MXPA00011712A - Herbicidal mixture containing a 3 heterocyclyl-substituted benzoyl derivative - Google Patents

Abstract

Herbicidal mixture containing a) a herbicidally effective amount of a 3 heterocyclyl-substituted benzoyl derivative of formula (I), wherein the variables have the following meanings:R1, R2=hydrogen, halogen, C1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 halogen alkyl, C1-C6 alkoxy, C1-C6 halogenalkoxy;R3=hydrogen, halogen, C1-C6 alkyl;X=a heterocycle from the group of isoxazolyl, 4,5-dihydroisoxazolyl and thiazolyl, whereby said heterocycle can be substituted once or more with halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4 alkylthio;R4=a cross-linked pyrazol in position 4 of formula (II), whereby R5=hydrogen or C1-C6 alkyl and R6=C1-C6 alkyl, or the environmentally compatible salts thereof;b) a fertiliser containing nitrogen in a synergistically effective quantity and c) an adjuvant in a synergistically effective quantity.

Description

"HERBICIDAL MIXTURES CONTAINING COMPOUNDS OF 3-HETEROCICLIL-BENZILO REPLACED, A FERTILIZER NITROGENATE AND AN ADJUVANT, PROCEDURE FOR FIGHTING THE GROWTH OF UNWANTED PLANTS APPLYING SUCH MIXES AND PROCEDURE FOR PREPARE THE MENTIONS MENTIONED " Description The present invention relates to a synergistic herbicidal mixture from a benzoyl derivative substituted by a 3-heterocyclyl, a nitrogen fertilizer and an adjuvant. Benzoyl derivatives substituted by a 3-heterocyclyl are known and described, for example, in WO 96/26206, WO 97/411 16, WO 97/41117 and WO 97/41 118. EP - B-0584 227 are known herbicidal compositions from substituted cyclohexandiones and nitrogen fertilizers. The object of the present invention was to provide a herbicidal mixture, which contains a benzoyl derivative substituted by a 3-heterocyclyl and whose herbicidal effect is greater, compared to that of the pure active substance. This object was achieved with a herbicidal mixture, which contains a) a herbicidal active amount of a benzoyl derivative substituted by 3-heterocyclyl of the formula I in which the variables have the following meanings: R1, R2 hydrogen, halogen, C, - - alkyl, C, -C6-alkylthio, C, -C6-alkylsulfinyl, C, -C6-alkylsulfonyl, C, -C6-halogenalkyl, C, -C6-alkoxy, C, -C6-halogenalkoxy; R3 hydrogen, halogen, C, -C6-alkyl; X heterocycle of the isoxazolyl, 4,5-dihydroisoxazolyl and thiazolyl group, wherein the heterocycle may be mono- or polysubstituted if appropriate by halogen, C, -C6-alkyl, C, -C4-alkoxy, C | - C4 - halogenalkyl, C - C4 - halogenalkoxy, C, - C4 - alkylthio; R4 a pyrazole linked at position 4 of formula II where R5 means hydrogen or C, -C6-alkyl, R6 means C.-C6-alkyl or its salts harmless to the environment; b) a nitrogenous fertilizer in an active synergistic amount and c) an adjuvant in an active synergistic amount. The herbicidal mixture according to the invention has a synergetic action and is selective against those crop plants, which also tolerate the individual active substances. With respect to their synergistic herbicidal action, especially preferred are benzoyl derivatives substituted by a 3-heterocyclyl of the formula Ib, in which R1, R2 signify chlorine, methyl, ethyl, SCH3, SOCH3, S02CH3; R3 hydrogen and methyl; R5 hydrogen, methyl, trifluoromethyl; R6 methyl, ethyl, i-propyl; x heterocycle of the group: isoxazolyl, 4,5-dihydroisoxazolyl and thiazolyl, the heterocycle being mono- or polysubstituted if appropriate by halogen, C, - - alkyl, C, - C4 - alkoxy, C - C4 - halogenalkyl, C [ -C4 - halogenalkoxy, C 1 -C 4 -alkylthio, or their salts harmless to the environment. Preferred compounds of the formula Ib are listed in the following table: N ° R1 R2 R3 Rs R6 X 1 Cl SO2CH3 H CH3 CH3. 