WO1998034480A1 - Herbicidal agent - Google Patents

Herbicidal agent Download PDF

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Publication number
WO1998034480A1
WO1998034480A1 PCT/EP1998/000621 EP9800621W WO9834480A1 WO 1998034480 A1 WO1998034480 A1 WO 1998034480A1 EP 9800621 W EP9800621 W EP 9800621W WO 9834480 A1 WO9834480 A1 WO 9834480A1
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WIPO (PCT)
Prior art keywords
formula
compound
alkyl
herbicide
crops
Prior art date
Application number
PCT/EP1998/000621
Other languages
German (de)
French (fr)
Inventor
Jutta Glock
Elmar Kerber
Willy Rüegg
Original Assignee
Novartis Ag
Novartis-Erfindungen Verwaltungsgesellschaft Mbh
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Application filed by Novartis Ag, Novartis-Erfindungen Verwaltungsgesellschaft Mbh filed Critical Novartis Ag
Priority to AU66204/98A priority Critical patent/AU6620498A/en
Publication of WO1998034480A1 publication Critical patent/WO1998034480A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom

Definitions

  • the present invention relates to new selective herbicidal compositions for controlling grasses and weeds in crops of useful plants, in particular in crops of cereals, which contain a herbicide and a safener (antidote, antidote) and which contain the useful plants but not the weeds before the phytotoxic Preserve the effect of the herbicide, and the use of this agent for weed control in crops.
  • the cultivated plants are also damaged to a considerable extent.
  • the invention thus proposes a selective herbicidal composition which is characterized in that, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, it is a mixture of active ingredients a) a herbicidally effective amount of a herbicide of the formula
  • X is halogen and Y is -S (O) mR or a radical of the formula in which RCC -
  • Alkyl or C 2 -C 4 alkenyl, Z is a direct chemical bond or CH 2 and m is 0, 1 or 2, where m is 0 when RC 2 -C 4 alkenyl, or a salt of the compound of the formula I , and b) a herbicide-antagonistically effective amount of a compound of the formula Ila
  • X 2 is hydrogen or chlorine, a compound of formula IIbi wherein
  • Ru is -CCI 3 or phenyl which is optionally substituted by halogen
  • R 12 and R 13 are independently hydrogen or halogen
  • R 14 is dC-alkyl, or a compound of the formula IIb 2
  • R 12 and R 13 have the meanings given above, and
  • Ree, ⁇ 7 and Re ⁇ are independently of one another C 1 -C 4 alkyl, contains.
  • the invention also includes the agronomically acceptable salts which the compounds of the formula I can form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali and alkaline earth metal hydroxides as salt formers, the hydroxides of lithium, sodium, potassium, magnesium or calcium should be emphasized, but especially those of sodium or potassium.
  • Suitable amines for the formation of ammonium salt include both ammonia and also primary, secondary and tertiary C 1 -C 8 -alkylamines, CrC -hydroxyalkylamines and C 2 -C -alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methyl nonylamine, methyl -pentadecylamine, methyl-octadecyl
  • alkyl groups occurring in the substituent definitions of the compounds of the formulas I and IIa to IIb 2 can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and pentyl, hexyl, heptyl, octyl and branched isomers thereof.
  • These alkyl groups can carry further substituents such as. B. alkoxy or alkenyloxy.
  • Examples of unsaturated substituent groups are ethenyloxy, propenyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy and octenyloxy as well as isomers which differ in the different position of the unsaturated bond or bonds in the molecule, isomers which contain branches, and cis and trans isomers . If Z in the substituent Y is a direct chemical bond, the result is for
  • Y is a residue of the formula
  • substituted indicates, where possible in the corresponding group, not only single substitution but also multiple substitution.
  • compositions according to the present invention contain, as herbicide, a compound of the formula I in which X is bromine and Y is -SCH 3 .
  • Preferred agents according to the present invention contain, as safeners, a compound of the formula IIIa and in particular such a compound of the formula IIIa, in which X 2 is chlorine and roio -CH (CH3) C 5 H ⁇ n.
  • herbicidal compositions according to the invention which contain one of the active ingredient combinations 1.02 + 2.01; 1.15 + 2.01 or 1.16 + 2.01 contain:
  • the invention also relates to a process for the selective control of weeds in crops, which consists in that the crops, their seeds or cuttings or their cultivated area are treated simultaneously or separately with a herbicidally active amount of the herbicide of the formula I and a herbicidally antagonistically effective amount of the safener of the formula Ila to llb 2 treated.
  • Cereals preferably wheat, are particularly suitable as cultivated plants which can be protected by the safeners against the damaging action of the herbicides mentioned above. Cultures are also to be understood as those which have been made tolerant to herbicides or classes of herbicides by means of conventional breeding or genetic engineering methods.
  • the weeds to be controlled can be both monocot and dicot weeds, such as Brachiaria, Polygonum, Kochia, Stellaria, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Sci ⁇ us, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • monocot and dicot weeds such as Brachiaria, Polygonum, Kochia, Stellaria, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Sci ⁇ us, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rott
  • the cultivated areas are the soil areas already overgrown with the cultivated plants or supplied with the seeds of these cultivated plants, as well as the soils intended for cultivation with these cultivated plants.
  • a safener of the formula IIa to IIb 2 can be used for the pretreatment of the seed of the crop (dressing the seed or the cuttings) or added to the soil before or after the seed.
  • it can also be applied on its own or together with the herbicide after the plants have emerged.
  • the treatment of the plants or the seed with the safener can therefore in principle be carried out independently of the time of application of the herbicide.
  • the treatment of the plant can also be carried out by simultaneous application of herbicide and safener (for example as a tank mix).
  • the application rate of safener to herbicide largely depends on the type of application. In the case of field treatment, which is carried out either using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, there is usually a ratio of heicide to safener of 1:10 to 10: 1 or 10: 1 to 2: 1 before.
  • 0.010 to 0.5 kg of safener / ha preferably 0.010 to 0.1 kg of safener / ha, are applied in the field treatment.
  • the application rates of herbicide are generally between 0.010 to 1 kg / ha, but preferably between 0.010 to 0.5 kg / ha.
  • the compositions according to the invention are suitable for all application methods customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. Post-emergence application (eg as a tank mix) is of particular importance.
  • safener solutions which contain the active compound in a concentration of 1 to 10,000, preferably 100 to 1000 ppm.
  • the safeners or combinations of these safeners with the herbicides of the formula are expediently processed into formulations together with the auxiliaries customary in formulation technology, e.g. to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • the formulations are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with liquid or solid formulation auxiliaries, e.g. Solvents or solid carriers.
  • surface-active compounds surfactants
  • surfactants can also be used in the preparation of the formulations.
  • Aromatic hydrocarbons preferably the fractions C ⁇ to C ⁇ 2 , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N, N-dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.
  • Aromatic hydrocarbons preferably the fractions C ⁇ to C ⁇ 2 , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioc
  • Natural rock flours such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders.
  • highly disperse silica or highly disperse absorbent polymers become.
  • Porous types such as pumice, broken bricks, sepiolite or bentonite can be used as granular, adsorbent granulate carriers, and non-so ⁇ tive carrier materials, such as calcite or sand.
  • a large number of pregranulated materials of inorganic or organic nature such as in particular dolomite or comminuted plant residues, can be used.
  • nonionic, cationic and / or anionic surfactants and surfactant mixtures with good emulsifying, dispersing and wetting properties are suitable as surface-active compounds.
  • Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Soaps which may be mentioned are the alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (C10-C 22 ), such as the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which, for example, from coconut or Tallow oil can be extracted.
  • the fatty acid methyl taurine salts should also be mentioned.
  • the fatty alcohol sulfates or sulfates are usually present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical having 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, e.g. the Na or Ca salt of lignin sulfonic acid, dodecylsulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids.
  • This subheading also includes the salts of sulfuric acid esters and sulphonic acids from fatty alcohol-ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms.
  • Alkylarylsulfonates are e.g. the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.
  • Corresponding phosphates such as, for example, salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids, are also suitable.
  • Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
  • nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain.
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate, are also suitable.
  • the cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyl trimethyl ammonium chloride or the benzyl di (2-chloroethyl) ethyl ammonium bromide.
  • the herbicidal formulations usually contain 0.1 to 99% by weight, in particular 0.1 to 95 wt .-% of active ingredient mixture of the compound of formula I with the compounds of the formulas IIa to IIb 2, 1 to 99.9 wt.% a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight of a surfactant.
  • the agents can also contain other additives such as stabilizers e.g. optionally epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, e.g. Contain silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients.
  • stabilizers e.g. optionally epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, e.g. Contain silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients.
  • Seed dressing a) Dressing the seeds with an active ingredient formulated as a wettable powder by shaking in a vessel until uniform distribution on the seed surface (dry dressing). About 1 to 500 g of active ingredient (4 g to 2 kg of wettable powder) per 100 kg of seed are used.
  • the dressing of the seeds or the treatment of the germinated seedlings are naturally the preferred methods of application because the treatment of the active ingredient is completely aimed at the target culture.
  • 1 to 1000 g of antidote are used, preferably 5 to 250 g of antidote, per 100 kg of seed, whereby depending on the method, which also allows the addition of other active ingredients or micronutrients, it can deviate upwards or downwards from the specified limit concentrations (repeat stain).
  • a liquid processing of a mixture of antidote and herbicide (mutual ratio between 10: 1 and 1: 100) is used, the amount of herbicide applied being 0.005 to 5.0 kg per hectare.
  • Such tank mixes are applied before or after sowing.
  • the safener is introduced into the open seeded furrow as an emulsion concentrate, wettable powder or as granules. After covering the furrow, the herbicide is applied in the pre-emergence process in the usual way.
