 percent. surface activity agent: from 0.5 to 20 percent, preferably from 1 to 15 percent. solid vehicle: from 5 to 95 percent, preferably from 15 to 90 percent.

Granules: mixture of active ingredients from 0.1 to 30 percent, preferably from 0.1 to 15 percent. solid vehicle: from 99.5 to 70 percent, preferably from 97 to 85 percent.

The following Examples further illustrate, but do not limit, the invention. g-jom iofl de Formulation: Mixtures of compounds of formulas I and II and / or III (everywhere, the percentages are by weight): Fl. Emulsifiable concentrates a) b) c) d) mixture of compound of formula I with one of the compounds of formula II and / or III 5% 10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8 Polyglycol ether of castor oil (36 moles of ethylene oxide) 4% - 4% 4% Polyglycol ether of octylphenol (7 to 8 moles of ethylene oxide) - 4% - 2% cyclohexanone - - 10% 20% mixture of aromatic hydrocarbons of 9 to 12 carbon atoms 85% 78% 55% 16% Emulsions of any desired concentration can be obtained from these concentrates by dilution with water.

F2 Solutions a) b) c) d) mixture of the compound of the formula I with one of the compounds of the formula II and / or III 5% 10% 50% 90% 1-methoxy-3- (3-methoxy-propoxy) -propane - 20% 20% glycolic polyethylene, molecular weight: 400 20% 10% pyrrolidone N-methyl - - 30% 10% aromatic hydrocarbon mixture from 9 to 12 carbon atoms 75% 60% These solutions are suitable to be applied in the form of microdroplets.

F3 Wettable powders a) b) c) d) mixture of compound of the formula I with one of the compounds of the formula II and / or III 5% 25% 50% 80% sodium lignosulfonate 4% -3% lauryl sulfate sodium 2% 3% - 4% sodium diisobutylnaphthalenesulfonate - 6% 5% 6% octylphenol polyglycol ether (7 to 8 moles of ethylene oxide) - 1% 2% - highly dispersed silicic acid 1% 3% 5% 10% kaolin 88% 62% 35% The active ingredient is mixed thoroughly with the auxiliaries, and the mixture is completely milled in a suitable mill, providing wettable powders that can be diluted with water to give suspensions of any desired concentration.

F4 Coated granules a) b) c) mixture of compound of the formula I with one of the compounds of the formula II and / or III 0.1% 5% 15% Silicic acid highly dispersed 0.9% 2% 2% inorganic carrier 99.0% 93% 83% (0.1-1 mm diameter) for example CaCO3 or SiO2 The active ingredient is dissolved in methylene chloride, and the solution is sprayed onto the vehicle, and the solvent subsequently evaporated in vacuo.

F5 Coated granules a) b) c) mixture of compound of the formula I with one of the compounds of the formula II and / or III 0.1% 5% 15% polyethylene glycol, molecular weight 200 1.0% 2% 3% highly silicic acid dispersed 0.9% 1% 2% inorganic vehicle 98.0% 92% 80% (diameter 0.1-1 mm) for example, CaC03 or Si02 The finely ground active ingredient is applied evenly in a mixer,. to the vehicle moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6 Extruder pellets a) b) c) d) mixture of compound of formula I with one of the compounds of formula II and / or III 0.1% 3% 5% 15% sodium lignosulfonate 1.5% 2% 3% 4% carboxymethyl cellulose 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79% The active ingredient is mixed and ground with the auxiliaries, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

F7 Dry powders a) b) c) mixture of compound of formula I with one of the compounds of formula II and / or III 0.1% 1% 5% talcum 39.9% 49% 35% kaolin 60.0% 50% 60% Dry powders are obtained ready for use by mixing the active ingredient with the vehicles, and grinding the mixture in a suitable mill.

