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WO2011067184A1 - Composés 3-(4,5-dihydroisoxazol-5-yl)benzoylpyrazole et leurs mélanges avec des phytoprotecteurs - Google Patents

Composés 3-(4,5-dihydroisoxazol-5-yl)benzoylpyrazole et leurs mélanges avec des phytoprotecteurs Download PDF

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Publication number
WO2011067184A1
WO2011067184A1 PCT/EP2010/068352 EP2010068352W WO2011067184A1 WO 2011067184 A1 WO2011067184 A1 WO 2011067184A1 EP 2010068352 W EP2010068352 W EP 2010068352W WO 2011067184 A1 WO2011067184 A1 WO 2011067184A1
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formula
alkyl
methyl
hydrogen
ethyl
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PCT/EP2010/068352
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German (de)
English (en)
Inventor
Matthias Witschel
Bernd Sievernich
Ernst Baumann
Andree Van Der Kloet
Michael Rack
Rex Liebl
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to mixtures of herbicidally active compounds and safeners.
  • Crop compatibility of 4-HPPD inhibitors is variable. Depending on the crop, it may therefore be advisable to use 4-HPPD inhibitors in combination with 20 so-called safeners (W099 / 66795). The mechanism by which a safener reduces the phytotoxic effects of a given herbicide on the crop is not always well known.
  • An object of the present invention is to provide herbicidal agents.
  • agents are to be provided which have a high herbicidal activity, even at low application rates, and their compatibility with crop plants is sufficient for commercial exploitation.
  • the present invention relates to herbicidal mixtures comprising
  • R 1 is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy;
  • R 3 is C 1 -C 4 -alkylsulfonyl
  • R 4 is hydrogen, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkynyl;
  • R 5 is C 2 -C 4 -alkyl, C 3 -C 4 -cycloalkyl
  • R 6 is hydrogen, C 1 -C 4 -alkyl
  • component B an antidote effective amount of a safener.
  • R 1 is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy;
  • R 3 is C 1 -C 4 -alkylsulfonyl
  • R 4 is C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl;
  • R 5 is C 2 -C 4 -alkyl, C 3 -C 4 -cycloalkyl
  • R 6 is hydrogen, C 1 -C 4 -alkyl
  • R 1 is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy;
  • R 3 is C 1 -C 4 -alkylsulfonyl
  • R 4 is Cs-Ce-alkynyl, C 3 -C 6 -haloalkynyl
  • R 5 is C 2 -C 4 -alkyl, C 3 -C 4 -cycloalkyl
  • R 6 is hydrogen, Ci-C 4 alkyl.
  • the invention relates to processes for the preparation of the benzoylpyrazoles of the formula I and the mixtures according to the invention and compositions comprising a herbicidal mixture according to the invention or a herbicidally effective amount of a benzoylpyrazole of the formula I and for the formulation of pesticides customary auxiliaries.
  • the invention further relates to methods for controlling undesired plant growth, in which a herbicidal mixture according to the invention or a herbicidally effective amount of a benzoylpyrazole of the formula I is allowed to act on plants, their seeds and / or their habitat.
  • the organic molecular moieties mentioned for the substituents of the compounds according to the invention are collective terms for individual listings of the individual group members.
  • halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
  • halogen in each case represents fluorine, chlorine, bromine or iodine.
  • Alkyl and the alkyl moieties for example, in alkoxy, alkylamino, dialkylamino, N-alkylsulfonylamino, alkylsulfonyl, alkylaminosulfonylamino, dialkylaminosulfonylamino, N- (alkenyl) -N- (alkyl) -amino, N- (alkynyl) -N- (alkyl) -amino, N- (alkoxy) -N- (alkyl) -amino: saturated, straight-chain or branched hydrocarbon radicals having one or more C atoms, eg 1 to 2, 1 to 4, 2 to 4, or 1 to 6 carbon atoms, e.g.
  • C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2 Dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1 -
  • alkyl is a small alkyl group such as C 1 -C 4 -alkyl.
  • alkyl is greater alkyl groups such as Cs-Ce-alkyl.
  • Haloalkyl also referred to as haloalkyl: an alkyl radical as mentioned above whose hydrogen atoms are partially or fully substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloroflu - ormethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2 -difluoroethyl, 2,2-dichloro-2
  • Cycloalkyl and the cycloalkyl moieties for example, in cycloalkoxy or cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups having three or more C atoms, e.g. 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkenyl and alkenyl moieties for example, in alkenylamino, alkenyloxy, N- (alkenyl) -N- (alkyl) -amino, N- (alkenyl) -N- (alkoxy) -amino: monounsaturated, straight-chain or branched hydrocarbon radicals having two or more carbon atoms. Atoms, z. 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond in any position, e.g.
  • C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 - Methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3 butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-prop
  • Cycloalkenyl monocyclic, monounsaturated hydrocarbon groups having 3 to 6, preferably 5 to 6 carbon ring members, such as cyclopentene-1-yl, cyclopentene-3-yl, cyclohexene-1-yl, cyclohexen-3-yl, cyclohexen-4-yl , Alkynyl and alkynyl moieties, for example, in alkynyloxy, alkynylamino, N- (alkynyl) -N- (alkyl) -amino or N- (alkynyl) -N- (alkoxy) -amino: straight-chain or branched hydrocarbon groups having two or more carbon atoms, eg , B.
  • C 2 to 4, 2 to 6, or 3 to 6 carbon atoms and a triple bond in any position for example C 2 -C 6 alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl , 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3 -Methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2 pentynyl, 1-methyl-3-pentyny
  • Haloalkynyl alkynyl, as defined above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, in particular C 3 -C 6 -haloalkynyls, such as 1,1-difluoroprop-2-yn-1-yl, 3-iodopropylene 2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 4-iodobutyl 3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluoro-hex-4-yn-1-yl or 6-iodo-hex-5 yn-1-yl.
  • Alkoxy alkyl, as defined above, which is bonded via an oxygen atom: z.
  • Trimethylpropoxy 1, 2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.
  • Aryl denotes a mono- to trinuclear aromatic carbocycle having 6 to 14 ring members, for example phenyl, naphthyl and anthracenyl.