  • the active ingredient is applied in solution to mineral granulate carriers or polymerized granules (urea / formaldehyde) and dried. If necessary, a coating can be applied (coating granules), which allows the active ingredient to be dispensed in doses over a certain period of time.
  • mineral granulate carriers or polymerized granules urea / formaldehyde
  • a coating can be applied (coating granules), which allows the active ingredient to be dispensed in doses over a certain period of time.
  • Emulsifiable concentrates are:
  • Active ingredient mixture 1 to 90%, preferably 5 to 20% surface-active agent: 1 to 30%, preferably 10 to 20% liquid carrier: 5 to 94%, preferably 70 to 85%
  • Active ingredient mixture 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates:
  • Active ingredient mixture 5 to 75%, preferably 10 to 50%
  • Active ingredient mixture 0.5 to 90%, preferably 1 to 80% surface-active agent: 0.5 to 20%, preferably 1 to 15% solid carrier material: 5 to 95%, preferably 15 to 90%
  • Active ingredient mixture 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
  • Emulsion concentrates a) b) c) d)
  • Active ingredient mixture 5% 10% 25% 50 ° /
  • Active ingredient mixture 5% 10% 50% 90%
  • the solutions are suitable for use in the form of tiny drops.
  • Active ingredient mixture 5% 25% 50% 80%
  • the active ingredient is mixed well with the additives and ground well in a suitable grinder.
  • Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
  • Active ingredient mixture 0.1% 5% 15%
  • the active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.
  • Active ingredient mixture 0.1% 5% 15%
  • Polyethylene glycol MG 200 1.0% 2% 3%
  • Inorg. Backing material 98.0% 92% 80% (00.1 - 1 mm) such as CaCO 3 or SiO 2
  • the finely ground active ingredient is evenly applied in a mixer to the carrier material moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
  • Active ingredient mixture 0.1% 3% 5% 15%
  • the active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
  • Active ingredient mixture 0.1% 1% 5%
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carrier substances and grinding them in a suitable mill.
  • Active ingredient mixture 3% 10% 25% 50%
  • the finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Example B1 Post-emergent applications of mixtures of a herbicide of the formula I with a safener of the formulas 11a to 11b 2 in cereals Wheat is grown in plastic pots up to the 2-4 leaf stage under greenhouse conditions. At this stage, on the one hand the heicides of the formula I alone and also the mixture of the herbicides with a safener of the formulas 11a to 11b 2 are applied to the test plants. The application takes place as an aqueous suspension of the test substances with 500 I water / ha. The application rates for the heicides are 250, 125 and 60, g / ha. 17 days after the application is evaluated with a percentage scale. 100% means that the test plant has died; 0% means that no phytotoxic effect can be seen.
  • Alopecurus 100 100 70 100 100 70
  • Polygonum 100 100 85 100 100 85

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

The invention relates to a selective herbicidal agent which, besides the usual inert formulation auxiliaries, contains as an active ingredient a mixture of a) a herbicide- active quantity of a herbicide of formula (I), in which X is a halogen and Y is S(O)mR or a radical of the formula (II), in which R is C1-C4-alkyl or C2-C4-alkenyl, Z is a direct chemical bond or CH2 and m is 0.1 or 2, whereby m is 0, when R is C2-C4-alkenyl; or of a salt of the compound with formula (I); and b) is a herbicide-antagonistically active quantity of a compound of formula (IIa), in which R010 is hydrogen, C1-C8-alkyl, or C1-C8-alkyl substituted by C1-C6-alkoxy or C3-C6-alkenyloxy, and X2 is hydrogen or chlorine; of a compound of formula (IIb1), in which E is nitrogen or methine, R11 is CCl3 or, optionally, halogen-substituted phenyl, and R12 and R13 are, independently of each other, hydrogen or halogen, and R14 is C1-C4-alkyl; or of a compound with formula (IIb2), in which R12 and R13 have the meanings given above, and R66, R67 and R68 are, independently of each other, C1-C4-alkyl.

Description

Herbizides MittelHerbicidal agent
Die vorliegende Erfindung betrifft neue selektiv-herbizide Mittel zur Bekämpfung von Gräsern und Unkräutern in Kulturen von Nutzpflanzen, insbesondere in Kulturen von Getreide, welche ein Herbizid und einen Safener (Gegenmittel, Antidot) enthalten und welche die Nutzpflanzen, nicht aber die Unkräuter vor der phytotoxischen Wirkung des Herbizides bewahren, sowie die Verwendung dieses Mittels zur Unkrautbekämpfung in Nutzpflanzenkulturen.The present invention relates to new selective herbicidal compositions for controlling grasses and weeds in crops of useful plants, in particular in crops of cereals, which contain a herbicide and a safener (antidote, antidote) and which contain the useful plants but not the weeds before the phytotoxic Preserve the effect of the herbicide, and the use of this agent for weed control in crops.
Beim Einsatz von Herbiziden können z.B. in Abhängigkeit von der Dosis des Herbizids und der Applikationsart, der Kulturpflanze, der Bodenbeschaffenheit und den klimatischen Bedingungen, wie Belichtungsdauer, Temperatur und Niederschlagsmengen auch die Kultuφflanzen in erheblichem Maße geschädigt werden.When using herbicides, e.g. Depending on the dose of the herbicide and the type of application, the crop, the soil conditions and the climatic conditions, such as exposure time, temperature and rainfall, the cultivated plants are also damaged to a considerable extent.
Um diesem und ähnlichen Problemen zu begegnen, sind schon verschiedene Stoffe als Safener vorgeschlagen worden, welche befähigt sind, die schädigende Wirkung des Herbizids auf die Kulturpflanze zu antagonisieren, das heißt, die Kulturpflanze davor zu schützen, wobei aber die Herbizidwirkung auf die zu bekämpfenden Unkräuter praktisch nicht beeinträchtigt wird. Dabei hat es sich gezeigt, daß die vorgeschlagenen Safener sowohl bezüglich der Kultuφflanzen als auch bezüglich des Herbizids und teilweise auch in Abhängigkeit von der Applikationsart oft sehr spezifisch wirken, das heißt, ein bestimmter Safener eignet sich oft nur für eine bestimmte Kulturpflanze und eine spezielle Herbizidstoffklasse oder ein bestimmtes Herbizid. • In order to counter this and similar problems, various substances have already been proposed as safeners which are capable of antagonizing the damaging effect of the herbicide on the crop, that is to say of protecting the crop from it, but the herbicide action on the weeds to be combated is practically not affected. It has been shown that the proposed safeners often act very specifically both with regard to the cultivated plants and with regard to the herbicide and in some cases also depending on the type of application, that is to say that a particular safener is often only suitable for a particular crop and a particular class of herbicide or a specific herbicide. •
Es wurde nun gefunden, daß sich aus EP-A-492 366, WO 91/7874 und WO 94/987 bekannte Safener zum Schützen von Kulturpflanzen vor der phytotoxischen Wirkung von gewissen Cyclohexandionherbiziden eignen, die in JP 8-136464 beschrieben sind.It has now been found that safeners known from EP-A-492 366, WO 91/7874 and WO 94/987 are suitable for protecting crop plants from the phytotoxic action of certain cyclohexanedione herbicides which are described in JP 8-136464.
Erfindungsgemäß wird somit ein selektiv-herbizides Mittel vorgeschlagen, welches dadurch gekennzeichnet ist, daß es neben üblichen inerten Formulierungshilfsmitteln wie Trägerstoffen, Lösungsmitteln und Netzmitteln als Wirkstoff eine Mischung aus a) einer herbizid-wirksamen Menge eines Herbizids der FormelThe invention thus proposes a selective herbicidal composition which is characterized in that, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, it is a mixture of active ingredients a) a herbicidally effective amount of a herbicide of the formula
worin X Halogen und
Figure imgf000004_0001
Y -S(O)mR oder ein Rest der Formel ist, worin R C C -wherein X is halogen and
Figure imgf000004_0001
Y is -S (O) mR or a radical of the formula in which RCC -
Alkyl oder C2-C4-Alkenyl, Z eine direkte chemische Bindung oder CH2 und m 0, 1 oder 2 ist, wobei m 0 ist, wenn R C2-C4-Alkenyl ist, oder eines Salzes der Verbindung der Formel I, und b) einer herbizid-antagonistisch wirksamen Menge einer Verbindung der Formel llaAlkyl or C 2 -C 4 alkenyl, Z is a direct chemical bond or CH 2 and m is 0, 1 or 2, where m is 0 when RC 2 -C 4 alkenyl, or a salt of the compound of the formula I , and b) a herbicide-antagonistically effective amount of a compound of the formula Ila
Figure imgf000004_0002
Figure imgf000004_0002
worinwherein
Roio Wasserstoff, CrC8-Alkyl oder durch CrC6-Alkόxy oder C3-C6-Alkenyloxy substituiertesRoio hydrogen, CrC 8 alkyl or substituted by CrC 6 alkoxy or C 3 -C 6 alkenyloxy
Cι-C8-Alkyl und-CC 8 alkyl and
X2 Wasserstoff oder Chlor ist, einer Verbindung der Formel llbi
Figure imgf000005_0001
worinX 2 is hydrogen or chlorine, a compound of formula IIbi
Figure imgf000005_0001
wherein
E Stickstoff oder Methin,E nitrogen or methine,
Ru -CCI3 oder gegebenenfalls durch Halogen substituiertes Phenyl ist,Ru is -CCI 3 or phenyl which is optionally substituted by halogen,
R12 und R13 unabhängig voneinander Wasserstoff oder Halogen sind, undR 12 and R 13 are independently hydrogen or halogen, and
R14 d-C -Alkyl ist, oder einer Verbindung der Formel llb2 R 14 is dC-alkyl, or a compound of the formula IIb 2
Figure imgf000005_0002
Figure imgf000005_0002
worinwherein
R12 und R13 die oben angegebenen Bedeutungen haben, undR 12 and R 13 have the meanings given above, and
Ree, β7 und Reβ unabhängig voneinander Cι-C4-Alkyl sind, enthält.Ree, β7 and Reβ are independently of one another C 1 -C 4 alkyl, contains.