2-thiazolyl 2 Cl SO 2 CH 3 H H CH 3 2- thiazolyl 3 Cl SO 2 CH 3 H CH 3 CH 3 4,5-Dihydro-isoxazol-3-yl 4 Cl Cl H CH 3 CH 3 4, 5-dihydro-isoxazol-3-yl Cl SO2CH3 H H CH3 4, 5-dihydro-isoxazol-3-yl 6 Cl SO 2 CH 3 H H CH 3 4,5-Dihydro-5-methyl-isoxazol-3-yl Cl SO, CH, HH CH 3 4,5-Dihydro-5,5-dimethyl-isoxazol-3-yl 8 Cl SO 2 CH 3 HH CH 3 , 5-Dihydro-5-ethyl-isoxazol-3-yl 9 Cl SO 2 CH 3 HH CH 3 4,5-Dihydro-5,5-diethyl-isoxazol-3-yl 10 Cl SO 2 CH 3 HH CH 3 4,5-Dihydro-5-chloromethyl- isoxazol-3-yl 11 Cl SCH 3 H H CH 3 4, 5-dihydro-isoxazol-3-yl 12 Cl SO 2 CH 3 H H CH 3 4,5-Dihydro-5-ethoxy-isoxazol-3-yl 13 Cl SO 2 CH 3 HH CH 3 4, 5 - dihydro-5-methoxy-isoxazol-3-yl 14 CH 3 SO 2 CH 3 HH CH 3 4,5-Dihydro-isoxazol-3-yl 15 Cl SO 2 CH 3 HH CH 3 4,5-Dihydro-4,5-dimethyl-isoxazol-3-yl Cl SO 2, C-Hi l 3, HH CH 3 4, 5-dihydro-5-thioethyl-isoxazol-3-yl Cl SO, CH, HH CH 3 4,5-Dihydro-5-trifluoromethyl-isoxazol-3-yl SCH3 SCH3 HH CH3 4, 5 - dihydro - isocazol - 3 - yl Cl SO2CH3 H H C2H5 2-thiazolyl Cl SO2CH3 H H C2H5 4, 5-dihydro-isocazol-3-yl Cl SO 2 CH 3 HH C 2 H 5 4, 5-dihydro-5-methyl-isozazol-3-yl Cl SO r, C 1 H 1, HH C 2 HS 4, 5-dihydro-5, 5-dimethyl-isoxazol-3-yl Cl HH C 2 H 5 4, 5-dihydro-5-ethyl-isoxazol-3-yl Cl SO, 2CV-HJ J.3, HH C2H5 4, 5-dihydro-5, 5-diethyl-isoxazol-3-yl Cl SCH3 HH C2H5 4, 5-dihydro-isoxazol-3-yl Cl SO, CH, HH C2H5 4, 5-dihydro-5-chloromethyl-isoxazol-3-yl Cl SO, CH, HH C2HS 4, 5-dihydro-5-ethoxy-isoxazole-3 - ilo Cl SO2CH3 HH C2H5 4, 5-dihydro-4,5-dimethyl-isoxazol-3-yl CH3 SO2CH3 HH C2H5 4, 5-dihydro-isoxazol-3-yl Cl SO2CH3 HH C2H5 4, 5-dihydro-5 - thioethyl-isoxazol-3-yl Cl SO2CH3 HH C2H5 4, 5-dihydro-5-trifluoromethyl-isoxazol-3-yl SCH3 SCH3 HH C2H5 4, 5-dihydro-isoxazol-3-yl Cl SO2CH3 H H i - C4H9 4, 5 - dihydro - isoxazol - 3 - yl Cl SO 2 CH 3 H H CH 3 3 -methyl-isoxazol-5-yl Cl SO2CH3 H H C2H5 3-methyl-isoxazol-5-yl CH 3 SO 2 CH 3 HH C 2 H 5 3-Methyl-isoxazol-5-yl 7 CH 3 SO 2 CH 3 H CH 3 CH 3 4,5-Dihydro-isoxazol-3-yl 8 CH 3 Cl H CH 3 CH 3 4,5-Dihydro-isoxazol-3-yl 9 CH 3 SO 2 CH 3 H H CH 3 4, 5-Dihydro-5-methyl-isoxazol-3-yl 0 CH, SO, CH, H H CH 3 4,5-Dihydro-5,5-dimethyl-isoxazol-3-yl 1 CH 3 SO 2 CH 3 HH CH 3 4, 5-Dihydro-5-ethyl-isoxazol-3-yl 2 CH, SO, CH, HH CH 3 4, 5-dihydro-5, 5-ethyl-isoxazol-3-yl 3 CH 3 SO 2 CH 3 HH CH 3 4, 5-dihydro- isoxazol-3-yl 4 CH 3 SO 2 CH 3 HH CH 3 4,5-dihydro-4,5-dimethyl-isoxazol-3-yl 5 CH 3 Cl HH C 2 H 5 4, 5-dihydro-isoxazol-3-yl 6 CH 3 SO 2 CH 3 HH C 2 H 3 4, 5-Dihydro-5-methyl-isoxazol-3-yl 7 CH 3 SO 2 CH 3 HH C 2 H 5 4, 5-dihydro-5,5-dimethyl-. isoxazol-3-yl 8 CH3 SO2CH3 HH C2H5 4, 5-dihydro-5-ethyl-isoxazol-3-yl 9 CH3 SO2CH3 HH C2H5 4, 5-dihydro-4, 5-dimethyl-isoxazol-3-yl 0 CH3 SO2CH3 HH 1 - C4Hg 4, 5 - dihydro - isoxazol - 3 - yl Compounds are especially preferred 4 - . 4 - [2-chloro-3 - (4,5-dihydro-isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole, 4 - [2-methyl-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole, 4 - [2-chloro-3 - (3-methyl-isoxazole-5- il) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole, or its salts harmless to the environment. Suitable salts, harmless to the environment are, for example, the salts of alkali metals, alkaline earth metals, ammonia or amines. Suitable nitrogen fertilizers b) are ammonia and ammonium salts, urea, thiourea and mixtures thereof. Examples of suitable fertilizers are aqueous solution of ammonia, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium acetate, ammonium formate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, ammonium thiosulfate, ammonium phosphate, ammonium hydrogen biphosphate, ammonium dihydrogen monophosphate, sodium ammonium hydrogen phosphate, ammonium thiocyanate, urea and thiourea, as well as mixtures thereof, as well as solutions of ammonium nitrate urea (UAN solutions or of AHL). Preferred nitrogen fertilizers are Urea, ammonium nitrate, solutions of ammonium nitrate - urea, ammonium sulfate, ammonium phosphate, ammonium hydrogenephosphate, ammonium dihydrogenmonophosphate and sodium ammonium hydrogen phosphate.

