WO2024078871A1 - Acides 1-pyridyl-5-phenylpyrazolyl-3-oxy- et -3-thioalkyl et leurs dérivés et leur utilisation pour lutter contre la croissance de plantes indésirables - Google Patents

Acides 1-pyridyl-5-phenylpyrazolyl-3-oxy- et -3-thioalkyl et leurs dérivés et leur utilisation pour lutter contre la croissance de plantes indésirables Download PDF

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WO2024078871A1
WO2024078871A1 PCT/EP2023/076659 EP2023076659W WO2024078871A1 WO 2024078871 A1 WO2024078871 A1 WO 2024078871A1 EP 2023076659 W EP2023076659 W EP 2023076659W WO 2024078871 A1 WO2024078871 A1 WO 2024078871A1
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alkyl
cycloalkyl
haloalkyl
hydrogen
group
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PCT/EP2023/076659
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German (de)
English (en)
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Estella BUSCATO
Thomas Müller
Harald Jakobi
Hendrik Helmke
Guido Bojack
Elmar Gatzweiler
Birgit BOLLENBACH-WAHL
Jan Dittgen
Elisabeth ASMUS
Anu Bheemaiah MACHETTIRA
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Bayer Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings

Definitions

  • the invention relates to the technical field of plant protection products, in particular that of herbicides for controlling weeds and grass weeds in crops and in ornamental gardens and for the general control of weeds and grass weeds in environmental areas in which plant growth is disruptive.
  • the invention relates to substituted l-pyridyl-5-phenylpyrazolyl-3-oxy- and -3-thioalkyl acids and their derivatives, processes for their preparation and their use for controlling harmful plants.
  • the derivatives of l-pyridyl-5-phenylpyrazolyl-3-oxy- and -3-thioalkyl acids include in particular their esters, salts and/or amides.
  • l-pyridyl-5-phenylpyrazolyl-3-oxy- and -3-thioalkyl acids according to the invention and their derivatives differ from the already known bisarylpyrazoles disclosed in WO2020/245044, WO 2021/122728 and WO2021/219527 by the specific substitution on the pyrazole ring (phenyl in 5-position; pyridyl in 1-position).
  • 1,5-Diphenyl-pyrazolyl-3-oxoacetic acid derivatives are disclosed as bactericidal agrochemicals in CN101284815. Further syntheses and the fungicidal activity of 1,5-diphenyl-pyrazolyl-3-oxoacetic acids are described in Journal of Heterocyclic Chemistry (2012), 49(6), 1370-1375.
  • the object of the present invention is to provide new pyrazole derivatives, namely l-pyridyl-5-phenylpyrazolyl-3-oxy- and -3-thioalkyl acids, which can be used as herbicides with a good herbicidal effect and a broad spectrum of activity against harmful plants.
  • substituted pyrazolyl-3-oxo- and -3-thioalkyl acids which are characterized by a phenyl radical in the 5-position and a pyridyl radical in the 1-position of the pyrazole ring, ie by substituted l-pyridyl-5-phenylpyrazolyl-3-oxy- and -3-thioalkyl acids and their derivatives, which have a very good herbicidal effect.
  • these compounds are highly effective against a wide range of economically important grass and weeds.
  • the present invention therefore relates to the substituted 1-pyridyl-5-phenylpyrazolyl-3-oxy- and -3-thioalkyl acid derivatives of the general formula (I) and their agrochemically acceptable salts, N-oxides, hydrates and hydrates of the salts and N-oxides, wherein Q is selected from the group consisting of Q1 - Q3 Q 1 Q2 Q3 , R1 is selected from the group consisting of - OR1a and - NR9R10; wherein R1a is hydrogen or (C1-C6)-alkyl which is unsubstituted or substituted by a radical selected from the group consisting of CO 8 5 2R , OR or (C1-C6)-haloalkyl, (C3-C7)-cycloalkyl-(C1-C6)-alkyl, cyano-(C1-C6)-alkyl, nitro-(C1-C6)-alkyl or (C3-C7)-
  • R1 is selected from the group consisting of - OR1a and - NR9R10; wherein R1a is hydrogen or (C1-C5)-alkyl which is unsubstituted or substituted by a radical selected from the group consisting of (C 1 -C 6 )-alkoxycarbonyl, (C 1 -C 6 )-alkoxy or (C 1 -C 3 )-haloalkyl, (C 3 -C 6 )-cycloalkyl-(C 1 -C 2 )-alkyl, cyano-(C 1 -C 2 )-alkyl, nitro-(C 1 -C 2 )-alkyl or (C3-C6)-cycloalkyl which is unsubstituted or substituted by a radical (C1-C6)-alkoxycarbonyl or (C3
  • the present invention further relates to compounds of the formula (Is) where the definitions described above apply, including all preferred, particularly preferred and very particularly preferred definitions.
  • the present invention further relates to compounds of the formula (It) where the definitions described above apply, including all preferred, particularly preferred and most particularly preferred definitions.
  • the present invention further relates to compounds of the formula (lu) where the definitions described above apply, including all preferred, particularly preferred and most particularly preferred definitions.
  • the present invention further relates to compounds of formula (Iv) where the definitions described above apply, including all preferred, particularly preferred and most particularly preferred definitions.
  • the present invention further relates to compounds of formula (Ix) where the definitions described above apply, including all preferred, particularly preferred and very particularly preferred definitions.
  • the present invention further relates to compounds of formula (ly) where the definitions described above apply, including all preferred, particularly preferred and very particularly preferred definitions.
  • the present invention further relates to compounds of formula (Iz) where the definitions described above apply, including all preferred, particularly preferred and very particularly preferred definitions.
  • the present invention further relates to compounds of the formula (II) where the definitions described above apply, including all preferred, particularly preferred and very particularly preferred definitions.
  • the substituents and symbols, unless defined otherwise, have the same meaning as described under formula (I). Not included are combinations which contradict the laws of nature and which the person skilled in the art would therefore exclude on the basis of his knowledge.
  • Alkyl means saturated, straight-chain or branched hydrocarbon radicals with the specified number of carbon atoms, e.g. C1-C12-alkyl, preferably C1-C6-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-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl
  • Alkyl substituted by halogen means straight-chain or branched alkyl groups, where in these groups the hydrogen atoms can be partially or completely replaced by halogen atoms, e.g. C iC ( , -haloalkyl.
  • Ci-C2-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and l,l,l-trifluoroprop-2-yl.
  • Ci-C2-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, flu
  • Alkenyl means unsaturated, straight-chain or branched hydrocarbon radicals with the specified number of carbon atoms and a double bond in any position, e.g. C2-Cs-alkenyl, preferably C2-Ce-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl- 1-propenyl, 2-methyl-l-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl- 1-butenyl, 2-methyl-l-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1 -Methyl - 3-butenyl, 2-Methyl-3
  • Alkynyl means straight-chain or branched hydrocarbon radicals with the specified number of carbon atoms and a triple bond in any position, e.g. C2-C12-alkynyl, preferably C2-G, -alkynyl such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl- 1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl- 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-Hexyny
  • Cycloalkyl means a carbocyclic, saturated ring system with preferably 3-8 ring carbon atoms, e.g. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cyclic systems with substituents are included, which also includes substituents with a double bond on the cycloalkyl radical, e.g. an alkylidene group such as methylidene.
  • polycyclic aliphatic systems are also included, such as bicyclo[1.1.0]butan-l-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5-yl, bicyclo[2.2.1]hept-2-yl (norbornyl), adamantan-l-yl and adamantan-2-yl.
  • spirocyclic aliphatic systems are also included, such as spiro[2.2]pent-l-yl, spiro[2.3]hex-l-yl and spiro[2.3]hex-4-yl, 3-spiro[2.3]hex-5-yl.
  • Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system with preferably 4-8 C atoms, e.g. 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexadienyl, which also includes substituents with a double bond on the cycloalkenyl radical, e.g. an alkylidene group such as methylidene.
  • the explanations for substituted cycloalkyl apply accordingly.
  • Alkoxy means saturated, straight-chain or branched alkoxy radicals with the specified number of carbon atoms, e.g. Ci-Ce-alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methyl-propoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -Ethylbutoxy, 2-Ethylbutoxy, 1,1,2-Trimethylpropoxy, 1,2,2-Trimethylpropoxy, 1-
  • Alkoxy substituted by halogen means straight-chain or branched alkoxy radicals with the respective number of carbon atoms stated, where in these groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, e.g.
  • C1-C2-halogenalkoxy such as chloromethoxy, bromomethoxy, dichlormethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-1,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l-trifluoroprop-2-oxy.
  • Aryl means a phenyl optionally substituted by 0 - 5 radicals from the group fluorine, chlorine, bromine, iodine, cyano, hydroxy, (Ci-C 3 )-alkyl, (Ci-C 3 )-alkoxy, (C 3 - C 4 )-cycloalkyl, (C 2 - C 3 )-alkenyl or (C 2 - C 3 )-alkynyl.
  • multicyclic systems are also included, such as 8-aza-bicyclo[3.2.1]octanyl, 8-aza-bicyclo[2.2.2]octanyl or 1-aza-bicyclo[2.2.1]heptyl.
  • spirocyclic systems are also included, such as, for example, l-oxa-5-aza-spiro[2.3]hexyl.
  • the heterocyclic ring preferably contains 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from the group N, O, and S, but two oxygen atoms should not be directly adjacent, such as, for example, with a heteroatom from the group N, O and S 1- or 2- or 3-pyrrolidinyl, 3,4-dihydro-2H-pyrrol-2- or 3-yl, 2,3-dihydro-lH-pyrrol-
  • 3-ring and 4-ring heterocycles are, for example, 1- or 2-aziridinyl, oxiranyl, thiiranyl, 1- or 2- or 3-azetidinyl, 2- or 3-oxetanyl, 2- or 3-thietanyl, l,3-dioxetan-2-yl.
