EP1194407A2 - N-cycloalkyl-3-alkenylbenzoyl-pyrazole derivatives - Google Patents

N-cycloalkyl-3-alkenylbenzoyl-pyrazole derivatives

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Publication number
EP1194407A2
EP1194407A2 EP00945814A EP00945814A EP1194407A2 EP 1194407 A2 EP1194407 A2 EP 1194407A2 EP 00945814 A EP00945814 A EP 00945814A EP 00945814 A EP00945814 A EP 00945814A EP 1194407 A2 EP1194407 A2 EP 1194407A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
hydrogen
haloalkyl
yloxy
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.)
Withdrawn
Application number
EP00945814A
Other languages
German (de)
French (fr)
Inventor
Ulf Neidlein
Norbert Götz
Ernst Baumann
Wolfgang Von Deyn
Steffen Kudis
Roland Götz
Klaus Langemann
Guido Mayer
Ulf Misslitz
Matthias Witschel
Martina Otten
Karl-Otto Westphalen
Helmut Walter
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1194407A2 publication Critical patent/EP1194407A2/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5

Definitions

  • the present invention relates to cycloalkyl-substituted benzoylpyrazoles of the formula I.
  • R2 is hydrogen, C ⁇ -0 6 -alkyl, C ⁇ -C 6 -alkoxy, C ⁇ -C 6 -alkyl thio, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, halogen, nitro, -S (0 ) n R 8 , -S0 2 OR 9 , -S0 2 NR 9 R 10 , -NR 10 SO 2 R 1: L , -NR ⁇ COR 11 , -PO (OR 12 ) (OR 13 ),;
  • R 3 is hydrogen, halogen, C; ⁇ .-C 6 alkyl, Ci-C ⁇ -halo- alkyl, Ci-COE-alkoxy, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl;
  • R 4 , R 5 hydrogen, nitro, halogen, cyano, rhodano,
  • C ⁇ -C6 alkyl, Ci-C ⁇ -haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 4 -C 6 cycloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 6 - Alkylthio, -C-C 6 -haloalkoxy, -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 12 R 13 , -C (R 14 ) NR 15 ,
  • -P0 (0R 12 ) (OR 13 ), -C -C alkyl, which carries a radical from the following group: -COR 12 , -CO 2 R 12 , -COSR 12 , -C0NR 12 R 13 or -C (R 14 ) NR 15 ; Heterocyclyl, heterocyclic -CC 4 -alkyl, phenyl, phenyl -CC 4 -alkyl, hetaryl or hetaryl -CC 4 -alkyl, where the latter six radicals may be substituted; or
  • R 4 and R 5 form a screened lonely C 2 -C 6 -alkanediyl chain which is mono- to tetrasubstituted by C ⁇ -C4 ⁇ alkyl may be substituted and / or by oxygen or sulfur or an optionally C ⁇ -C 4 alkyl substituted nitrogen interrupted can be;
  • R 6 is hydrogen, halogen, Ci-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, C 3 -C 8 cycloalkyl;
  • R 7 cyclic ring system with 3 - 14 ring atoms, which is optionally substituted by Ci-C ⁇ -alkyl, Ci-C ⁇ - alkoxy, Ci-C ⁇ -haloalkyl, Ci-C ⁇ -haloalkoxy, halogen; or Ci-C ⁇ -alkyl which is substituted by a cyclic ring system;
  • n 0, 1 or 2;
  • R 8 C ⁇ -C 6 -alkyl, C 6 haloalkyl, C! -C 6 alkoxy- C 2 -C 6 al yl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
  • R 9 is hydrogen, Ci-C ⁇ -alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -C 6 -alkoxy-C 2 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
  • R 10 is hydrogen or -CC 6 alkyl
  • R 12 is hydrogen, Ci-C ⁇ -alkyl, C 3 -C 6 cycloalkyl,
  • Ci-C ⁇ -haloalkyl C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, penyl or benzyl, where the latter two radicals can be partially or completely halogenated and / or carry one to three radicals from the following group can:
  • R 13 is hydrogen, Ci-C ⁇ -alkyl, C 3 -C 6 -Al enyl or C 3 -C 6 ⁇ alkynyl; or
  • R 12 and R 13 together form a C 2 -C 6 -alkanediyl chain which is mono- to tetrasubstituted by C ⁇ -C4 alkyl may be substituted and / or interrupted by oxygen or sulfur or an optionally C ⁇ -C4 ⁇ alkyl substituted nitrogen can be;
  • R 14 is hydrogen, Ci-C ⁇ - alkyl, Ci-C ⁇ -haloalkyl,
  • R 15 C ⁇ -C 6 -alkyl, C 6 haloalkyl, C 3 -C 6 cycloalkyl,
  • the invention also relates to processes for the preparation of compounds of the formula I, compositions which contain them, and to the use of the compounds of the formula I and compositions containing them for controlling harmful plants.
  • Herbicidal active ingredients from the class of benzoylpyrazoles are known from EP-A 282 944; WO 98/42677; WO 98/45273; WO98 / 50366; WO 98/52926; WO 98/56766; US 5,807,806.