Urea, ammonium nitrate and the solutions of ammonium nitrate-urea are especially preferred. The solutions of ammonium nitrate-urea preferably have a total nitrogen content of 28-33% (w / w) and are marketed, for example, under the trademark Ensol '"' 28 by BASF. ) are vegetable oils, which may be partially hydrogenated and hydrogenated, modified vegetable oils, mineral oils, alcohol alkoxylates, alcohol ethoxylates, alkylated ethylene oxide / propylene oxide block copolymers, alkylphenol ethoxylates, polyols, ethylene oxide / propylene oxide block copolymers, organosilicon, alkyl glycosides, alkyl polyglycosides, alkyl sulphates, sulphated alcohol alkoxylates, alkylaryl sulfonates, alkyl sulfonates, dialkyl sulfosuccinates, phosphated alcohol alkoxylates, fatty amine alkoxylates, esters, carboxylates, ester ethoxylates, dialkyl adipates, derivatives of dicarboxylic acids, such as p. ex. so-called alkenyl succinic anhydride condensates with polyalkylene or polyhydroxyamine oxides, dialkyl phthalates, sorbitol esters ethoxylated with natural glycerides and ethoxylates of natural fatty acids. Preferred adjuvants are alcohol alkoxylates, such as alkyl ethers of copolymerized ethylene oxide / propylene oxide, e.g. ex. Plurafac * (BASF AG), Synperionic® LF (ICI), alcohol ethoxylates, the alcohol being able to be one with 8 to 18 carbon atoms of synthetic or natural origin, which can be both linear and branched. The ethoxylate part contains, depending on the alcohol used, 3-20 moles of ethylene oxide on average. Examples of products used are: Lutensol® ON, TO, AO and A of the BASF company, alkylaryl sulfonates, such as p. ex. nonylphenol ethoxylates with 5-15 moles of ethylene oxide, polyols, such as polyethylene glycol or polypropylene glycol, block copolymers of ethylene oxide / ethylene oxide, as p. ex. Pluronic® PE (BASF AG) or Synperionic® PE (ICI), organosilicone compounds, alkyl polyglycosides, e.g. ex. Agrimul® (Henkel KGA), AG 6202 (Akzo-Nobel) Atplus® 450 (ICI) or Lutensol® GD 70 (BASF AG), fatty amine alkoxylates, such as p. ex. Ethomeen® and Armobleem® from Akzo Nobel, esters of natural and synthetic fatty acids, such as p. ex. methyl oleates or methyl cocoates, dialkyl adipates, ethoxylated sorbitol esters of natural fatty acids, e.g. ex. Tween® from the company ICI Surfactants (Tween® 20, Tweeno 85, Tween® 80), ethoxylated glycerides of natural fatty acids, such as p. ex. Glycerox® from the company Croda. Other examples are described in: McCutcheon's; Emulsifiers and Detergents, Volume I: Emulsifiers and Detergents 1994 North American Edition; McCutcheon's Division, Glen Rock NJ, USA, McCutcheon's; Emulsifiers and Detergents, Volume 2: Emulsifiers and Detergents 1994 International Edition; McCutcheon Division, Glen Rock NJ, USA, Surfactants in Europe; A Directory of active surface agents available in Europe 2nd Ed. 1989; Terg Data, Darlington, England, Ash, Michael; Handbook of cosmetic and personal care additives 1994; Gower Publishing Ltd., Aldershot, England Ash, Michael; Handbook of industrial Surfactants 1993; Gower Publishing Ltd., Aldershot, England.