  • heterocyclyl are a partially or fully hydrogenated heterocyclic radical with two heteroatoms from the group N, O and S, such as, for example,
  • 6- or 7-yl 2,5-dihydro-l,2-oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 2,7-dihydro-l,2- oxazepin-2- or 3- or 4- or 5- or 6- or 7-yl; 4,5-dihydro-l,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; 4,7-dihydro-l,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; 6,7-dihydro-l,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; l,2-oxazepin-3- or 4- or 5- or 6- or 7-yl; l,3-oxazepan-2- or
  • heterocyclyl are a partially or fully hydrogenated heterocyclic radical with 3 heteroatoms from the group N, O and S, such as, for example, l,4,2-dioxazolidin-2- or 3- or 5-yl; l,4,2-dioxazol-3- or 5-yl; l,4,2-dioxazinan-2- or -3- or 5- or 6-yl; 5,6-dihydro-l,4,2-dioxazin-3- or 5- or 6-yl; l,4,2-dioxazin-3- or 5- or 6-yl; l,4,2-dioxazepan-2- or 3- or 5- or 6- or 7-yl; 6,7-dihydro-5H-l,4,2-dioxazepin-3- or 5- or 6- or 7-yl; 2,3-dihydro-7H-l,4,2-dioxazepin-2- or 3- or 5- or 6- or 7-yl; 2,3- dihydro-5
  • heterocycles listed above are preferably, for example, hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, hydroxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, alkoxycarbonylalkyl, arylalkoxycarbonyl, arylalkoxycarbonylalkylalkyl,
  • Alkylaminocarbonyl bis-alkylaminocarbonyl, cycloalkylaminocarbonyl,
  • the above-mentioned substituents can be used as substituents for a substituted heterocyclic radical, as well as oxo and thioxo.
  • the oxo group as a substituent on a ring -C atom then means, for example, a carbonyl group in the heterocyclic ring. This preferably also includes lactones and lactams.
  • the oxo group can also appear on the hetero ring atoms, which can exist in different oxidation states, e.g. N and S, and then forms, for example, the divalent groups N(O), S(O) (also abbreviated to SO) and S(O)2 (also abbreviated to SO2) in the heterocyclic ring. In the case of -N(O)- and -S(O)- groups, both enantiomers are included.
  • heteroaryl stands for heteroaromatic compounds, ie completely unsaturated aromatic heterocyclic compounds, preferably for 5- to 7-membered rings with 1 to 4, preferably 1 or 2 identical or different heteroatoms, preferably O, S or N.
  • Heteroaryls according to the invention are, for example, IH-pyrrol-1-yl; IH-pyrrol-2-yl; IH-pyrrol-3-yl; furan-2-yl; furan-3-yl; thien-2-yl; thien-3-yl, IH-imidazol-1-yl; IH-imidazol-2-yl; IH-imidazol-4-yl; IH-imidazol-5-yl; IH-pyrazol-1-yl; IH-pyrazol-3-yl; IH-pyrazol-4-yl; lH-pyrazol-5-yl, 1H-1,2,3-triazol-l-yl, lH-l,2,3-triazol-4-yl, lH-l,2,3-triazol-5-yl, 2H-l,2,3-triazol-2-yl, 2H-l,2,3-triazol-4-yl, lH-
  • heteroaryl groups according to the invention can also be substituted by one or more identical or different radicals. If two adjacent carbon atoms are part of another aromatic ring, these are fused heteroaromatic systems, such as benzo-fused or multiply fused heteroaromatics. Preference is given to, for example, quinolines (e.g. quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl); Isoquinolines (e.g.
  • heteroaryl are also 5- or 6-membered benzo-fused rings from the group IH-indol-l-yl, lH-indol-2-yl, lH-indol-3-yl, lH-indol-4-yl, lH-indol-5-yl, lH-indol-6-yl, lH-indol-7-yl, l-benzofiiran-2-yl, l-benzofiiran-3-yl, l-benzofiiran-4-yl, l-benzofiiran-5-yl, 1-benzofiiran-6-yl, l-benzofiiran-7-yl, l-benzothiophen-2-yl, l-benzothiophen-3-yl, l-benzothiophen-4- yl, l-benzothiophen-5-yl, l-benzothiophen-6-yl,
  • halogen means fluorine, chlorine, bromine or iodine. If the term is used for a radical, then "halogen" means a fluorine, chlorine, bromine or iodine atom.
  • the compounds of formula (I) have acidic properties and can form salts, optionally also internal salts or adducts, with inorganic or organic bases or with metal ions. If the compounds of formula (I) carry hydroxy, carboxy or other groups that induce acidic properties, these compounds can be converted to salts with bases.
  • Suitable bases are, for example, hydroxides, carbonates, Hydrogen carbonates of alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (Ci-C4-)-alkyl groups, mono-, di- and trialkanolamines of (Ci-CO-alkanols, choline and chlorocholine, as well as organic amines, such as trialkylamines, morpholine, piperidine or pyridine.
  • salts are compounds in which the acidic hydrogen is replaced by a cation suitable for agriculture, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NRR'R "R '] + , in which R to R each independently represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.
  • Alkylsulfonium and Alkylsulfoxonium salts such as (C1-C4)-trialkylsulfonium and (Ci-C4)-trialkylsulfoxonium salts.
  • the compounds of formula (I) can form salts by addition of a suitable inorganic or organic acid, such as mineral acids such as HCl, HBr, H2SO4, H3PO4 or HNO3, or organic acids, e.g. carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or sulfonic acids such as p-toluenesulfonic acid, to a basic group such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino.
  • a suitable inorganic or organic acid such as mineral acids such as HCl, HBr, H2SO4, H3PO4 or HNO3, or organic acids, e.g. carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or sulfonic acids such as p-toluenesul
  • Suitable substituents that are present in deprotonated form can form inner salts with protonatable groups, such as amino groups.
  • the present compounds of general formula (I) have a chiral carbon atom on the second carbon of the alkyl acid structure, which is indicated in the structure shown below by the marking (*):
  • this carbon atom can have both an (R) and an (S) configuration.
  • the present invention covers compounds of the general formula (I) with both (S) and (R) configuration, i.e. the present invention covers the compounds of the general formula (I) in which the carbon atom in question
  • the present invention also relates to
  • a further aspect of the invention relates to the preparation of the compounds of the general formula (I) according to the invention.
  • the compounds of the invention can be prepared in different ways.
  • Compounds according to the invention can be prepared, for example, from substituted l-pyridyl-5-phenyl-lH-pyrazol-3-ols (II) according to the synthesis processes listed in Scheme 1 below.
  • the compound of general formula (Ia) can be prepared by alkylating the compound of general formula (II) with a halide of general formula (III) in the presence of a base by or analogously to methods known to those skilled in the art (see Scheme 1).
  • the base can be a carbonate salt of an alkali metal.
  • a preferred base is a carbonate salt of an alkali metal selected from the group consisting of lithium, sodium, potassium and cesium, and the reaction preferably takes place in the temperature range between room temperature and 150 °C in an appropriate solvent such as dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate.
  • an appropriate solvent such as dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate.
  • Scheme 2 describes the synthesis of the compound of general formula (Ib) by reaction of a pyrazole of general formula (XXI) with a halogenosuccinimide of general formula (IV) in an appropriate solvent such as N,N-dimethylformamide.
  • a compound of the general formula (Ic) can be prepared, for example, by reacting a compound of the formula (Ib) in a suitable solvent with a metal cyanide M-CN (V) with the addition of an adequate amount of a transition metal catalyst, in particular palladium catalysts such as palladium(0)-tetrakis(triphenylphosphine) or palladium diacetate or Bis(triphenylphosphine)palladium(II) dichloride or nickel catalysts such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride, preferably at elevated temperature in an organic solvent such as 1,2-dimethoxyethane or N,N-dimethylformamide (Scheme 2).
  • a transition metal catalyst in particular palladium catalysts such as palladium(0)-tetrakis(triphenylphosphine) or palladium diacetate or Bis(triphenylphosphine)palladium
  • the radical "M” stands for magnesium, zinc, lithium or sodium, for example.
  • cross-coupling methods are suitable, as described in RD Larsen, Organometallics in Process Chemistry 2004 Springer Verlag, in I. Tsuji, Palladium Reagents and Catalysts 2004 Wiley, in M. Belier, C. Bolm, Transition Metals for Organic Synthesis 2004 VCH-Wiley.
  • Other suitable synthesis methods are described in Chem. Rev. 2006, 106, 2651; Platinum Metals Review, 2009, 53, 183; Platinum Metals Review 2008, 52, 172 and Acc. Chem. Res. 2008, 41, 1486.
  • the 3-hydroxypyrazoles (II) can be prepared analogously to literature-known methods from substituted 3-phenylpropionic acid derivatives and pyridylhydrazines (Scheme 3; e.g.: Adv. Synth. Catal. 2014, 356, 3135-3147) or from substituted phenylacrylic acid derivatives and pyridylhydrazines (Scheme 3; e.g.: J. Heterocyclic Chem., 49, 130 (2012)).
  • the synthesis of the compounds of the general formula (VIII) is carried out via an amide coupling of an acid of the general formula (VI) with a pyridylhydrazine of the general formula (VII) in the presence of an amide coupling reagent such as T3P, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-A'-methylcarbodiimide, A'A'-carbonyldiimidazole, 2-chloro-1,3-dimethyl-imidazolium chloride or 2-chloro-1-methylpyridinium iodide (see Chemistry of Peptide Synthesis, Ed. N.
  • Polymer-bound reagents such as polymer-bound dicyclohexylcarbodiimide are also suitable for this coupling reaction.
  • the reaction preferably takes place in the temperature range between 0 °C and 80 °C, in an appropriate solvent such as dichloromethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide or ethyl acetate and in the presence of a base such as triethylamine, N,N-diisopropylethylamine or l,8-diazabicyclo[5.4.0]undec-7-cene (see Scheme 3).