  • compositions which comprise the compounds I.
  • processes for the preparation of these compositions and processes for controlling or reducing undesired plant growth with the compounds I were found.
  • the present invention also relates to stereoisomers of the compounds of the formula I. Both pure stereoisomers and mixtures thereof are covered.
  • the compounds of the formula I contain a carbon-carbon double bond and are therefore present as E isomers or Z isomers or as E / Z isomer mixtures.
  • the compounds of the formula I can furthermore contain further carbon or carbon-nitrogen double bonds.
  • the invention relates to both the pure geometric isomers and mixtures thereof.
  • the compounds of the formula I can also contain one or more centers of chirality and are then present as enantiomers or mixtures of diastereomers.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • the compounds of the formula I can also be present in the form of their tautomers or as a mixture of tamers.
  • the tautomeric forms result in particular from the hydroxy substituent on Pyrazole.
  • the compounds can be referred to both as 5-hydroxypyrazoles or as 5-oxopyrazolines.
  • the compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important.
  • the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I are suitable.
  • the cations used are in particular ions of the alkali metals, preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where one to four hydrogen atoms by C ⁇ - C 4 alkyl or hydroxy -CC 4 alkyl and / or a phenyl or benzyl can be replaced, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri (C ⁇ -C 4 alkyl) - sulfonium and sulfoxonium ions, preferably tri (-C 4 alkyl) sulfoxonium, into consideration.
  • the alkali metals preferably lithium, sodium and potassium
  • the alkaline earth metals preferably calcium and magnesium
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 -alkane acids, preferably formate, acetate Propionate and butyrate.
  • the organic molecule parts mentioned for the substituents R i -R 16 represent collective terms for individual lists of the individual group members. All hydrocarbon chains, that is to say all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, cycloalkoxy, Alkyl hio, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenyl, cycloalkenyl, alkynyl, alkenyloxy, alkynyloxy parts can be straight-chain or branched. Unless otherwise stated, halogenated substituents preferably have one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
  • C 2 -C 4 alkyl ethyl, n-propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl;
  • C 2 -C 6 alkyl and the alkyl parts of, for example, -C 6 alkoxy-C 2 -C 6 alkyl: C 2 -C 4 alkyl, as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-tri- methylpropyl, 1-ethyl-l-methylpropyl or l-ethyl-3-methyl
  • Ci-Ce-alkyl as well as the alkyl parts of, for example, Ci-C ⁇ -alkoxy-Ci-Ce alkyl and -CC 6 alkylcarbonyl: C 2 -C 6 alkyl, as mentioned above, and methyl;
  • C ⁇ ⁇ C 4 -haloalkyl a C ⁇ -C 4 -alkyl radical as mentioned above which, chlorine, bromine / or iodine partially or fully substituted by fluorine, and is substituted, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoroprop
  • -C ⁇ C 4 alkoxy and the alkoxy parts of -C -C 4 alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy; Ci-C ⁇ -alkoxy, and the alkoxy parts of -C-C6-alkoxy-C ⁇ -C6 _ alkyl, C ⁇ -C 6 -alkoxy-C 2 -C 6 -alkyl and C ⁇ -C 6 ⁇ alkoxycarbonyl: C 1 -C 4 - Alkoxy as mentioned above, and pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1- Methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1,
  • C ⁇ -C 4 -haloalkoxy a C ⁇ -C 4 alkoxy radical as mentioned above which is partially or fully substituted by fluorine, iodine, chlorine, bromine and / or substituted, eg fluoromethoxy,
  • Ci-C ⁇ -haloalkoxy C ⁇ -C 4 -haloalkoxy, as mentioned above, as well as, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromogenoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6- Bromhexoxy, 6-iodohexoxy or dodecafluorhexoxy;
  • Ci-C ⁇ - alkylthio e.g. methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3- Methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio
  • Ci-C ⁇ -haloalkylsulfonyl a -CC 6 alkylsulfonyl, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifonyl 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, 2,2, 2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl
  • C 3 -C 6 alkenyl prop-1-en-l-yl, prop-2-en-l-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3- yl, 1-methyl-prop-1-en-l-yl, 2-methyl-prop-l-en-l-yl, l-methyl-prop-2-en- 1-yl, 2-methyl-prop-2-en-l-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methyl-but-l- en-l-yl, 2-methyl-but-1-en-l-yl, 3-methyl-but-l-en-l-yl, 1-methyl-but-2-en-l-yl, 2- Methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl, 2-methyl-but-3-en- l-yl
  • C 3 -C 6 alkenyloxy e.g. B. Prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, buten-1-yloxy, buten-2-yloxy, buten-3-yl-oxy, 1-methyl-prop- l-en-l-yloxy, 2-methyl-prop-l-en-l-yloxy, l-methyl-prop-2-en-l-yloxy, 2-methyl-prop-2-en-l-yloxy, Penten-1-yloxy, penten-2-yloxy, penten-3-yloxy, penten-4-yl - oxy, 1-methyl-but-l-en-l-yloxy, 2-methyl-but-l-en- l-yloxy,
  • C 3 -C 6 alkynyl prop-1-in-1-yl, prop-2-in-1-yl, but-1-in-1-yl, but-1-in-3-yl, but- l-in-4-yl, but-2-in-l-yl, pent-1-in-l-yl, pent-l-in-3-yl, pent-l-in-4-yl, pent l-in-5-yl, pent-2-in-l-yl, pent-2-in-4-yl, pent-2-in-5-yl, 3-methyl-but-l-in-3- yl, 3-methyl-but-l-in-4-yl, hex-1-in-l-yl, hex-l-in-3-yl, hex-l-in-4-yl, hex-l- in-5-yl, hex-1-in-6-yl, hex-2-in-1-yl, hex-2-in-4-yl, hex
  • C 2 -C 6 alkynyl C 3 -C 6 alkynyl, as mentioned above, and ethynyl:
  • Cs-C ⁇ -alkynyloxy for example prop-1-in-1-yloxy, prop-2-in-1-yloxy, but-1-in-1-yloxy, but-1-in-3-yloxy, but-1 -in-4-yloxy, but-2-in-1-yloxy, pent-1-in-1-yloxy, pent-1-in-3-yloxy, pent-1-in-4-yloxy, pent-1 -in-5-yloxy, pent-2-in-1-yloxy, pent-2-in-4-yloxy, pent-2-in-5-yloxy, 3-methyl-but-l-in-3-yloxy , 3-methyl-but-1-in-4-yloxy, hex-1-in-1-yloxy, hex-1-in-3-yloxy, hex-1-in-4-yloxy, hex-1-in -5-yloxy, hex-1-in-6-yloxy, hex-2-in-1-yloxy,
  • C 3 -C 6 cycloalkyl cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • C 3 -C 6 cycloalkoxy cyclopropoxy, cyclobutoxy, cyclopentoxy or cycloexoxy;
  • C 3 -C 6 cycloalkenyl cyclopropen-1-yl, cyclobuten-1-yl, cyclobutenen-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexene 3-yl or cyclohexen-4-yl;
  • Hetaryl, as well as the hetaryl residues in hetaryloxy and hetaryl -CC-C 4 ⁇ alkyl aromatic mono- or polycyclic residues which, in addition to carbon ring members, also contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one May contain sulfur atom, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5 -Isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1
  • C 2 -C 6 alkanediyl for example ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl or hexane-1, 6-diyl;
  • C 3 -C 8 cycloalkyl in particular C 3 -C6 cycloalkyl as mentioned above, furthermore
  • Carbocyclic bi- or tricyclic ring systems are for example adamantyl, norbornyl, camphyl or camphenyl.
  • the bi- or tricyclic ring systems can optionally be substituted by Ci-C ⁇ -alkyl, Ci-C ⁇ -alkoxy,
  • Ci-C ⁇ -haloalkyl, -CC 6 -haloalkoxy or halogen be substituted one or more times.
  • Ci-C ⁇ -alkyl which is substituted by a cyclic ring system with 3 - 14 ring atoms: a straight-chain or branched Ci-C ⁇ -alkyl group which is characterized by the aforementioned C 3 -C 6 cycloalkyl, C 3 -C 6 - Cycloalkenyl groups or carbocyclic or heterocyclic ring systems with up to 14 ring atoms is substituted. Examples include: cyclopropyl-methyl, 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl,
  • ring systems optionally may be prepared by C ⁇ -C ö -alkyl, C 6 alkoxy, C ⁇ -C6-halo-alkyl, C ⁇ -C -haloalkoxy or halogen or mono- 6 be substituted multiple times.
  • All phenyl, hetaryl and heterocyclyl rings are preferably unsubstituted or carry one to three halogen atoms and / or one or two radicals from the following group: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.
  • the variables preferably have the following meanings, in each case individually or in combination with one another: Ri is nitro, halogen, cyano, thiocyanato, Ci-C ⁇ -alkyl, C 6 haloalkyl, C ⁇ -C 6 -alkoxy-C ⁇ -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 -Alkynyl, -OR 6 or -S (0) n R 8 ; in particular nitro, fluorine, chlorine, bromine, methyl, ethyl, methoxy; preferably chlorine, methyl or methoxy.
  • R2 is hydrogen, nitro, halogen, cyano, thiocyanato, C ⁇ -C 6 -alkyl, C 6 haloalkyl, Ci-C ⁇ -alcohol xy-C ⁇ -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -OR 6 or particularly preferably hydrogen, nitro, halogen, such as fluorine, chlorine or bromine, Ci-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, -OR 6 or -S0R 8 ; in particular nitro, halo such as fluorine, chlorine or bromine, C ⁇ -C 6 -alkyl, C 6 haloalkyl, -OR 6, or S0 2 R 8; preferably -S0 2 -R 8 , where R 8 is Ci-C ⁇ -alkyl, especially methyl or ethyl.
