EP3975720A1 - Acides 1-phényl-5-azinylpyrazolyl-3-oxyalkyliques et leur utilisation pour lutter contre la croissance de plantes adventices - Google Patents

Acides 1-phényl-5-azinylpyrazolyl-3-oxyalkyliques et leur utilisation pour lutter contre la croissance de plantes adventices

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Publication number
EP3975720A1
EP3975720A1 EP20727906.8A EP20727906A EP3975720A1 EP 3975720 A1 EP3975720 A1 EP 3975720A1 EP 20727906 A EP20727906 A EP 20727906A EP 3975720 A1 EP3975720 A1 EP 3975720A1
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EP
European Patent Office
Prior art keywords
alkyl
group
hydrogen
plants
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20727906.8A
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German (de)
English (en)
Inventor
Michael Gerhard Hoffmann
Estella Buscato Arsequell
Harald Jakobi
Thomas Müller
Erin Nicole SMITH
Elisabeth ASMUS
Anu Bheemaiah MACHETTIRA
Elmar Gatzweiler
Christopher Hugh Rosinger
Dirk Schmutzler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP3975720A1 publication Critical patent/EP3975720A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • A01P13/02—Herbicides; Algicides selective
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • 1-Phenyl-5-azinylpyrazolyl-3-oxyalkyl acids and their use for combating undesired plant growth Weed grass in environmental areas where vegetation is disruptive.
  • the invention relates to substituted 1-phenyl-5-azinylpyrazolyl-3-oxyalkyl acids and their derivatives, processes for their preparation and their use for controlling harmful plants.
  • the derivatives of the 1-phenyl-5-azinylpyrazolyl-3-oxyalkyl acids include in particular their esters, salts and / or amides.
  • the phenyl-5-azinylpyrazolyl-3-oxyalkyl acids according to the invention and their derivatives differ from the already known 1,5-diphenyl-pyrazolyl-3-oxoacetic acids by a variable azinyl radical (A1-A15) in the 5 position of the pyrazole ring.
  • A1-A15 variable azinyl radical
  • 2828529 A1 describes the production and the lipid-lowering effect of 1,5-diphenyl-pyrazolyl-3-oxoacetic acids.
  • 1,5-Diphenyl-pyrazolyl-3-oxoacetic acid derivatives are disclosed in CN 101284815 as bactericidal agrochemicals.
  • Journal of Heterocyclic Chemistry (2012), 49 (6), 1370-1375 further syntheses and the fungicidal effect of 1,5-diphenyl-pyrazolyl-3-oxoacetic acids are described.
  • 1-phenyl-5-azynylpyrazolyl-3-oxyacetic acids or phenyl-5-azynylpyrazolyl-3-oxyalkyl acids and their derivatives are so far unknown.
  • the object of the present invention is to provide new pyrazole derivatives, namely 1-phenyl-5-azinylpyrazolyl-3-oxyalkyl acids and their derivatives, which can be used as herbicides or plant growth regulators, with a satisfactory herbicidal effect and a
  • substituted pyrazolyl-3-oxoalkyl acids which are characterized by an azinyl radical in the 5-position of the pyrazole ring, i.e. by substituted 1-phenyl-5-azinylpyrazolyl-3-oxyalkyl acid derivatives, which have a very good herbicidal effect and also very good selectivity.
  • these compounds are highly effective against a wide range of economically important grass weeds and weeds.
  • the compounds are well tolerated by crop plants. Thus, they can be used selectively in crop plants with good activity against harmful plants.
  • the present invention therefore provides substituted 1-phenyl-5-azinylpyrazolyl-3-oxyalkyl acids of the general formula (I)
  • A is selected from the group consisting of A1-A15
  • R 1 is selected from the group consisting of
  • R 1a is hydrogen or
  • Aryl means or
  • R 9 is selected from the group consisting of hydrogen, (C 1 -C 12 ) alkyl
  • R 10 is selected from the group consisting of
  • alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals are unsubstituted or are each independently substituted by m radicals selected from the group consisting of
  • R 9 and R 10 with the nitrogen atom to which they are attached, optionally one to
  • C (R 6 ) NOR 8 substituted, saturated, partially or fully unsaturated five-, six- or seven-membered ring, which in addition to this nitrogen atom r carbon atoms, o oxygen atoms, p sulfur atoms and q elements from the group consisting of NR 7 , CO and contains NCOR 7 as ring atoms;
  • R 5 is (C 1 -C 8 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -haloalkyl, or aryl;
  • R 6 is hydrogen or R 5 ;
  • R 7 is hydrogen, (C 1 -C 6 ) -alkyl, (C3-C6) -cycloalkyl, (C3-C4) -alkenyl, (C 1 -C 6 ) -alkyl-COO (C1-C2-alkyl or (C3 -C4) alkynyl;
  • R 8 denotes hydrogen, (C 1 -C 6 ) -alkyl, (C3-C6) -cycloalkyl, (C3-C4) -alkenyl or (C3-C4) -alkynyl;
  • R 2 is selected from the group consisting of
  • R 3 is selected from the group consisting of
  • R 4 is a phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of
  • n 0, 1 or 2;
  • A is preferably selected from the group consisting of
  • A is particularly preferably selected from the group consisting of
  • R 1 is selected from the group consisting of
  • R 1a is selected from the group consisting of
  • substituents selected from the group consisting of halogen, (C 1 -C 6) - alkyl, (C 1 -C 6) -haloalkyl, (C3-C6) -cycloalkyl, (C 1 -C 6) alkoxy, cyano and nitro;
  • Aryl, heterocyclyl and heteroaryl is unsubstituted or substituted by halogen, (C 1 -C 6 ) -alkyl and / or (C 1 -C 6 ) -haloalkyl.
  • R 9 is selected from the group consisting of hydrogen, (C 1 -C 12 ) -alkyl
  • R 10 is selected from the group consisting of
  • alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals are unsubstituted or are each independently substituted by m radicals selected from the group consisting of
  • R 1 is preferably selected from the group consisting of
  • R 1a is preferably selected from the group consisting of
  • Substituents selected from the group consisting of halogen, (C 1 -C 6) alkyl, (C 1 -C 6) - haloalkyl, (C 1 -C 6) alkoxy, cyano and nitro;
  • Aryl (C1-C4) -alkyl the aryl being unsubstituted or with halogen, (C 1 -C 6 ) -alkyl and / or
  • R 9 is preferably hydrogen or (C 1 -C 4 ) -alkyl
  • R 10 is preferably selected from the group consisting of
  • alkyl, cycloalkyl and alkenyl radicals are unsubstituted or are each independently substituted by m radicals selected from the group consisting of
  • R 9 and R 10 preferably form one with the nitrogen atom to which they are attached
  • radicals from the group consisting of halogen, (C 1 -C 4 ) -alkyl, OR 5 , substituted, saturated, partially or completely unsaturated five-, six- or seven-membered ring, in addition to this
  • R 1 is particularly preferably selected from the group consisting of
  • R 1a is particularly preferably selected from the group consisting of
  • Substituents selected from the group consisting of halogen, (C 1 -C 6) alkyl, (C 1 -C 6) - haloalkyl, (C 1 -C 6) alkoxy;
  • Aryl (C1-C4) -alkyl the aryl being substituted by (C 1 -C 6 ) -alkyl.