  • Heteroaryl denotes a 5- or 6-membered aromatic ring system having one to four nitrogen atoms or having one to three nitrogen atoms and one oxygen or sulfur atom, or having one oxygen or sulfur atom.
  • the benzoylpyrazoles of the formula I can, depending on the substitution pattern, contain one or more chiral centers.
  • the compounds according to the invention can therefore be present as pure enantiomers or diastereomers or as mixtures of enantiomers or diastereomers.
  • the invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
  • the benzoylpyrazoles of the formula I can also be present in the form of the N-oxides and / or their agriculturally useful salts, wherein the nature of the salt generally does not matter.
  • the salts of those cations or the acid addition salts of those acids come into consideration whose cations, or anions, do not adversely affect the herbicidal action of the benzoylpyrazoles of the formula I.
  • ions of the alkali metals preferably lithium, sodium or potassium, the alkaline earth metals, preferably calcium or magnesium, and the transition metals, preferably manganese, copper, zinc or iron are suitable as cations. It is likewise possible to use ammonium as cation, in which case one to four hydrogen atoms are optionally substituted by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxyC 1 -C 4 -alkyl.
  • alkoxy-C 1 -C 4 -alkyl phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth -1 -yl) ammonium, methylbenzylammonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate, Butyrate or trifluoroacetate.
  • Table 2 the compounds of formula 1.2.1 -1.2.560, which is the compounds of formula 1.1 .1 -1.1.
  • Table 9 the compounds of formula 1.9.1 -1.9.560, which is the compounds of formula 1.1 .1 -1.1.
  • Table 17 the compounds of the formula 1.17.1 -1.17.560, which is based on the compounds of the Fo.
  • Table 18 the compounds of the formula 1.18.1 -1.18.560, which differ from the compounds of the formula 1.1 .1 -1.1 .560 in that R 6 is CH 3 and R 3 is CH 3 CH 2 SO 2 - ,
  • Table 19 the compounds of the formula 1.19.1-1.19.560, which differ from the compounds of the formula 1.1.1-1.1.560, in that R 6 is CH 3 - and R 4
  • Table 21 the compounds of the formula 1.21.1-1.21.560, which differ from the compounds of the formula 1.1.1-1.1.560, in that R 6 is CH 3 - and R 4
  • Table 24 the compounds of the formula 1.24.1-1.24.560, which differ from the compounds of the formula 1.1.1-1.1.560, in that R 6 is CH 3 -, R 4
  • BrO is CCH 2 - and R 3 is CH 3 CH 2 SO 2 -.
  • HO is CCHF- and R 3 is CH 3 CH 2 SO 2 -.
  • Table 28 the compounds of the formula 1.28.1 -1.28.560, which differ from the compounds of the formula 1.1 .1 -1.1 .560 in that R 6 is CH 3 -, R 4
  • HC CCHCl and R 3 is CH 3 CH 2 SO 2 -.
  • HO is CCH (CHs) - and R 3 is CH 3 CH 2 SO 2 -.
  • Table 31 the compounds of the formula 1.31.1-1.31.560, which differ from the compounds of the formula 1.1.1-1.1.560 in that R 6 is CH 3 - and R 4 is H 3 C- O CCH (CH 3) - ,
  • Table 32 the compounds of the formula 1.32.1-1.32.560, which are different from the compounds of the formula 1.1.1-1.1.560, in that R 6 is CH 3 -, R 4 is H 3 C- O C CH (CH 3 ) - and R 3 is CH 3 CH 2 SO 2 -.
  • the herbicidal mixture comprises, as component A), a herbicidally effective amount of a benzoylpyrazole of the formula I in which the variables have the following meanings:
  • R 1 is C 1 -C 4 -alkyl
  • R 2 is dC 4 alkyl
  • R 3 is C 1 -C 4 -alkylsulfonyl
  • R 4 is hydrogen, Cs-Ce-alkynyl
  • R 5 is ethyl, propan-2-yl, cyclopropyl
  • R 6 is hydrogen; or its agriculturally suitable salt.
  • the herbicidal mixture comprises, as component A), a herbicidally effective amount of a benzoylpyrazole of the formula I in which the variables have the following meanings:
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is hydrogen, prop-2-ynyl
  • R 5 is ethyl, propan-2-yl, cyclopropyl
  • R 6 is hydrogen; or its agriculturally suitable salt.
  • component A) of the mixture according to the invention is the compound 1.3.81, corresponding to the compound of the formula I, in which the variables have the following meanings:
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is prop-2-ynyl
  • R 5 is ethyl
  • R 6 is hydrogen
  • component A) of the mixture according to the invention is the compound 1.1.81 corresponding to the compound of the formula I, the variables having the following meanings:
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is hydrogen
  • R 5 is ethyl
  • R 6 is hydrogen; or its agriculturally suitable salt.
  • Benzoylpyrazoles of the formula I which are preferred by virtue of their properties are the compounds where R 4 is hydrogen, in particular the compounds 1.3.1 -1.3.560, 1.4.1 - I.4.560, 1.5.1 -1.5.560, 1.6.1 -1.6.560 , 1.7.1 -1.7.560, 1.8.1 -1.8.560, 1.9.1 -1.9.560, 1.10.1 - 1.10.560, 1.1 1.1 -1.1 1 .560, 1.12.1 -1.12.560, 1.13 .1 -1.13.560, 1.14.1 -1.14.560, 1.15.1 - 1.15.560, 1.16.1 -1.16.560, 1.19.1 -1.19.560, 1.20.1 -1.20.560, 1.21.1 -1.21.560, 1.22.1 - I.22.560, 1.23.1 -1.23.560, 1.24.1 -1.24.560, 1.25.1 -1.25.560, 1.26.1 -1.26.560, 1.2
  • R 1 is C 1 -C 4 -alkyl
  • R 2 is dC 4 alkyl
  • R 3 is C 1 -C 4 -alkylsulfonyl
  • R 4 is Cs-Ce-alkynyl
  • R 5 is ethyl, propan-2-yl, cyclopropyl
  • R 6 is hydrogen
  • R 1 is C 1 -C 2 -alkyl
  • R 2 is C 1 -C 2 -alkyl
  • R 3 is C 1 -C 2 -alkylsulfonyl
  • R 4 is Cs-Ce-alkynyl
  • R 5 is ethyl, propan-2-yl, cyclopropyl
  • R 6 is hydrogen
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is prop-2-ynyl
  • R 5 is ethyl
  • R 6 is hydrogen
  • benzoylpyrazoles of the formula I are obtainable in various ways, for example by the following process:
  • L 1 represents a nucleophilic displaceable leaving group, such as halogen, hetaryl or carboxylate.