  • the substituent R 2 is preferably in the 4- or 5-position of the phen
  • R 3 is hydrogen, halogen, Ci-C ⁇ -alkyl, -C-C 6 haloalkyl, Ci-C ⁇ -alkoxy, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl; particularly preferably hydrogen, halogen such as
  • R 4 is hydrogen, nitro, halogen, cyano, rhodano,
  • R6 is hydrogen, methyl; especially hydrogen.
  • R 7 cyclopropyl, cyclopentyl, cyclohexyl, adamantyl,
  • Ci-C ⁇ -alkyl especially methyl.
  • R 8 Ci-C ö alkyl, especially methyl, ethyl
  • R 9 is hydrogen, -CC 6 alkyl
  • R 12 is hydrogen, Ci-C ⁇ -alkyl
  • R 3 is hydrogen, C ⁇ -C 6 alkyl
  • R 14 is hydrogen, -CC 6 alkyl
  • Ri5 hydrogen, C ⁇ -C 6 alkyl, -CC 6 alkoxy.
  • R 16 hydroxy.
  • R 1 -R 15 each independently have the following meanings:
  • R 4 is hydrogen
  • R 5 is hydrogen
  • R 6 is hydrogen
  • R 7 cyclopropyl, cyclopentyl, adamantyl, norbornyl, camphyl or camphenyl, which are unsubstituted or mono- or disubstituted by methyl.
  • R 1 -C 6 alkyl; Halogen; C ⁇ -C 6 alkoxy.
  • R 2 Ci-C ß- alkylsulfonyl; where R 2 is preferably in the para position to the pyrazolylcarbonyl group on the phenyl ring.
  • R 5 hydrogen or -CC 6 alkyl
  • R 7 cyclopropyl, cyclopentyl.
  • R 16 hydroxy or phenylsulfonyloxy
  • Preferred embodiments are the following compounds of the formulas Ial-Ia6:
  • compounds Ia2 in particular the compounds Ia2.001-Ia2.018, which differ from the corresponding compounds Ial .001-Ial .018 in that R 5 in formula I is methoxy:
  • compounds Ia3 in particular the compounds Ia3.001-la3.018, which differ from the corresponding compounds Ial .001-Ial.018 in that R 5 in formula I is methyl:
  • compounds Ia6 in particular the compounds Ia6.001-Ia6.018, which differ from the corresponding compounds Ial .001-Ial.018 in that R 5 in formula I is i-propyl:
  • the compounds of the formula I are essentially prepared by the processes described in WO 98/50366.
  • R 7 with a carboxylic acid III or an activated derivative thereof
  • variables R 1 to R 5 have the meanings given in claim 1 and L 1 represents hydroxyl or a nucleophilically displaceable leaving group (for example halogen, anhydride), acylated and the acylation product rearranged to the compounds I, if appropriate in the presence of a catalyst.
  • L 1 represents hydroxyl or a nucleophilically displaceable leaving group (for example halogen, anhydride), acylated and the acylation product rearranged to the compounds I, if appropriate in the presence of a catalyst.
  • the compounds I can be in the form of their agriculturally useful salts, the type of salt generally not being important. Usually the salts of such bases will be considered which do not adversely affect the herbicidal activity of I.
  • Particularly suitable basic salts are those of the alkali metals, preferably the lithium, sodium and potassium salts, those of the alkaline earth metals, preferably calcium, magnesium and barium salts and those of the transition metals, preferably manganese, copper, zinc and iron salts, ammonium salts , and ammonium salts which can carry one to four C ⁇ -C 4 alkyl, hydroxy-C ⁇ -C 4 alkyl substituents, a phenyl or benzyl substituent, preferably diethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium -, And trimethyl (2-hydroxyethyl) ammonium salts, the phosphonium salts, the sulfonium salts, preferably tri- (C 4 -C 4 -alkyl) sulfonium salts, and the sulfoxonium salts, preferably tri- (
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. They can also be used as growth regulators for plants (harmful plants, crops and useful plants).
  • the herbicidal compositions containing the compounds I control vegetation on nonculture areas very good, especially with high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active substances are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active compounds grow more rapidly on the leaves below unwanted plants or the uncovered floor area (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules , Dusting, scattering or pouring.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, al
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the compounds I as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylp enol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, alkylphenol
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urine and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • I 20 parts by weight of a compound I are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 Moles of ethylene oxide to 1 mole of castor oil.
  • aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • V 3 parts by weight of an active ingredient of the formula I are mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3% by weight of the active ingredient.
  • VI 20 parts by weight of a compound I are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
  • 1, 2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2-aroyl come as mixing partners -l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzene , Dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, urine substances, 3-
  • the active compound application rates are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see also)
  • Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to 2 types.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote "germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm and then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • Evaluation is based on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are preferably composed of the following types:

Abstract

The invention relates to cycloalkyl-substituted benzoyl pyrazoles of formula (I) wherein said variables can, for example, have the following meanings: R<1> = hydrogen, nitro, halogen, cyano, rhodano or an optionally substituted aliphatic radical; R<2> = an optionally substituted aliphatic radical, halogen, nitro, in addition to substituted sulfonyl or amino groups; R<3> = hydrogen, halogen, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C2-C6-alkenyl or C2-C6-alkinyl; R<4>, R<5> = hydrogen, nitro, halogen, cyano, rhodano, an optionally substituted aliphatic radical or substituted sulfonyl or amino groups; R<6> = hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C3-C8-cycloalkyl; R<7> = a cyclic ring system with 3 - 14 ring atoms; R<16> = hydroxy or a substituted hydroxy group; in addition to tautomers or agriculturally useful salts thereof. The invention also relates to methods for the production of compounds of formula (I), agents containing said compounds, the use of compounds of formula (I) and agents containing said compounds as pesticides.