  • R 9 is particularly preferably hydrogen;
  • R 10 is particularly preferably selected from the group consisting of
  • alkyl, cycloalkyl and alkenyl are unsubstituted or are each independently substituted by m radicals selected from the group consisting of S (O) 7
  • R 9 and R 10 particularly preferably form with the nitrogen atom to which they are bonded an unsubstituted, saturated, partially or fully unsaturated five-, six- or seven-membered ring which, in addition to this nitrogen atom, has r carbon atoms, o oxygen atoms, p sulfur atoms and q Contains elements from the group consisting of NR 7 , CO and NCOR 7 as ring atoms.
  • R 1 is very particularly preferably selected from the group consisting of
  • R 1a is very particularly preferably selected from the group consisting of
  • R 9 is very particularly preferably hydrogen and
  • R 10 is very particularly preferably selected from the group consisting of (C 1 -C 12 ) -alkyl,
  • R 5 R 5 denotes (C1-C4) -alkyl, (C3-C6) -cycloalkyl, (C1-C4) -haloalkyl or aryl.
  • R 5 preferably denotes (C1-C4) -alkyl, (C3-C6) -cycloalkyl, or (C1-C4) -haloalkyl.
  • R 5 particularly preferably denotes (C1-C4) -alkyl or (C1-C4) -haloalkyl.
  • R 5 very particularly preferably denotes ethyl, methyl, CF 3 or CH 2 CF 3 . Further embodiments of the invention relate to the radical R 6
  • R 6 means hydrogen or R 5 .
  • R 6 is preferably hydrogen. Further embodiments of the invention relate to the radical R 7 R 7 denotes hydrogen, (C 1 -C 6 ) -alkyl, (C3-C6) cycloalkyl, (C3-C4) -alkenyl, (C 1 -C 6 ) -alkyl COO (C 1 -C 2 ) -alkyl or (C 3 -C 4 ) -alkynyl.
  • R 7 is preferably hydrogen or (C 1 -C 6 ) -alkyl.
  • R 7 particularly preferably denotes hydrogen, methyl or ethyl.
  • R 8 denotes hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 3 -C 4 ) -alkenyl or (C 3 -C 4 ) - alkynyl.
  • R 8 preferably denotes hydrogen or (C 1 -C 6 ) -alkyl.
  • R 8 particularly preferably denotes (C 1 -C 6 ) -alkyl.
  • R 8 very particularly preferably denotes methyl or ethyl. Further embodiments of the invention relate to the radical R 2 R 2 is selected from the group consisting of
  • R 2 is preferably selected from the group consisting of
  • R 2 is particularly preferably selected from the group consisting of
  • R 2 is very particularly preferably selected from the group consisting of
  • R 3 is selected from the group consisting of
  • R 3 is preferably selected from the group consisting of
  • R 3 is particularly preferably selected from the group consisting of
  • R 3 is very particularly preferably selected from the group consisting of
  • R 3 is most preferably selected from the group consisting of
  • R 4 R 4 is a phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of
  • R 4 is preferably a phenyl, the phenyl radical being unsubstituted or substituted one or more times by a radical selected from the group consisting of
  • R 4 is particularly preferably a phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of
  • R 4 is very particularly preferably a phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of hydrogen, fluorine and chlorine. R 4 is most preferably a mono- or polysubstituted by fluorine and / or by chlorine phenyl. Further embodiments of the invention relate to the radical R 12 R 12 is selected from the group consisting of
  • R 12 is preferably selected from the group consisting of
  • R 12 is particularly preferably selected from the group consisting of
  • R 12 is very particularly preferably selected from the group consisting of
  • R 12 is most preferably selected from the group consisting of
  • n 0, 1 or 2;
  • serial numbers are preferably
  • n 0, 1 or 2;
  • s is 0 or 1.
  • the running numbers are particularly preferably
  • n 0, 1 or 2;
  • the present invention encompasses compounds of the general formula (I) in which, for example, the substituent R 1 has a preferred meaning and the substituents R 1a to R 12 have the general meaning or the substituent R 1a has a preferred meaning has, the substituent R 9 has a particularly preferred, or a very particularly preferred, meaning and the other substituents have a general meaning.
  • substituents R 1 , R 1a , R 9 , R 10 , R 5 Three of these combinations of the above for the substituents for the substituents R 1 , R 1a , R 9 , R 10 , R 5 ,
  • R 12 and the sequence numbers m, n, o, p, q, r, s are each designated as being most preferred
  • R 1 is selected from the group consisting of
  • R 1a is selected from the group consisting of
  • Substituents selected from the group consisting of halogen, (C 1 -C 6) alkyl, (C 1 -C 6) - haloalkyl, (C 1 -C 6) alkoxy, cyano and nitro;
  • aryl (C 1- C 4) alkyl, wherein the aryl group unsubstituted or substituted by halogen, (C 1 -C 6) alkyl and / or
  • R 9 is hydrogen, (C 1 -C 4 ) -alkyl
  • R 10 is selected from the group consisting of
  • R 9 and R 10 with the nitrogen atom to which they are attached, optionally one to
  • R 5 is (C1-C4) -alkyl, (C3-C6) -cycloalkyl or (C1-C4) -haloalkyl;
  • R 6 is hydrogen or R 5 ;
  • R 7 is hydrogen or (C 1 -C 4 ) -alkyl;
  • R 8 denotes hydrogen or (C1-C4) -alkyl;
  • R 2 is selected from the group consisting of
  • R 3 is selected from the group consisting of
  • R 4 is a phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of
  • R 12 is selected from the group consisting of
  • n 0, 1 or 2;
  • A is selected from the group consisting of
  • R 1 is selected from the group consisting of
  • R 1a is selected from the group consisting of
  • Substituents selected from the group consisting of halogen, (C 1 -C 6) alkyl, (C 1 -C 6) - haloalkyl, (C 1 -C 6) alkoxy;
  • R 10 is selected from the group consisting of
  • R 9 and R 10 with the nitrogen atom to which they are attached are unsubstituted, saturated,
  • R 5 is (C1-C8) -alkyl, or (C 1 -C 6 ) -haloalkyl
  • R 6 is hydrogen
  • R 7 is hydrogen or (C 1 -C 6 ) -alkyl
  • R 8 is (C 1 -C 6 ) -alkyl
  • R 2 is selected from the group consisting of
  • R 3 is selected from the group consisting of
  • R 4 is a phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of
  • R 12 is selected from the group consisting of
  • n 0, 1 or 2;
  • R 1 is selected from the group consisting of
  • R 1a is selected from the group consisting of
  • R 9 is hydrogen
  • R 10 is selected from the group consisting of (C 1 -C 12 ) -alkyl, S (O) n R 5 , SO 2 NR 6 R 7 ,
  • R 5 is ethyl, methyl, CF 3 , CH 2 CF 3 ;
  • R 6 is hydrogen or R 5 ;
  • R 7 is hydrogen, methyl or ethyl;
  • R 8 is methyl or ethyl;
  • R 2 is selected from the group consisting of
  • R 3 is selected from the group consisting of
  • R 4 is phenyl, the phenyl radical being unsubstituted or mono- or polysubstituted by a radical selected from the group consisting of hydrogen, fluorine and chlorine;
  • R 12 is selected from the group consisting of
  • R 3 is most preferably selected from the group consisting of - fluorine, chlorine, bromine, iodine, cyano, NO 2 ;
  • R 4 is most preferably a mono- or polysubstituted by fluorine and / or by chlorine phenyl.