  • Suitable halogen groups are, for example, bromine and chlorine.
  • hetaryl groups are, for example, imidazolyl and pyridyl into consideration.
  • carboxylates are acetate and trifluoroacetate.
  • the activated benzoic acid can be used directly, as in the case of benzoyl halides or generated in situ, for.
  • dicyclohexylcarbodiimide triphe nylphosphine / azodicarboxylic acid ester, 2-pyridine disulfide / triphenylphosphine, carbonyldiimidazole, etc.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently used in equimolar amounts.
  • a slight excess of the auxiliary base, z. B. 1, 2 to 1, 5 molar equivalents, based on the compound of formula II, may be advantageous under certain circumstances.
  • Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates.
  • suitable solvents are chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene,
  • ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane
  • polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof may be used.
  • benzoyl halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10 ° C. when adding this reaction partner. The mixture is then stirred at 20-100 ° C, preferably at 25-50 ° C until the reaction is complete. The workup is carried out in the usual manner, for. For example, the reaction mixture is poured onto water and the desired product extre- hiert. Particularly suitable solvents for this are methylene chloride, diethyl ether and ethyl acetate.
  • the crude ester After drying the organic phase and removing the solvent, the crude ester can be used without further purification for rearrangement.
  • the rearrangement of the esters to give the benzoylpyrazoles of the formula I is expediently carried out at from 20.degree. To 40.degree. C. in a solvent and in the presence of a base and optionally with the aid of a cyano compound as catalyst.
  • a solvent for.
  • acetonitrile methylene chloride, 1, 2-dichloroethane, dioxane, dimethoxyethane, ethyl acetate, toluene or mixtures thereof may be used.
  • Preferred solvents are acetonitrile, dioxane and dimethoxyethane.
  • Suitable bases are tertiary amines such as triethylamine, pyridine or alkali metal carbonates, such as sodium carbonate, potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester.
  • triethylamine or alkali carbonates are used, preferably in twice equimolar ratio with respect to the ester.
  • Suitable cyano compounds are inorganic cyanides, such as sodium cyanide, potassium cyanide and organic cyano compounds, such as acetone cyanohydrin, trimethylsilyl cyanide. They are used in an amount of 1 to 50 mole percent, based on the ester. Preferably, acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of 5 to 15, preferably 10 mole percent, based on the ester used.
  • the workup can be done in a conventional manner.
  • the reaction mixture is treated, for example, with dilute mineral acid, such as 5% hydrochloric acid or sulfuric acid.
  • ferric acid acidified, extracted with an organic solvent, for example methylene chloride, ethyl acetate.
  • the organic extract can be extracted with 5-10% alkali carbonate solution, for example sodium carbonate, potassium carbonate solution.
  • the aqueous phase is acidified and the precipitate formed is filtered off with suction and / or extracted with methylene chloride or ethyl acetate, dried and concentrated.
  • esters of hydroxypyrazoles examples include, for. In EP-A 282 944 and US Pat. No. 4,643,757.
  • L 2 is a nucleophilically displaceable leaving group, such as halogen, z.
  • halogen such as bromine, chlorine, iodine, or groups such as methylsulfonyl, toluenesulfonyl.
  • R 4 in the compound of formula V is hydrogen.
  • the compounds of formula V can be used directly, such as. B. in the case of halogens, or generated in situ, for. B. activated sulfonic acid esters (from the alcohol and a sulfonic anhydride or halide).
  • the starting compounds are usually used in equimolar ratio. However, it can also be advantageous to use one or the other component in excess.
  • auxiliary base it may be advantageous to carry out the reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently used in equimolar amounts.
  • An excess of the auxiliary base, z. B. 1 .5 to 3 molar equivalents, based on the compound of formula II, may be advantageous under certain circumstances.
  • Suitable auxiliary bases are tertiary alkylamines, such as triethylamine, pyridine, alkali metal carbonates, eg. For example, sodium carbonate, potassium carbonate and alkali metal hydrides, eg. For example, sodium hydride.
  • alkali metal carbonates eg.
  • sodium carbonate, potassium carbonate and alkali metal hydrides eg.
  • sodium hydride Preferably used are triethylamine and pyridine.
  • chlorinated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, aromatic hydrocarbons, eg. As toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide or esters such as ethyl acetate, or mixtures thereof into consideration.
  • reaction temperature is in the range of 0 ° C to the height of the boiling point of the reaction mixture.
  • the workup can take place in a manner known per se for the product.
  • the benzoylpyrazoles of the formula I and their agriculturally suitable salts are suitable as herbicides, both as mixtures of isomers and in the form of pure isomers. They are suitable as such or as appropriately formulated agent.
  • the herbicidal compositions containing the compound I in particular the preferred embodiments thereof, control plant growth on non-crop surfaces very well, especially at high application rates. In crops such as cereals, rice, maize, soya, cotton, canola and sugarcane, especially in maize and cereals such as wheat, rye,
  • the benzoylpyrazoles of the formula I can be used as such and also as component A) of a herbicidal mixture comprising the components A) and B) for controlling undesired plant growth.
  • the herbicidal mixture according to the invention comprises an antidote effective amount of a safener.
  • Safeners are chemical compounds that prevent or reduce damage to crops without significantly affecting the herbicidal action of Benzoylpyrazole of formula I on undesirable plants. They can be used both before sowing (for example, in seed treatments, cuttings or seedlings) as well as in the pre- or post-emergence of the crop.
  • the safeners and the benzoylpyrazoles of the formula I can be used be used early or in succession.