Die Erfindung umfaßt ebenfalls die agronomisch verträglichen Salze, die die Verbindungen der Formel I mit Aminen, Alkali- und Erdalkalimetallbasen oder quatemären Ammoniumbasen bilden können. Unter den Alkali- und Erdalkalimetallhydroxiden als Salzbildner sind die Hydroxide von Lithium, Natrium, Kalium, Magnesium oder Caicium hervorzuheben, insbesondere aber die von Natrium oder Kalium.The invention also includes the agronomically acceptable salts which the compounds of the formula I can form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali and alkaline earth metal hydroxides as salt formers, the hydroxides of lithium, sodium, potassium, magnesium or calcium should be emphasized, but especially those of sodium or potassium.
Als Beispiele für zur Ammoniumsalzbildung geeignete Amine kommen sowohl Ammoniak wie auch primäre, sekundäre und tertiäre Cι-Cι8-Alkylamine, CrC -Hydroxyalkylamine und C2-C -Alkoxyalkylamine in Betracht, beispielsweise Methylamin, Ethylamin, n-Propylamin, iso-Propylamin, die vier isomeren Butylamine, n-Amylamin, iso-Amylamin, Hexylamin, Heptylamin, Octylamin, Nonylamin, Decylamin, Pentadecylamin, Hexadecylamin, Heptadecylamin, Octadecylamin, Methyl-ethylamin, Methyl-iso-propylamin, Methyl- hexylamin, Methyl-nonylamin, Methyl-pentadecylamin, Methyl-octadecylamin, Ethyl- butylamin, Ethyl-heptylamin, Ethyl-octylamin, Hexyl-heptylamin, Hexyl-octylamin, Dimethylamin, Diethylamin, Di-n-propylamin, Di-iso-propylamin, Di-n-butylamin, Di-n- amylamin, Di-iso-amylamin, Dihexylamin, Diheptylamin, Dioctylamin, Ethanolamin, n- Propanolamin, iso-Propanolamin, N.N-Diethanolamin, N-Ethylpropanolamin, N- Butylethanolamin, Allylamin, n-Butenyl-2-amin, n-Pentenyl-2-amin, 2,3-Dimethylbutenyl-2- amin, Di-butenyl-2-amin, n-Hexenyl-2-amin, Propylendiamin, Trimethylamin, Triethylamin, Tri-n-propylamin, Tri-iso-propylamin, Tri-n-butylamin, Tri-iso-butylamin, Tri-sek.-butylamin, Tri-n-amylamin, Methoxyethylamin und Ethoxyethylamin; heterocyclische Amine wie z.B. Pyridin, Chinolin, iso-Chinolin, Moφholin, Piperidin, Pyrrolidin, Indolin, Chinuclidin und Azepin; primäre Arylamine wie z.B. Aniline, Methoxyaniline, Ethoxyaniline, o,m,p-Toluidine, Phenylendiamine, Benzidine, Naphthylamine und o,m,p-Chloraniline; insbesondere aber Triethylamin, iso-Propylamin und Di-iso-propylamin.Examples of suitable amines for the formation of ammonium salt include both ammonia and also primary, secondary and tertiary C 1 -C 8 -alkylamines, CrC -hydroxyalkylamines and C 2 -C -alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methyl nonylamine, methyl -pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di -n- amylamine, di-iso-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, NN-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n -Pentenyl-2-amine, 2,3-dimethylbutenyl-2-am in, di-butenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri- sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, iso-quinoline, Moφholin, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as anilines, methoxyanilines, ethoxyanilines, o, m, p-tolidines, phenylenediamines, benzidines, naphthylamines and o, m, p-chloroanilines; but especially triethylamine, iso-propylamine and di-iso-propylamine.
Die in den Substituentendefinitionen der Verbindungen der Formeln I und lla bis llb2 vorkommenden Alkylgruppen können geradkettig oder verzweigt sein und stehen beispielsweise für Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, sek.-Butyl, iso-Butyl, tert.-Butyl sowie Pentyl, Hexyl, Heptyl, Octyl und verzweigte Isomere davon. Diese Alkylgruppen können weitere Substituenten tragen wie z. B. Alkoxy oder Alkenyloxy. Beispiele für ungesättigte Substituentengruppen sind Aethenyloxy, Propenyloxy, Butenyloxy, Pentenyloxy, Hexenyloxy, Heptenyloxy und Octenyloxy sowie Isomere, welche sich durch die unterschiedliche Lage der ungesättigten Bindung bzw. Bindungen im Molekül unterscheiden, Isomere, welche Verzweigungen enthalten, und eis- und trans-lsomere. Bedeutet Z im Substituenten Y eine direkte chemische Bindung, so ergibt sich fürThe alkyl groups occurring in the substituent definitions of the compounds of the formulas I and IIa to IIb 2 can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and pentyl, hexyl, heptyl, octyl and branched isomers thereof. These alkyl groups can carry further substituents such as. B. alkoxy or alkenyloxy. Examples of unsaturated substituent groups are ethenyloxy, propenyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy and octenyloxy as well as isomers which differ in the different position of the unsaturated bond or bonds in the molecule, isomers which contain branches, and cis and trans isomers . If Z in the substituent Y is a direct chemical bond, the result is for
Y ein Rest der Formel
Figure imgf000007_0001
Y is a residue of the formula
Figure imgf000007_0001
Der Ausdruck "substituiert" weist, sofern an der entsprechenden Gruppe möglich, neben Einfachsubstitution auch auf Mehrfachsubstitution hin.The term "substituted" indicates, where possible in the corresponding group, not only single substitution but also multiple substitution.
Bevorzugte Mittel gemass vorliegender Erfindung enthalten als Herbizid eine Verbindung der Formel I, worin X Brom und Y -SCH3 ist.Preferred compositions according to the present invention contain, as herbicide, a compound of the formula I in which X is bromine and Y is -SCH 3 .
Beispiele für besonders geeignete Herbizide sind in der folgenden Tabelle 1 zusammengestellt.Examples of particularly suitable herbicides are listed in Table 1 below.
Tabelle 1 : Verbindungen der Formel ITable 1: Compounds of formula I.
Figure imgf000007_0002
Figure imgf000007_0002
Verb. Nr.Verb.No.
1.01 Cl SCH3 1.02 Br SCH3 1.03 Cl SC2H5 1.04 Br SC2H5 1.05 Cl S-n-C3H7 1.06 Br S-n-C3H7 1.07 Cl S-i-C3H7 1.08 Br S-i-C3H7
Figure imgf000007_0003
Figure imgf000008_0001
1.11 Cl S-CH2CH=CH2 1.12 Br S-CH2GH=GH2 1.13 Cl S-CH2GH2GH=GH2 1.01 Cl SCH 3 1.02 Br SCH 3 1.03 Cl SC 2 H 5 1.04 Br SC 2 H 5 1.05 Cl SnC 3 H 7 1.06 Br SnC 3 H 7 1.07 Cl SiC 3 H 7 1.08 Br SiC 3 H 7
Figure imgf000007_0003
Figure imgf000008_0001
1.11 Cl S-CH 2 CH = CH 2 1.12 Br S-CH 2 GH = GH 2 1.13 Cl S-CH 2 GH 2 GH = GH 2
Figure imgf000008_0002
Figure imgf000008_0002
Bevorzugte Mittel gemass vorliegender Erfindung enthalten als Safener eine Verbindung der Formel lla und insbesondere eine solche Verbindung der Formel lla, worin X2 Chlor und Roio -CH(CH3)C5Hι n ist.Preferred agents according to the present invention contain, as safeners, a compound of the formula IIIa and in particular such a compound of the formula IIIa, in which X 2 is chlorine and roio -CH (CH3) C 5 H ι n.
Zur Verwendung in den erfindungsgemässen Mitteln besonders geeignete Safener sind in den folgenden Tabellen aufgeführt.Safeners which are particularly suitable for use in the agents according to the invention are listed in the following tables.
Tabelle 2: Verbindungen der Formel lla:Table 2: Compounds of the formula Ila:
Figure imgf000008_0003
Verb. Nr. X2 R 010
Figure imgf000008_0003
X 2 R 010
2.01 Cl -CH(CH3)-C5Hι n 2.02 Cl -CH(CH3)-CH2OCH2CH=CH2 2.03 Cl H 2.04 Cl C4H9-n2.01 Cl -CH (CH 3 ) -C 5 H ι n 2.02 Cl -CH (CH 3 ) -CH 2 OCH 2 CH = CH 2 2.03 Cl H 2.04 Cl C 4 H 9 -n
Tabelle 3: Verbindungen der Formel llbiTable 3: Compounds of the formula IIbi
Figure imgf000009_0001
Figure imgf000009_0001
Verb. Nr. Rl4 R11 R12 F«13 EVerb. No. Rl4 R11 R12 F «13 E
3.01 CH3 Phenyl 2-CI H CH3.01 CH 3 phenyl 2-CI H CH
3.02 CH3 Phenyl 2-CI 4-CI CH3.02 CH 3 phenyl 2-CI 4-CI CH
3.03 CH3 Phenyl 2-F H CH3.03 CH 3 phenyl 2-FH CH
3.04 CH3 2-Chloφhenyl 2-F H CH3.04 CH 3 2-chloro-phenyl 2-FH CH
3.05 C2H5 CCI3 2-CI 4-CI N3.05 C 2 H 5 CCI3 2-CI 4-CI N
3.06 CH3 Phenyl 2-CI 4-CF3 N3.06 CH 3 phenyl 2-CI 4-CF3 N
3.07 CH3 Phenyl 2-CI 4-CF3 N3.07 CH 3 phenyl 2-CI 4-CF3 N
3.08 CH3 2-Fluoφhenyl 2-CI H CH Tabelle 4: Verbindungen der Formel llb2 3.08 CH 3 2-Fluoφhenyl 2-CI H CH Table 4: Compounds of the formula IIb 2
Figure imgf000010_0001
Figure imgf000010_0001
Verb. Nr. R, 68 R 67 R, 66 R 12 R 13No. R, 68 R 67 R, 66 R 12 R 13
4.01 CH3 CH3 CH3 2-CI 4-CI4.01 CH 3 CH 3 CH 3 2-CI 4-CI
4.02 CH3 C2Hδ CH3 2-CI 4-CI4.02 CH 3 C 2 H δ CH 3 2-CI 4-CI
4.03 CH3 C2H5 C2H5 2-CI 4-CI4.03 CH 3 C 2 H 5 C 2 H 5 2-CI 4-CI
Die in den Tabellen 2 bis 4 aufgeführten Safener und ihre Herstellung sind z. B. aus EP-A- 492 366, WO 91/7874 und WO 94/987 bekannt.The safeners listed in Tables 2 to 4 and their preparation are e.g. B. from EP-A-492 366, WO 91/7874 and WO 94/987.