  • R 12 is most preferably selected from the group consisting of
  • Alkyl means saturated, straight-chain or branched hydrocarbon radicals with the specified number of carbon atoms, for example C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-d
  • Alkyl substituted by halogen means straight-chain or branched alkyl groups, in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms, for example C1-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 1,
  • Alkenyl means unsaturated, straight-chain or branched hydrocarbon radicals with the number of carbon atoms indicated in each case and a double bond in any position, e.g. C2-C6-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1- Methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl- 1- butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2- methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2
  • C2-C6- 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-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl- 1-pentynyl, 1-pentynyl, 1-pentynyl, 1-propyny
  • Cycloalkyl means a carbocyclic, saturated ring system with preferably 3-8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cyclic systems with substituents are included, with substituents with a double bond on the cycloalkyl radical, e.g. B. an alkylidene group such as
  • multicyclic aliphatic systems are also included, such as, for example, bicyclo [1.1.0] butan-1-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-1-yl and adamantan-2- yl.
  • Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system with preferably 4-8 C atoms, e.g.
  • Cycloalkenyl radical e.g. B. an alkylidene group such as methylidene are included.
  • alkylidene group such as methylidene
  • substituted cycloalkyl the explanations for substituted cycloalkyl apply accordingly.
  • Alkoxy denotes saturated, straight-chain or branched alkoxy radicals as indicated in each case
  • C 1 -C 6 alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 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-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy.
  • Alkoxy substituted by halogen means straight-chain or branched alkoxy radicals with the specified number of carbon atoms, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C1-C2 haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, 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-trichloro
  • Heterocyclyl means saturated or partially unsaturated mono-, bi- or tricyclic ring system group, composed of carbon atoms and at least one heteroatom, preferably selected from N, O and / or S.
  • Heteroaryl unless otherwise defined: mono-, bi - Or tricyclic heterocyclic group of carbon atoms and at least one heteroatom, with at least one
  • At least one heteroatom is N, O or S. In one embodiment, all heteroatoms are selected from N, O or S. In one embodiment, the ring system is a 5 to 10 or a 5 to 6-membered ring system. In one embodiment, heteroaryl is an aromatic monocyclic ring system composed of 5 or 6 ring atoms. In another
  • Embodiment heteroaryl is an aromatic monocyclic ring system containing 1 to 4
  • heteroaryl can represent a bicyclic ring system that consists of 8 to 14 ring atoms or a tricyclic ring system that consists of 13 to 14
  • aryl means an optionally substituted mono-, bi- or polycyclic aromatic system with preferably 6 to 14, in particular 6 to 10 ring carbon atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
  • aryl also encompasses multicyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, the binding site being on the aromatic system. From a systematic point of view, “aryl” is usually also included in the term “optionally substituted phenyl”.
  • aryls listed above are preferably, independently of one another, one to five times, for example, by 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, arylalkoxycarbonylalkyl, alkynyl, alkynylalkyl, Alkylalkinyl, tris alkylsilylalkinyl, nitro,
  • halogen means fluorine, chlorine, bromine or iodine.
  • halogen means a fluorine, chlorine, bromine or iodine atom.
  • the compounds of the formula (I) have acidic properties and can form salts, optionally also internal salts or adducts, with inorganic or organic bases or with metal ions.
  • bases can be reacted with bases to form salts.
  • suitable bases are hydroxides, carbonates, hydrogen carbonates of the alkali and alkaline earth metals, in particular those of sodium, Potassium, magnesium and calcium, also ammonia, primary, secondary and tertiary amines with (C 1 -C 4 -) - alkyl groups, mono-, di- and trialkanolamines of (C 1 -C 4 ) -alkanols, choline and chlorcholine , and 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 ammonium salts, salts with organic amines or quaternary (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 are also suitable.
  • the compounds of the formula (I) can be prepared by adding a suitable inorganic or organic acid, such as, for example, mineral acids, such as, for example, HCl, HBr, H2SO4, H3PO4 or HNO 3 , or organic acids, e.g. B.
  • 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, form salts.
  • a basic group such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino
  • Suitable substituents which are deprotonated, e.g. Sulphonic acids or carboxylic acids, are present, can form internal salts with groups that can be protonated, such as amino groups.
  • this carbon atom can have either an (R) or 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 concerned is included
  • the present invention therefore relates in particular to compounds of the general formula (I *) in which the stereochemical configuration at the carbon atom marked with (*) has a stereochemical purity of 60 to 100% (R), preferably 80 to 100% (R), in particular 90 to 100% (R), very particularly 95 to 100% (R), is present.
  • further stereo elements can be present in the compounds of the general formula (I) according to the invention.
  • the compounds mentioned in the tables below are preferred.
  • Another aspect of the invention relates to the preparation of the compounds of the general formula (I) according to the invention.
  • the compounds according to the invention can be prepared in different ways.
  • Compounds according to the invention can be prepared from substituted 1-phenyl-5-azynyl-1H-pyrazol-3-ols (II), for example, by the synthesis processes listed in Scheme 1 below.
  • the synthesis of the compound of the general formula (I) can be carried out by alkylating the compound of the general formula (Ia) with a halide of the general formula (III) in
  • the base can be a carbonate salt of an alkali metal.
  • the base carbonate salt of an alkali metal is preferably selected from the group consisting of lithium, sodium, potassium and cesium.
  • Scheme 1 describes the synthesis of the compound of the general formula (Ib) by reacting a pyrazole of the general formula (Ia) with a halosuccinimide of the general formula (IV) in an adequate solvent such as, for example, 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 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 around nickel catalysts such as nickel (II) acetylacetonate or bis (triphenylphosphine) nickel (II) chloride, preferably at elevated temperature in an organic solvent such as for example Represent 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 (triphenylphosphin
  • M stands for magnesium, zinc, lithium or sodium, for example.
  • Methods of cross-coupling which are 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 -
  • the 3-hydroxypyrazoles (II) can be prepared from substituted 3-azinylpropinic acid derivatives and phenyhydrazines (Scheme 3; e.g. Adv. Synth. Catal. 2014, 356, 3135-3147) or from substituted azinylacrylic acid derivatives and phenylhydrazines (Scheme 3 ; z.
  • the synthesis of the compounds of the general formula (VIII) takes place via an amide coupling of an acid of the general formula (VI) with an aryl hydrazine or hetaryl hydrazine of the general formula (VII) in the presence of an amide coupling reagent such as T3P, dicyclohexylcarbodiimide, N- (3- Dimethylaminopropyl) -N ⁇ -ethylcarbodiimide, N, N ⁇ - cabonyldiimidazole, 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 takes place preferably in the temperature range between 0 ° C and 80 ° C, in an adequate 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 1,8-diazabicyclo [5.4.0] undec-7-cene instead (see Scheme 3).
  • a base such as triethylamine, N, N- Diisopropylethylamine or 1,8-diazabicyclo [5.4.0] undec-7-cene instead (see Scheme 3).
  • T3P peptide coupling conditions see Organic Process Research & Development 2009, 13, 900-906.
  • Scheme 3 describes the synthesis of the compound of the general formula (II) by reacting a pyrazole of the general formula (IIa) with an electrophile such as, for example, N-bromosuccinimide.
  • the reaction preferably takes place in the temperature range between 0 ° C. and 120 ° C. in an adequate solvent such as, for example, N, 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 Example copper (I) iodide, copper (I) bromide or an acid such as methanesulfonic acid.
  • a copper halide such as 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 adequate solvent such as 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, n-propanol or ethyl acetate.
  • the reaction takes place preferably in N, N-dimethylformamide.