F8..Concentrates in suspension a) b) c) d) mixture of compound of formula I with one of the compounds of formula II and / or III 3% 10% 25% 50% ethylene glycol 5% 5% % 5% polyglycol ether of nonylphenol (15 moles of ethylene oxide) - 1% 2% - sodium lignosulfonate 3% 3% 4% 5% carboxymethyl cellulose 1% 1% 1% 1% aqueous formaldehyde solution 37 percent 0.2% 0.2% 0.2% 0.2% silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87% 79% 62% 38% The finely ground active ingredient is intimately mixed with the auxiliaries, giving a suspension concentrate to from which suspensions of any desired concentration can be obtained by dilution with water. It is often more practical for the compounds of the formula I and the mixing partner of the formula II and / or III to be formulated separately and to be combined only a short time before application in the applicator in the desired mixing ratio in the form of a "tank mix" in water.

Biological Examples: Example Bl: Post emergence test: In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in plastic pots containing conventional soil, and in the 4 to 6 leaves stage they are sprayed with an aqueous suspension of the compounds of formula I, prepared from a 25 percent wettable powder formulation (Example F3, b)) corresponding to an application concentration of 2000 grams of active ingredient per hectare (500 liters of water per hectare). The test plants are then grown in the greenhouse under optimum conditions. After approximately 18 days, the test is evaluated according to a scale of nine points (1 = total damage, 9 = no action). Evaluations from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action. In this test, the compounds of formula I exhibit a strong herbicidal action. The same results are obtained when the compounds of the formula I are formulated according to Examples Fl and F2, and F4 to F8.

Claims (9)

NOVELTY OF THE INVENTION Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: CLAIMS

1. A herbicidal composition, which comprises at least one compound of the formula I: where Rj is -C02CH3 or -CH2CH2CF3, R2 is methyl, methoxy, or -OCHF, R3 is methyl or -0CHF2, and E is = CH- or = N-, where E = N- when R2 is methoxy, or an agrochemically acceptable salt of at least one of the compounds of the formula I, and a compound of the formula II: OR CH3-P-CH2CH2-CH-COOH (II) OH NH2 and / or of formula III: OR II HO-P-CH2NHCH2-COOH (III), OH or an agrochemically acceptable salt of the compound of the formula II and / or III, in admixture with one another, with the exception of the compositions comprising: a) l- [(2-methoxycarbonyl-phenyl) -sulfonyl] -3- [ 4, 6-bis- (difluoromethoxy) -pyrimidin-2-yl] -urea and a compound of the formula II and / or III, and b) 1- [(2-methoxycarbonyl-phenyl) -sulfonyl] -3- [4-methoxy-6-methyl) -triazin-2-yl] -ureayun compound of the formula II and / or III.

2. A composition according to claim 1, which comprises as the compound of the formula I a compound of the formula la: of the formula Ib: ib) and / or from the formula

3. A herbicidal composition according to claim 1, which comprises a compound of the formula la, Ib, or 'le, and the compound of the formula II and / or III.

4. A herbicidal composition according to claim 3, which comprises a compound of the formula la, Ib, or le, and the compound of the formula II or III.

5. A herbicidal composition according to claim 1. which comprises the compound or the compounds of the formula I, in a weight ratio of 1: 100 to 1: 0.001 with respect to the compound of the formula II and / or III.

6. A method for controlling the growth of unwanted plants in crops of useful plants, which comprises allowing a herbicidally effective amount of a composition according to claim 1 to act on the cultivated plant or on the site thereof.

7. A method according to claim 6, wherein the cultivated plant is corn or soybeans. A method according to claim 6, wherein the cultivated plants are treated with the compositions in application concentrations of a total amount of active ingredient of 0.25 to 2.5 kilograms per hectare. 9. A composition according to claim 1, which comprises, as the compound of the formula I, a compound of the formula Ib: and from the formula you: SUMMARY OF THE INVENTION A herbicidal composition, comprising at least one compound of the formula I: where Ri is -CO2- < ? Q '"C02CH3 ° -CH2CH2CF3, R2 is methyl, methoxy, or -OCHF2, R3 is methyl or -OCHF2, and E is = CH- or = N-, where E = N- when R2 is methoxy, or an agrochemically acceptable salt of at least one of the compounds of the formula I, and a compound of the formula II: OR CH3-P-CH2CH2-CH-COOH (II) OH NH2 and / or of formula III: OR II. HO-P-CH2NHCH2-COOH (III), | OH or an agrochemically acceptable salt of the compound of formula II and / or III, in admixture with one another. * * * * *