Von ganz besonderer Bedeutung sind jene erfindungsgemässen herbiziden Mittel, die eine der Wirkstoff kombinationen 1.02 + 2.01 ; 1.15 + 2.01 oder 1.16 + 2.01 enthalten:Of particular importance are those herbicidal compositions according to the invention which contain one of the active ingredient combinations 1.02 + 2.01; 1.15 + 2.01 or 1.16 + 2.01 contain:
Die Erfindung betrifft auch ein Verfahren zum selektiven Bekämpfen von Unkräutern in Nutzpflanzenkulturen, welches darin besteht, daß man die Nutzpflanzen, deren Samen oder Stecklinge oder deren Anbaufläche gleichzeitig oder getrennt mit einer herbizid wirksamen Menge des Herbizids der Formel I und einer herbizid-antagonistisch wirksamen Menge des Safeners der Formel lla bis llb2 behandelt.The invention also relates to a process for the selective control of weeds in crops, which consists in that the crops, their seeds or cuttings or their cultivated area are treated simultaneously or separately with a herbicidally active amount of the herbicide of the formula I and a herbicidally antagonistically effective amount of the safener of the formula Ila to llb 2 treated.
Als Kultuφflanzen, welche durch die Safener gegen die schädigende Wirkung der oben erwähnten Herbizide geschützt werden können, kommen insbesondere Getreide, vorzugsweise Weizen in Betracht. Unter Kulturen sind auch solche zu verstehen, die durch konventionelle züchterische oder gentechnologische Methoden gegen Herbizide bzw. Herbizidklassen tolerant gemacht worden sind. Bei den zu bekämpfenden Unkräutern kann es sich sowohl um monokotyle wie um dikotyle Unkräuter handeln, wie zum Beispiel Brachiaria, Polygonum, Kochia, Stellaria, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Sciφus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola und Veronica.Cereals, preferably wheat, are particularly suitable as cultivated plants which can be protected by the safeners against the damaging action of the herbicides mentioned above. Cultures are also to be understood as those which have been made tolerant to herbicides or classes of herbicides by means of conventional breeding or genetic engineering methods. The weeds to be controlled can be both monocot and dicot weeds, such as Brachiaria, Polygonum, Kochia, Stellaria, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Sciφus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
Als Anbauflächen gelten die bereits mit den Kultuφflanzen bewachsenen oder mit dem Saatgut dieser Kultuφflanzen beschickten Bodenareale wie auch die zur Bebauung mit diesen Kultuφflanzen bestimmten Böden.The cultivated areas are the soil areas already overgrown with the cultivated plants or supplied with the seeds of these cultivated plants, as well as the soils intended for cultivation with these cultivated plants.
Ein Safener der Formel lla bis llb2 kann je nach Anwendungszweck zur VoΦehandlung des Saatgutes der Kulturpflanze (Beizung des Samens oder der Stecklinge) eingesetzt oder vor oder nach der Saat in den Boden gegeben werden. Er kann aber auch für sich allein oder zusammen mit dem Herbizid nach dem Auflaufen der Pflanzen appliziert werden. Die Behandlung der Pflanzen oder des Saatgutes mit dem Safener kann daher grundsätzlich unabhängig vom Zeitpunkt der Applikation des Herbizids erfolgen. Die Behandlung der Pflanze kann man jedoch auch durch gleichzeitige Applikation von Herbizid und Safener (z.B. als Tankmischung) vornehmen.Depending on the application, a safener of the formula IIa to IIb 2 can be used for the pretreatment of the seed of the crop (dressing the seed or the cuttings) or added to the soil before or after the seed. However, it can also be applied on its own or together with the herbicide after the plants have emerged. The treatment of the plants or the seed with the safener can therefore in principle be carried out independently of the time of application of the herbicide. However, the treatment of the plant can also be carried out by simultaneous application of herbicide and safener (for example as a tank mix).
Die zu applizierende Aufwandmenge Safener zu Herbizid richtet sich weitgehend nach der Anwendungsart. Bei einer Feldbehandlung, welche entweder unter Verwendung einer Tankmischung mit einer Kombination von Safener und Herbizid oder durch getrennte Applikation von Safener und Herbizid erfolgt, liegt in der Regel ein Verhältnis von HeΦizid zu Safener von 1 :10 bis 10:1 bzw. 10:1 bis 2:1 vor.The application rate of safener to herbicide largely depends on the type of application. In the case of field treatment, which is carried out either using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, there is usually a ratio of heicide to safener of 1:10 to 10: 1 or 10: 1 to 2: 1 before.
In der Regel werden bei der Feldbehandlung 0,010 bis 0,5 kg Safener/ha, vorzugsweise 0,010 bis 0,1 kg Safener/ha, appliziert.As a rule, 0.010 to 0.5 kg of safener / ha, preferably 0.010 to 0.1 kg of safener / ha, are applied in the field treatment.
Die Aufwandmengen an Herbizid liegt in der Regel zwischen 0,010 bis 1 kg/ha, vorzugsweise jedoch zwischen 0,010 bis 0,5 kg/ha. Die erfindungsgemäßen Mittel sind für alle in der Landwirtschaft üblichen Applikationsmethoden wie z.B. preemergente Applikation, postemergente Applikation und Saatbeizung geeignet. Der postemergenten Applikation (z.B. als Tankmischung) kommt dabei besondere Bedeutung zu.The application rates of herbicide are generally between 0.010 to 1 kg / ha, but preferably between 0.010 to 0.5 kg / ha. The compositions according to the invention are suitable for all application methods customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. Post-emergence application (eg as a tank mix) is of particular importance.
Bei der Samenbeizung werden im allgemeinen 0,001 bis 10 g Safener/kg Samen, vorzugsweise 0,05 bis 2 g Safener/kg Samen, appliziert. Wird der Safener in flüssiger Form kurz vor der Aussaat unter Samenquellung appliziert, so werden zweckmäßigerweise Safenerlösungen verwendet, welche den Wirkstoff in einer Konzentration von 1 bis 10000, vorzugsweise von 100 bis 1000 ppm, enthalten.In the seed dressing, 0.001 to 10 g safener / kg seed, preferably 0.05 to 2 g safener / kg seed, are generally applied. If the safener is applied in liquid form shortly before sowing with seed swelling, then safener solutions are advantageously used which contain the active compound in a concentration of 1 to 10,000, preferably 100 to 1000 ppm.
Zur Applikation werden die Safener oder Kombinationen von diesen Safenern mit den Herbiziden der Formel zweckmäßigerweise zusammen mit den in der Formulierungstechnik üblichen Hilfsmitteln zu Formulierungen verarbeitet, z.B. zu Emulsionskonzentraten, streichfähigen Pasten, direkt versprühbaren oder verdünnbaren Lösungen, verdünnten Emulsionen, Spritzpulvem, löslichen Pulvern, Stäubemitteln, Granulaten oder Mikrokapseln. Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch inniges Vermischen und/oder Vermählen der Wirkstoffe mit flüssigen oder festen Formulierungshilfsmitteln wie z.B. Lösungsmitteln oder festen Trägerstoffen. Ferner können zusätzlich oberflächenaktive Verbindungen (Tenside) bei der Herstellung der Formulierungen verwendet werden.For application, the safeners or combinations of these safeners with the herbicides of the formula are expediently processed into formulations together with the auxiliaries customary in formulation technology, e.g. to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The formulations are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with liquid or solid formulation auxiliaries, e.g. Solvents or solid carriers. Furthermore, surface-active compounds (surfactants) can also be used in the preparation of the formulations.
Als Lösungsmittel können in Frage kommen: Aromatische Kohlenwasserstoffe, bevorzugt die Fraktionen Cβ bis Cι2, wie z.B. Xylolgemische oder substituierte Naphthaline, Phthalsäureester wie Dibutyl- oder Dioctylphthalat, aliphatische Kohlenwasserstoffe wie Cyclohexan oder Paraffine, Alkohole und Glykole, sowie deren Ether und Ester wie Ethanol, Ethylenglykol, Ethylenglykolmonomethyl- oder -ethylether, Ketone wie Cyclohexanon, stark polare Lösungsmittel wie N-Methyl-2-pyrrolidon, Dimethylsulfoxid oder N,N- Dimethylformamid, sowie gegebenenfalls epoxidierte Pflanzenöle wie epoxidiertes Kokosnußöl oder Sojaöl; oder Wasser.Possible solvents are: Aromatic hydrocarbons, preferably the fractions C β to Cι 2 , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N, N-dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.