  • Copper halides such as copper (I) iodide. The reaction takes place preferentially in the
  • a compound of the formula (XVI) can be prepared, for example, by reacting a compound of the formula (XIV) in a suitable solvent with an AM (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 to represent nickel catalysts such as nickel (II) acetylacetonate or bis (triphenylphosphine) nickel (II) chloride, preferably at an elevated temperature in an organic solvent such as 1,2-dimethoxyethane.
  • the 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, (C b
  • 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 adequate solvent such as dichloromethane, acetonitrile , N, N-dimethylformamide or ethyl acetate instead.
  • an adequate solvent such as dichloromethane, acetonitrile , N, N-dimethylformamide or ethyl acetate instead.
  • the compounds of the general formula (XVII) are commercially available. Compounds of the general formula (XIX) can be obtained by diazotization or Sandmeyer
  • inorganic nitrites such as 1,1-dimethylethyl nitrite, tert-butyl nitrite or isoamyl nitrite in the presence of usable reagents such as mixtures of copper (I) and
  • reaction takes place preferably in the temperature range between room temperature and 0 and 120 ° C in an adequate solvent such as dichloromethane, acetonitrile, N, N-dimethylformamide or diiodomethane.
  • an adequate solvent such as dichloromethane, acetonitrile, N, N-dimethylformamide or diiodomethane.
  • the radical "X” stands for chlorine, bromine or iodine, for example.
  • a compound of the formula (Ia) can be, for example, by reaction of a compound of the formula (XIX) in a suitable solvent with an AM (XVI) with the addition of an adequate amount of a transition metal catalyst, in particular palladium catalysts such as
  • the radical "M” stands, for example, for Mg-Hal, Zn-Hal, Sn ((C1-C4) alkyl) 3, lithium, copper or B (OR b ) (OR c ), the radicals R b and R c being independent from one another, for example, hydrogen, (C1-C4) -alkyl, or, if the radicals R b and R c are bonded to one another, together denote ethylene or propylene.
  • Another aspect of the invention relates to compounds of the general formula (II) and their salts
  • an additional aspect of the invention relates to a process for the preparation of the compounds of the general formula (II) and / or their agrochemically acceptable salts,
  • radicals R 3 , R 4 and A are each defined according to one of the above-mentioned embodiments.
  • R4 is defined according to one of the above-mentioned embodiments, - in a solvent
  • Another aspect relates to the use of a compound of the general formula (II) and one of its salts as an intermediate for the production of fine chemicals and
  • the present invention therefore also relates to a method for controlling undesired plants or for regulating the growth of plants, preferably in plant crops, in which one or more compound (s) according to the invention are applied to the plants (e.g.
  • Harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seeds (e.g. grains, seeds or vegetative reproductive organs such as tubers or sprouts with buds) or the area on which the plants grow (e.g. the cultivated area).
  • the compounds according to the invention can be applied, for example, by the pre-sowing method (optionally also by incorporation into the soil), pre-emergence or post-emergence method.
  • Monocotyledonous harmful plants of the genera Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Fagrostis, Festylochata , Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
  • the compounds according to the invention are applied to the surface of the earth before germination, either the emergence of the weed seedlings is completely prevented or the weeds grow to the cotyledon stage, but then stop growing.
  • the active ingredients are applied to the green parts of the plant using the post-emergence method, growth arrests after the treatment and the harmful plants remain in the growth stage present at the time of application or die completely after a certain time, so that in this way competition from weeds that is harmful to the crop plants is very early and is permanently eliminated.
  • the compounds according to the invention can have selectivities in useful crops and can also be used as non-selective herbicides.
  • the active compounds can also be used for combating harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are usually characterized by particularly advantageous properties, for example by resistance to certain active ingredients used in the agricultural industry, especially certain herbicides, resistances to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or
  • Viruses Other special properties concern e.g. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with an increased starch content or a changed quality of the starch or those with a different fatty acid composition of the harvested material are known.
  • Other special properties are tolerance or resistance to abiotic stressors e.g. Heat, cold, drought, salt and ultraviolet radiation.
  • Preference is given to using the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants.
  • the compounds of the formula (I) can be used as herbicides in useful plant crops which are resistant to the phytotoxic effects of the herbicides or made genetically resistant.
  • Conventional ways of producing new plants that have modified properties compared to previously occurring plants consist, for example, in classic breeding processes and the creation of mutants.
  • new plants with modified properties can be produced with the help of genetic engineering (see e.g.
  • EP 0221044 EP 0131624
  • genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants e.g. WO 92/011376 A, WO 92/014827 A, WO 91/019806 A
  • transgenic crop plants which are resistant to certain herbicides of the glufosinate type See, for example, EP 0242236 A, EP 0242246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0257993 A, US 5,013,659) or are resistant to combinations or mixtures of these herbicides by “gene stacking”, such as transgenic crops e.g. . B.
  • Optimum TM GAT TM Glyphosate ALS Tolerant.
  • Bt toxins Bacillus thuringiensis toxins
  • transgenic crop plants which are characterized by a combination e.g. the above distinguishing new properties (“gene stacking”)
  • gene stacking Numerous molecular biological techniques with which new transgenic plants with modified properties can be produced are known in principle; see e.g. I. Potrykus and G.
  • nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombining DNA sequences. With the help of standard procedures, e.g. Base exchanges carried out, partial sequences removed or natural or synthetic sequences added.
  • adapters or linkers can be attached to the fragments, see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2.
  • DNA molecules can be used that include the entire coding sequence of a gene product including any flanking sequences that may be present, as well as DNA molecules that only include parts of the coding sequence, these parts having to be long enough to be in the cells to bring about an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
  • the synthesized protein can be localized in any desired compartment of the plant cell.
  • the coding region can be linked to DNA sequences that ensure localization in a specific compartment.
  • nucleic acid molecules can also take place in the organelles of the plant cells.
  • transgenic plant cells can be regenerated into whole plants using known techniques.
  • the transgenic plants can be plants of any plant species, i.e. both monocotyledonous and dicotyledonous plants.
  • the compounds (I) according to the invention can preferably be used in transgenic crops which are resistant to growth substances such as e.g. 2,4-D, dicamba or against herbicides, the essential plant enzymes, e.g. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydoxyphenylpyruvate dioxygenases (HPPD) inhibit or are resistant to herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogous active ingredients, or any combination of these active ingredients.
  • the essential plant enzymes e.g. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydoxyphenylpyruvate dioxygenases (HPPD) inhibit or are resistant to herbicides from the group of sulfonylureas, glyphosates, glufos
  • 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. B. corn or soy with the
  • OptimumTM GATTM Glyphosate ALS Tolerant
  • active ingredients according to the invention are used in transgenic crops, in addition to the effects on harmful plants observed in other crops, effects that are specific to the application in the respective transgenic crop, for example a modified or specially expanded weed spectrum that can be controlled, often occur
  • Application rates which can be used for the application preferably good compatibility with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crop plants.