Description

N-Cycloalkyl-3-alkenylbenzoyl-Pyrazole-DerivateN-cycloalkyl-3-alkenylbenzoyl-pyrazoles derivatives
Beschreibungdescription
Die vorliegende Erfindung betrifft cycloalkylsubstituierte Benzoylpyrazole der Formel IThe present invention relates to cycloalkyl-substituted benzoylpyrazoles of the formula I.
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
Ri Wasserstoff, Nitro, Halogen, Cyano, Rhodano,Ri hydrogen, nitro, halogen, cyano, rhodano,
Cι-C6-Alkyl, Cx-Cö-Halogenalkyl, Ci-Cö-Alkoxy, Cj.-C6-Alkylthio, C1-C6-Alkoxy-C1-C6-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, -S(0)nR8, -S02OR9, -S02NR9R10, -NR10SO2R1:L, -NR^COR11, -PO (OR12) (OR13) ; Cι-C6 alkyl, Cx-C ö haloalkyl, Ci-COE-alkoxy, Cj.-C 6 alkylthio, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 2 -C 6 - Alkenyl, C 2 -C 6 alkynyl, -S (0) n R 8 , -S0 2 OR 9 , -S0 2 NR 9 R 10 , -NR 10 SO 2 R 1: L , -NR ^ COR 11 , - PO (OR 12 ) (OR 13 );
R2 Wasserstoff, Cχ-06-Alkyl, Cι-C6-Alkoxy, Cι-C6-Alkyl- thio, C2-C6-Alkenyl, C2-C6-Alkinyl, Halogen, Nitro, -S(0)nR8, -S02OR9, -S02NR9R10, -NR10SO2R1:L, -NR^COR11 , -PO(OR12) (OR13) , ;R2 is hydrogen, Cχ-0 6 -alkyl, Cι-C 6 -alkoxy, Cι-C 6 -alkyl thio, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, halogen, nitro, -S (0 ) n R 8 , -S0 2 OR 9 , -S0 2 NR 9 R 10 , -NR 10 SO 2 R 1: L , -NR ^ COR 11 , -PO (OR 12 ) (OR 13 ),;
R3 Wasserstoff, Halogen, C;ι.-C6-Alkyl, Ci-Cβ-Halogen- alkyl, Ci-Cö-Alkoxy, C2-C6-Alkenyl oder C2-C6-Alkinyl;R 3 is hydrogen, halogen, C; ι.-C 6 alkyl, Ci-Cβ-halo- alkyl, Ci-COE-alkoxy, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl;
R4, R5 Wasserstoff, Nitro, Halogen, Cyano, Rhodano,R 4 , R 5 hydrogen, nitro, halogen, cyano, rhodano,
Cι-C6-Alkyl, Ci-Cβ-Halogenalkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C4-C6-Cycloalkenyl, C2-C6-Alkinyl, Cι-C6-Alkylthio, Cι-C6-Halogenalkoxy, -COR12, -C02R12, -COSR12, -CONR12R13, -C (R14) =NR15, Cι-C6 alkyl, Ci-Cβ-haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 4 -C 6 cycloalkenyl, C 2 -C 6 alkynyl, Cι-C 6 - Alkylthio, -C-C 6 -haloalkoxy, -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 12 R 13 , -C (R 14 ) = NR 15 ,
-P0(0R12) (OR13) , Cι-C -Alkyl, das einen Rest aus folgender Gruppe trägt: -COR12, -CO2R12, -COSR12, -C0NR12R13 oder -C (R14) =NR15; Heterocyclyl, Hetero- cyclyl-Cι-C4-alkyl, Phenyl, Phenyl-Cι-C4-alkyl, Hetaryl oder Hetaryl-Cι-C4-alkyl, wobei die sechs letztgenannten Reste substituiert sein können; oder-P0 (0R 12 ) (OR 13 ), -C -C alkyl, which carries a radical from the following group: -COR 12 , -CO 2 R 12 , -COSR 12 , -C0NR 12 R 13 or -C (R 14 ) = NR 15 ; Heterocyclyl, heterocyclic -CC 4 -alkyl, phenyl, phenyl -CC 4 -alkyl, hetaryl or hetaryl -CC 4 -alkyl, where the latter six radicals may be substituted; or
R4 und R5 bilden geraeinsam eine C2-C6-Alkandiylkette, die ein- bis vierfach durch Cι-C4~Alkyl substituiert sein kann und/oder durch Sauerstoff oder Schwefel oder einen gegebenenfalls Cι-C4-Alkyl substituierten Stickstoff unterbrochen sein kann;R 4 and R 5 form a screened lonely C 2 -C 6 -alkanediyl chain which is mono- to tetrasubstituted by Cι-C4 ~ alkyl may be substituted and / or by oxygen or sulfur or an optionally Cι-C 4 alkyl substituted nitrogen interrupted can be;
R6 Wasserstoff, Halogen, Ci-Cβ-Alkyl, Ci-Cβ-Alkoxy, C3-C8-Cycloalkyl ;R 6 is hydrogen, halogen, Ci-Cβ-alkyl, Ci-Cβ-alkoxy, C 3 -C 8 cycloalkyl;