  • an appropriate solvent such as dichloromethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide or ethyl acetate
  • a base such as triethylamine, N,N-diisopropylethylamine or l,8-diazabicyclo
  • Scheme 3 describes the synthesis of the compound of general formula (II) by reaction of a pyrazole of general formula (IIa) with an electrophile such as N-bromosuccinimide.
  • the reaction preferably takes place in the temperature range between 0°C and 120°C in an appropriate solvent such as n-dimethylformamide, 1,2-dichloroethane or acetonitrile.
  • the synthesis of the 3-hydroxypyrazoles of the general formula (IIa) is carried out by reacting the compounds of the general formula (VIII) in the presence of a copper halide such as, for example, copper(I) iodide, copper(I) bromide or an acid such as methanesulfonic acid.
  • a copper halide such as, for example, copper(I) iodide, copper(I) bromide or an acid such as methanesulfonic acid.
  • the reaction preferably takes place in the temperature range between 0 °C and 120 °C, in an appropriate solvent such as, for example, 1,2-dichloroethane, acetonitrile, ethyl acetate, n-propanol or ethyl acetate.
  • the reaction preferably takes place in ethyl acetate.
  • Compounds of the general formula (X) can be prepared by an amide coupling of an acid of the general formula (IX) with a pyridylhydrazine of the general formula (VII) in the presence of an amide coupling reagent such as T3P, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-A'-methylcarbodiimide, A'A'-carbonyldiimidazole, 2-chloro-1,3-dimethyl-imidazolium chloride or 2-chloro-1-methylpyridinium iodide.
  • an amide coupling reagent such as T3P, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-A'-methylcarbodiimide, A'A'-carbonyldiimidazole, 2-chloro-1,3-dimethyl-imidazolium chloride or 2-chloro
  • the reaction preferably takes place in the temperature range between 0 °C and 80 °C, in an appropriate solvent such as dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate and in the presence of a base such as triethylamine, W-diisopropylmethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (see Scheme 4).
  • an appropriate solvent such as dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate
  • a base such as triethylamine, W-diisopropylmethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (see Scheme 4).
  • the synthesis of the 3-hydroxypyrazoles of the general formula (IIa) is carried out by reacting the compounds of the general formula (X) in the presence of an iron halide such as iron(III) chloride.
  • the reaction preferably takes place in the temperature range between 0°C and 120°C, in an appropriate solvent such as 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide or ethyl acetate.
  • the synthesis of the 5-iodopyrazoles of the general formula (XIV) is carried out by reacting the compounds of the general formula (XIII) in the presence of a base such as lithium diisopropylamide and iodine.
  • the reaction (Scheme 5) preferably takes place in the temperature range between -78 °C and -60 °C, in an adequate solvent such as diethyl ether and tetrahydrofuran.
  • a compound of formula (XV) can be prepared, for example, by reacting a compound of formula (XIV) in a suitable solvent with a phenyl compound AM of general formula (XVI) with the addition of an adequate amount of a transition metal catalyst, in particular palladium catalysts such as palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride or nickel catalysts such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride, preferably at elevated temperature in an organic solvent such as 1,2-dimethoxyethane.
  • a transition metal catalyst in particular palladium catalysts such as palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride or nickel catalysts such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride, preferably at elevated temperature in an organic solvent such
  • radical "M” stands, for example, for B(OR b )(OR c ), where the radicals R b and R c independently of one another are, for example, hydrogen, (Ci-C ⁇ -alkyl, or, when the radicals R b and R c are linked to one another, together are ethylene or propylene (Scheme 6).
  • the synthesis of the compound of general formula (XVIII) can be carried out by alkylation of the compound of general formula (XVII) with a halide of general formula (III) in presence of a base by or analogously to methods known to those skilled in the art (see Scheme 7).
  • the base can be a carbonate salt of an alkali metal (such as lithium, sodium, potassium or cesium) and the reaction preferably takes place in the temperature range between room temperature and 150 °C in an appropriate solvent such as dichloromethane, acetonitrile, VA'-dimethylformamide or ethyl acetate.
  • the compounds of the general formula (XVII) are commercially available.
  • Compounds of the general formula (XIX) can be prepared by diazotization (Sandmeyer reaction) with the compound of the general formula (XVIII) with the usual organic and inorganic nitrites such as 1,1-dimethylethyl nitrite, tert-butyl nitrite or isoamyl nitrite in the presence of reagents such as mixtures of copper(I) and copper(II) bromide/chloride or iodine (Scheme 7).
  • the reaction preferably takes place in the temperature range between room temperature and 0 and 120°C in an appropriate solvent such as dichloromethane, acetonitrile, VN-dimethylformamide or diiodomethane.
  • the radical "X” stands for chlorine, bromine or iodine, for example.
  • a compound of formula (Ia) can be prepared, for example, by reacting a compound of formula (XIX) in a suitable solvent with a compound of general formula MA (XVI) with the addition of an adequate amount of a transition metal catalyst, in particular palladium catalysts such as palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride or nickel catalysts such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride, preferably at elevated temperature in an organic solvent such as 1,2-dimethoxyethane.
  • a transition metal catalyst in particular palladium catalysts such as palladium diacetate or bis(triphenylphosphine)palladium(II) dichloride or nickel catalysts such as nickel(II) acetylacetonate or bis(triphenylphosphine)nickel(II) chloride, preferably at elevated temperature in an organic solvent such as 1,2-
  • the radical "M” stands, for example, for Mg-Hal, Zn-Hal, Sn((Ci-C4)alkyl)3, lithium, copper or B(OR b )(OR c ), where the radicals R b and R c independently of one another are, for example, hydrogen, (Ci-CO-alkyl, or, when the radicals R b and R c are linked to one another, together are ethylene or propylene.
  • Compounds of the general formulas (Ig) and (Ih) can be prepared by reacting a compound of the formula (If) in the presence of an oxidizing agent such as mCPBA (3-chloroperbenzoic acid) in an appropriate solvent such as dichloromethane or 1,2-dichloroethane (Scheme 8).
  • an oxidizing agent such as mCPBA (3-chloroperbenzoic acid)
  • an appropriate solvent such as dichloromethane or 1,2-dichloroethane (Scheme 8).
  • the reaction preferably takes place in the temperature range between -30 °C and 100 °C.
  • a compound of the general formula (If) can be carried out by reacting a 3-aminopyrazol of the general formula (XXIII) with a disulfide of the general formula (XXIV) in the presence of an organic nitrite such as 1,1-dimethylethyl nitrite, tert-butyl nitrite or isoamyl nitrite in the presence of a metal M such as copper (see Scheme 9).
  • the reaction preferably takes place in the temperature range between room temperature and 120°C in an appropriate solvent such as dichloromethane, acetonitrile, VA-dimethylformamide or 1,2-dichloroethane.
  • the synthesis of the compounds of general formula (XXIII) is carried out via a Curtius reaction of an acid of general formula (XXII) with an azide of general formula (XXV).
  • the reaction preferably takes place in the temperature range between 0 °C and 100 °C, in an adequate Solvents such as tert-butanol and in the presence of a base such as triethylamine, W-diisopropylethylamine or l,8-diazabicyclo[5.4.0]undec-7-ene.
  • the intermediate product of general formula (XXVI) formed can then be converted into the amine (XXIII) in the presence of a Lewis acid such as trifluoroacetic acid, a hydrogen chloride solution in dioxane or analogously using methods known to those skilled in the art (Scheme 10).
  • a Lewis acid such as trifluoroacetic acid, a hydrogen chloride solution in dioxane or analogously using methods known to those skilled in the art (Scheme 10).
  • the reaction preferably takes place in the temperature range between room temperature and 140 °C.
  • the synthesis of the compounds of the general formula (XX) is carried out via the condensation of a diketoester of the general formula (XXVII) with a pyridylhydrazine of the general formula (VII) in the presence of a Broensted acid such as acetic acid or hydrogen chloride in an appropriate solvent such as methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, dioxane, toluene or chlorobenzene (Scheme 11).
  • the reaction preferably takes place in the temperature range between 0 °C and 150 °C.
  • the compounds of the general formulas (XXVII) and (VII) are commercially available or can be prepared analogously using methods known to the person skilled in the art.
  • a further option for the synthesis of thio compounds of the general formula (If) consists in the construction of the precursor (XXVIII), which can be alkylated and further functionalized according to the methods described in this application analogous to the hydroxypyrazole of the formula (Ila).
  • This precursor (XXVIII) can be obtained by reacting a hydroxypyrazole of the general formula (Ila) in the presence of a sulfurizing reagent such as phosphorus pentasulfide or the Lawesson reagent in an adequate solvent such as toluene.
  • a further aspect of the invention relates to compounds of the general formula (II) and their salts wherein the radicals R 3 , Q and A are each defined according to one of the abovementioned embodiments and their preparation according to Scheme 3.
  • an additional aspect of the invention relates to a process for preparing the compounds of general formula (II) and/or their agrochemically acceptable salts, wherein the radicals R 3 , Q and A are each defined according to one of the abovementioned embodiments, by reacting a substituted propionic acid of the formula (VI), wherein A is defined according to one of the above embodiments, with a compound of formula (VII), wherein Q is defined according to any of the above embodiments. in a suitable solvent in the presence of a metal halide.
  • a further aspect concerns the use of compounds of the general formula (II) and their salts as intermediates for the production of fine chemicals and active ingredients for
  • the present invention therefore also relates to a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, in which one or more compounds according to the invention are applied to the plants (e.g. harmful plants such as monocotyledonous or dicotyledonous weeds or undesirable crop plants), the seed (e.g. grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds) or the area on which the plants grow (e.g. the cultivation area).
  • the compounds according to the invention can be applied, for example, before sowing (if appropriate also by incorporation into the soil), pre-emergence or post-emergence.
  • some representatives of the monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds according to the invention are mentioned by way of example, without the mention being intended to restrict the use to certain species.