  • Suitable safeners are, for example, (quinolin-8-oxy) acetic acids, 1-phenyl-5-haloalkyl-1H-1, 2,4-triazole-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl 1 H-pyrazole-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N- [ [4- (Aminocarbonyl) phenyl] sulfonyl] -2-benzoic acid amides, 1,8-naphthalic anhydride, 2-halo-4- (haloalkyl) -5-thiazolecarboxylic acids, phosphorothiolates, N-alkyl-O-phenylc
  • the component B) of the herbicidal mixture is selected from the group of safeners Benoxacor (B1), cloquintocet (B2), cyometrinil (B3), cyprosulfamide (B4), dichloromide (B5), dicyclonone (B6), dietholate (B7), fenchlorazole (B8), fenclorim (B9), flurazole (B10), fluxofenim (B1 1), furilazole (B12), isoxadifen (B13), mefenpyr (B14), mephenate (B15), Naphtalic anhydride (B16), oxabetrinil (B17), 4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane
  • mixtures according to the invention are the mixtures B1.1.1.1 - B19.I.32.560 according to Table 33, which in each case as component A) a benzoylpyrazole of the formula I, selected from Tables 1 to 32, that is in each case one of the compounds 1.1.
  • a safener selected from the group Benoxacor (B1), Cloquintocet (B2), Cyometrinil (B3), Cyprosulfamid (B4), dichloromide (B5), dicyclonone (B6), dietholate (B7), fenchlorazole (B8), fenclorim (B9), flurazole (B10), fluxofenim (B1 1), furilazole (B12), isoxadifen (B13), mefenpyr (B14), mephenate (B15), naphthalic anhydride (B16), Oxabetrinil (B17), 4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane (MON4660, CAS 71526-07-3) (B18) and 2,2,5-trimethyl-3- (dichloroacetyl) - 1, 3-oxazolidine (R-29148,
  • a safener selected from the group Benox
  • Examples of preferred mixtures according to the invention are mixtures which contain as component A) in each case a benzoylpyrazole of the formula I selected from Tables 1 to 32, and as component B) a safener selected from the group Cloquintocet (B2), isoxadifen (B13) and Mefenpyr (B14).
  • Examples of particularly preferred mixtures according to the invention are mixtures which contain, as component A), the benzoylpyrazole of the formula I.1.81, ie the compound of the formula I ## STR4 ## with
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is hydrogen
  • R 5 is ethyl
  • R 6 is hydrogen; or its agriculturally suitable salt
  • a safener selected from the group Benoxacor (B1), Cloquintocet (B2), Cyometrinil (B3), Cyprosulfamide (B4), Dichlormid (B5), Dicyclonone (B6), Dietholate (B7), Fenchlorazole ( B8), fenclorim (B9), flurazole (B10), Fluxofenim (B11), Furilazole (B12), Isoxadifen (B13), Mefenpyr (B14), Mephenate (B15), Naphtalic Acid Anhydride (B16), Oxabetrinil (B17), 4- (Dichloroacetyl) -1-oxa-4 azaspiro [4.5] decane (B18) and 2,2,5-trimethyl-3- (dichloroacetyl) -1,3-oxazolidine (B19), ie the mixtures B1.I.1.81, B2.1.1.81, B3.1.1 .81,
  • mixtures according to the invention are mixtures which contain, as component A), the benzoylpyrazole of the formula 1.3.81, that is to say the compound of the formula I ## STR5 ## with
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is prop-2-ynyl
  • R 5 is ethyl
  • R 6 is hydrogen
  • a safener selected from the group Benoxacor (B1), Cloquintocet (B2), Cyometrinil (B3), Cyprosulfamide (B4), Dichlormid (B5), Dicyclonone (B6), Dietholate (B7), Fenchlorazole ( B8), Fenclorim (B9), Flurazole (B10), Fluxofenim (B11), Furilazole (B12), Isoxadifen (B13), Mefenpyr (B14), Mephenate (B15), Naphtalic Acid Anhydride (B16), Oxabetrinil (B17), 4- (Dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane (B18) and 2,2,5-trimethyl-3- (dichloroacetyl) -1,3-oxazolidine (B19), ie mixtures B1.1.3.81 , B2.1.3.81, B3.1.3.81, B4.I
  • Examples of extraordinarily preferred mixtures are the mixtures containing as component A) the compound 1.1.81 and as component B) a safener selected from the group Cloquintocet (B2), isoxadifen (B13) and Mefenpyr (B14), ie the mixtures B2.1.1.81, B13.1.1.81 and B14.I.1.81.
  • a safener selected from the group Cloquintocet (B2), isoxadifen (B13) and Mefenpyr (B14), ie the mixtures B2.1.1.81, B13.1.1.81 and B14.I.1.81.
  • a safener selected from the group Cloquintocet (B2), isoxadifen (B13) and Mefenpyr (B14), that is the mixtures B2.1.3.81, B13.1.3.81 and B14.1.3.81.
  • the benzoylpyrazoles of the formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and / or with safeners and applied together.
  • 1,2,4-thiadiazoles, 1, 3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, amides are used as mixing components.
  • notriazoles anilides, aryloxy / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2- (hetaroyl / aroyl) -1, 3-cyclohexanediones, heteroaryl-aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and derivatives thereof, dihydrobenzofurans, dihydro-furan-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,
  • benzoylpyrazoles of the formula I alone or in combination with other herbicides or mixed with other pesticides, together, for example, with agents for controlling pests or phytopathogenic fungi or bacteria.
  • agents for controlling pests or phytopathogenic fungi or bacteria are also of interest.
  • miscibility with mineral salt solutions which are used for the elimination of nutritional and trace element deficiencies.
  • Other additives such as non-phytotoxic oils and oil concentrates may also be added.
  • herbicides C) which can be used in combination with the benzoylpyrazoles of the formula I according to the present invention are:
  • Bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; C8) from the group of DHP synthase inhibitors: asulam;
  • Y is phenyl or 5- or 6-membered heteroaryl as defined above, which may be mono- to trisubstituted;
  • R 21 , R 22 , R 23 , R 24 are H, halogen, or C 1 -C 4 -alkyl;
  • X is O or NH; n 0 or 1.