R7 cyclisches Ringsystem mit 3 - 14 Ringatomen, das gegebenenfalls substituiert ist durch Ci-Cβ-Alkyl, Ci-Cδ-Alkoxy, Ci-Cβ-Halogenalkyl, Ci-Cδ-Halogen- alkoxy, Halogen; oder Ci-Cβ-Alkyl, das durch ein cyclisches Ringsystem substituiert ist;R 7 cyclic ring system with 3 - 14 ring atoms, which is optionally substituted by Ci-Cβ-alkyl, Ci-C δ- alkoxy, Ci-Cβ-haloalkyl, Ci-C δ -haloalkoxy, halogen; or Ci-Cβ-alkyl which is substituted by a cyclic ring system;
n 0, 1 oder 2 ;n 0, 1 or 2;
R8 Cι-C6-Alkyl, Cι-C6-Halogenalkyl, C!-C6-Alkoxy- C2-C6-al yl, C3-C6-Alkenyl oder C3-C6-Alkinyl;R 8 Cι-C 6 -alkyl, C 6 haloalkyl, C! -C 6 alkoxy- C 2 -C 6 al yl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R9 Wasserstoff, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkoxy-C2-C6-alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl;R 9 is hydrogen, Ci-Cβ-alkyl, Cι-C 6 haloalkyl, Cι-C 6 -alkoxy-C 2 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R10 Wasserstoff oder Cι-C6-Alkyl;R 10 is hydrogen or -CC 6 alkyl;
R11 Cι-C6-Alkyl oder Cχ-C6-Halogenalkyl;R 11 -C 6 -alkyl or Cχ-C 6 haloalkyl;
R12 Wasserstoff, Ci-Cβ-Alkyl, C3-C6-Cycloalkyl,R 12 is hydrogen, Ci-Cβ-alkyl, C 3 -C 6 cycloalkyl,
Ci-Cβ-Halogenalkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, P enyl oder Benzyl, wobei die beiden letztgenannten Reste partiell oder vollständig halogeniert sein können und/oder einen bis drei Reste aus der folgenden Gruppe tragen können:Ci-Cβ-haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, penyl or benzyl, where the latter two radicals can be partially or completely halogenated and / or carry one to three radicals from the following group can:
Nitro, Cyano, Cι-C4-Alkyl, Ci-C^-Halogenalkyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C4-Alkyl- carbonyl oder Cι-C4-Alkoxycarbonyl;Nitro, cyano, C 4 alkyl, Ci-C ^ haloalkyl, Cι-C 4 -alkoxy, C 4 haloalkoxy, Cι-C 4 alkyl carbonyl or Cι-C 4 alkoxycarbonyl;
R13 Wasserstoff, Ci-Cβ-Alkyl, C3-C6-Al enyl oder C3-C6~Alkinyl; oderR 13 is hydrogen, Ci-Cβ-alkyl, C 3 -C 6 -Al enyl or C 3 -C 6 ~ alkynyl; or
R12 und R13 bilden gemeinsam eine C2-C6-Alkandiylkette, die ein- bis vierfach durch Cχ-C4-Alkyl substituiert sein kann und/oder durch Sauerstoff oder Schwefel oder einen gegebenenfalls Cι-C4~Alkyl substituierten Stickstoff unterbrochen sein kann;R 12 and R 13 together form a C 2 -C 6 -alkanediyl chain which is mono- to tetrasubstituted by Cχ-C4 alkyl may be substituted and / or interrupted by oxygen or sulfur or an optionally Cι-C4 ~ alkyl substituted nitrogen can be;
R14 Wasserstoff, Ci-Cδ-Alkyl, Ci-Cβ-Halogenalkyl,R 14 is hydrogen, Ci-C δ- alkyl, Ci-Cβ-haloalkyl,
Ci-Ce-Alkoxy, Ci-Cg-Alkoxycarbonyl, C3-C6-Cyclo- alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Phenyl oder Benzyl, wobei die beiden letz genannten Reste partiell oder vollständig halogeniert sein können und/oder einen bis drei Reste aus der folgenden Gruppe tragen können: Nitro, Cyano, Cι-C4-Alkyl, Cι-C-Halogenalkyl, Cχ-C4-Alkoxy, Cι-C4-Halogen- alkoxy, Cι-C4-Alkylcarbonyl oder Cχ-C4-Alkoxy- carbonyl ;Ci-Ce-alkoxy, Ci-Cg-alkoxycarbonyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl or benzyl, the latter two radicals being partial or can be completely halogenated and / or can carry one to three radicals from the following group: nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, Cχ-C 4 alkoxy, C 1 -C 4 haloalkoxy , -C-C 4 alkylcarbonyl or Cχ-C 4 alkoxy carbonyl;
R15 Cι-C6-Alkyl, Cι-C6-Halogenalkyl, C3-C6-Cycloalkyl,R 15 Cι-C 6 -alkyl, C 6 haloalkyl, C 3 -C 6 cycloalkyl,