  • the compounds according to the invention are applied to the soil surface before germination, either the emergence of weed seedlings is completely prevented or the weeds grow to the cotyledon stage but then stop growing.
  • the compounds of the invention can exhibit selectivities in crops and can also be used as non-selective herbicides.
  • the transgenic plants are generally characterized by particularly advantageous properties, for example resistance to certain active ingredients used in the agricultural industry, in particular certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate, for example, to the harvested material in terms of quantity, quality, storability, composition and special ingredients.
  • Transgenic plants with an increased starch content or altered quality of the starch or those with a different fatty acid composition of the harvested material are known.
  • Other special properties include tolerance or resistance to abiotic stressors, e.g. heat, cold, drought, salt and ultraviolet radiation.
  • the compounds of formula (I) can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
  • new plants with modified properties can be created using genetic engineering techniques (see e.g. EP 0221044, EP 0131624).
  • genetic engineering techniques see e.g. EP 0221044, EP 0131624.
  • transgenic crop plants which are resistant to certain herbicides of the glufosinate type cf. e.g.
  • transgenic crops such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924 A, EP 0193259 A).
  • Bt toxins Bacillus thuringiensis toxins
  • genetically modified crops with new ingredients or secondary substances e.g. new phytoalexins, which cause increased disease resistance (EP 0309862 A, EP 0464461 A).
  • genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance EP 0305398 A).
  • transgenic crops that produce pharmaceutically or diagnostically important proteins (“molecular pharming”).
  • transgenic crops that are characterized by higher yields or better quality transgenic crops that are characterized by a combination of the above-mentioned new properties (“gene stacking”).
  • nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence changes through recombination of DNA sequences.
  • base exchanges can be carried out, partial sequences can be removed, or natural or synthetic sequences can be added.
  • Adapters or linkers can be attached to the fragments to connect the DNA fragments to one another, see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene and Clones", VCH Weinheim 2nd edition 1996
  • the production of plant cells with a reduced activity of a gene product can be achieved, for example, by expressing at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme that specifically cleaves transcripts of the above-mentioned gene product.
  • DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules that comprise only parts of the coding sequence, whereby these parts must be long enough to cause an antisense effect in the cells. It is also possible to use DNA sequences that have a high degree of homology to the coding sequences of a gene product, but are not completely identical.
  • the synthesized protein can be localized in any compartment of the plant cell.
  • the coding region can be linked to DNA sequences that ensure localization in a specific compartment.
  • sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
  • the expression of the nucleic acid molecules can also take place in the organelles of the plant cells.
  • the transgenic plant cells can be regenerated into whole plants using known techniques.
  • the compounds (I) according to the invention can be used in transgenic cultures which are resistant to growth factors such as 2,4-D, dicamba or to herbicides which inhibit essential plant enzymes, e.g. acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogous active substances, or to any combination of these active substances.
  • ALS acetolactate synthases
  • EPSP synthases glutamine synthases
  • HPPD hydroxyphenylpyruvate dioxygenases
  • the compounds according to the invention can particularly preferably be used in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones.
  • the compounds according to the invention can very particularly preferably be used in transgenic crop plants such as corn or soy with the trade name or designation OptimumTM GATTM (Glyphosate ALS Tolerant).
  • the invention therefore also relates to the use of the compounds according to the invention of Formula (I) as herbicides for controlling weeds in transgenic crops.
  • the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual preparations.
  • the invention therefore also relates to herbicidal and plant growth regulating agents which contain the compounds according to the invention.
  • the compounds according to the invention can be formulated in various ways, depending on which biological and/or chemical-physical parameters are specified.
  • Possible formulation options include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting agents (DP), dressing agents, granules for broadcast and soil application, granules (GR) in the form of micro-, spray, coating and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powders
  • SP water-soluble powders
  • EC emulsifiable concentrates
  • the necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y., C. Marsden, “Solvents Guide”, 2nd Ed., Interscience, N.Y. 1963, McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.
  • combinations with other active ingredients can also be produced, e.g. in the form of a ready-made formulation or as a tank mix.
  • active substances are, for example, based on an inhibition of, for example, Acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate 3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase or act as plant growth regulators, as described e.g. in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 19th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2021 and literature cited therein.
  • Known herbicides or plant growth regulators that can be combined with compounds of the general formula (I) include the following active ingredients (the compounds are designated either by the "common name” according to the International Organization for Standardization (ISO) or by the chemical name or by the code number) and always include all application forms such as acids, salts, esters and isomers such as stereoisomers and optical isomers.
  • ISO International Organization for Standardization
  • One and sometimes several application forms are mentioned as examples:
  • dicamba biproamine dicamba N,N-bis(3-aminopropyl)methylamine, dicamba butotyl, dicamba choline, dicamba diglycolamine, dicamba dimethylammonium, dicamba diethanolamine ammonium, dicamba diethylammonium, dicamba isopropylammonium, dicamba methyl, dicamba monoethanolamine, dicamba olamine, dicamba potassium, dicamba sodium, dicamba triethanolamine), dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl- 1 ,2-oxazolidin-3 -one, 2-(2,5 -dichlorobenzyl)-4,4-dimethyl- 1 ,2-oxazolidin-3 -one, Dichlorprop, Dichlorprop-butotyl, Dichlorprop-dimethylammonium, Dichlorprop-etexyl, Dichlorpropethylammonium, Dichlor
  • Abscisic acid and related analogues [e.g. (2Z,4E)-5-[6-ethynyl-l-hydroxy-2,6-dimethyl-4- oxocyclohex-2-en- 1 -yl] -3 -methylpenta-2,4-dienoic acid, methyl-(2Z,4E)-5-[6-ethynyl- 1 -hydroxy-2,6- dimethyl-4-oxocyclohex-2-en-l-yl]-3-methylpenta-2,4-dienoate, (2Z,4E)-3-ethyl-5-(l-hydroxy-2,6,6- trimethyl-4-oxocyclohex-2-en- 1 -yl)penta-2,4-dienoic acid, (2E,4E)-5-( 1 -hydroxy-2,6,6-trimethyl-4- oxocyclohex-2-en- 1 -yl)-3 -(trifluoromethyl)pent
  • COs differ from LCOs in that they lack the fatty acid side chain characteristic of LCOs.
  • COs sometimes referred to as N-acetylchitooligosaccharides, are also composed of GlcNAc units but have side chains that distinguish them from chitin molecules [(CSHBNOS) ⁇ CAS NO. 1398-61-4] and chitosan molecules [(CsHnNO-On, CAS No.
  • chitin-like compounds chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop- l-enyl)propionic acid, l-[2-(4-cyano-3,5-dicyclopropylphenyl)acetamido]cyclohexanecarboxylic acid, l-[2-(4-cyano-3- cyclopropylphenyl)acetamido]cyclohexanecarboxylic acid, 1-cyclopropenylmethanol, daminozide, dazomet, dazomet sodium, n-decanol, dikegulac, dikegulac sodium, endothal, endothal-di-potassium, -di- sodium, and mono(N,N-dimethylalkylammonium), ethephon, l-ethylcyclopropene, flumetralin, flurenol, flurenol-butyl,
  • LCO lipochitooligosaccharides
  • Nod or Nod factors symbiotic nodulation signals
  • Myc factors consist of an oligosaccharide backbone of ß-l,4-linked JV-acetyl-D-glucosamine residues (“GlcNAc”) with an N-linked Fatty acid side chain condensed at the non-reducing end.
  • LCOs differ in the number of GlcNAc units in the backbone structure, in the length and degree of saturation of the fatty acid chain as well as in the substitution of the reducing and non-reducing sugar units), linoleic acid or its derivatives, linolenic acid or its derivatives, maleic hydrazide, mepiquat chloride, mepiquat pentaborate, 1-methylcyclopropene, 3-methylcyclopropene, methoxyvinylglycine (MVG), 3'-methylabscisic acid, l-(4-methylphenyl)-N-(2-oxo-1-propyl- 1,2, 3, 4-tetrahydroquinolin-6-yl)methanesulfonamide and related substituted (tetrahydroquinolin-6-yl)methanesulfonamides, (3E,3aR,8bS)-3-( ⁇ [(2R)-4-methyl-5-oxo-2,
  • Safeners are preferably selected from the group consisting of:
  • n A is a natural number from 0 to 5, preferably 0 to 3;
  • R 1 A is halogen, (C1-C4)alkyl, (C1-C4)alkoxy, nitro or (C1-C4)haloalkyl;
  • W A is an unsubstituted or substituted divalent heterocyclic radical from the group of partially saturated or aromatic five-membered ring heterocycles with 1 to 3 hetero ring atoms from the group N and O, where at least one N atom and at most one O atom is contained in the ring, preferably a radical from the group (W 1) b 5 A is (WA ), m A is 0 or 1;
  • R A 2 is OR A 3, SR A 3 or NR A 3R A 4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is
  • R 1 B is halogen, (C1-C4)alkyl, (C1-C4)alkoxy, nitro or (C1-C4)haloalkyl
  • nB is a natural number from 0 to 5, preferably 0 to 3
  • R 2 is OR 3, S 3 3 4 BB RB or NRB RB or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is linked via the N atom to the carbonyl group in (S2) and is unsubstituted or substituted by radicals from the group (C1-C4)alkyl, (C1-C4)alkoxy or optionally substituted phenyl, preferably a radical of the formula OR 3 B , NHR 4 or N(CH ) , in particular 3 B 3 2 in particular of the formula ORB ; R B 3
  • R 1 C is (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C3-C7)cycloalkyl, preferably dichloromethyl;
  • R 2 C , R 3 C are identical or different and are hydrogen, (C1-C4)alkyl, (C2-C4)alkenyl, (C 2 -C 4 )alkynyl, (C 1 -C 4 )haloalkyl, (C 2 -C 4 )haloalkenyl, (C 1 -C 4 )alkylcarbamoyl-(C 1 -C 4 )alkyl, (C 2 - C4)alkenylcarbamoyl-(C1-C4)alkyl, (C1-C4)alkoxy-(C1-C4)alkyl, dio
  • XD is CH or N;
  • R D 1 is CO-NR D 5R D 6 or NHCO-R D 7;
  • R D 2 is halogen, (C 1 -C 4 )-haloalkyl, (C 1 -C 4 )-haloalkoxy, nitro, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, (C 1 - C 4 )-alkylsulfonyl, (C 1 -C 4 )-alkoxycarbonyl or (C 1 -C 4 )-alkylcarbonyl;
  • R D 3 is hydrogen, (C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl or (C 2 -C 4 )alkynyl;
  • R 4 D is halogen,
  • R D 7 is (C 1 -C 6 )alkyl, (C 3 -C 6 )cycloalkyl, the last 2 radicals being substituted by v D substituents from the group halogen, (C 1 -C 4 )alkoxy, (C 1 -C 6 )haloalkoxy and (C 1 -C 4 )alkylthio and in the case of cyclic radicals also (C 1 -C 4 )alkyl and (C 1 -C 4 )haloalkyl; R D 4 is halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, CF 3; m D is 1 or 2; v D is 0, 1, 2 or 3; and acylsulfamoylbenzoic acid amides, eg of the following formula (S4b), which are known e
  • compounds of the type of N-acylsulfamoylphenylureas of the formula (S4c) which are known e.g.