  • R 25 is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl;
  • R 26 is C 1 -C 4 -alkyl;
  • R 27 is halogen, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;
  • R 28 is H, halogen, Ci-C 4 - alkyl, Ci-C 4 haloalkyl or Ci-C4-haloalkoxy;
  • m is 0, 1, 2 or 3;
  • Particularly preferred compounds of the formula 2 are: 3- [5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethanesulfonyl] -4-fluoro-5,5-dimethyl-4,5-dihydro-isoxazole (2-1); 3 - ⁇ [5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] -fluoro-methanesulfonyl ⁇ -5,5-dimethyl-4,5 dihydro-isoxazole (2- 2); 4- (4-Fluoro-5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonylmethyl) -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-3); 4 - [(5,5-Dimethyl-4,5-dihydro-isoxazol-3
  • 2,4-D, 2,4-DB aminopyralid, aminopyralid-tris (2-hydroxypropyl) ammonium, benazolin, benazolin-ethyl, Chloramben, Clomeprop, Clopyralid, Dicamba, dichlorprop, dichlorprop-P, fluroxypyr, Fluroxypyr-butometyl, fluroxypyr-meptyl, MCPA, MCPA-thioethyl, MCPB, mecoprop (CMPP), mecoprop-P (CMPP-P), picloram, quinclorac, quinmerac, TBA (2,3,6), triclopyr, and 5 6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (CAS 858956-08-8);
  • auxin transport inhibitors diflufenzopyr, diflufenzopyr- none, naptalam and naptalam-sodium;
  • the herbicides of groups C1) to C15) can be used as such or in the form of their agriculturally suitable salts or, provided they have an acid function, in the form of their agriculturally suitable derivatives such as amides, esters and thioesters as mixing partners for the benzoylpyrazoles of the formula I. ,
  • the safeners B and the herbicides C of the groups C1) to C15) are known active ingredients, see, for. B. The Compendium of Pesticide Common Names (Http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, RR Schmidt, herbicides, Georg Thieme Verlag, Stuttgart 1995. Further herbicidal active ingredients are known from WO 96/26202, WO 97/41 1 16, WO 97/41 1 17, WO 97/41 1 18 WO 01/83459 and WO 2008/074991 and W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1, Wiley VCH, 2007 and the literature cited therein.
  • the abovementioned herbicides C) are particularly suitable, in particular those in Table 34 mentioned herbicides c1 to c150.
  • the compound of the formula 1.3.81 or for herbicidal mixtures containing as component A) the compound of the formula 1.3.81 and as component B) a safener are particularly suitable, in particular those in Table 34 herbicides c1 to c150.
  • mixtures according to the invention are the mixtures c1 .1.1.1 to c150.L32.560 according to Table 34, which in each case as component A) a benzoylpyrazole of the formula I, selected from Tables 1 to 32, that is in each case one of the compounds 1.1.1 -1.32.560, and as component C) contain a further herbicide according to Table 34:
  • c51.L1.1 - c51.L32.560 1.1.1-1.32.560 c51 halosulfuron-methyl c52.L1.1 - c52.L32.560 1.1.1-1.32.560 c52 primisulfuron-methyl c53.L1.1 - c53.L32.560 1.1.1-1.32.560 c53 rrimsulfuron herbicidal mixture component A): component C) containing A) and C) compound I herbicide
  • the novel mixtures of Table 34 are abbreviated to mixtures c1.l.1.1-c150.l.32.560 hereinafter.
  • Examples of particularly preferred mixtures according to the invention are mixtures which contain two herbicidal active substances, namely, as component A), the benzene ylpyrazole of the formula 1.1.81 and as component C) a further herbicide C according to Table 34, that is the mixtures d .1.1.81, c2.l.1.81, c3.l.1.81, c4.l.1.81, c5.L1 .81, c6.l-1.81, c7.L1.81, c8.l.1.81, c9.l.1.81, c10.l.1.81, c11.1.1.81, c12.1.1.81, c13.
  • compositions which contain two herbicidal active compounds, namely as component A) the benzoylpyrazole of the formula 1.3.81 and as component C) a further herbicide C according to Table 34, that is to say the mixtures d .1.3.81 , c2.1.3.81, c3.1.3.81, c4.1.3.81, c5.l. 3.81, c6.L3.81, c7.L3.81, c8.L3.81, c9.1.3.81, c10.1.3.81, d 1.1.3.81, c12.l.3.81, c13. 1.3.81, c14.
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is prop-2-ynyl
  • R 5 is ethyl
  • R 6 is hydrogen
  • C56 pendimethalin (c1 16) c132.c56.L3.81 c56.L3.81 (1.3.81 + thifensulfuron-m. (C56)) pyroxasulfones (c132) c123.c56.L3.81 c56.L3.81 (1.3.81 + thifensulfuron-m. (c56)) flufenacet (c123) c101 .c56.L3.81 c56.L3.81 (1.3.81 + thifensulfuron-m.
  • c133.1.3.81 c133.L3.81 (1.3.81 + 2,4-D (c133)) florasulam (c27) c57.c133.1.3.81 c133.L3.81 (1.3.81 + 2,4-D (c133)) tribenuron (c57) c39.c133.1.3.81 c133.L3.81 (1.3.81 + 2,4-D (c133)) lodosulfuron (c39) c42.c133.1.3.81 c133.L3.81 (1.3.81 + 2,4-D (c133)) metsulfuron-m.
  • the mixtures according to Table 35 each additionally contain a component B selected from the group cloquintocet, mefenpyr, fenchlorazole, isoxadifen, and cyprosulfamide.
  • Table 37 In a particularly preferred embodiment of the invention, the mixtures according to Table 35 each additionally contain, as component B, cloquintocet (B2).
  • Table 38 In a further particularly preferred embodiment of the invention, the mixtures according to Table 35 each additionally contain, as component B, Mefenpyr (B14).
  • the mixtures according to Table 35 additionally contain, as component B, isoxadifen (B13).