C3-C6-Alkenyl, C3-C6-Alkinyl, Cι-C6-Alkoxy, Ci-Cδ-Halogenalkoxy, C3-C6-Cycloalkoxy, C3-C6-Alkenyloxy, C3~C6-Alkinyloxy, Phenyl, Benzyl oder Benzyloxy, wobei die drei letztgenannten Reste partiell oder vollständig halogeniert sein können und/oder einen bis drei Reste aus der folgenden Gruppe tragen können: Nitro, Cyano, Cι-C4-Alkyl, Cι~C-Halogenalkyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C4-Alkylcarbonyl oderC 3 -C 6 alkenyl, C 3 -C 6 alkynyl, -C-C 6 alkoxy, Ci-C δ -haloalkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 alkenyloxy, C 3 ~ C 6 -alkynyloxy, phenyl, benzyl or benzyloxy, where the three latter radicals can be partially or completely halogenated and / or can carry one to three radicals from the following group: nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 Haloalkyl, -CC 4 alkoxy, -C-C 4 haloalkoxy, -C-C 4 alkylcarbonyl or
Cχ-C4-Alkoxycarbonyl ;Cχ-C 4 alkoxycarbonyl;
R16 Hydroxy, Cι-C6 -Alkoxy, C3-C6-Alkenyloxy,R 16 hydroxy, -CC 6 alkoxy, C 3 -C 6 alkenyloxy,
Ci-Cβ-Alkylsulfonyloxy, Cχ-C6-Alkylcarbonyloxy, Phenyl-C1-C4 -alkoxy, Phenylcarbonyloxy, Phenylcar- bonyl-Cι-C4 -alkoxy, Phenylsulfonyloxy, wobei der Phenylrest der vier letztgenannten Substituenten partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tra- gen kann: Nitro, Cyano, Cι-C4-Alkyl, Cι-C4-Halogen- alkyl, C1-C4 -Alkoxy oder Cι-C4-Halogenalkoxy;Ci-Cβ-alkylsulfonyloxy, Cχ-C 6 -alkylcarbonyloxy, phenyl-C1-C 4 -alkoxy, phenylcarbonyloxy, phenylcarbonyl-Cι-C 4 -alkoxy, phenylsulfonyloxy, where the phenyl radical of the latter four substituents can be partially or completely halogenated and / or a gene tra- to three of the following groups: nitro, cyano, C 4 -alkyl, halo-C 4 alkyl, C 1 -C 4 alkoxy or Cι-C 4 haloalkoxy;
sowie deren Tautomere oder landwirtschaftlich brauchbaren Salze. Außerdem betrifft die Erfindung Verfahren zur Herstellung von Verbindungen der Formel I, Mittel welche diese enthalten, sowie die Verwendung der Verbindungen der Formel I und diese enthaltende Mittel zur Schadpflanzenbekämpfung.as well as their tautomers or agriculturally useful salts. The invention also relates to processes for the preparation of compounds of the formula I, compositions which contain them, and to the use of the compounds of the formula I and compositions containing them for controlling harmful plants.
Herbizide Wirkstoffe aus der Klasse der Benzoylpyrazole sind bekannt aus EP-A 282 944; WO 98/42677; WO 98/45273; WO98/50366; WO 98/52926; WO 98/56766; US 5,807,806.Herbicidal active ingredients from the class of benzoylpyrazoles are known from EP-A 282 944; WO 98/42677; WO 98/45273; WO98 / 50366; WO 98/52926; WO 98/56766; US 5,807,806.
Die herbiziden Eigenschaften dieser Verbindungen sowie die Verträglichkeiten gegenüber Kulturpflanzen können jedoch nur bedingt befriedigen. Es lag daher dieser Erfindung die Aufgabe zugrunde, neue Verbindungen mit verbesserten Eigenschaften zu finden, die als Wirkstoff im Pflanzenschutzbereich, insbesondere als Herbizide, eingesetzt werden können.The herbicidal properties of these compounds and the tolerances to crop plants, however, can only satisfy to a limited extent. It was therefore the object of this invention to find new compounds with improved properties which can be used as active ingredients in the crop protection sector, in particular as herbicides.
Diese Aufgabe wird durch die oben definierten Benzoylpyrazole gelöst, die in 1-Stellung des Pyrazolderviates durch ein cyclisches Ringsystem substituiert sind.This object is achieved by the benzoylpyrazoles defined above, which are substituted by a cyclic ring system in the 1-position of the pyrazole derivative.