Als feste Trägerstoffe, z.B. für Stäubemittel und dispergierbare Pulver, werden in der Regel natürliche Gesteinsmehle verwendet, wie Calcit, Talkum, Kaolin, Montmorillonit oder Attapulgit. Zur Verbesserung der physikalischen Eigenschaften der Formulierung können auch hochdisperse Kieselsäure oder hochdisperse saugfähige Polymerisate zugesetzt werden. Als gekörnte, adsoφtive Granulatträger kommen poröse Typen wie z.B. Bimsstein, Ziegelbruch, Sepiolit oder Bentonit, als nicht soφtive Trägermaterialien z.B. Calcit oder Sand in Frage. Darüber hinaus kann eine Vielzahl von vorgranulierten Materialien anorganischer oder organischer Natur wie insbesondere Dolomit oder zerkleinerte Pflanzenrückstände verwendet werden.Natural rock flours, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders. To improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorbent polymers become. Porous types such as pumice, broken bricks, sepiolite or bentonite can be used as granular, adsorbent granulate carriers, and non-soφtive carrier materials, such as calcite or sand. In addition, a large number of pregranulated materials of inorganic or organic nature, such as in particular dolomite or comminuted plant residues, can be used.
Als oberflächenaktive VeΦindungen kommen je nach der Art des zu formulierenden Wirkstoffes der Formel I nichtionogene, kation- und/oder anionaktive Tenside und Tensidgemische mit guten Emulgier-, Dispergier- und Netzeigenschaften in Betracht.Depending on the nature of the active ingredient of the formula I to be formulated, nonionic, cationic and / or anionic surfactants and surfactant mixtures with good emulsifying, dispersing and wetting properties are suitable as surface-active compounds.
Geeignete anionische Tenside können sowohl sog. wasserlösliche Seifen wie wasserlösliche synthetische oberflächenaktive Verbindungen sein.Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
Als Seifen seien die Alkali-, Erdalkali- oder gegebenenfalls substituierte Ammoniumsalze von höheren Fettsäuren (C10-C22), wie z.B. die Na- oder K-Salze der Öl- oder Stearinsäure, oder von natürlichen Fettsäuregemischen genannt, die z.B. aus Kokosnuß- oder Talgöl gewonnen werden können. Femer sind auch die Fettsäure-methyl-taurinsalze zu erwähnen.Soaps which may be mentioned are the alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (C10-C 22 ), such as the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which, for example, from coconut or Tallow oil can be extracted. The fatty acid methyl taurine salts should also be mentioned.
Häufiger werden jedoch sog. synthetische Tenside verwendet, insbesondere Fettalkohol- sulfonate, Fettalkoholsulfate, sulfonierte Benzimidazolderivate oder Alkylarylsulfonate.However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
Die Fettalkoholsulf onate oder -sulfate liegen in der Regel als Alkali-, Erdalkali- oder gegebenenfalls substituierte Ammoniumsalze vor und weisen einen Alkylrest mit 8 bis 22 C- Atomen auf, wobei Alkyl auch den Alkylteil von Acylresten einschließt, z.B. das Na- oder Ca-Salz der Ligninsulfonsäure, des Dodecylschwefelsäureesters oder eines aus natürlichen Fettsäuren hergestellten Fettalkoholsulfatgemisches. Hierher gehören auch die Salze der Schwefelsäureester und Sulfonsäuren von Fettalkohol-Ethylenoxid-Addukten. Die sulfonierten Benzimidazolderivate enthalten vorzugsweise 2 Sulfonsäuregruppen und einen Fettsäurerest mit 8-22 C-Atomen. Alkylarylsulfonate sind z.B. die Na-, Ca- oder Triethanolaminsalze der Dodecylbenzolsulfonsäure, der Dibutylnaphthalinsulfonsäure, oder eines Naphthalinsulfonsäure-Formaldehydkondensationsproduktes.The fatty alcohol sulfates or sulfates are usually present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical having 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, e.g. the Na or Ca salt of lignin sulfonic acid, dodecylsulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulphonic acids from fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are e.g. the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.
Femer kommen auch entsprechende Phosphate wie z.B. Salze des Phosphorsäureesters eines p-Nonylphenol-(4-14)-Ethylenoxid-Adduktes oder Phospholipide in Frage. Als nichtionische Tenside kommen in erster Linie Polyglykoletherderivate von aliphatischen oder cycloaliphatischen Alkoholen, gesättigten oder ungesättigten Fettsäuren und Alkylphenolen in Frage, die 3 bis 30 Glykolethergruppen und 8 bis 20 Kohlenstoffatome im (aliphatischen) Kohlenwasserstoffrest und 6 bis18 Kohlenstoffatome im Alkylrest der Alkylphenole enthalten können.Corresponding phosphates, such as, for example, salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids, are also suitable. Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Weitere geeignete nichtionische Tenside sind die wasserlöslichen, 20 bis 250 Ethylen- glykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Polyethylen- oxidaddukte an Polypropylenglykol, Ethylendiaminopolypropylengiykol und Alkyl- polypropylenglykol mit 1 bis 10 Kohlenstoffatomen in der Alkylkette. Die genannten Verbindungen enthalten üblicherweise pro Propylenglykol-Einheit 1 bis 5 Ethylen- glykoleinheiten.Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Als Beispiele nichtionischer Tenside seien Nonylphenolpolyethoxyethanole, Ricinusölpoly- glykolether, Polypropylen-Polyethylenoxidaddukte, Tributylphenoxypolyethoxyethanol, Polyethylenglykol und Octylphenoxypolyethoxyethanol erwähnt.Examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Femer kommen auch Fettsäureester von Polyoxyethylensorbitan wie das Polyoxyethylen- sorbitan-trioleat in Betracht.Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.
Bei den kationischen Tensiden handelt es sich vor allem um quartäre Ammoniumsalze, welche als N-Substituenten mindestens einen Alkylrest mit 8 bis 22 C-Atomen enthalten und als weitere Substituenten niedrige, gegebenenfalls halogenierte Alkyl-, Benzyl- oder niedrige Hydroxyalkylreste aufweisen. Die Salze liegen vorzugsweise als Halogenide, Methylsulfate oder Ethylsulfate vor, z.B. das Stearyltrimethylammoniumchlorid oder das Benzyldi-(2-chlorethyl)-ethylammoniumbromid.The cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyl trimethyl ammonium chloride or the benzyl di (2-chloroethyl) ethyl ammonium bromide.
Die in der Formulierungstechnik gebräuchlichen Tenside, die auch in den erfindungsgemäßen Mitteln verwendet werden können, sind u.a. in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stäche, H., "Tensid-Taschenbuch", Carl Hanser Verlag, München/Wien, 1981 und M. und J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81 beschrieben. Die herbiziden Formulierungen enthalten in der Regel 0,1 bis 99 Gew%, insbesondere 0,1 bis 95 Gew.-% Wirkstoffgemisch aus der Verbindung der Formel I mit den Verbindungen der Formeln lla bis llb2, 1 bis 99,9 Gew.% eines festen oder flüssigen Formulierungshilfstoffes und 0 bis 25 Gew.%, insbesondere 0,1 bis 25 Gew.% eines Tensides.The surfactants commonly used in formulation technology, which can also be used in the agents according to the invention, are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stächen, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich / Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol III, Chemical Publishing Co., New York, 1980-81. The herbicidal formulations usually contain 0.1 to 99% by weight, in particular 0.1 to 95 wt .-% of active ingredient mixture of the compound of formula I with the compounds of the formulas IIa to IIb 2, 1 to 99.9 wt.% a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight of a surfactant.
Während als Handelsware üblicherweise konzentrierte Mittel bevorzugt werden, verwendet der Endverbraucher in der Regel verdünnte Mittel.While concentrated agents are usually preferred as commercial goods, the end user generally uses diluted agents.
Die Mittel können auch weitere Zusätze wie Stabilisatoren z.B. gegebenenfalls epoxydierte Pflanzenöle (epoxydiertes Kokosnußöl, Rapsöl oder Sojaöl), Entschäumer, z.B. Silikonöl, Konservierungsmittel, Viskositätsregulatoren, Bindemittel, Haftmittel sowie Dünger oder andere Wirkstoffe enthalten.The agents can also contain other additives such as stabilizers e.g. optionally epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, e.g. Contain silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients.
Für die Verwendung der Safener oder sie enthaltender Mittel zum Schützen von Kultuφflanzen gegen schädigende Wirkungen von Herbiziden der Formel I kommen verschiedene Methoden und Techniken in Betracht, wie beispielsweise die folgenden:Various methods and techniques can be used for the use of the safeners or compositions containing them to protect crop plants against the damaging effects of herbicides of the formula I, for example the following:
i) Samenbeizung a) Beizung der Samen mit einem als Spritzpulver formulierten Wirkstoff durch Schütteln in einem Gefäß bis zur gleichmäßigen Verteilung auf der Samenoberfläche (Trockenbeizung). Man verwendet dabei etwa 1 bis 500 g Wirkstoff (4 g bis 2 kg Spritzpulver) pro 100 kg Saatgut.i) Seed dressing a) Dressing the seeds with an active ingredient formulated as a wettable powder by shaking in a vessel until uniform distribution on the seed surface (dry dressing). About 1 to 500 g of active ingredient (4 g to 2 kg of wettable powder) per 100 kg of seed are used.
b) Beizung der Samen mit einem Emulsionskonzentrat des nach der Methode a) (Naßbeizung).b) dressing the seeds with an emulsion concentrate of the method a) (wet dressing).
c) Beizung durch Tauchen des Saatguts in eine Brühe mit 100-1000 ppm Wirkstoff während 1 bis 72 Stunden und gegebenenfalls nachfolgendes Trocknen der Samen (Tauchbeizung).c) Dressing by immersing the seed in a broth with 100-1000 ppm of active ingredient for 1 to 72 hours and, if appropriate, subsequently drying the seeds (immersion dressing).