  • R 8 D and R 9 D independently of one another are hydrogen, (C1-C8)alkyl, (C3-C8)cycloalkyl, (C3-C6)alkenyl, (C3-C6)alkynyl, R 4 D is halogen, (C1-C4)alkyl, (C1-C4)alkoxy, CF3 mD 1 or 2; for example 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea.
  • S5 Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), e.g. ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
  • S6 Active substances from the class of 1,2-dihydroquinoxalin-2-ones (S6), e.g.
  • R E 1, R E 2 are independently of one another halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkylamino, di-(C 1 -C 4 )alkylamino, nitro;
  • a E is COOR E 3 or COSR E 4 R E 3, R E 4 are independently hydrogen, (C 1 -C 4 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 4 )alkynyl, cyanoalkyl, (C 1 -C 4 )haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium,
  • R 3 F hydrogen, (C1-C8)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, or aryl, where each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy; or their salts, preferably compounds in which XF is CH, nF is an integer from 0 to 2, R 1 F is halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, R 2 F is hydrogen or (C1-C4)alkyl, R 3 F is hydrogen, (C1-C8)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, or
  • S9 Active substances from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), e.g. 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2), 1,2- Dihydro-4-hydroxy-1-methyl-3-(5-tetrazolyl-carbonyl)-2-quinolone (CAS Reg. No. 95855-00-8), as described in WO-A-1999/000020.
  • S9 3-(5-tetrazolylcarbonyl)-2-quinolones
  • R 1 G is halogen, (C1-C4)alkyl, methoxy, nitro, cyano, CF3, OCF3 YG, ZG is independently O or S
  • nG is an integer from 0 to 4
  • R 2 G is (C1-C16)alkyl, (C2-C6)alkenyl, (C3-C6)cycloalkyl, aryl; benzyl, halobenzyl
  • R 3 G is hydrogen or (C1-C6)alkyl.
  • S11 Active ingredients of the oxyimino compound type (S11), which are known as seed dressers, such as. E.g., "Oxabetrinil” ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for millet against metolachlor damage, "Fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone-O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as a seed dressing safener for millet against metolachlor damage, and "Cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as a seed dressing safener for millet against metolachlor damage.
  • S12 Active ingredients from the class of isothiochromanones (S12), such as methyl [(3-oxo-lH-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (S 12-1) and related compounds from WO-A-1998/13361.
  • S12 isothiochromanones
  • Active substances which, in addition to a herbicidal effect against harmful plants, also have a safener effect on cultivated plants such as rice, such as
  • R H 1 is a (C 1 -C 6 )haloalkyl radical and R H 2 is hydrogen or halogen and R H 3, R H 4 are independently hydrogen, (C 1 -C 16 )alkyl, (C 2 -C 16 )alkenyl or (C 2 -C 16 )alkynyl, where each of the last-mentioned 3 radicals is unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, cyano, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )alkylamino, di[(C 1 -C 4 )alkyl]amino, [(C 1 -C 4 )
  • Wettable powders are preparations that can be evenly dispersed in water and which, in addition to the active ingredient and a diluent or inert substance, also contain ionic and/or non-ionic surfactants (wetting agents, dispersants), e.g.
  • the herbicidal active ingredients are finely ground in conventional equipment such as hammer mills, blower mills and air jet mills and mixed simultaneously or subsequently with the formulation aids.
  • Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and/or non-ionic nature (emulsifiers).
  • organic solvent e.g. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents.
  • Emulsifiers can be used, for example: alkylarylsulfonic acid calcium salts such as -Ca-dodecylbenzenesulfonate or non-ionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty acid esters.
  • alkylarylsulfonic acid calcium salts such as -Ca-dodecylbenzenesulfonate
  • non-ionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan est
  • Dusting agents are obtained by grinding the active ingredient with finely divided solid substances, e.g. talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely divided solid substances e.g. talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates can be water- or oil-based. They can be produced, for example, by wet grinding using commercially available bead mills and, if necessary, by adding surfactants, such as those listed above for the other formulation types.
  • Emulsions e.g. oil-in-water emulsions (EW)
  • EW oil-in-water emulsions
  • Granules can be produced either by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. polyvinyl alcohol, polyacrylic acid sodium or mineral oils, to the surface of carrier materials such as sand, kaolinite or granulated inert material.
  • adhesives e.g. polyvinyl alcohol, polyacrylic acid sodium or mineral oils
  • Suitable active ingredients can also be granulated in the usual way for the production of fertilizer granules - if desired in a mixture with fertilizers.
  • Water-dispersible granules are usually produced by conventional processes such as spray drying, fluid bed granulation, disc granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations usually contain 0.1 to 99 wt.%, in particular 0.1 to 95 % by weight of compounds according to the invention.
  • the active ingredient concentration is, for example, about 10 to 90 wt. %, the remainder to 100 wt. % consists of conventional formulation components.
  • the active ingredient concentration can be about 1 to 90, preferably 5 to 80 wt. %.
  • Dust-like formulations contain 1 to 30 wt. % of active ingredient, preferably mostly 5 to 20 wt. % of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt. % of active ingredient.
  • the active ingredient content depends in part on whether the active compound is liquid or solid and which granulation aids, fillers, etc. are used.
  • the active ingredient content is, for example, between 1 and 95 wt. %, preferably between 10 and 80 wt. %.
  • the active ingredient formulations mentioned may contain the usual adhesive, wetting, dispersing, emulsifying, penetrating, preservative, antifreeze and solvent agents, fillers, carriers and colorants, defoamers, evaporation inhibitors and agents which influence the pH value and viscosity.
  • combinations with other pesticidally active substances such as insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and/or growth regulators, can also be produced, e.g. in the form of a ready-made formulation or as a tank mix.
  • the formulations in commercial form are diluted in the usual way, e.g. with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Dust-like preparations, soil or spreading granules and sprayable solutions are usually not diluted with other inert substances before use.
  • the required application rate of the compounds of formula (I) and their salts varies with external conditions such as temperature, humidity, the type of herbicide used, etc. It can vary within wide limits, e.g. between 0.001 and 10.0 kg/ha or more of active substance, but is preferably between 0.005 and 5 kg/ha, more preferably in the range from 0.01 to 1.5 kg/ha, particularly preferably in the range from 0.05 to 1 kg/ha g/ha. This applies both to pre-emergence and post-emergence applications.
  • Carrier means a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, especially for application to plants or parts of plants or seeds.
  • the carrier which can be solid or liquid, is generally inert and should be usable in agriculture.
  • Solid or liquid carriers can be used: e.g. ammonium salts and natural rock flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral flours such as highly dispersed silica, aluminium oxide and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, particularly butanol, organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures of such carriers can also be used.
  • Solid carriers for granules include: e.g.
  • broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
  • Suitable liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and pressure, e.g. aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
  • aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
  • Adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • organic solvents can also be used as auxiliary solvents.
  • the following liquid solvents are essentially suitable: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • the agents according to the invention can additionally contain other components, such as surface-active substances.
  • Suitable surface-active substances are emulsifying and/or foam-producing agents, dispersing agents or wetting agents with ionic or non-ionic properties or mixtures of these surface-active substances.
  • salts of polyacrylic acid salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphobenzene esters, taurine derivatives (preferably alkyl taurates), phosphoric acid esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of compounds containing sulphates, sulphonates and phosphates, e.g.
  • alkylaryl polyglycol ethers alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignin sulphite waste liquors and methylcellulose.
  • the presence of a surface-active substance is necessary if one of the active ingredients and/or one of the inert Carrier substances are not soluble in water and when the application takes place in water.
  • the proportion of surface-active substances is between 5 and 40 percent by weight of the agent according to the invention.
  • Dyes such as inorganic pigments, eg iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the active ingredients can be combined with any solid or liquid additive that is usually used for formulation purposes.
  • the agents and formulations according to the invention contain between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, particularly preferably between 0.5 and 90% active ingredient, very particularly preferably between 10 and 70% by weight.
  • the active ingredients or agents according to the invention can be used as such or depending on their respective physical and/or chemical properties in the form of their formulations or the application forms prepared therefrom, such as aerosols, capsule suspensions, cold mist concentrates, hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seed, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, pastes, pesticide-coated seed, suspension concentrates, suspension-emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble granules or tablets, water-soluble powders for seed treatment, wettable powders, Active
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one conventional extender, solvent or diluent, emulsifier, dispersant and/or binder or fixing agent, wetting agent, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and other processing aids.