  • Table 40 Another preferred subject matter of the present invention are mixtures which differ from the mixtures according to Tables 35 to 39 in that as component A) of the mixture, the benzoylpyrazole of the formula 1.1.81, that is the compound of the formula I with R 1 is methyl;
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is hydrogen
  • R 5 is ethyl
  • R 6 is hydrogen; or its agriculturally suitable salt.
  • the mixtures according to Tables 35 to 40 are particularly suitable for combating harmful plants in cereal crops, such as wheat, rye, oats, barley and triticale.
  • mixtures according to the following Table 41 containing as component A) the compound of the formula 1.3.81, that is to say the benzoylpyrazole of the formula I ## STR4 ## with
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is prop-2-ynyl
  • R 5 is ethyl
  • R 6 is hydrogen
  • the mixtures according to Table 41 each additionally contain a component B selected from the group cloquintocet, mefenpyr, fenchlorazole, isoxadifen, cyprosulfamide, benoxa cor, dichloromide, furilazole and 4- (dichloroacetyl) -1 oxa-4-azaspiro [4.5] decane.
  • a component B selected from the group cloquintocet, mefenpyr, fenchlorazole, isoxadifen, cyprosulfamide, benoxa cor, dichloromide, furilazole and 4- (dichloroacetyl) -1 oxa-4-azaspiro [4.5] decane.
  • Table 43 In a particularly preferred embodiment of the invention, the mixtures according to Table 41 each additionally contain, as component B, cloquintocet (B2).
  • Table 44 In a further particularly preferred embodiment of the invention, the mixtures according to Table 41 each additionally contain, as component B, Mefenpyr (B14).
  • Table 45 In a further particularly preferred embodiment of the invention, the mixtures according to Table 41 each additionally contain, as component B, isoxadifen (B13).
  • Table 46 Another preferred subject matter of the present invention are mixtures which differ from the mixtures according to Tables 41 to 45 in that as component A) of the mixture it is the benzoylpyrazole of the formula 1.1.81, that is the compound of the formula I with
  • R 1 is methyl
  • R 2 is methyl
  • R 3 is methylsulfonyl
  • R 4 is hydrogen
  • R 5 is ethyl
  • R 6 is hydrogen; or its agriculturally suitable salt.
  • Table 47 The mixtures according to Tables 41 to 46 are particularly suitable for combating harmful plants in maize crops.
  • the components of the mixture according to the invention can be formulated together, but also separately, and / or applied together or separately to the plants, their habitat and / or seeds.
  • the active ingredients are applied simultaneously. But it is also possible to deploy them separately.
  • the invention also relates to compositions in the form of a plant protection composition formulated as a 1-component composition comprising a combination of active substances comprising at least one benzoylpyrazole of the formula I and at least one further active ingredient and at least one solid or liquid carrier and / or one or more surface-active substances and, if desired, one or more several other auxiliaries customary for pesticides.
  • the invention also relates to compositions in the form of a 2-
  • Component composition formulated crop protection agent comprising a first component containing at least one Benzoylpyrazol of formula I, a solid or liquid carrier and / or one or more surfactants, and a second component containing at least one further active ingredient, a solid or liquid carrier and / or one or more surface-active substances, wherein in addition both components may also contain other, customary for crop protection agents.
  • the weight ratio of the active compounds A: B is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1.
  • the weight ratio of the active compounds A: C is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1.
  • the relative proportions by weight of the components A: B are generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and more preferably in the range from 1: 75 to 75: 1,
  • the weight ratio of component A: C is generally in the range of 1 : 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1
  • the weight ratio of the components B: C usually in the range of 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.
  • the weight ratio of components A + B to component C is preferably in the range from 1: 500 to 500: 1,
  • compositions which comprise at least one benzoylpyrazole of the formula I as component A and two herbicides C (C a and C b ) the weight ratio of the active compounds A: C a and A: C b is generally in the range independently of one another from 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1.
  • the active ingredients in the described compositions are each preferably present in synergistically effective amounts.
  • the benzoylpyrazoles of the formula I and the mixtures according to the invention may also have a plant-strengthening effect. They are therefore suitable for mobilizing plant-specific defenses against attack by undesired microorganisms, such as harmful fungi, but also viruses and bacteria.
  • plant-strengthening (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defense system of treated plants in such a way that they develop extensive resistance to these microorganisms during subsequent inoculation with undesired microorganisms.
  • the benzoylpyrazoles of the formula I and the mixtures according to the invention can be used to protect plants against attack by undesired microorganisms within a certain period of time after the treatment.
  • the period within which protection is provided generally extends to 1 to 28 days, preferably 1 to 14 days after the treatment of the plants with the benzoylpyrazoles of the formula I or after treatment of the seed, for up to 9 months after sowing.
  • the benzoylpyrazoles of the formula I and the mixtures according to the invention are also suitable for increasing the crop yield.
  • the benzoylpyrazoles of the formula I and the mixtures according to the invention in particular the preferred embodiments thereof, or agents containing them, can be used in a further number of crop plants for the removal of undesired plants.
  • the following cultures may be considered: Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapeseed, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var.
  • crops also includes those that have been modified by breeding, mutagenesis or genetic engineering methods.
  • Genetically engineered plants are plants whose genetic material has been altered in a manner that does not occur under natural conditions by crossing, mutations or natural recombination (i.e., rearrangement of genetic information).
  • one or more genes are integrated into the genome of the plant in order to improve the properties of the plant.
  • crops thus also encompasses plants which, by breeding and genetic engineering measures, tolerate certain classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, e.g. Sulfonylureas (EP-A-0257993, US5,013,659) or imidazolinones (see for example US6,222,100, WO01 / 82685, WO00 / 26390, WO97 / 41218,
  • herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, e.g. Sulfonylureas (EP-A-0257993, US5,013,659) or imidazolinones (see for example US6,222,100, WO01 / 82685, WO00 / 26390, WO97 / 41218
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • Glyphosate see, for example, WO92 / 00377
  • glutamine synthetase (GS) inhibitors e.g. Glufosinate
  • EP-A-0242236, EP-A-242246 e.g., EP-A-0242236, EP-A-242246
  • oxynil herbicides see, e.g., U.S. 5,559,024.