  • the invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds according to the invention can be in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary
  • 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 chemico-physical parameters are given. 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), dusts (DP), dressings, granules for litter and soil application, granules (GR) in the form of micro, spray, lift - and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules
  • combination partners for the compounds according to the invention in mixture formulations or in the tank mix for example, known active ingredients which act 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 or protoporphyrinogen oxidase, can be used, for example from Weed Research 26 (1986) 441-445 or "The Pesticide Manual",
  • herbicidal mixing partners are:
  • karbutilate KUH-043, ie 3 - ( ⁇ [5- (difluoromethyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl] methyl ⁇ sulfonyl) -5,5-dimethyl-4,5 -dihydro-1,2-oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl and - mecoprop, mecoprop-sodium, and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, me
  • plant growth regulators as possible mixing partners are:
  • Safeners which are used in combination with the compounds of the formula (I) according to the invention and optionally in combinations with other active ingredients such as e.g. Insecticides, acaricides, herbicides, fungicides as listed above can be used, are preferably selected from the group consisting of:
  • nA is a natural number from 0 to 5, preferably 0 to 3;
  • 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 unsaturated or aromatic five-membered ring heterocycles with 1 to 3 hetero ring atoms from the group N and O, with at least one N atom and at most one O atom in the ring, preferably a residue from the group (W 1
  • n A is 0 or 1;
  • A is OR 3
  • A is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 carbon atoms;
  • A is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl;
  • A is H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) haloalkyl, (C 1 -C 4 ) alkoxy (C 1 -C 8 ) alkyl, cyano, or COOR 9
  • A is hydrogen, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) haloalkyl, (C 1 -C 4 ) alkoxy- (C 1 -C 4 ) alkyl, (C 1 -C 6 ) hydroxyalkyl, (C3 -C12) is cycloalkyl or tri- (C1-C4) -alkyl-silyl;
  • A are identically or differently hydrogen, (C1-C8) alkyl, (C1-C8) haloalkyl, (C3-C12) cycloalkyl or substituted or unsubstituted phenyl;
  • dichlorophenylpyrazole carboxylic acid S1 b
  • compounds such as 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (S1-2), 1- (2,4-dichlorophenyl) -5- isopropyl-pyrazole-3-carboxylic acid ethyl ester (S1-3), 1- (2,4-dichlorophenyl) -5- (1,1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds, as described in EP-A-333131 and EP-A-269806;
  • S1 c Derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1 c ), preferably compounds such as 1- (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (S1-5), 1- (2-chlorophenyl ) -5-phenylpyrazole-3-carboxylic acid methyl ester (S1-6) and related compounds
  • 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;
  • B is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 carbon atoms;
  • B is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl;
  • TB is a (C1 or C2) -alkanediyl chain which is unsubstituted or substituted by one or two (C1-C4) alkyl radicals or by [(C1-C3) -alkoxy] -carbonyl;
  • C is (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl, (C 3 -C 7 ) cycloalkyl, preferably dichloromethyl;
  • C are identically or differently hydrogen, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C1-C4) haloalkyl, (C2-C4) haloalkenyl, (C1 -C4) alkylcarbamoyl- (C1-C4) alkyl, (C2-C4) alkenylcarbamoyl- (C1-C4) alkyl, (C1-C4) alkoxy- (C1-C4) alkyl, dioxolanyl- (C1-C4) alkyl, thiazolyl , Furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R 2
  • C together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring;
  • a D is SO 2 -NR 3
  • X D is CH or N
  • D is halogen, (C1-C4) haloalkyl, (C1-C4) haloalkoxy, nitro, (C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylsulfonyl, (C1-C4) alkoxycarbonyl or (C1 -C4) alkylcarbonyl;
  • D is hydrogen, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl or (C 2 -C 4 ) alkynyl;
  • D is halogen, nitro, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy, (C 3 -C 6 ) cycloalkyl, phenyl, (C 1 -C 4 ) Alkoxy, cyano, (C 1 -C 4 ) alkylthio, (C 1 -C 4 ) alkylsulfinyl, (C 1 -C 4 ) alkylsulfonyl, (C 1 -C4) alkoxycarbonyl or (C1-C4) alkylcarbonyl;
  • D is hydrogen, (C 1 -C 6 ) alkyl, (C3-C6) cycloalkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, (C5-
  • C 6 Cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing v D heteroatoms from the group nitrogen, oxygen and sulfur, the last seven radicals being replaced by v D substituents from the group halogen, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) haloalkoxy, (C 1 -C 2 ) alkylsulfinyl, (C1-C2) alkylsulfonyl, (C3-C6) cycloalkyl, (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonyl and phenyl and in the case cyclic radicals are also substituted (C1-C4) alkyl and (C1-C4) haloalkyl;
  • D is hydrogen, (C 1 -C 6 ) alkyl, (C2-C6) alkenyl or (C2-C6) alkynyl, the last three radicals mentioned by v D radicals from the group halogen, hydroxy, (C 1 -C 4 ) Alkyl, (C 1 -C 4 ) alkoxy and (C 1 -C 4 ) alkylthio are substituted, or
  • D is hydrogen, (C1-C4) alkylamino, di- (C1-C4) alkylamino, (C 1 -C 6 ) alkyl, (C3-C6) cycloalkyl, where the last two radicals are replaced by vD 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 are substituted ;
  • n D 0, 1 or 2;
  • mD 1 or 2;
  • vD 0, 1, 2, or 3;
  • v D 0, 1, 2 or 3;
  • D is independently hydrogen, (C 1 -C 8) alkyl, (C 3 -C 8) cycloalkyl, (C 3 - C 6) alkenyl, (C 3 -C 6) alkynyl,
  • mD 1 or 2;
  • Ethyl 3,4,5-triacetoxybenzoate 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A 2004/084631, WO-A-2005/015994, WO-A-2005/016001.
  • E are independently halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C1-C4) haloalkyl, (C1-C4) alkylamino, di- (C1-C4) alkylamino, nitro;
  • E, RE are independently hydrogen, (C1-C4) alkyl, (C2-C6) alkenyl, (C 2 -C 4 ) alkynyl, cyanoalkyl, (C 1 -C 4 ) haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, Pyridinylalkyl and alkylammonium,
  • E is 0 or 1
  • E are independently 0, 1 or 2
  • nF N, an integer from 0 to 4.
  • F is hydrogen, (C1-C8) alkyl, (C2-C4) alkenyl, (C2-C4) alkynyl, or aryl, where each of the aforementioned C-containing radicals is unsubstituted or by one or more, preferably up to three, identical or different radicals is substituted from the group consisting of halogen and alkoxy; mean, or their salts,
  • nF is an integer from 0 to 2
  • F is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, or aryl, each of the aforementioned C-containing radicals being unsubstituted or by one or more, preferably up to to three identical or different radicals from the group consisting of halogen and alkoxy is substituted, or their salts.
  • nG is an integer from 0 to 4,
  • G is hydrogen or (C 1 -C 6 ) alkyl.
  • S11 Active ingredients of the type of oxyimino compounds (S11), which are known as seed dressings, such as. B.
  • Oxabetrinil ((Z) -1,3-Dioxolan-2-ylmethoxyimino (phenyl) acetonitril) (S11-1), which is known as a seed dressing safener for millet against damage from metolachlor,
  • Fluorofenim (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) oxime) (S11-2), which is used as a seed dressing Safener for millet is known against damage from metolachlor, and
  • Cyometrinil or “CGA-43089” ((Z) -Cyanomethoxyimino (phenyl) acetonitrile) (S11-3), which is known as a seed dressing safener for millet against damage from metolachlor.
  • S12 Active ingredients from the class of isothiochromanones (S12), such as e.g. Methyl - [(3-oxo-1H-2- benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS reg. No. 205121-04-6) (S12-1) and related compounds from WO-A- 1998/13361.
  • S12 isothiochromanones
  • Naphthalic anhydride (1,8-naphthalenedicarboxylic acid anhydride) (S13-1), which is known as a seed dressing safener for maize against damage from thiocarbamate herbicides,
  • MG 191 (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a safener for maize,
  • CSB (1-bromo-4- (chloromethylsulfonyl) benzene) from Kumiai, (CAS Reg. No. 54091-06-4), which is known as a safener against damage from some herbicides in rice.