Die Beizung des Saatguts oder die Behandlung des angekeimten Sämlings sind naturgemäß die bevorzugten Methoden der Applikation, weil die Wirkstoffbehandlung vollständig auf die Zielkultur gerichtet ist. Man verwendet in der Regel 1 bis 1000 g Antidot, vor- zugsweise 5 bis 250 g Antidot, pro 100 kg Saatgut, wobei man je nach Methodik, die auch den Zusatz anderer Wirkstoffe oder Mikronährstoffe ermöglicht, von den angegebenen Grenzkonzentrationen nach oben oder unten abweichen kann (Wiederholungsbeize).The dressing of the seeds or the treatment of the germinated seedlings are naturally the preferred methods of application because the treatment of the active ingredient is completely aimed at the target culture. As a rule, 1 to 1000 g of antidote are used, preferably 5 to 250 g of antidote, per 100 kg of seed, whereby depending on the method, which also allows the addition of other active ingredients or micronutrients, it can deviate upwards or downwards from the specified limit concentrations (repeat stain).
ii) Applikation als Tankmischunαii) Application as a tank mix
Eine flüssige Aufarbeitung eines Gemisches von Antidot und Herbizid (gegenseitiges Mengenverhältnis zwischen 10:1 und 1 :100) wird verwendet, wobei die Aufwandmenge an Herbizid 0,005 bis 5,0 kg pro Hektar beträgt. Solche Tankmischungen werden vor oder nach der Aussaat appliziert.A liquid processing of a mixture of antidote and herbicide (mutual ratio between 10: 1 and 1: 100) is used, the amount of herbicide applied being 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after sowing.
iii) Applikation in der Saatfurcheiii) Application in the seed furrow
Der Safener wird als Emulsionskonzentrat, Spritzpulver oder als Granulat in die offene besäte Saatfurche eingebracht. Nach dem Decken der Saatfurche wird in üblicher Weise das Herbizid im Vorauflaufverfahren appliziert.The safener is introduced into the open seeded furrow as an emulsion concentrate, wettable powder or as granules. After covering the furrow, the herbicide is applied in the pre-emergence process in the usual way.
v) Kontrollierte Wirkstoff abgäbev) Deliver controlled active ingredient
Der Wirkstoff wird in Lösung auf mineralische Granulatträger oder polymerisierte Granulate (Harnstoff/Formaldehyd) aufgezogen und getrocknet. Gegebenenfalls kann ein Überzug aufgebracht werden (Umhüllungsgranulate), der es erlaubt, den Wirkstoff über einen bestimmten Zeitraum dosiert abzugeben.The active ingredient is applied in solution to mineral granulate carriers or polymerized granules (urea / formaldehyde) and dried. If necessary, a coating can be applied (coating granules), which allows the active ingredient to be dispensed in doses over a certain period of time.
Insbesondere setzen sich bevorzugte Formulierungen folgendermaßen zusammen: (% = Gewichtsprozent)In particular, preferred formulations are composed as follows: (% = weight percent)
Emulgierbare Konzentrate:Emulsifiable concentrates:
Aktives Wirkstoffgemisch: 1 bis 90 %, vorzugsweise 5 bis 20 % oberflächenaktives Mittel: 1 bis 30 %, vorzugsweise 10 bis 20 % flüssiges Trägermittel: 5 bis 94 %, vorzugsweise 70 bis 85 %Active ingredient mixture: 1 to 90%, preferably 5 to 20% surface-active agent: 1 to 30%, preferably 10 to 20% liquid carrier: 5 to 94%, preferably 70 to 85%
Stäube:Dusts:
Aktives Wirkstoffgemisch: 0,1 bis 10 %, vorzugsweise 0,1 bis 5 % festes Trägermittel: 99,9 bis 90 %, vorzugsweise 99,9 bis 99 % Suspensions-Konzentrate:Active ingredient mixture: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates:
Aktives Wirkstoffgemisch: 5 bis 75 %, vorzugsweise 10 bis 50 %Active ingredient mixture: 5 to 75%, preferably 10 to 50%
Wasser: 94 bis 24 %, vorzugsweise 88 bis 30 % oberflächenaktives Mittel: 1 bis 40 %, vorzugsweise 2 bis 30 %Water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%
Benetzbare Pulver:Wettable powders:
Aktives Wirkstoffgemisch: 0,5 bis 90 %, vorzugsweise 1 bis 80 % oberflächenaktives Mittel: 0,5 bis 20 %, vorzugsweise 1 bis 15 % festes Trägermaterial: 5 bis 95 %, vorzugsweise 15 bis 90 %Active ingredient mixture: 0.5 to 90%, preferably 1 to 80% surface-active agent: 0.5 to 20%, preferably 1 to 15% solid carrier material: 5 to 95%, preferably 15 to 90%
Granulate:Granules:
Aktives Wirkstoffgemisch: 0,1 bis 30 %, vorzugsweise 0,1 bis 15 % festes Trägermittel: 99,5 bis 70 %, vorzugsweise 97 bis 85 %Active ingredient mixture: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
Die folgenden Beispiele erläutern die Erfindung weiter, ohne sie zu beschränken.The following examples further illustrate the invention without restricting it.
Formulierungsbeispiele für Mischungen aus HeΦiziden der Formel I und Safener der Formel lla bis llb?(% = Gewichtsprozent)Formulation examples for mixtures of heicides of the formula I and safeners of the formulas Ila to IIb? (% = Percent by weight)
F1. Emulsionskonzentrate a) b) c) d)F1. Emulsion concentrates a) b) c) d)
Wirkstoffmischung 5 % 10 % 25 % 50 °/Active ingredient mixture 5% 10% 25% 50 ° /
Ca-Dodecylbenzolsulfonat 6 % 8 % 6 % 8 %Ca-dodecylbenzenesulfonate 6% 8% 6% 8%
Ricinusöl-polyglykolether 4 % . 4 % 4 %Castor oil polyglycol ether 4%. 4% 4%
(36 Mol EO)(36 moles of EO)
Octylphenol-polyglykolether - 4 % - 2 %Octylphenol polyglycol ether - 4% - 2%
(7-8 Mol EO)(7-8 mol EO)
Cyclohexanon - - 10 % 20 %Cyclohexanone - - 10% 20%
Arom. Kohlenwasserstoff- 85 % 78 % 55 % 16 % gemisch C9-C12 Aroma. Hydrocarbon- 85% 78% 55% 16% mixed C 9 -C1 2
Aus solchen Konzentraten können durch Verdünnung mit Wasser Emulsionen jeder gewünschten Konzentration hergestellt werden. F2. Lösungen a) b) c) d)Such concentrates can be used to prepare emulsions of any desired concentration by dilution with water. F2. Solutions a) b) c) d)
Wirkstoffmischung 5% 10% 50% 90%Active ingredient mixture 5% 10% 50% 90%
1 -Methoxy-3-(3-methoxy- propoxy)-propan - 20% 20%1-methoxy-3- (3-methoxy-propoxy) propane - 20% 20%
Polyethylenglykol MG 400 20% 10%Polyethylene glycol MG 400 20% 10%
N-Methyl-2-pyrrolidon - - 30% 10%N-methyl-2-pyrrolidone - - 30% 10%
Arom. Kohlenwasserstoff- 75 % 60 % gemisch C9-d2 Aroma. Hydrocarbon- 75% 60% mixed C 9 -d 2
Die Lösungen sind zur Anwendung in Form kleinster Tropfen geeignet.The solutions are suitable for use in the form of tiny drops.
F3. Spritzpulver a) b) c) d)F3. Spray powder a) b) c) d)
Wirkstoffmischung 5% 25% 50% 80%Active ingredient mixture 5% 25% 50% 80%
Na-Ligninsulfonat 4% - 3% -Na lignin sulfonate 4% - 3% -
Na-Laurylsulfat 2% 3% - 4%Na lauryl sulfate 2% 3% - 4%
Na-Diisobutyl-naphthalinsulfonat - 6% 5% 6%Na diisobutyl naphthalenesulfonate - 6% 5% 6%
Octylphenol-polyglykolether - 1 % 2% -Octylphenol polyglycol ether - 1% 2% -
(7-8 Mol EO)(7-8 mol EO)
Hochdisperse Kieselsäure 1 % 3% 5% 10%Fumed silica 1% 3% 5% 10%
Kaolin 88% 62% 35% .Kaolin 88% 62% 35%.
Der Wirkstoff wird mit den Zusatzstoffen gut vermischt und in einer geeigneten Mühle gut vermählen. Man erhält Spritzpulver, die sich mit Wasser zu Suspensionen jeder gewünschten Konzentration verdünnen lassen.The active ingredient is mixed well with the additives and ground well in a suitable grinder. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
F4. Umhüllungs-Granulate a) b) c)F4. Coating granules a) b) c)
Wirkstoffmischung 0.1 % 5% 15%Active ingredient mixture 0.1% 5% 15%
Hochdisperse Kieselsäure 0.9 % 2 % 2 %Fumed silica 0.9% 2% 2%
Anorg. Trägermaterial 99.0 % 93 % 83 % (00.1 - 1 mm) wie z.B. CaCO3 oder SiO2 Inorg. Backing material 99.0% 93% 83% (00.1 - 1 mm) such as CaCO 3 or SiO 2
Der Wirkstoff wird in Methylenchlorid gelöst, auf den Träger aufgesprüht und das Lösungsmittel anschließend im Vakuum abgedampft.The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.