  • the agents according to the invention include not only formulations which are already ready for use and can be applied to the plant or seed using suitable equipment, but also commercial concentrates which must be diluted with water before use.
  • the active ingredients according to the invention can be used as such or in their (commercially available) formulations as well as in the application forms prepared from these formulations in mixture with other (known) active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners or semiochemicals.
  • the treatment of plants and plant parts with the active substances or agents according to the invention takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, atomizing, sprinkling, evaporating, atomizing, misting, scattering, foaming, coating, spreading, watering (drenching), drip irrigation and, in the case of propagation material, in particular seeds, by dry dressing, wet dressing, slurry dressing, encrustation, single or multi-layer coating, etc. It is also possible to apply the active substances using the ultra-low-volume method or to inject the active substance preparation or the active substance itself into the soil.
  • transgenic seed As also described below, the treatment of transgenic seed with the active substances or agents according to the invention is of particular importance.
  • This relates to the seed of plants which contain at least one heterologous gene which enables the expression of a polypeptide or protein with insecticidal properties.
  • the heterologous gene in transgenic seed can originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • this heterologous gene originates from Bacillus sp., the gene product having an effect against the European corn borer and/or Western corn rootworm.
  • the heterologous gene originates from Bacillus thuringiensis.
  • the agent according to the invention is applied to the seed alone or in a suitable formulation.
  • the seed is preferably treated in a state in which it is so stable that no damage occurs during the treatment.
  • the treatment of the seed can take place at any time between harvesting and sowing.
  • seed is used which is separated from the plant and freed from cobs, shells, stems, husks, wool or pulp.
  • seed can be used which is harvested, cleaned and dried to a moisture content of less than 15% by weight.
  • seed can be used which is treated after drying, e.g. with water and then dried again.
  • care when treating the seed, care must be taken to ensure that the amount of the agent according to the invention and/or other additives applied to the seed is selected so that the germination of the seed is not impaired or the resulting plant is not damaged. This is particularly important for active substances that can have phytotoxic effects at certain application rates.
  • the agents according to the invention can be applied directly, i.e. without further components and without having been diluted.
  • suitable formulations and methods for seed treatment are known to the person skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430, US 5,876,739, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.
  • the active ingredients according to the invention can be converted into the usual seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating masses for seed, as well as UEV formulations.
  • formulations are prepared in a known manner by mixing the active ingredients with conventional additives, such as conventional extenders as well as solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • conventional additives such as conventional extenders as well as solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • dyes that are customary for such purposes can be considered as dyes that can be contained in the mordant formulations that can be used according to the invention. Both pigments that are slightly soluble in water and dyes that are soluble in water can be used. Examples include the dyes known under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
  • Wetting agents which can be contained in the seed dressing formulations which can be used according to the invention are all substances which promote wetting and which are customary for the formulation of agrochemical active ingredients.
  • Alkyl naphthalene sulfonates such as diisopropyl or diisobutyl naphthalene sulfonates, can preferably be used.
  • non-ionic, anionic and cationic dispersants customary for the formulation of agrochemical active ingredients are suitable as dispersants and/or emulsifiers which can be contained in the seed dressing formulations which can be used according to the invention.
  • Non-ionic or anionic dispersants or mixtures of non-ionic or anionic dispersants can preferably be used.
  • Suitable non-ionic dispersants are in particular ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are in particular lignin sulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • Defoamers that can be contained in the seed dressing formulations used according to the invention include all foam-inhibiting substances that are customary for the formulation of agrochemical active ingredients. Silicone defoamers and magnesium stearate are preferably used.
  • Preservatives that can be used in the pickling agent formulations according to the invention are all substances that can be used in agrochemical products for such purposes must be present. Examples include dichlorophene and benzyl alcohol hemiformal.
  • Suitable secondary thickeners which can be contained in the seed dressing formulations used according to the invention are all substances which can be used for such purposes in agrochemical agents. Cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly disperse silica are preferred.
  • binding agents that can be used in mordants are suitable as adhesives that can be contained in the mordant formulations that can be used according to the invention.
  • the seed dressing formulations that can be used according to the invention can be used either directly or after prior dilution with water to treat seeds of various types, including seeds of transgenic plants. In this case, additional synergistic effects can also occur in conjunction with the substances formed by expression.
  • All mixing devices that can usually be used for seed dressing can be used to treat seed with the seed dressing formulations that can be used according to the invention or with the preparations made from them by adding water.
  • the seed dressing procedure involves placing the seed in a mixer, adding the desired amount of seed dressing formulations either as such or after diluting with water, and mixing until the formulation is evenly distributed over the seed. A drying process follows if necessary.
  • the active ingredients according to the invention are suitable for protecting plants and plant organs, increasing crop yields and improving the quality of the harvested crop, as they are well tolerated by plants, have favorable toxicity to warm-blooded animals and are environmentally friendly. They can preferably be used as plant protection products. They are effective against normally sensitive and resistant species and against all or individual stages of development.
  • plants which can be treated according to the invention corn, soybeans, cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, wine and various fruits and vegetables from various botanical taxa such as Rosaceae sp. (e.g.
  • pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches and berries such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g.
  • Theaceae sp. Sterculiceae sp., Rutaceae sp. (e.g. lemons, oranges and grapefruit); Solanaceae sp. (e.g. tomatoes, potatoes, peppers, aubergines), Liliaceae sp., Compositae sp. (e.g. lettuce, artichoke and chicory - including chicory root, endive or common chicory), Umbelliferae sp. (e.g. carrot, parsley, celery and celeriac), Cucurbitaceae sp. (e.g. cucumber - including gherkin, pumpkin, watermelon, gourd and melons), Alliaceae sp.
  • Solanaceae sp. e.g. tomatoes, potatoes, peppers, aubergines
  • Liliaceae sp. Compositae sp.
  • Umbelliferae sp. e.g. carrot, parsley,
  • Cruciferae sp. e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and Chinese cabbage
  • Leguminosae sp. e.g. peanuts, peas, and beans - such as runner beans and broad beans
  • Chenopodiaceae sp. e.g. chard, fodder beet, spinach, beetroot
  • Malvaceae e.g. okra
  • Asparagaceae e.g. asparagus
  • plants and parts thereof can be treated according to the invention.
  • plant species and plant varieties that occur in the wild or that have been obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and their parts are treated.
  • transgenic plants and plant varieties that have been obtained by genetic engineering methods, optionally in combination with conventional methods (genetically modified organisms) and their parts are treated.
  • the term "parts” or “parts of plants” or “plant parts” is explained above.
  • plants of the respective commercially available or in-use plant varieties are treated according to the invention.
  • Plant varieties are understood to mean plants with new properties ("traits") that have been bred by conventional breeding, mutagenesis or recombinant DNA techniques. These can be varieties, races, biotypes and genotypes.
  • the treatment method according to the invention can be used for the treatment of genetically modified organisms (GMOs), e.g. plants or seeds.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants in which a heterologous gene has been stably integrated into the genome.
  • heterologous gene essentially means a gene which is provided or assembled outside the plant and which, when introduced into the nuclear genome, the chloroplast genome or the mitochondrial genome of the transformed plant, confers new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by down-regulating or switching off another gene(s) present in the plant (for example by means of antisense technology, cosuppression technology or RNAi technology [RNA interference]).
  • a heterologous gene present in the genome is also referred to as a transgene.
  • a transgene which, by its specific presence in the plant genome is called a transformation or transgenic event.
  • the treatment according to the invention can also lead to superadditive (“synergistic”) effects.
  • superadditive the following effects are possible which go beyond the effects actually expected: reduced application rates and/or expanded spectrum of action and/or increased effectiveness of the active ingredients and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or soil salinity, increased flowering performance, easier harvesting, accelerated ripening, higher yields, larger fruits, greater plant height, more intense green leaf color, earlier flowering, higher quality and/or higher nutritional value of the harvest products, higher sugar concentration in the fruits, better storage capacity and/or processability of the harvest products.
  • Plants and plant varieties which are preferably treated according to the invention include all plants which have genetic material which gives these plants particularly advantageous, useful characteristics (regardless of whether this is achieved by breeding and/or biotechnology).
  • nematode-resistant plants are described in the following US patent applications: 11/765,491, 11/765,494, 10/926,819, 10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396 and 12/497,221.
  • Plants that can be treated according to the invention are hybrid plants that already express the properties of heterosis or the hybrid effect, which generally result in higher yield, higher vigor, better health and better resistance to biotic and abiotic stress factors.
  • Such plants are typically produced by crossing an inbred male sterile parent line (the female crossing partner) with another inbred male fertile parent line (the male crossing partner).
  • the hybrid seed is typically harvested from the male sterile plants and sold to propagators.
  • Male sterile plants can sometimes (e.g. in maize) be produced by defatting (i.e. mechanically removing the male sex organs or male flowers), but it is more common for male sterility to be due to genetic determinants in the plant genome.
  • pollen fertility is fully restored in hybrid plants containing the genetic determinants responsible for pollen sterility.
  • This can be achieved by ensuring that the male Crossing partners possess appropriate fertility restorer genes that are capable of restoring pollen fertility in hybrid plants containing the genetic determinants responsible for pollen sterility.
  • Genetic determinants for pollen sterility can be localized in the cytoplasm. Examples of cytoplasmic pollen sterility (CMS) have been described for Brassica species, for example. However, genetic determinants for pollen sterility can also be localized in the nuclear genome. Pollen-sterile plants can also be obtained using plant biotechnology methods, such as genetic engineering.
  • a ribonuclease such as bamase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expressing a ribonuclease inhibitor such as barstar in the tapetum cells.
  • Plants or plant varieties obtained by plant biotechnology techniques such as genetic engineering which can be treated according to the invention are herbicide-tolerant plants, i.e. plants which have been rendered tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation or by selection of plants containing a mutation conferring such herbicide tolerance.
  • Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, i.e. plants that have been made tolerant to the herbicide glyphosate or its salts. Plants can be made tolerant to glyphosate using various methods. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene that codes for the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.
  • EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
  • Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate oxidoreductase enzyme.
  • Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally occurring mutations of the above-mentioned genes. Plants expressing EPSPS genes conferring glyphosate tolerance are described. Plants expressing other genes conferring glyphosate tolerance, e.g. decarboxylase genes, are described.
  • herbicide-resistant plants include plants that have been made tolerant to herbicides that inhibit the enzyme glutamine synthase, such as bialaphos, phosphinotricin or glufosinate. Such plants can be obtained by expressing an enzyme which detoxifies the herbicide or a mutant of the enzyme glutamine synthase which is resistant to inhibition.
  • an effective detoxifying enzyme is, for example, an enzyme encoding a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants which express an exogenous phosphinotricin acetyltransferase have been described.
  • herbicide-tolerant plants include plants that have been made tolerant to herbicides that inhibit the enzyme hydroxyphenylpyruvate dioxygenase (HPPD).
  • HPPD hydroxyphenylpyruvate dioxygenase
  • Hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate.
  • Plants that are tolerant to HPPD inhibitors can be transformed with a gene that encodes a naturally occurring resistant HPPD enzyme or a gene that encodes a mutated or chimeric HPPD enzyme, as described in WO 96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387 or US 6,768,044.
  • Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes encoding certain enzymes that enable the formation of homogentisate despite inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are described in WO 99/34008 and WO 02/36787.
  • the tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding a prephenate dehydrogenase enzyme in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928.
  • plants can be made even more tolerant to HPPD inhibitors by inserting a gene into their genome that encodes an enzyme that metabolizes or degrades HPPD inhibitors, such as CYP450 enzymes (see WO 2007/103567 and WO 2008/150473).
  • ALS inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy(thio)benzoates and/or sulfonylaminocarbonyltriazolinone herbicides.
  • ALS also known as acetohydroxyacid synthase, AHAS
  • AHAS acetohydroxyacid synthase
  • plants that are tolerant to imidazolinones and/or sulfonylureas can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or by mutation breeding (see, for example, for soybean US 5,084,082, for rice WO 97/41218, for sugar beet US 5,773,702 and WO 99/057965, for lettuce US 5,198,599 or for sunflower WO 01/065922).
  • Plants or plant varieties which can also be treated according to the invention are tolerant to abiotic stress factors. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such stress resistance.
  • Particularly useful plants with stress tolerance include the following: a. plants containing a transgene capable of reducing the expression and/or activity of the gene encoding poly(ADP-ribose) polymerase (PARP) in the plant cells or plants.
  • PARP poly(ADP-ribose) polymerase
  • Plants containing a stress tolerance-promoting transgene encoding a plant-functional enzyme of the nicotinamide adenine dinucleotide salvage biosynthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase or nicotinamide phosphoribosyltransferase.
  • Plants or plant varieties obtained by methods of plant biotechnology, such as genetic engineering
  • Plants or plant varieties which can also be treated according to the invention, have an altered quantity, quality and/or storage capacity of the harvest product and/or altered properties of certain components of the harvest product, such as:
  • Transgenic plants that synthesize non-starch carbohydrate polymers or non-starch carbohydrate polymers whose properties are altered compared to wild-type plants without genetic modification. Examples are plants that produce polyfmctose, particularly of the inulin and levan type, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans and plants that produce Alteman.
  • Transgenic plants or hybrid plants such as onions with certain properties such as ‘high soluble solids content’, ‘low pungency’ (LP) and/or ‘long storage’ (LS).
  • LP low pungency
  • LS long storage
  • Plants or plant varieties which can also be treated according to the invention are plants such as cotton plants with altered fibre properties.
  • Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered fibre properties; these include: a) plants such as cotton plants which contain an altered form of cellulose synthase genes, b) plants such as cotton plants which contain an altered form of rsw2 or rsw3 homologous nucleic acids, such as cotton plants with an increased expression of sucrose phosphate synthase; c) plants such as cotton plants with an increased expression of sucrose synthase; d) plants such as cotton plants in which the timing of the gate control of the plasmodesmata at the base of the fibre cell is altered, e.g.
  • Plants or plant varieties which can also be treated according to the invention are plants such as rapeseed or related Brassica plants with altered oil composition properties.
  • Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered oil properties; these include: a) plants such as rapeseed plants which produce oil with a high oleic acid content; b) plants such as rapeseed plants which produce oil with a low linolenic acid content. c) plants such as rapeseed plants which produce oil with a low saturated fatty acid content.
  • Plants or plant varieties which can be obtained by methods of plant biotechnology, such as genetic engineering
  • plants which can also be treated according to the invention are plants such as potatoes which are virus-resistant, e.g. against the potato virus Y (Event SY230 and SY233 from Tecnoplant, Argentina), or which are resistant to diseases such as potato late blight (e.g. RB gene), or which show reduced cold-induced sweetness (which which carry the genes Nt-Inh, II-INV) or which show the dwarf phenotype (gene A-20 oxidase).
  • viruses which are virus-resistant, e.g. against the potato virus Y (Event SY230 and SY233 from Tecnoplant, Argentina), or which are resistant to diseases such as potato late blight (e.g. RB gene), or which show reduced cold-induced sweetness (which which carry the genes Nt-Inh, II-INV) or which show the dwarf phenotype (gene A-20 oxidase).
  • Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention are plants such as oilseed rape or related Brassica plants having altered seed shattering properties. Such plants may be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered properties, and include plants such as oilseed rape having delayed or reduced seed shattering.
  • transgenic plants that can be treated according to the invention are plants with transformation events or combinations of transformation events that are the subject of granted or pending petitions for non-regulated status with the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) in the USA. Information on this is available at any time from APHIS (4700 River Road Riverdale, MD 20737, USA), e.g. via the Internet site http://www.aphis.usda.gov/brs/not_reg.html. On the filing date of this application, petitions with the following information were either granted or pending with APHIS:
  • Transgenic phenotype the property (“trait”) conferred on the plant by the transformation event.
  • APHIS Documents various documents published by APHIS regarding the petition or available from APHIS upon request.
  • transgenic plants that can be treated according to the invention are plants with one or more genes encoding one or more toxins, the transgenic plants offered under the following trade names: YIELD GARD® (for example maize, cotton, soybeans), KnockOut® (e.g. maize), BiteGard® (e.g. maize), BT-Xtra® (e.g. maize), StarLink® (e.g. maize), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (e.g. maize), Protecta® and NewLeaf® (potato).
  • YIELD GARD® for example maize, cotton, soybeans
  • KnockOut® e.g. maize
  • BiteGard® e.g. maize
  • BT-Xtra® e.g. maize
  • StarLink® e.g. maize
  • Bollgard® cotton
  • Nucotn® cotton
  • Nucotn 33B®
  • Herbicide-tolerant plants that should be mentioned include maize, cotton and soybean varieties sold under the following trade names: Roundup Ready® (glyphosate tolerance, e.g. maize, cotton, soybeans), Liberty Link® (phosphinotric acid tolerance, e.g. rapeseed), IMI® (imidazolinone tolerance) and SCS® (sulfonylurea tolerance), e.g. maize.
  • Herbicide-resistant plants plants traditionally bred for herbicide tolerance
  • Clearfield® for example, maize.
  • a 1 M lithium trimethyl-N-(trimethylsilyl)silanaminide solution in THF (33.63 mL, 33.63 mmol, 1.05 equiv) was placed in diethyl ether (80 mL) under a nitrogen atmosphere and cooled to -78 °C using a dry ice bath.
  • a solution of l-(3,4-difluorophenyl-ethanone (5.0 g, 32 mmol, 1.0 equiv.) in diethyl ether (20 ml) is added dropwise to this solution over a period of 10 minutes and the mixture is stirred at -78°C for 1 hour.
  • reaction solution is then mixed with diethyl oxalate (4.35 ml, 32 mmol, 1.0 equiv.).
  • diethyl oxalate (4.35 ml, 32 mmol, 1.0 equiv.).
  • the resulting reaction mixture is stirred at -78°C for 3 hours and then at room temperature overnight.
  • the suspension is then cooled to 0 to 4°C using an ice bath, mixed with 1M hydrochloric acid and stirred at room temperature for 30 minutes.
  • the reaction mixture is extracted three times with 100 ml of ethyl acetate each time.
  • the organic phase is dried over magnesium sulfate and the solvent is removed in vacuo.
  • Ethyl (3Z)-4-(3,4-difluorophenyl)-4-hydroxy-2-oxobut-3-enoate (6.0 g, 22.89 mmol, 1.0 equiv) and 2-hydrazinopyridine (2.62 g, 24.03 mmol, 1.05 equiv) are suspended in acetic acid (30 ml) and heated to boiling for 4 h. After cooling to room temperature, the solvent is removed in vacuo.
  • Ethyl 4-bromo-5-(3,4-difluorophenyl)-l-(pyridin-2-yl)-lH-pyrazole-3-carboxylate (0.90 g, 2.21 mmol, 1.0 equiv), zinc(II) cyanide (246 mg, 2.10 mmol, 0.95 equiv) and tetrakis(triphenylphosphine)palladium(0) (255 mg, 0.22 mmol, 0.1 equiv) are suspended in degassed DMF (12 ml) in a 30 ml microwave vessel under nitrogen atmosphere and heated for 40 min at 180°C in a Biotage Initator + microwave.
  • reaction is stirred for 4 h at 60 °C, during which gas evolution occurs.
  • reaction solution is treated with a saturated sodium hydrogen carbonate solution (10 ml) and extracted twice with ethyl acetate (50 ml).
  • the organic phase is dried over magnesium sulfate and the solvent is removed in vacuo.
  • the crude intermediate is dissolved in dichloromethane (30 ml) and trifluoroacetic acid (0.28 ml, 3.68 mmol, 1 equiv) is added.
  • the reaction mixture is stirred overnight at room temperature.