The herbicidal mixture according to the invention contains the components a) to c) in the following amounts: 0.5 to 90% by weight of the benzoyl derivative substituted by a 3 -heterocyclyl a); 5 to 94.5% by weight of the nitrogen fertilizer b); 5 to 50% by weight of the adjuvant c).

Preferred quantitative ratios are: 0.5 to 50% by weight of the benzoyl derivative substituted by a 3 -heterocyclyl a); 5 to 90% by weight of the nitrogen fertilizer b); 5 to 50% by weight of the adjuvant c). Here, the components are completed at 100% by weight. The individual components a) to c) of the herbicidal mixture according to the invention can be formulated and packaged together or separately. In addition, component a) can be formulated and packaged with component b), or component a) with component c). The farmer uses the herbicide mixture or its individual components for applications per spray tank. Here, the herbicidal mixture is dissolved with water, and other auxiliaries or additives may be added if necessary. The individual components a) to c) of the herbicidal mixture according to the invention can also be mixed in the spray tank and, if necessary, added by other auxiliaries and additives (tank mixing method). In the tank mixing process, components a) through c) are mixed in the spray tank and diluted with water to the desired application concentration. For the tank mixing processes, the following adjuvants have been proven: Mineral oils, paraffin oils, vegetable oils, hydrogenated or methylated vegetable oils, such as p. ex. soybean oil, oil rapeseed, sunflower oil, esters and salts of natural carboxylic acids, such as p. ex. Methyl oleate, the so-called methylated seed oils, non-ionic surfactants, such as p. ex. ethoxylated alcohols, ethoxylated phenols, ethoxylates of fatty amines, as well as mixtures thereof. To improve the processing, other auxiliaries and additives can be added. The following components have been accredited as auxiliaries and additives: Solvents, defoamers, buffer substances, thickeners, dispersants, products that promote compatibility. Examples and brands of adjuvants and auxiliaries and additives are described in Farm Chemicals Handbook 1997; Meister Publishing 1997 p. CIO "adjuvant" or 1998 Weed Control Manual p. 86. The mixture according to the invention is suitable as a herbicide. The herbicidal mixture is suitable for combating the growth of unwanted plants very well in areas not intended for cultivation, especially in high amounts of application. In crops, such as wheat, rice, corn, soybeans and cotton, it is active against bad weeds and noxious grasses, without causing damage worthy of mention in crop plants. This effect occurs mainly with low amounts of application. Depending on the respective application method, the herbicidal mixture can be used in other additional plant crops to eliminate unwanted plants there. For example, the following crops are included: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus lemon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum , Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saeeharum officinarum, Sécale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays. In addition, the herbicidal mixture can also be used in crops that have been made tolerant to the action of herbicides by culture or genetic engineering methods. The herbicidal mixture can be applied before or after emergence. When the herbicidal mixture is less tolerated by the crop plants, then application methods may be used in which the herbicidal mixture is sprayed with the aid of spray apparatus in such a way that it does not fall on the leaves of the sensitive crop plants. , but only on the leaves of the unwanted plants that grow below the first ones or on the ground covered with unwanted plants (post - directed, lay - by). The herbicidal mixture can be used, for example, in the form of aqueous solutions, powders directly sprayable suspensions, also in the form of suspensions, dispersions or emulsions of high aqueous, oleic or other percentage, dispersions of oil, pastes, spraying agents, of dusting or granules, by means of spraying, fogging, spraying, sprinkling or watering. The forms of application depend on the purpose of the use; In any case, they must guarantee one. distribution as fine as possible of the herbicidal mixture of the invention. Suitable inert additives are mineral oil fractions from the medium to high boiling point, such as kerosene or diesel oil, in addition, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, such as paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar sots, such as amines, N-methylpyrrolidone or water. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders or granules dispersible in water by the addition of water. To obtain emulsions, pastes or oil dispersions, the substances can be homogenized as such or disso in an oil or sot, by means of wetting agents, tackifiers, dispersants or emulsifiers, in water. However, a humectant, adherent, dispersant or emulsifier and, optionally, a sot or an oil, which are suitable for dilution with water, can also be prepared from the active substance. Suitable surface-active substances are: alkali metal, alkaline earth metal, ammonium salts of aromatic sulfonic acids, e.g. ex. lignin sulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylaryl sulphonates, alkyl ether, lauryl ether and fatty alcohol sulfates, as well as sulphated hexa, hepta and octadecanole salts, as well as glycol fatty alcohol ethers, sulfonated naphthalene condensates and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylenctyl phenol ethers, isooctylphenol, octylphenol or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenylpolyglycol ethers , alkylaryl alcohol alcohols, isotridecyl alcohol, fatty alcohol - ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, polyglycol ether acetate lauric alcohol, sorbitol esters, sulfuric residual liquors or methylcellulose. The spraying, spraying and atomizing agents can be obtained by mixing the herbicidal mixture together with a solid carrier. The granulates, p. ex. Coated granules, impregnated granules and homogeneous granules can be prepared by joining the herbicide mixture with solid supports. Suitable solid supports are mineral soils, such as silica gel, silicic acids, silicas gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, Ioess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate , magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flours, stone powders, tree bark powders, wood and shell powders of nuts, cellulose powders or other solid supports. The concentrations of the herbicidal mixture in ready-to-use preparations can vary widely. The formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight of the herbicidal mixture. The components of the mixture are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).; The herbicidal mixture according to the invention can be formulated, for example, in the following form: A) Concentrates for the preparation of the mixture according to the invention 1) Suspension concentrate 108 g of 4 - [2-chloro-3 - (4,5) - dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole (technical 92%), 20 g / 1 of Wettol® DI from Cía. BASF, 30 g of Pluronic® PE 10500 from BASF AG, 3 g of Kelzan®, 1.4 g of Kathon® MK, 70 g of 1, 2-propylene glycol and 5 g of silicone emulsion from Co. Wacker is completed with water at 1 1 and then milled in a ball mill to a particle size of 60% <; 2 microns. 2) Suspension concentrate 503 g of 4 - [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonylbenzoyl] -1-methyl-5-hydroxy-1 H-pyrazole (technical 99) %), 20 g / 1 of Wettol® DI de la Cía. BASF, 30 g of Pluronic® PE 10500 from BASF AG, 3 g of Kelzan®, 1.4 g of Kathon® MK, 70 g of 1,2-propylene glycol and 5 g of silicone emulsion from Co. Wacker is completed with water at 1 1 and then milled in a ball mill at a particle size of 60% < 2 microns. 3) Water-soluble concentrate of component a) 100 g of the active substance 4 - [2-chloro-3 ~ (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5- hydroxy-1 H-pyrazole (technical 99%) are dispersed in approx. 800 ml of water. The active substance is neutralized with dilute potassium hydroxide solution (KOH) and the formulation is adjusted to pH 8.5. Then, the product is completed to 1 liter. B) Herbicidal mixtures according to the invention 4) Suspension concentrate 100 ml of the concentrate prepared in 2) are mixed with 220 ml of water and 360 ml of ammonium nitrate-urea solution (ENSOL®28, BASF AG). By means of an intensive stirrer, a solution of 14 g of a Ca-dodecylbenzenesulfonate (Wettol® EM 1, BASF AG), 14 g of a castor oil ethoxylate with 40 moles of ethylene oxide (Wettol® EM 31) are emulsified in this mixture. , BASF AG) and 250 ml of the adipic acid dioctyl ester (Plastomoll® DOA, BASF AG). A stable suspension of 4 - [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole having a content of active substance 50 g / 1. 5) Suspension concentrate 100 ml of the concentrate prepared in 2) are mixed with 220 ml of water and 360 ml of ammonium nitrate - urea solution (ENSOL ® 28, BASF AG). By means of an intensive stirrer, 250 ml of methyl oleate are emulsified in this mixture. A stable suspension of 4 - [2-chloro-3 - (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy is obtained. - 1 H - pyrazole with an active substance content of 50 g / 1. 6) Water-dispersible granules 50 g of the active substance 4 - [2-chloro-3 - (4,5-dihydroisoxazol-3-yl) - 4-Methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole (technical 99%), 50 g of naphthalenesulfonic acid-formaldehyde condensate, 10 g of Na ligninsulfonate and 600 g of ammonium sulfate are added. they mix intimately and are ground in an air jet mill. The powder obtained is mixed in a mixer with 31 g of ethylhexyl glucoside (65% aqueous solution). The mixture is extruded in an extruder (DGL-1 Co. Fitzpatrick, Belgium, orifice diameter 0.8 mm). Eventually, more liquid is added for this purpose, so that the mixture is extrudable. The granulates are dried and a water-dispersible granulate with an active substance content of 5% is obtained. 7) Water-soluble concentrate 50 g of the active substance 4 - [2-chloro-3- (4,5-dihydro-isoxazol -3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole (technical 99%) are dispersed in 200 ml of water and neutralized with dilute potassium hydroxide solution (KOH). To this end, 360 g of ammonium nitrate-urea solution (ENSOL® 28, BASF AG) and 250 g Lutensol® ON 80 (BASF AG) are added. The product is regulated with KOH at pH 8.5 and is completed with water to one liter. 8) Water-soluble concentrate 100 g of the active substance 4 - [2-chloro-3 ~ (4,5-dihydroisoxazol -3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole (99% techn) are dispersed in approx. 300 ml of water With dilute potassium hydroxide solution (KOH) the active substance is neutralized and the formulation is adjusted to pH 8.5, for which 500 g of AG 6202 are added with stirring. After homogenization the pH value is checked again and It is corrected eventually. Then, the product is completed to one liter.