F5. Umhüllungs-Granulate a) b) c)F5. Coating granules a) b) c)
Wirkstoffmischung 0.1 % 5% 15%Active ingredient mixture 0.1% 5% 15%
Polyethylenglykol MG 200 1.0% 2% 3%Polyethylene glycol MG 200 1.0% 2% 3%
Hochdisperse Kieselsäure 0.9 % 1 % 2 %Fumed silica 0.9% 1% 2%
Anorg. Trägermaterial 98.0 % 92 % 80 % (00.1 - 1 mm) wie z.B. CaCO3 oder SiO2 Inorg. Backing material 98.0% 92% 80% (00.1 - 1 mm) such as CaCO 3 or SiO 2
Der fein gemahlene Wirkstoff wird in einem Mischer auf das mit Polyethylenglykol angefeuchtete Trägermaterial gleichmäßig aufgetragen. Auf diese Weise erhält man staubfreie Umhüllungs-Granulate.The finely ground active ingredient is evenly applied in a mixer to the carrier material moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
F6. Extruder-Granulate a) b) c) d)F6. Extruder granules a) b) c) d)
Wirkstoff mischung 0.1 % 3% 5% 15%Active ingredient mixture 0.1% 3% 5% 15%
Na-Ligninsulfonat 1.5% 2% 3% 4%Na lignin sulfonate 1.5% 2% 3% 4%
CaΦoxymethylcellulose 1.4 % • 2 % 2 % 2 %CaΦoxymethylcellulose 1.4% • 2% 2% 2%
Kaolin 97.0% 93% 90% 79%Kaolin 97.0% 93% 90% 79%
Der Wirkstoff wird mit den Zusatzstoffen vermischt, vermählen und mit Wasser angefeuchtet. Dieses Gemisch wird extrudiert und anschließend im Luftstrom getrocknet.The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
F7. Stäubemittel a) b) c)F7. Dusts a) b) c)
Wirkstoffmischung 0.1 % 1 % 5%Active ingredient mixture 0.1% 1% 5%
Talkum 39.9 % 49% 35% Kaolin 60.0 % 50 % 60 %Talc 39.9% 49% 35% Kaolin 60.0% 50% 60%
Man erhält anwendungsfertige Stäubemittel, indem der Wirkstoff mit den Trägerstoffen vermischt und auf einer geeigneten Mühle vermählen wird.Ready-to-use dusts are obtained by mixing the active ingredient with the carrier substances and grinding them in a suitable mill.
F8. Suspensions-Konzentrate a) b) c) d)F8. Suspension concentrates a) b) c) d)
Wirkstoffmischung 3 % 10 % 25 % 50 %Active ingredient mixture 3% 10% 25% 50%
Ethylenglykol 5 % 5 % 5 % 5 %Ethylene glycol 5% 5% 5% 5%
Nonylphenol-polyglykolether - 1 % 2 % oNonylphenol polyglycol ether - 1% 2% o
(15 Mol EO)(15 moles of EO)
Na-Ligninsulfonat 3 % 3 % 4 % 5 %Na lignin sulfonate 3% 3% 4% 5%
Carboxymethylcellulose 1 % 1 % 1 % 1 %Carboxymethyl cellulose 1% 1% 1% 1%
37%ige wäßrige Formaldehyd- 0.2 % 0.2 % 0.2 % 0.2 % o37% aqueous formaldehyde- 0.2% 0.2% 0.2% 0.2% o
Lösungsolution
Silikonöl-Emulsion 0.8 % 0.8 % 0.8 % 0.8 %Silicone oil emulsion 0.8% 0.8% 0.8% 0.8%
Wasser 87 % 79 % 62 % 38 %Water 87% 79% 62% 38%
Der feingemahlene Wirkstoff wird mit den Zusatzstoffen innig vermischt. Man erhält so ein Suspensions-Konzentrat, aus welchem durch Verdünnen mit Wasser Suspensionen jeder gewünschten Konzentration hergestellt werden können.The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Es ist oft praktischer, den Wirkstoff der Formel I und den Mischungspartner der Formel lla bis llb2 einzeln zu formulieren und sie dann kurz vor dem Ausbringen in Applikator im gewünschten Mischungsverhältnis als "Tankmischung" im Wasser zusammenzubringen.It is often more practical to individually formulate the active ingredient of the formula I and the mixing partner of the formula Ila to IIb 2 and then to bring them together in the desired mixing ratio as "tank mixture" in water shortly before application in the applicator.
Die Fähigkeit der Safener Kulturpflanzen vor der phytotoxischen Wirkung von Herbiziden der Formel zu schützen, wird in den folgenden Beispielen veranschaulicht.The ability of the safener crop plants to protect against the phytotoxic action of herbicides of the formula is illustrated in the following examples.
Biologische BeispieleBiological examples
Beispiel B1 : Post-emergente Anwendungen von Mischungen eines Herbizids der Formel I mit einem Safener der Formeln lla bis llb2 in Getreide Unter Gewächshausbedingungen wird Weizen in Kunststofftöpfen bis zum 2-4-Blattstadium angezogen. In diesem Stadium werden zum einen die HeΦizide der Formel I allein als auch die Mischung der Herbizide mit einem Safener der Formeln lla bis llb2auf die Testpflanzen appliziert. Die Applikation erfolgt als wässrige Suspension der Prüfsubstanzen mit 500I Wasser/ha. Die Aufwandmengen für die HeΦizide betragen 250, 125 bzw. 60, g/ha. 17 Tage nach der Applikation wird mit einer Prozentskala ausgewertet. 100% bedeutet, dass die Testpflanze abgestorben ist; 0% bedeutet, dass keine phytotoxische Wirkung zu erkennen ist.Example B1: Post-emergent applications of mixtures of a herbicide of the formula I with a safener of the formulas 11a to 11b 2 in cereals Wheat is grown in plastic pots up to the 2-4 leaf stage under greenhouse conditions. At this stage, on the one hand the heicides of the formula I alone and also the mixture of the herbicides with a safener of the formulas 11a to 11b 2 are applied to the test plants. The application takes place as an aqueous suspension of the test substances with 500 I water / ha. The application rates for the heicides are 250, 125 and 60, g / ha. 17 days after the application is evaluated with a percentage scale. 100% means that the test plant has died; 0% means that no phytotoxic effect can be seen.
Es wurden die in den folgenden Tabellen B1 bis B3 erhaltenen Resultate erhalten. Diese zeigen, dass der verwendete Safener die durch die Herbizide auf den Kulturpflanzen verursachte Schädigung deutlich reduzieren kann.The results obtained in Tables B1 to B3 below were obtained. These show that the safener used can significantly reduce the damage caused by the herbicides on the crop plants.
Tabelle B1Table B1
Verb. Nr. Aufwandmengen (g/ha)Verb. No. Application rates (g / ha)
1.02 250 125 60 250 125 601.02 250 125 60 250 125 60
2.01 0 0 0 60 60 602.01 0 0 0 60 60 60
Weizen 60 50 30 10 0 0Wheat 60 50 30 10 0 0
Mais 20 10 0 5 0 0Corn 20 10 0 5 0 0
Alopecurus 100 100 70 100 100 70Alopecurus 100 100 70 100 100 70
Avena 100 100 90 100 100 90Avena 100 100 90 100 100 90
Lolium 100 100 95 100 100 95Lolium 100 100 95 100 100 95
Digitaria 100 100 100 100 100 100Digitaria 100 100 100 100 100 100
Brachiaria 100 100 100 100 100 100Brachiaria 100 100 100 100 100 100
Abutilon 100 100 100 100 100 100Abutilon 100 100 100 100 100 100
Xanthium 100 100 100 100 100 100Xanthium 100 100 100 100 100 100
Polygonum 100 100 85 100 100 85Polygonum 100 100 85 100 100 85
Kochia 100 100 100 100 100 100Kochia 100 100 100 100 100 100
Sinapis 100 100 100 100 100 100Sinapis 100 100 100 100 100 100
Galium 100 100 95 100 100 95 Tabelle B2Galium 100 100 95 100 100 95 Table B2
Verb. Nr. Aufwandmengen (g/ha)Verb. No. Application rates (g / ha)
1.16 250 125 60 250 125 601.16 250 125 60 250 125 60
2.01 0 0 0 60 60 602.01 0 0 0 60 60 60
Weizen 30 15 0 0 0 0Wheat 30 15 0 0 0 0
Mais 40 20 0 15 0 0Maize 40 20 0 15 0 0
Alopecurus 100 95 50 100 95 50Alopecurus 100 95 50 100 95 50
Avena 95 90 50 90 75 30Avena 95 90 50 90 75 30
Lolium 30 10 0 30 10 0Lolium 30 10 0 30 10 0
Digitaria 100 100 90 100 100 85Digitaria 100 100 90 100 100 85
Brachiaria 95 80 40 95 80 40Brachiaria 95 80 40 95 80 40
Abutilon 100 100 100 100 100 100Abutilon 100 100 100 100 100 100
Xanthium 100 100 100 100 100 100Xanthium 100 100 100 100 100 100
Polygonum 80 50 30 80 50 30Polygonum 80 50 30 80 50 30
Kochia 100 100 90 100 100 90Kochia 100 100 90 100 100 90
Sinapis 100 100 100 100 100 100Sinapis 100 100 100 100 100 100
Galium 90 80 50 90 80 50Galium 90 80 50 90 80 50
Tabelle B3Table B3
Verb. Nr. Aufwandmengen (g/ha)Verb. No. Application rates (g / ha)
1.15 250 125 60 250 125. 601.15 250 125 60 250 125. 60
2.01 0 0 0 60 60 602.01 0 0 0 60 60 60
Weizen 70 50 40 40 10 0Wheat 70 50 40 40 10 0
Mais 80 40 20 50 5 0Corn 80 40 20 50 5 0
Alopecurus 100 95 60 100 95 60Alopecurus 100 95 60 100 95 60
Avena 100 95 85 100 95 85Avena 100 95 85 100 95 85
Lolium 70 50 20 60 30 0Lolium 70 50 20 60 30 0
Digitaria 100 100 95 100 100 95Digitaria 100 100 95 100 100 95
Brachiaria 95 80 60 95 80 60 Abutilon 100 100 100 100 95 90Brachiaria 95 80 60 95 80 60 Abutilon 100 100 100 100 95 90
Xanthium 100 100 100 100 100 100Xanthium 100 100 100 100 100 100
Polygonum 100 100 100 100 100 100Polygonum 100 100 100 100 100 100
Kochia 100 100 100 100 100 100Kochia 100 100 100 100 100 100
Sinapis 100 100 100 100 100 100Sinapis 100 100 100 100 100 100
Galium 100 95 90 100 95 90Galium 100 95 90 100 95 90
Dieselben Resultate werden erhalten, wenn man die Wirkstoffe gemäß einem der Beispiele F1. bis F8. formuliert. The same results are obtained when the active ingredients according to one of Examples F1. to F8. formulated.