  • H is a (C 1 -C 6 ) haloalkyl radical
  • H is hydrogen or halogen
  • H independently of one another hydrogen, (C 1 -C 16 ) alkyl, (C 2 -C 16 ) alkenyl or (C2-C16) alkynyl,
  • each of the last-mentioned 3 radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxy, cyano, (C1-C4) alkoxy, (C1-C4) haloalkoxy, (C1-C4) alkylthio, (C 1 -C 4 ) Alkylamino, di [(C 1 -C 4 ) alkyl] amino, [(C 1 -C 4 ) alkoxy] carbonyl, [(C 1 -C 4 ) haloalkoxy] carbonyl, (C 3 -C 6 ) cycloalkyl that is unsubstituted or substituted, phenyl that is unsubstituted or substituted, and heterocyclyl that is unsubstituted or substituted, is substituted,
  • each of the last-mentioned 4 radicals is unsubstituted or by one or more radicals from the group consisting of halogen, hydroxy, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy, (C1-C4) alkylthio, (C1-C4) alkylamino, di [(C1-C4) alkyl] -amino,
  • H is hydrogen or (C1-C4) -alkyl or
  • N atom H together with the directly bonded N atom forms a four- to eight-membered heterocyclic ring which, in addition to the N atom, can also contain further hetero ring atoms, preferably up to two further hetero ring atoms from the group N, O and S and which is unsubstituted or by one or a plurality of radicals from the group consisting of halogen, cyano, nitro, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy and (C1-C4) alkylthio is substituted.
  • Dicamba 3,6-dichloro-2-methoxybenzoic acid
  • 1- (ethoxycarbonyl) ethyl-3,6-dichloro-2-methoxybenzoate lactidichloro-ethyl
  • Particularly preferred safeners are Mefenpyr-diethyl, Cyprosulfamid, Isoxadifen-ethyl, Cloquintocet-Mexyl, Dichlormid and Metcamifen.
  • Wettable powders are preparations that are uniformly dispersible in water which, in addition to the active ingredient, in addition to a diluent or inert substance, ionic and / or non-ionic surfactants (wetting agents, dispersants), e.g. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols,
  • the herbicidally active ingredients are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of an ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons or mixtures of organic solvents.
  • alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers
  • fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene sorbitan fatty acid ester.
  • Dusts 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.
  • Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and, if necessary, addition of surfactants, such as are e.g. are already listed above for the other formulation types.
  • Emulsions e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as are e.g. are already listed above for the other formulation types.
  • EW Oil-in-water emulsions
  • Granules can be produced either by spraying the active ingredient onto adsorptive, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carrier materials such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers. Water-dispersible granules are generally produced by the customary processes such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • adhesives e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils
  • the agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds according to the invention.
  • the active ingredient concentration is e.g. about 10 to 90% by weight, the remainder to 100% by weight consists of conventional formulation components.
  • the active ingredient concentration can be about 1 to 90, preferably 5 to 80% by weight.
  • Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight 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 content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active ingredient formulations mentioned contain, if appropriate, the respective customary adhesives, wetting agents, dispersants, emulsifiers, penetration agents, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and the Viscosity influencing agents.
  • the formulations which are available in commercially available form are optionally diluted in the usual way, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Dust-like preparations, soil or
  • Scatter granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate of the compounds of the formula (I) and their salts varies. It can vary within wide limits, for example between 0.001 and 10.0 kg / ha or more 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 to both pre-emergence and post-emergence use.
  • Carrier means a natural or synthetic, organic or inorganic substance with which the active ingredients for better applicability, especially for application to plants or parts of plants or seeds, mixed or combined.
  • the carrier which can be solid or liquid, is generally inert and should be agriculturally useful.
  • Possible solid or liquid carriers are: e.g. Ammonium salts and natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as highly dispersed silica, aluminum oxide and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, in particular Butanol, organic solvents, mineral and vegetable oils and derivatives thereof.
  • natural rock flour such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth
  • synthetic rock flour such as highly dispersed silica, aluminum oxide and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, in particular Butanol, organic solvents, mineral and vegetable oils and derivatives thereof.
  • Solid carriers for granulates are: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
  • Liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
  • Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
  • organic solvents can also be used as auxiliary solvents.
  • the main liquid solvents that can be used are:
  • Aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylene or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • the agents according to the invention can additionally contain further components, such as e.g.
  • Suitable surface-active substances are emulsifiers and / or foam-generating agents, dispersants or wetting agents with ionic or non-ionic properties or mixtures of these surface-active substances. Examples of this are salts
  • a surface-active substance is necessary if one of the active substances and / or one of the inert carriers is not soluble in water and if 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, e.g. 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 commonly 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 percent 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 use forms prepared therefrom, such as aerosols, capsule suspensions, cold mist concentrates, hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seeds, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranulates, microgranulates, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids , Foams, pastes, pesticide-coated seeds, suspension concentrates, suspension-emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granulates, water-soluble granulates or tablets, water-soluble powders for seed treatment, wettable powders, active ingredient
  • formulations mentioned can be prepared in a manner known per se, for example by
  • the agents according to the invention not only include formulations which are already ready to use and can be applied to the plant or the seed with a suitable apparatus, but also commercial concentrates which have to be diluted with water before use.
  • the active compounds according to the invention can be used as such or in their (commercially available) formulations and in the use forms prepared from these formulations as a mixture with other (known) active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides , Fertilizers, safeners or semiochemicals are present.
  • active compounds such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides , Fertilizers, safeners or semiochemicals are present.
  • the treatment according to the invention of the plants and parts of plants with the active ingredients or agents is carried out directly or by acting on their environment, habitat or storage room by the usual treatment methods, e.g. by dipping, spraying, spraying, sprinkling, vaporizing, atomizing, atomizing, scattering, foaming, brushing, spreading, watering (drenching), drip irrigation and for propagation material, especially seeds by dry pickling, wet pickling, slurry pickling, encrusting, single or multilayer coating, etc. It is also possible to apply the active ingredients using the ultra-low volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • transgenic seeds with the active ingredients or agents according to the invention are of particular importance.
  • This relates to the seeds of plants which contain at least one heterologous gene that enables the expression of a polypeptide or protein with insecticidal properties.
  • the heterologous gene in transgenic seeds can e.g. originate from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • This heterologous gene is preferably derived from Bacillus sp., The gene product having an effect against the European corn borer and / or Western corn rootworm.
  • the heterologous gene is particularly preferably derived 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 seed can be treated at any point in time between harvest and sowing.
  • seeds can be used that have been harvested, cleaned and dried to a moisture content of less than 15% by weight.
  • seeds can also be used which, after drying, e.g. treated 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 further 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 ingredients that can show phytotoxic effects when applied in certain amounts.
  • the agents according to the invention can be applied immediately, that is to say without containing further components and without having been diluted.
  • suitable formulations and methods for seed treatment are known to those skilled in the art and are e.g. described 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 compounds according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, and also ULV formulations.
  • formulations are prepared in a known manner by mixing the active ingredients with customary additives, such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
  • customary additives such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
  • Suitable dyes which can be contained in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both pigments which are sparingly soluble in water and dyes which are soluble in water can be used here. Examples are those under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes.
  • Suitable wetting agents which can be contained in the seed dressing formulations which can be used according to the invention are all substances which are customary for the formulation of agrochemical active ingredients and which promote wetting.