To extend the spectrum of action and to achieve synergistic effects, the herbicidal mixture can be mixed with numerous representatives of other groups of herbicidal active substances and growth regulators and applied in conjunction with these. Suitable mixing components are, for example, 1, 2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anuides, (het) -aryl oxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1, 3-cyclohexandiones, hetaryl-aryl-ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-amines, dinitroanilines , dinitrophenols, diphenyl ethers, dipyridyls, halogenated carboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionates , phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

Depending on the species, the plants were maintained at 10-25 ° C or 20-35 ° C. The trial period lasted for 2 to 4 weeks. During this time, the plants were monitored, and their response to individual treatments was evaluated. The evaluation was carried out using a scale of 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth. The plants that were used in the greenhouse experiments belonged to the following species: Example 1 or Table 1 Table 2 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha i 3.a. ZEAMX CHEAL Example 1 0.0625 0 50 Example 1 0.0625 * + + 0 75 Pluronic® PE 6800 0.25 Example 1 0.0625 80 + + Pluronic® PE 6800 0.25 0 + + ENSOL®28 0.375 Table 3 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. ECHCG Example 1 0.0625 50 Example 1 0.0625 + + 75 Agrimul® PG 2067 0.25 Example 1 0.0625 + + Agrimul® PG 2067 0.25 80 + + ENSOL®28 0.375 Table 4 Selective herbicidal activity in the procedure after emergence in the greenhouse Phytotoxicity Active substance AWM kg / ha s.a. ABUTH Example 1 0.0156 20 Example 1 0.0156 + + 70 Agrimul® PG 2067 0.25 Example I 0.0156 + + Agrimul® PG 2067 0.25 80 + + ENSOL, 28 0.375 Table 5 Selective herbicide activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. ECHCG ABUTH Example 1 0.0312 030 75 Example 1 0.0312 + + 40 80 Agrimul® PG 600 0.25 Example 1 0.0312 + + Agrimul® PG 600 0.25 70 85 + + ENSOL®28 0.375 Table 6 Selective herbicidal activity in the procedure after emergence in the greenhouse Phytotoxicity Active substance AWM kg / ha s.a. CHEAL Example 1 0.0078 20 Example 1 0.0078 + + 70 Agrimul® PG 600 0.25 Example 1 0.0078 + + Agrimul® PG 600 0.25 98 + + ENSOL®28 0.375 Table 7 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha: > .to. CHEAL Example 1 0.0156 20 Example 1 0.0156 + + 90 Lutensol® GD 70 0.25 Example 1 0.0156 + + Lutensol® PG 600 0.25 95 + + ENSOL®28 0.375 Table 8 Selective herbicide activity in the procedure after emergence in the greenhouse Fitotoxicity active presence AWM kg / ha s.a. ZEAMX CHEAL Example 1 0.0625 0 50 Example 1 0.0625 + + 0 60 AG® 6202 0.25 Example 1 0.0625 + + AG®6202 0.25 0 80 + + ENSOL®28 0.375 Table 9 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. ECHCG Example 1 0.0625 50 Example I 0.0625 + + 90 Lutensol * ON 30 0.25 Example 1 0.0625 + +. Lutensol® ON 30 0.25 100 + + ENSOL®28 0.375 Table 10 Selective herbicide activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. CHEAL Example 1 0.0078 20 Example 1 0.0078 + + 80 Lutensol® QN 80 0.25 Example 1 0.0078 + + Lutensol® ON 80 0.25 98 + + ENSOL®28 0.375 Table 11 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. SETV1 [CHEAL Example 1 0.0078 30 20 Example 1 0.0078 * + + 40 60 Lutensol® ON 1 10 0.25 Example 1 0.0078 + + Lutensol®ON 1 10 0.25 95 95 + + ENSOL®28 0.375 Table 12 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s