  • the solvent is then removed in vacuo.
  • reaction mixture is then poured into H2O and extracted several times with CH2Cl2.
  • organic phase is dried over Na2SO4, concentrated and the crude product thus obtained is purified by column chromatography on silica gel with heptane/ethyl acetate (8:2). In this way, 0.13 g (91%) of product is obtained.
  • NMR data of selected examples NMR data of selected examples
  • the spectroscopic data of selected table examples listed below were evaluated either using classical NMR interpretation and/or 1H NMR peak list methods.
  • Example No. I-221 1H NMR (401 MHz, CDCl3): ⁇ H 1.28-1.35 (t, 3H), 4.28-4.35 (q, 2H), 4.95 (s, 2H), 7.01-7.15 (m, 3H), 7.28-7.34 (m, 2H), 7.40-7.44 (d, 1H), 7.66-7
  • I-218 1H-NMR (400 MHz, d6-DMSO d, ppm) 12.96 (bs, 1H), 8.62 (m, 1H), 8.44 (m, 1H), 7.70 (m, 1H), 7.50- 7.35 (m, 2H), 7.02 (m, 1H), 4.77 (s, 2H).
  • Example No. I-217 1H NMR (400 MHz, CDCl3 d, ppm) 8.49 (m, 1H), 8.12 (m, 1H), 7.42 (m, 1H), 7.19-7.02 (m, 3H), 4.86 (s, 2H), 4.24 (q, 2H), 1.28 (t, 3H).
  • I-145 1H NMR (400 MHz, d6-DMSO d, ppm): 13.1 (bs, 1H), 8.30 (d, 1H), 7.94 (t, 1H), 7.59 (m, 1H), 7.48 (d, 2H), 7.28 (d, 2H), 4.84 (s, 2H).
  • peaks or the center of the signal and their relative intensity compared to the most intense signal in the spectrum can be shown.
  • the tetramethylsilane peak may or may not appear in NMR peak lists.
  • the lists of 1H NMR peaks are similar to classical 1H NMR printouts and thus usually contain all peaks that are listed in a classical NMR interpretation.
  • they may include solvent signals, signals of stereoisomers of the target compounds, which are also the subject of of the invention and/or show peaks of impurities.
  • a dust is obtained by mixing 10 parts by weight of a compound of formula (I) and/or salts thereof and 90 parts by weight of talc as an inert substance and grinding in a hammer mill.
  • a wettable powder which is easily dispersible in water is obtained by mixing 25 parts by weight of a compound of formula (I) and/or salts thereof, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurine as a wetting agent and dispersant and grinding in a pin mill.
  • a dispersion concentrate which is easily dispersible in water is obtained by mixing 20 parts by weight of a compound of formula (I) and/or its salts with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. approx. 255 to over 277 C) and grinding in a ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I) and/or its salts, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
  • a granulate which is easily dispersible in water is obtained by
  • a water-dispersible granulate is also obtained by
  • ABUTH Abutilon theophrasti
  • ECHCG Echinochloa crus-galli
  • KCHSC Kochia scoparia
  • MATIN Matricaria inodora
  • PHBPU Pharbitis purpurea
  • POLCO Polygonum sylvatica
  • VERPE Veronica persica VIOTR: Viola tricolor
  • BRSNW Brassica napus
  • ORYZA Oryza sativa
  • TRZAS Triticum aestivum
  • Seeds of monocotyledonous and dicotyledonous weeds are placed in plastic pots in sandy loam soil (double sowings with one species of monocotyledonous or dicotyledonous weed per pot) and covered with soil.
  • Tables 1a to 12c below show the effects of selected compounds of general formula (I) according to Table 1 on various weeds and at an application rate corresponding to 1280 g/ha and lower, obtained according to the test procedure mentioned above.
  • Table la Pre-emergence effect at 320g/ha against ABUTH in %
  • Table 12b Pre-emergence effect at 320g/ha against AMARE in Table 12c : Pre-emergence effect at 1280g/ha against AMARE in
  • compounds according to the invention such as compounds Nos. 1-18, 1-16 and 1-23 and other compounds from Tables 1a to 12c, have good herbicidal activity against harmful plants when treated pre-emergence.
  • compounds Nos. 1-18, 1-16 and 1-23 have a very good herbicidal activity (90% to 100% herbicidal activity) in the pre-emergence process against harmful plants such as Alopecurus myrosoroides, Digitaria sanguinalis, Echinochloa crus-galli and Setaria viridis at an application rate of 1.28 kg of active substance.
  • the compounds according to the invention are therefore suitable for use in the pre-emergence process for controlling unwanted plant growth.
  • Seeds of monocotyledonous and dicotyledonous weeds and cultivated plants were placed in plastic or organic plant pots and covered with soil.
  • Tables 13a to 30c below show the effects of selected compounds of general formula (I) according to Table 1 on various pests and crops and at an application rate corresponding to 320 g/ha or lower, which were obtained according to the test procedure mentioned above.
  • Tables 13a to 17c below show the crop tolerances of selected compounds of general formula (I) at an application rate corresponding to 320 g/ha or lower, which were observed in tests according to the test procedure mentioned above. The observed effects on selected crops are given in comparison with the untreated controls (values in %).
  • Table 15a Pre-emergence effect at 20g/ha against ORYSA in %
  • Table 15b Pre-emergence effect at 80g/ha against ORYSA in %
  • Table 15c Pre-emergence effect at 320g/ha against ORYSA in %
  • Table 16a Pre-emergence effect at 20g/ha against GLXMA in %
  • compounds according to the invention such as compounds 1-22, 1-100 and 1-104 and other compounds from Tables 18a to 30c, have good herbicidal activity against harmful plants when treated pre-emergence.
  • compound No. 1-22 has a very good herbicidal activity in the pre-emergence method (90% herbicidal activity).
  • Seeds of monocotyledonous or dicotyledonous weeds are placed in plastic pots in sandy loam soil (double sowings with one species of monocotyledonous or dicotyledonous weed per pot), covered with soil and grown in the greenhouse under controlled growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single-leaf stage.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are applied to the green parts of the plant as an aqueous suspension or emulsion, with the addition of 0.5% additive, at a water application rate of the equivalent of 600 liters per hectare.
  • the effect of the preparations is assessed visually in comparison to untreated controls. For example, 100% effect means plants have died, 0% effect means like control plants.
  • Tables 3la to 42c below show the effects of selected compounds of general formula (I) according to Table 1 on various weeds and at an application rate corresponding to 1280 g/ha and lower, obtained according to the test procedure mentioned above.
  • Table 35b Post-emergence effect at 320g/ha against KCHSC in %
  • Table 35c Post-emergence effect at 1280g/ha against KCHSC in
  • Table 39c Post-emergence effect at 1280g/ha against SETVI in %
  • Table 40a Post-emergence effect at 80g/ha against STEME in %
  • Table 40b Post-emergence effect at 320g/ha against STEME in %
  • Table 40c Post-emergence effect at 1280g/ha against STEME in
  • compounds according to the invention such as compounds Nos. 1-51, 1-05 and 1-120 and other compounds from Tables 31a to 42c, have good herbicidal activity against harmful plants when treated post-emergence.
  • compounds Nos. 1-51, 1-05 and 1-120 have very good herbicidal activity in the post-emergence process.
  • Effectiveness (90% to 100% herbicidal activity) against weeds such as Abutylon threophrasti, Alopecurus myosuroides, Digitaria sanguinalis and Echinochloa crus-galli at an application rate of 1.28 kg active substance per hectare.
  • the compounds according to the invention are therefore suitable for post-emergence control of undesirable plant growth.
  • the following tables show the effects of selected compounds of general formula (I) according to Tables 43a to 61c on various weeds and crops and at an application rate corresponding to 320 g/ha and lower, which were obtained according to the test procedure mentioned above.
  • the following tables 43a to 47c show the crop tolerances of selected compounds of general formula (I) at an application rate corresponding to 320 g/ha or lower, which were observed in tests according to the test procedure mentioned above. The observed effects on selected crops are given in comparison with the untreated controls (values in %).
  • Table 43a Post-emergence effect at 20g/ha against ZEAMX in %
  • Table 43b Post-emergence effect at 80g/ha against ZEAMX in %
  • Table 55b Post-emergence effect at 80g/ha against PHBPU in %
  • Table 55c Post-emergence effect at 320g/ha against PHBPU in %
  • Table 60c Post-emergence effect at 320g/ha against DIGSA in %
  • Table 61a Post-emergence effect at 20g/ha against KCHSC in %
  • compounds according to the invention such as compound 1-26 and other compounds from Tables 48a to 61c, have good herbicidal activity against harmful plants when applied post-emergence.
  • compound 1-26 has
  • Post-emergence treatment has a very good herbicidal effect (80% to 100% herbicidal effect) against harmful plants such as Abutilon theophrasti and Setaria viridis at an application rate of 320 g of active substance or less per hectare.
  • compounds according to the invention such as compound 1-61 and other compounds from Tables 43a to 47c, have good tolerance in crop plants when treated post-emergence.

Abstract

L'invention relève du domaine technique des agents phytosanitaires, en particulier ceux des herbicides pour lutter contre les mauvaises herbes et/ou les mauvaises herbes graminées dans les cultures et dans le jardinage ornemental et pour lutter de manière générale contre les mauvaises herbes et les mauvaises herbes graminées dans des zones environnementales où la croissance des plantes n'est pas souhaitée. L'invention concerne en particulier des acides 1-pyridyl-5-phénylpyrazolyl-3-oxy- et -3-thioalkyle substitués et leurs dérivés, leurs procédés de production et leur utilisation pour lutter contre des plantes nuisibles.
PCT/EP2023/076659 2022-10-14 2023-09-27 Acides 1-pyridyl-5-phenylpyrazolyl-3-oxy- et -3-thioalkyl et leurs dérivés et leur utilisation pour lutter contre la croissance de plantes indésirables WO2024078871A1 (fr)

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