  • mutagenesis Using classical breeding methods (mutagenesis) were produced numerous crops, including Clearfield ® canola, which have a tolerance to imidazolinones, eg imazamox. With Crop plants were as soybeans, cotton, corn, beets and oilseed rape were generated which are resistant to glyphosate or glufosinate, and sold under the trade name RoudupReady ® (glyphosate) and Liberty Link ® (glufosinate) are available. The term crops thus also includes plants which produce one or more toxins, for example those from the bacterial strain Bacillus ssp., By means of genetic engineering.
  • Toxins produced by such genetically modified plants include, for example, insecticides proteins of Bacillus spp., In particular B. thuringiensis, such as the endotoxins CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1 ; or vegetative insecticidal proteins (VIPs), eg VIP1, VIP2, VIP3, or VIP3A; Insecticidal proteins of nematode-colonizing bacteria, eg, Photorhabdus spp.
  • insecticides proteins of Bacillus spp. In particular B. thuringiensis, such as the endotoxins CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1 ; or vegetative insecticidal proteins (VIPs), eg VIP
  • Toxins from animal organisms eg wasp, spider or scorpion toxins
  • fungal toxins eg from streptomycetes
  • vegetable lectins for example from pea or barley
  • agglutinins Proteinase inhibitors, eg trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • Ribosome-inactivating proteins RIPs
  • Steroid metabolizing enzymes eg 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase
  • ion channel blockers eg inhibitors of sodium or calcium channels
  • toxins can also be produced in the plants as proteoxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are distinguished by a novel combination of different protein domains (see, for example, WO2002 / 015701). Further examples of such toxins or genetically engineered plants that produce these toxins are described in EP-A374753, WO93 / 007278, WO95 / 34656, EP-A-427529, EP-A451878, WO03 / 018810 and EP-A-0 438 9
  • crops thus also encompasses plants which, by means of genetic engineering, produce one or more proteins which bring about increased resistance or resistance to bacterial, viral or fungal pathogens, e.g. so-called pathogenesis-related proteins (PR proteins, see EP-A0392225), resistance proteins (eg potato varieties that produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (eg potato varieties produced by the production of this protein resistant to bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related proteins
  • resistance proteins eg potato varieties that produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum
  • T4 lysozyme eg potato varieties produced by the production of this protein resistant to bacteria such as Erwinia amylvora
  • crops thus also includes plants whose productivity has been improved by genetic engineering methods, e.g. productivity (e.g., biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens is increased.
  • productivity e.g., biomass, grain yield, starch, oil or protein content
  • tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens is increased.
  • crop plants also includes plants whose ingredients particular to improve human or animal nutrition using genetic engineering methods have been changed by, for example oil plants producing health long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Ne xera ® Oilseed rape).
  • oil plants producing health long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Ne xera ® Oilseed rape).
  • the term also includes crop plants that have been modified for improved production of raw materials with the aid of recombinant methods by, for example, the amylopectin content of potatoes (Amflora ® potato) increased.
  • the benzoylpyrazoles of the formula I and the mixtures according to the invention are also suitable for the defoliation and / or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, come into consideration .
  • crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton
  • Suitable desiccants are the benzoylpyrazoles of the formula I and the mixtures according to the invention, in particular for dehydration of the aerial parts of crop plants such as potato, rape, sunflower and soybean, but also cereals. This allows a completely mechanical harvesting of these important crops. Of economic interest is also the harvest relief, which is made possible by the time-concentrated dropping or reducing the adhesion to the tree in citrus fruits, olives or other types and varieties of pome, stone and peel fruit. The same mechanism, ie the promotion of the formation of separating tissue between fruit or leaf and shoot part of the plants is also essential for a well controllable defoliation of crops, especially cotton.
  • the benzoylpyrazoles of the formula I and the mixtures according to the invention or the herbicidal compositions containing them can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules are applied by spraying, atomizing, dusting, scattering, pouring or treatment of the seed or mixing with the seed.
  • the forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions contain a herbicidally effective amount of at least one Benzoylpyrazoles of formula I or an agriculturally useful salt of I or the mixtures according to the invention and for the formulation of pesticides usual excipients.
  • auxiliaries are preferred auxiliaries, solid carriers, surface-active substances (such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.
  • surface-active substances such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives
  • organic and inorganic thickeners such as bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.
  • thickeners ie, compounds which impart modified flowability to the formulation, ie, high-level at low viscosity and low viscosity in the agitated state
  • polysaccharides such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum ® (company RT Vanderbilt) and organic and inorganic layer minerals such as Attaclay® (Engelhardt).
  • antifoams examples include silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides may be added to stabilize the aqueous herbicidal formulation.
  • bactericides are bactericides based on diclorophene and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS der Fa. Thor Chemie)
  • antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
  • colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned are the dyes known under the names Rhodamine B, Cl Pigment Red 1 12 and Cl Solvent Red 1, and pigment blue 15: 4, pigment blue 15: 3, pigment blue 15: 2, pigment blue 15: 1, pig pigment blue 1, pigment red 1, pigment red 48: 2, pigment red 48: 1, pigment red 57: 1, pigment red 53: 1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • adhesives examples include polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • Suitable inert additives are, for example:
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. As amines such as N-methylpyrrolidone or water.
  • amines such as N-methylpyrrolidone or water.
  • Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, 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 flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, 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 flour, tree bark, wood and nutshell flour
  • alkali alkaline earth
  • ammonium salts of aromatic sulfonic acids eg lignosulfonic acids (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types , Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE)
  • fatty acids alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.
  • Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the compounds of the formula I as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier.
  • concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
  • the concentrations of the benzoylpyrazoles of the formula I in the ready-to-use formulations can be varied within wide limits.
  • the formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • benzoylpyrazoles of the formula I according to the invention can be formulated, for example, as follows:
  • active compound 20 parts by weight are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • a dispersant e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • the active ingredient content is 20% by weight
  • active compound 15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (for example alkylaromatics) with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion.
  • the formulation has 15% by weight active ingredient content.