  • Alkylnaphthalene sulfonates such as diisopropyl or diisobutyl naphthalene sulfonates, can preferably be used.
  • Suitable dispersants and / or emulsifiers which can be contained in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active ingredients.
  • Nonionic or anionic dispersants or mixtures of can preferably be used
  • nonionic or anionic dispersants are, in particular, ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are, in particular, lignin sulfonates, polyacrylic acid salts and aryl sulfonate-formaldehyde condensates.
  • the seed dressing formulations which can be used according to the invention can contain all foam-inhibiting substances customary for the formulation of agrochemical active ingredients as defoamers.
  • Silicone defoamers and magnesium stearate can preferably be used.
  • All substances which can be used for such purposes in agrochemical agents can be present as preservatives in the seed dressing formulations which can be used according to the invention.
  • Examples include dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which can be contained in the seed dressing formulations which can be used according to the invention are all substances which can be used in agrochemical compositions for such purposes. Cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly disperse silicic acid are preferred.
  • Suitable adhesives which can be contained in the seed dressing formulations which can be used according to the invention are all conventional binders which can be used in seed dressings.
  • Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose may be mentioned as preferred.
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seeds of the most varied of types, including seeds of transgenic plants.
  • additional synergistic effects can also occur in cooperation with the substances formed by expression.
  • the process of dressing is to put the seed in a mixer, add the desired amount of dressing formulations either as such or after prior dilution with water and mix until the formulation is evenly distributed on the seed . If necessary, this is followed by a drying process.
  • the active compounds according to the invention are suitable for protecting plants and plant organs, for increasing crop yields and improving the quality of the harvested crop, given good plant tolerance, favorable warm-blooded toxicity and good environmental compatibility. They can preferably be used as crop protection agents. 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 are the following:
  • pome fruits such as apple and pear, 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. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g. lemons, organs and grapefruit);
  • Solanaceae sp. for example tomatoes, potatoes, pepper, eggplant
  • Liliaceae sp. Compositae sp.
  • Umbelliferae sp. e.g., carrot, parsley, celery and celeriac
  • Cucurbitaceae sp. for example, cucumber - including pickles, squash, watermelon, bottle gourd, and melons
  • Alliaceae sp. e.g. leek and onion
  • Leguminosae sp. e.g., peanuts, peas, and beans - such as runner beans and field beans
  • plants and their parts can be treated according to the invention.
  • plant species and plant cultivars occurring in the wild or obtained by conventional biological breeding methods such as crossing or protoplast fusion, as well as their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and their parts are treated.
  • the term “parts” or “parts of plants” or “plant parts” has been explained above.
  • Plant cultivars are understood to be plants with new properties (“traits”) that have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, races, bio and genotypes.
  • the treatment method according to the invention can be used for the treatment of genetically modified organisms (GMOs), e.g. B. plants or seeds can be used.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants in which a heterologous gene is stable in the genome
  • heterologous gene means essentially a gene which is provided or assembled outside the plant and which, when introduced into the nucleus genome, the chloroplast genome or the mitochondrial genome of the transformed plant, gives new or improved agronomic or other properties that it gives an interesting Expresses protein or polypeptide or that it downregulates or switches off another gene that is present in the plant or other genes that are present in the plant (for example by means of antisense technology, cosuppression technology or RNAi technology [RNA interference]).
  • a heterologous gene that is present in the genome is also called a transgene.
  • a transgene that is defined 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. So are the
  • Plants and plant cultivars 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 was achieved by breeding and / or biotechnology).
  • Examples of nematode-resistant plants are e.g. 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 which can be treated according to the invention are hybrid plants which already express the properties of the heterosis or the hybrid effect, which generally leads to a higher level
  • Such plants are typically created by mixing an inbred male sterile parent line (the female cross mate) with another
  • the hybrid seeds are typically harvested from the male-sterile plants and sold to propagators. Male-sterile plants can sometimes (e.g. in maize) by detasseling (i.e.
  • male sterility is based on genetic determinants in the
  • Plant genome In this case, especially if the desired product, since one wants to harvest from the hybrid plants, is the seeds, it is usually beneficial to ensure that the pollen fertility in hybrid plants that contain the genetic determinants responsible for male sterility , will be completely restored. This can be achieved by ensuring that the male mating partners have appropriate fertility restorer genes capable of restoring male fertility in hybrid plants that contain the genetic determinants responsible for male sterility.
  • CMS cytoplasmic male sterility
  • genetic determinants for male sterility can also be located in the nucleus genome.
  • Male-sterile plants can also be obtained using methods of plant biotechnology, such as genetic engineering.
  • a particularly favorable means for producing male-sterile plants is in WO
  • ribonuclease such as a barnase 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 cultivars which are obtained using methods of plant biotechnology, such as genetic engineering which can be treated according to the invention are herbicide-tolerant plants;
  • Plants that have been made tolerant to one or more specified herbicides can be obtained either by genetic transformation or by selection of plants which contain a mutation which confers such herbicide tolerance.
  • Herbicide tolerant plants are, for example, glyphosate tolerant plants; H. 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 which 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
  • Glyphosate-tolerant plants can also be obtained by expressing a gene which codes for a glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing a gene which codes for a glyphosate acetyltransferase enzyme. Glyphosate tolerant plants can also be obtained by selecting plants which contain naturally occurring mutations of the genes mentioned above. Plants expressing EPSPS genes that confer glyphosate tolerance are described. Plants that confer other genes that confer glyphosate tolerance, e.g. Decarboxylase genes are described.
  • herbicide-resistant plants are, for example, plants which have been made tolerant to herbicides which inhibit the enzyme glutamine synthase, such as bialaphos, phosphinotricin or glufosinate.
  • Such plants can be obtained by expressing an enzyme that detoxifies the herbicide or a mutant of the enzyme glutamine synthase that is resistant to inhibition.
  • an effective detoxifying enzyme is, for example, an enzyme which codes for a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinotricin acetyltransferase have been described.
  • herbicide-tolerant plants are also plants that are resistant to the herbicides that use the enzyme
  • HPPD hydroxyphenylpyruvate dioxygenase
  • HPPD inhibitors are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogenate.
  • Plants that are tolerant of HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding a mutated or chimeric HPPD enzyme, as 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 which code for certain enzymes that enable the formation of homogenate despite the inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are in WO
  • the tolerance of plants to HPPD inhibitors can also be improved by transforming plants, in addition to a gene that codes for an HPPD-tolerant enzyme, with a gene that codes for a prephenate dehydrogenase enzyme, as in WO 2004/024928 is described.
  • plants can be made even more tolerant of HPPD inhibitors by inserting a gene into their genome which codes for an enzyme that metabolizes or degrades HPPD inhibitors, such as B. CYP450 enzymes (see WO
  • herbicide-resistant plants are plants that are resistant to acetolactate synthase (ALS) -
  • ALS inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or sulfonylaminocarbonyltriazolinone herbicides. It is known that various mutations in the
  • Enzyme ALS also known as acetohydroxy acid synthase, AHAS
  • AHAS acetohydroxy acid 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 (cf., for example, US Pat. No. 5,084,082 for soybeans, WO 97/41218 for rice, US Pat. No. 5,773,702 for sugar beet and WO 99/057965, for lettuce US 5,198,599 or for sunflower WO
  • Plants or plant varieties which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are tolerant of abiotic stress factors. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such stress resistance. Particularly useful plants with stress tolerance include the following:
  • Plants which contain a transgene which is able to reduce the expression and / or activity of the gene for the poly (ADP-ribose) polymerase (PARP) in the plant cells or plants.