i.a. CHEAL Example 1 0.0156 20 Example 1 0.0156 + + 50 Lutensol® TO 8 0.25 Example 1 0.0156 + + Lutensol® TO 8 0.25 80 + + ENSOL®28 0.375 Table 13 Selective herbiological activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha i s.a. CHEAL Example 1 0.0156 20 Example 1 0.0156 + + 60 Pluriol® E 600 0.25 Example 1 0.0156 + + Pluriol® E 600 0.25 98 + + ENSOL®28 0.375 Table 14 Selective herbicidal activity in < 3l procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg ha s.a. CHEAL Example I 0.0156 20 Example 1 0.0156 + + 90 Pluriol® E 4000 0.25 Example 1 0.0156 + + Pluriol® E 4000 0.25 98 + + ENSOL®28 0.375 Table 15 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. Example 1 0.0625 50 Example 1 0.0625 * + + 85 Glycerox® L 8 0.25 Example 1 0.0625 + + Glycerox® L 8 0.25 90 + + ENSOL®28 0.375 Table 16 Selective herbicidal activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. ABUTH Example 1 0.0156 20 Example 1 0.0156 + + 70 Glycerox® L 8 0.25 Example 1 0.0156 + + Glycerox® L 8 0.25 80 + + ENSOL®28 0.375 Table 17 Selective herbicide activity in the 1 procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha; s.a. SETVI POLPE Example 1 0.0078 30 20 Example 1 0.0078 + + 20 40 Glycerox® HE 0.25 Example 1 0.0078 + + Glycerox® HE 0.25 95 95 + + ENSOL®28 0.375 Table 18 Selective herbicidal activity in the; procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. POLPE Example 1 0.0078 70 Example 1 0.0078 + + 80 PlastomoII® DOA 0.25 Example 1 0.0078 + + PlastomolI®DOA 0.25 95 + + ENSOL®28 0.375 Table 19 Selective herbicide activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s s.a. SETVI POLPE Example 1 0.0078 40 70 Example 1 0.0078 »+ + 60 80 Lutensol® TO 15 0.25 Example 1 0.0078 + + Lutensol® TO 15 0.25 95 90 + + ENSOL®28 0.375 Table 20 Selective herbicide activity in the procedure after emergence in the greenhouse Fitotoxicity Active substance AWM kg / ha s.a. ZEAMX SETVI Example 1 0.0078 0 40 Example 1 0.0078 + + 0 55 Lutensol® AT 1 1 0.25 Example 1 0.0078 + + Lutensol® AT 1 1 0.25 0 95 + + ENSOL®28 0.375 Table 21 Herbii activity: selective outflow in [procedure after emergence in the greenhouse Phytotoxicity Active substance AWM kg / ha: 5.a. SETVI POLPE Example 1 0.0078 40 70 Example 1 0.0078 + + 45 90 Lutensol® AT 25 0.25 Example 1 0.0078 + + Lutensol® AT 25 0.25 90 95 + + ENSOL®28 0.375 Legend of the adjuvants used: Name Pluronic® PE 6400 BASF AG copolymerized block of ethylene oxide / propylene oxide Pluronic® PE 6800 BASF AG copolymerized block of ethylene oxide / propylene oxide Agrimul® PG 2067 Henkel alkyl glycoside APG Agrimul® PG 600 Henkel alkyl glycoside APG AG® 6202 Akzo alkyl glycoside APG Lutensol® GD 70 BASF AG alkyl glycoside APG Lutensol ® ON 30 BASF AG alkyl ethoxylate Lutensol® ON 80 BASF AG alkyl ethoxylate Lutensol® ON 1 10 BASF AG alkyl ethoxylate Lutensol® TO 8 BASF AG alkyl ethoxylate Lutensol® TO 15 BASF AG alkyl ethoxylate Lutensol® AT 1 1 BASF AG alkyl ethoxylate Lutensol® AT 25 BASF AG alkyl ethoxylate Pluriol® E 600 BASF AG polyethylene glycol Pluriol® E 4000 BASF AG polyethylene glycol Plastomoll® DOA BASF AG dioctyl adipate Glycerox® L 8 Croda monoglyceride ethoxylate Glycerox® HE Croda monoglyceride ethoxylate ENSOL ® 28 BASF AG solution of ammonium nitrate - urea (total N 28%) From the values in Tables 1 to 21, the synergistic effect of the herbicidal mixture according to the invention is clearly apparent compared to the pure active substance, the mixtures at the same time having a high selectivity towards the maize crop plant.