Claims

Patentansprüche: Claims:
1. Selektiv-herbizides Mittel, dadurch gekennzeichnet, dass es neben üblichen inerten1. Selective herbicidal agent, characterized in that it is in addition to customary inert
Formulierungshilfsmitteln als Wirkstoff eine Mischung aus a) einer herbizid wirksamen Menge eines Herbizids der Formel IFormulation aids as an active ingredient, a mixture of a) a herbicidally effective amount of a herbicide of the formula I.
Figure imgf000024_0001
Figure imgf000024_0001
worinwherein
X Halogen und Y -S(O)mR oder ein Rest der Formel
Figure imgf000024_0002
ist, worin R C C -Alkyl oderX halogen and Y -S (O) mR or a radical of the formula
Figure imgf000024_0002
in which RCC is alkyl or
C2-C4-Alkenyl, Z eine direkte chemische Bindung oder CH2 und m 0, 1 oder 2 ist, wobei m 0 ist, wenn R C2-C4-Alkenyl ist, oder eines Salzes der Verbindung der Formel I, und b) einer herbizid-antagonistisch wirksamen Menge einer Verbindung der Formel llaC 2 -C 4 alkenyl, Z is a direct chemical bond or CH 2 and m is 0, 1 or 2, where m is 0 when RC 2 -C 4 alkenyl, or a salt of the compound of the formula I, and b) a herbicidally antagonistically effective amount of a compound of the formula IIa
Figure imgf000024_0003
Figure imgf000024_0003
worin R010 Wasserstoff, Ci-Cβ-Alkyl oder durch Cι-C6-Alkoxy oder C3-C6-Alkenyloxy substituierteswherein R 010 is hydrogen, Ci-Cβ-alkyl or substituted by -CC 6 alkoxy or C 3 -C 6 alkenyloxy
Ci-Cβ-Alkyl undCi-Cβ-alkyl and
X2 Wasserstoff oder Chlor ist, einer Verbindung der Formel llbiX 2 is hydrogen or chlorine, a compound of formula IIbi
Figure imgf000025_0001
worin
Figure imgf000025_0001
wherein
E Stickstoff oder Methin,E nitrogen or methine,
R11 -CCI3 oder gegebenenfalls durch Halogen substituiertes Phenyl ist,R 11 is -CCI 3 or phenyl which is optionally substituted by halogen,
Ri2 und R13 unabhängig voneinander Wasserstoff oder Halogen sind, undR i2 and R13 are independently hydrogen or halogen, and
Ri4 Cι-C -Alkyl ist, oder einer Verbindung der Formel llb2 R i4 is -CC alkyl, or a compound of formula IIb 2nd
Figure imgf000025_0002
Figure imgf000025_0002
worinwherein
Rι2 und R13 die oben angegebenen Bedeutungen haben, und Rββ, Rβ7 und Reβ unabhängig voneinander Cι-C -Alkyl sind, enthält. Rι 2 and R13 have the meanings given above, and Rββ, Rβ7 and Reβ are independently Cι-C-alkyl, contains.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es eine Verbindung der Formel I enthält, worin X Brom und Y -SCH3ist.2. Composition according to claim 1, characterized in that it contains a compound of formula I, wherein X is bromine and Y is -SCH 3 .
3. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es als Safener eine VeΦindung der Formel lla enthält.3. Composition according to claim 1, characterized in that it contains a compound of the formula IIIa as a safener.
4. Mittel nach Anspruch 3, dadurch gekennzeichnet, dass es als Safener eine VeΦindung der Formel lla enthält, worin X2 Chlor und R0ιo -CH(CH3)C5Hn-n ist.4. Composition according to claim 3, characterized in that it contains a compound of the formula Ila as safener, in which X 2 is chlorine and R 0 ιo -CH (CH 3 ) C 5 Hn-n.
5. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es eine Wirkstoffkombination aus den Verbindungen 1.02 + 2.01 , 1.15 + 2.01 oder 1.16 + 2.01 enthält.5. Composition according to claim 1, characterized in that it contains an active ingredient combination of the compounds 1.02 + 2.01, 1.15 + 2.01 or 1.16 + 2.01.
6. Verfahren zum selektiven Bekämpfen von Unkräutern und Gräsern in Nutzpflanzenkulturen, dadurch gekennzeichnet, daß man die Nutzpflanzen, deren Samen oder Stecklinge oder deren Anbaufläche gleichzeitig oder getrennt mit einer herbizid wirksamen Menge eines Herbizids der Formel I und einer heΦizid-antagonistisch wirksamen Menge eines Safeners der Formel lla, llbi oder llb2 behandelt.6. A process for the selective control of weeds and grasses in crops, characterized in that the crop plants, their seeds or cuttings or the area under cultivation are used simultaneously or separately with a herbicidally active amount of a herbicide of the formula I and a heicide-antagonistically effective amount of a safener of the formula Ila, llbi or llb 2 treated.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß man Nutzpflanzenkulturen oder Anbauflächen für die Nutzpflanzenkulturen mit 0,010 bis 1 kg/ha eines Herbizids der Formel I und mit 0,010 bis 0,5 kg/ha eines Safeners der Formel lla, llbi oder llb2 behandelt.7. The method according to claim 6, characterized in that crops or acreage for crops with crops with 0.010 to 1 kg / ha of a herbicide of the formula I and with 0.010 to 0.5 kg / ha of a safener of the formula IIA, IIBI or IIB 2nd treated.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß es sich bei den Nutzpflanzenkulturen um Getreide, insbesondere um Weizen handelt. 8. The method according to claim 7, characterized in that the crops of crops are cereals, in particular wheat.
PCT/EP1998/000621 1997-02-07 1998-02-05 Herbicidal agent WO1998034480A1 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2350298A (en) * 1999-05-28 2000-11-29 Zeneca Ltd The safening of 2-benzoylcyclohexane-1,3-dione herbicides with 1-phenyl-1,2,4-triazole, 1-phenyl-pyrazolin-3-carboxylate & 8-oxy-quinoline derivatives
WO2002085120A2 (en) * 2001-04-21 2002-10-31 Bayer Cropscience Gmbh Herbicidal agent comprising benzoylcyclohexanediones and safeners
WO2003020033A1 (en) * 2001-08-30 2003-03-13 Bayer Cropscience Ag Herbicidal mixtures based on substituted aryl ketones
WO2008031507A2 (en) * 2006-09-13 2008-03-20 Bayer Cropscience Ag Herbicidal compositions with reduced phytotoxicity
WO2013176282A1 (en) * 2012-05-22 2013-11-28 Ishihara Sangyo Kaisha, Ltd. Herbicidal composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0551650A2 (en) * 1991-12-31 1993-07-21 Hoechst Schering AgrEvo GmbH Combinations of herbicides and plant protecting agents
WO1997045404A1 (en) * 1996-05-30 1997-12-04 Hokko Chemical Industry Co., Ltd. Cyclohexanedione derivatives and herbicidal compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0551650A2 (en) * 1991-12-31 1993-07-21 Hoechst Schering AgrEvo GmbH Combinations of herbicides and plant protecting agents
WO1997045404A1 (en) * 1996-05-30 1997-12-04 Hokko Chemical Industry Co., Ltd. Cyclohexanedione derivatives and herbicidal compositions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2350298A (en) * 1999-05-28 2000-11-29 Zeneca Ltd The safening of 2-benzoylcyclohexane-1,3-dione herbicides with 1-phenyl-1,2,4-triazole, 1-phenyl-pyrazolin-3-carboxylate & 8-oxy-quinoline derivatives
WO2002085120A2 (en) * 2001-04-21 2002-10-31 Bayer Cropscience Gmbh Herbicidal agent comprising benzoylcyclohexanediones and safeners
WO2002085120A3 (en) * 2001-04-21 2003-02-20 Bayer Cropscience Gmbh Herbicidal agent comprising benzoylcyclohexanediones and safeners
US6884757B2 (en) 2001-04-21 2005-04-26 Aventis Cropscience Gmbh Herbicides comprising benzoylcyclohexanediones and safeners
US7101827B2 (en) 2001-04-21 2006-09-05 Aventis Cropscience Gmbh Herbicides comprising benzoylcyclohexanediones and safeners
WO2003020033A1 (en) * 2001-08-30 2003-03-13 Bayer Cropscience Ag Herbicidal mixtures based on substituted aryl ketones
WO2008031507A2 (en) * 2006-09-13 2008-03-20 Bayer Cropscience Ag Herbicidal compositions with reduced phytotoxicity
WO2008031507A3 (en) * 2006-09-13 2009-04-16 Bayer Cropscience Ag Herbicidal compositions with reduced phytotoxicity
KR101432627B1 (en) 2006-09-13 2014-08-21 바이엘 크롭사이언스 아게 Herbicidal compositions with reduced phytotoxicity
WO2013176282A1 (en) * 2012-05-22 2013-11-28 Ishihara Sangyo Kaisha, Ltd. Herbicidal composition
JP2014001202A (en) * 2012-05-22 2014-01-09 Ishihara Sangyo Kaisha Ltd Herbicidal composition

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