  • PARP poly (ADP-ribose) polymerase
  • Plants which contain a stress tolerance-promoting transgene which codes for an enzyme of the nicotinamide adenine dinucleotide salvage biosynthetic pathway that is functional in plants including nicotinamidase, nicotinate phosphoribosyl transferase, nicotinic acid mononucleotide adenine dinucleotide transferase, nicotinamide adenine adenine dinucleotide transferase, nicotinamide adenine dinucleotide.
  • Plants or plant varieties (which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, have a changed quantity, quality and / or shelf life of the harvested product and / or changed properties of certain components of the harvested product, such as:
  • Starch grain morphology is changed in comparison with the synthesized starch in wild-type plant cells or plants, so that this modified starch is better suited for certain applications.
  • Transgenic plants that synthesize non-starch carbohydrate polymers or non-starch carbohydrate polymers whose properties are changed compared to wild-type plants without genetic modification. Examples are plants that produce polyfructose, especially of the inulin and levan types, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans and plants that produce Produce alternan.
  • Transgenic plants or hybrid plants such as onions with certain properties such as “high soluble solids content”, low pungency (LP) and / or long storage life (“long storage”, LS ).
  • Plants or plant cultivars which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are plants such as cotton plants with modified fiber properties. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered fiber properties; these include:
  • Plants such as cotton plants which contain a modified form of rsw2- or rsw3-homologous nucleic acids, such as cotton plants with an increased expression of sucrose phosphate synthase;
  • Plants such as cotton plants with fibers with modified reactivity, e.g. B. by expression of the N-acetylglucosamine transferase gene, including nodC, and of chitin synthase genes.
  • Plants or plant cultivars which were obtained by methods of plant biotechnology, such as genetic engineering), which can likewise be treated according to the invention, are plants such as rapeseed or related Brassica plants with modified properties of the oil composition. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered oil properties; these include:
  • Plants such as rape plants that produce oil with a high oleic acid content
  • Plants such as rape plants, that produce oil with a low linolenic acid content.
  • Plants such as rape plants that produce oil with a low content of saturated fat.
  • Plants or plant varieties which can be obtained by methods of plant biotechnology, such as genetic engineering), 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 late blight (potato late blight) (e.g. RB gene), or which show a reduced sweetness induced by cold (which the genes Nt- Inh, carry 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 late blight (potato late blight) (e.g. RB gene), or which show a reduced sweetness induced by cold (which the genes Nt- Inh, carry II-INV) or which show the dwarf phenotype (
  • Plants or plant cultivars obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are plants such as oilseed rape or related Brassica plants with changed properties in the case of seed shattering. Such plants can, by genetic transformation or by selection of plants that contain a mutation, confer such altered properties and include plants such as oilseed rape with delayed or reduced seed loss.
  • transgenic plants that can be treated according to the invention are plants with transformation events or combinations of transformation events which are the subject of petitions issued or pending in the USA at the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) are for the non-regulated status. Information on this is available at any time from APHIS (4700 River Road Riverdale, MD 20737, USA), e.g. via the website http://www.aphis.usda.gov/brs/not_reg.html. At the
  • Transgenic phenotype the trait given to the plant by the transformation event.
  • ⁇ Transformation Event or Line the name of the event or events (sometimes referred to as the Line (s)) for which non-regulated status is requested.
  • APHIS documents various documents that are published by APHIS regarding the petition or can be obtained from APHIS on request.
  • transgenic plants which can be treated according to the invention are plants with one or more genes which code for one or more toxins, are the transgenic plants which are sold under the following trade names: YIELD GARD ⁇ (for example maize, cotton, Soybeans), KnockOut ⁇ (e.g. corn), BiteGard ⁇ (e.g. corn), BT-Xtra ⁇
  • Herbicide-tolerant plants to be mentioned are, for example, maize varieties, cotton varieties and soybean varieties sold under the following trade names: Roundup Ready ⁇
  • a reaction mixture consisting of 0.17g (0.42mmol) methyl - ⁇ [4-bromo-1- (2-fluorophenyl) -5- (pyrimidin-5-yl) -1H-pyrazol-3-yl] oxy ⁇ acetate, 14mg (0.58mmol) lithium hydroxide in 3.8ml H2O and 1.7ml THF is stirred for 5 hours at 65 ° C.
  • the THF is then removed on a rotary evaporator and the aqueous phase is adjusted to pH 2 with 2N HCl solution.
  • the resulting solid is filtered off with suction and dried. In this way, 0.113 g (65%) of product is obtained as a solid.
  • a reaction mixture consisting of 0.6g (1.52mmol) 3- (benzyloxy) -1- (2-fluorophenyl) -5-iodo-1H-pyrazole, 0.21g (1.52mmol) 2-fluoropyridine-5-boronic acid, 53mg (0.076mmol) bis (triphenylphosphine) palladium (II) chloride and 1ml H 2 O in 10ml dioxane is stirred under reflux for 6 hours and then left to stand overnight. The reaction mixture is poured into H2O and extracted several times with CH 2 Cl 2 . The organic phase is dried over Na 2 SO 4 and concentrated. Purification by column chromatography on silica gel with heptane / ethyl acetate (1: 1) yields 0.43 g (77%) of product.
  • the 1H-NMR data of selected examples are noted in the form of 1H-NMR peak lists. For each signal peak the Value in ppm and then the signal intensity in round brackets. The Value - signal intensity - number pairs from different signal peaks are listed separated by semicolons.
  • the peak list of an example therefore has the form:
  • the intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the real relationships between the signal intensities. For broad signals, multiple peaks or the center of the signal and their relative intensity compared to the most intense signal in the spectrum can be shown.
  • connection signals in the delta range of solvents and / or water our lists of 1H-NMR peaks show the usual solvent peaks, for example peaks from DMSO in DMSO-D6 and the peak from water, which are usually averaged have a high intensity.
  • the peaks of stereoisomers of the target compounds and / or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for
  • Such stereoisomers and / or impurities can be typical of the particular manufacturing process. Your peaks can thus help to identify the reproduction of our manufacturing process using “by-product fingerprints”.
  • An expert who calculates the peaks of the target compounds with known methods can isolate the peaks of the target compounds as required, with additional intensity filters if necessary

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  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

L'invention concerne des composés représentés par la formule générale (I) et leurs sels compatibles sur le plan agrochimique (I), ainsi que leur préparation et leur utilisation dans le domaine de la protection phytosanitaire.
EP20727906.8A 2019-06-03 2020-05-29 Acides 1-phényl-5-azinylpyrazolyl-3-oxyalkyliques et leur utilisation pour lutter contre la croissance de plantes adventices Pending EP3975720A1 (fr)

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CN117615652A (zh) 2021-06-25 2024-02-27 拜耳公司 (1,4,5-三取代-1h-吡唑-3-基)氧基-2-烷氧基烷基酸及其衍生物、其盐及其作为除草剂的用途
WO2023099381A1 (fr) 2021-12-01 2023-06-08 Bayer Aktiengesellschaft Acides (1,4,5-trisubstitués-1h-pyrazole-3-yl)oxy-2-alcoxy alkyle et leurs dérivés, leurs sels et leur utilisation comme agents actifs herbicides
WO2024078871A1 (fr) 2022-10-14 2024-04-18 Bayer Aktiengesellschaft Acides 1-pyridyl-5-phenylpyrazolyl-3-oxy- et -3-thioalkyl et leurs dérivés et leur utilisation pour lutter contre la croissance de plantes indésirables

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