Claims (6)

2. A herbicidal mixture containing: a) an amount for herbicidal activity of a benzoyl derivative substituted with 3-heterocyclyl, of the formula I wherein the variables have the following meanings: R'jR2 are hydrogen, halogen, Ci-Cß alkyl, C?-C6 alkylthio, C?-C6 alkylsulfinyl, C?-C6 alkylsulfonyl, Ci-Cß haloalkyl , Ci-Cβ alkoxy, Ci-Cg haloalkoxy; R3 is hydrogen, halogen, Ci-Ce alkyl; X is a heterocycle from the group consisting of: Isoxazalyl, 4,5-dihydroisoxazolyl and thiazolyl, it being possible for the heterocycle to be optionally monosubstituted or polysubstituted by halogen, Ci-Cß alkyl, C? -C alkoxy, haloalkyl C? -C4, C? -C4 haloalkoxy, C? -C4 alkylthio;
3. R is a pyrazole of formula II s «OB which is linked at position 4, and where R1 is hydrogen or C? -C6 alkyl, R6 is C? -C6 alkyl, or its salts compatible with the environment; b) a nitrogen fertilizer in an effective amount for synergistic effect; and c) an adjuvant in an effective amount for a synergistic effect. The herbicidal mixture as claimed in the claim 1, contains a benzoyl derivative substituted with 3-heterocyclyl of the formula I, as claimed in claim 1, wherein R3 is hydrogen. The herbicidal mixture as claimed in the claim 1 or 2, which contains a benzoyl derivative substituted with 3-heterocyclyl of the formula I, as claimed in claim 1, wherein R, R are halogen, C 1 -C 6 Ci-Cß alkylthio alkyl, Ci alkylsulfinyl -Cß, Ci-Ce alkylsulfonyl. The herbicidal mixture as claimed in any of claims 1 to 3, contains a benzoyl derivative substituted with 3-heterocyclyl of the formula I, as claimed in claim 1, wherein X is isoxazolyl and 5-dihydroisoxazolyl, each of which may optionally be substituted by C? -C6 alkyl. The herbicidal mixture as claimed in any of claims 1 to 4, contains a benzoyl derivative substituted with 3-heterocyclyl of the formula I, as claimed in claim 1, wherein X is isoxazol-5-yl, 3-methylisoxazole -5-yl, 4, 5-dihydroisoxazol-3-yl,
4. 4-
5. 5-dihydro-5-methylisoxazol-3-yl, 4,5-dihydro-5-ethyl-isoxazol-3-yl, 4,5-dihydro-4,5-dimethylisoxazol-3-yl. The herbicidal mixture as claimed in the claim 1, contains 4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonylbenzoyl] -l-methyl-5-hydroxy-1H-pyrazole. The herbicidal mixture as claimed in the claim 1, contains 4- [2-methyl-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonylbenzoyl] -l-methyl-5-hydroxy-1H-pyrazole. The herbicidal mixture as claimed in any of claims 1 to 7, contains a nitrogen fertilizer b) selected from the series consisting of: ammonia, ammonium salts, urea, thiourea and mixtures thereof. The herbicidal mixture as claimed in any of claims 1 to 8, contains: 0. 5-90% by weight of derivative a) of benzoyl substituted with 3-heterocyclyl; 5-94.5% by weight of a nitrogen fertilizer b); 5-50% by weight of the adjuvant c). A process for the preparation of a herbicidal mixture, as claimed in any of claims 1 to 9, which consists in mixing components a) to c) of the herbicidal mixture together. On method for controlling the undesirable vegetation, which consists of mixing together an amount for herbicidal action of the components a) to c) of the herbicidal mixture, as claimed in any of claims 1 to 9 and allowing the mixture to act about plants or their environment. SUMMARY OF THE INVENTION These are herbicidal mixtures, which contain a) herbicidally effective amounts of 3-heterocyclyl-benzoyl compounds of the formula I where: R1, R2 hydrogen, halogen, C, -C
6. 6 -alkyl, C6-C6-alkylthio, C [- C6-alkylsulfinyl, C, -C6-alkylsulfonyl, C6-C6-haloalkyl, Ct-C6-alkoxy, Ci-C6-halogenalkoxy; R3 hydrogen, halogen, C, -C6-alkyl; X heterocycle of the isoxazolyl, 4,5-dihydroisoxazolyl and thiazolyl group, wherein the heterocycle may, if appropriate, be mono- or polysubstituted by halogen, C, -C6-alkyl, -C4-alkoxy, C, -C4 -halogenalkyl, - C4 - halogenalkoxy, - C4-alkylthio; R4 a pyrazole linked at position 4 of formula II Rs OH wherein R5 means hydrogen or C, -C6-alkyl, R6 means C, -C6-alkyl or its salts harmless to the environment; b) synergistically effective compounds of a nitrogen fertilizer. c) adjuvants in synergistically effective amounts. It is also proposed the preparation of said mixtures and a procedure to combat undesirable plants.