  • active compound 25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (for example alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • organic solvent for example alkylaromatics
  • calcium dodecylbenzenesulfonate and castor oil ethoxylate in each case 5 parts by weight.
  • This mixture is added by means of an emulsifying machine (eg Ultraturax) in 30 parts by weight of water and a homogeneous emulsion brought. Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 25% by weight.
  • active compound 20 parts by weight of active compound are comminuted with the addition of 10 parts by weight dispersing and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the formulation is 20% by weight.
  • active compound 50 parts by weight are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • active compound 75 parts by weight of active compound are ground with the addition of 25 parts by weight of dispersing and wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the active ingredient content of the formulation is 75% by weight.
  • 0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.
  • the active substances are less compatible with certain crops, application techniques may be used in which the herbicidal agents are sprayed with the aid of the sprayers so that the leaves of the sensitive crops are not struck if possible, while the active ingredients on the leaves below grow unwanted plants or the uncovered soil surface (post-directed, lay-by).
  • the application of the benzoylpyrazoles of the formula I or the mixtures according to the invention or the herbicidal agents can be carried out by treating seed.
  • the treatment of seed comprises essentially all techniques familiar to the skilled worker (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed pelleting and seed pelleting) based on the benzoylpyrazoles of the formula according to the invention I or the mixtures according to the invention or agents produced therefrom.
  • the herbicidal agents can be diluted or applied undiluted.
  • seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms.
  • seed preferably describes grains and seeds here.
  • Seeds of the abovementioned crops but also the seeds of transgenic or obtained by conventional breeding methods plants can be used as seeds.
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a. S.).
  • the benzoylpyrazoles of the formula I are usually used in amounts of 0.001 to 10 kg per 100 kg of seed.
  • the culture vessels used were plastic pots with loamy sand with about 3% -5% humus as substrate.
  • the seeds of the test plants were sown separately by species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
  • the jars were lightly rained to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes a uniform germination of the test plants, if it was not affected by the active ingredients.
  • test plants were grown depending on the growth form only to a height of from 3 to 15 cm and then treated with the suspended or emulsified in water agents.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively.
  • the trial period lasted for 2 to 4 weeks. During this Time the plants were cared for, and their response to each treatment was evaluated.
  • the rating was based on a scale of 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal growth course.
  • a good herbicidal activity is at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
  • the plants used in the greenhouse experiments are composed of the following species:

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un mélange herbicide comprenant a) en tant que composant A, une quantité à action herbicide efficace d'un benzoylpyrazole de formule (I), dans laquelle les variables ont les significations suivantes : R1 désigne halogène, alkyle C1-C4, alcoxy C1-C4; R2 désigne alkyle en C1-C4, halogénoalkyle en C1-C4, alcoxy en C1-C4; R3 alkylsulfonyle C1-C4; R4 désigne hydrogène, alcynyle C3-C6, halogénure d'alcynyle C3-C6; R5 désigne alkyle C2-C4, cycloalkyle C3-C4; R6 désigne hydrogène, alkyle C1-C4; ou son sel convenant à un usage agricole; et b) en tant que composant B, une quantité à action antidotique efficace d'un phytoprotecteur. L'invention concerne également des composés de formule I, dans laquelle les variables ont les significations indiquées ci-dessus, à l'exception de R4 qui est d'ifférent de l'hydrogène.
PCT/EP2010/068352 2009-12-01 2010-11-29 Composés 3-(4,5-dihydroisoxazol-5-yl)benzoylpyrazole et leurs mélanges avec des phytoprotecteurs WO2011067184A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8822377B2 (en) 2011-02-11 2014-09-02 Basf Se Herbicidal compositions comprising topramezone and pinoxaden
CN111285863A (zh) * 2018-12-07 2020-06-16 青岛清原化合物有限公司 4-（3-杂环基-1-苯甲酰基）吡唑类化合物或其盐、制备方法、除草剂组合物及用途
EP3829308A1 (fr) * 2018-07-31 2021-06-09 Belchim Crop Protection NV Composition herbicide à effet synergique comprenant du pyridate et au moins un inhibiteur de la 4-hppd défini
RU2803120C2 (ru) * 2018-07-31 2023-09-06 Белчим Кроп Протекшн Нв Синергетически эффективная гербицидная композиция, содержащая пиридат и мезотрион

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WO2003014357A1 (fr) 2001-08-09 2003-02-20 University Of Saskatchewan Plants de ble presentant une resistance accrue aux herbicides a base d'imidazolinone
WO2003013225A2 (fr) 2001-08-09 2003-02-20 Northwest Plant Breeding Company Plants de ble presentant une resistance accrue aux herbicides a l'imidazolinone
WO2003014356A1 (fr) 2001-08-09 2003-02-20 University Of Saskatchewan Plants de ble presentant une resistance accrue aux herbicides a base d'imidazolinone
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
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WO2004106529A2 (fr) 2003-05-28 2004-12-09 Basf Aktiengesellschaft Plantes de ble presentant une tolerance accrue aux herbicides d'imidazolinone
WO2005020673A1 (fr) 2003-08-29 2005-03-10 Instituto Nacional De Technologia Agropecuaria Plants de riz presentant une tolerance accrue aux herbicides imidazolinone
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8822377B2 (en) 2011-02-11 2014-09-02 Basf Se Herbicidal compositions comprising topramezone and pinoxaden
EP3829308A1 (fr) * 2018-07-31 2021-06-09 Belchim Crop Protection NV Composition herbicide à effet synergique comprenant du pyridate et au moins un inhibiteur de la 4-hppd défini
RU2803120C2 (ru) * 2018-07-31 2023-09-06 Белчим Кроп Протекшн Нв Синергетически эффективная гербицидная композиция, содержащая пиридат и мезотрион
CN111285863A (zh) * 2018-12-07 2020-06-16 青岛清原化合物有限公司 4-（3-杂环基-1-苯甲酰基）吡唑类化合物或其盐、制备方法、除草剂组合物及用途
CN111285863B (zh) * 2018-12-07 2022-04-26 青岛清原化合物有限公司 4-(3-杂环基-1-苯甲酰基)吡唑类化合物或其盐、制备方法、除草剂组合物及用途

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