Ferner wurden sehr gut wirksame herbizide Mittel gefunden, die die Verbindungen I enthalten. Außerdem wurden Verfahren zur Herstellung dieser Mittel und Verfahren zur Bekämpfung oder Verminderung von unerwünschtem Pflanzenwuchs mit den Verbindungen I ge- funden.We have also found very effective herbicidal compositions which comprise the compounds I. In addition, processes for the preparation of these compositions and processes for controlling or reducing undesired plant growth with the compounds I were found.
Gegenstand der vorliegenden Erfindung sind auch Stereoisomere der Verbindungen der Formel I. Es werden sowohl reine Stereoisomere als auch Gemische hiervon erfaßt.The present invention also relates to stereoisomers of the compounds of the formula I. Both pure stereoisomers and mixtures thereof are covered.
Die Verbindungen der Formel I enthalten eine Kohlenstoff-Kohlenstoff-Doppelbindung und liegen daher als E-Isomere oder Z-Isomere oder als E/Z-Isomerengemische vor. Weiterhin können die Verbindungen der Formel I weitere Kohlenstoff- bzw. Kohlenstoff- Stickstoff-Doppelbindungen enthalten. Gegenstand der Erfindung sind sowohl die reinen geometrischen Isomere als auch Gemische hiervon.The compounds of the formula I contain a carbon-carbon double bond and are therefore present as E isomers or Z isomers or as E / Z isomer mixtures. The compounds of the formula I can furthermore contain further carbon or carbon-nitrogen double bonds. The invention relates to both the pure geometric isomers and mixtures thereof.
Die Verbindungen der Formel I können ebenso je nach Substituti- onsmuster ein oder mehrere Chiralitätszentren enthalten und liegen dann als Enantiomeren oder Diastereomerengemische vor. Gegenstand der Erfindung sind sowohl die reinen Enantiomeren oder Diastereomeren als auch deren Gemische.Depending on the substitution pattern, the compounds of the formula I can also contain one or more centers of chirality and are then present as enantiomers or mixtures of diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.
Die Verbindungen der Formel I können ebenso in Form ihrer Tautomeren bzw. als Ta tomerengemische vorliegen. Die tautomeren Formen ergeben sich insbesondere durch den Hydroxysubstituenten am Pyrazolring. Insofern können die Verbindungen sowohl als 5-Hydroxypyrazole oder als 5-Oxo-pyrazoline bezeichnet werden.The compounds of the formula I can also be present in the form of their tautomers or as a mixture of tamers. The tautomeric forms result in particular from the hydroxy substituent on Pyrazole. In this respect, the compounds can be referred to both as 5-hydroxypyrazoles or as 5-oxopyrazolines.
Die Verbindungen der Formel I können auch in Form ihrer landwirt- schaftlich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes in der Regel nicht ankommt. Im allgemeinen kommen die Salze derjenigen Kationen oder die Säureadditionssalze derjenigen Säuren in Betracht, deren Kationen, beziehungsweise Anionen, die herbizide Wirkung der Verbindungen I nicht negativ beein- trächtigen.The compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I are suitable.
Es kommen als Kationen insbesondere Ionen der Alkalimetalle, vorzugsweise Lithium, Natrium und Kalium, der Erdalkalimetalle, vorzugsweise Calcium und Magnesium, und der Übergangsmetalle, vorzugsweise Mangan, Kupfer, Zink und Eisen, sowie Ammonium, wobei hier gewünschtenfalls ein bis vier Wasserstoffatome durch Cχ-C4-Alkyl oder Hydroxy-Cι-C4-alkyl und/oder ein Phenyl oder Benzyl ersetzt sein können, vorzugsweise Diisopropylammonium, Tetramethylammonium, Tetrabutylammonium, Trimethylbenzylammonium, des weiteren Phosphoniumionen, Sulfoniumionen, vorzugsweise Tri (Cι-C4-alkyl) -sulfonium und Sulfoxoniumionen, vorzugsweise Tri (Cι-C4-alkyl) -sulfoxonium, in Betracht.The cations used are in particular ions of the alkali metals, preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where one to four hydrogen atoms by Cχ- C 4 alkyl or hydroxy -CC 4 alkyl and / or a phenyl or benzyl can be replaced, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri (Cι-C 4 alkyl) - sulfonium and sulfoxonium ions, preferably tri (-C 4 alkyl) sulfoxonium, into consideration.
Anionen von brauchbaren Säureadditionsalzen sind in erster Linie Chlorid, Bromid, Fluorid, Hydrogensulfat, Sulfat, Dihydrogen- phosphat, Hydrogenphosphat, Nitrat, Hydrogencarbonat, Carbonat, Hexafluorosilikat, Hexafluorophosphat, Benzoat sowie die Anionen von Cι-C -Alkansäuren, vorzugsweise Formiat, Acetat, Propionat und Butyrat.Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 -alkane acids, preferably formate, acetate Propionate and butyrate.
Die für die Substi uenten Ri-R16 genannten organischen Molekül - teile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenwasserstoffketten, also alle Alkyl-, Halogenalkyl-, Cycloalkyl-, Alkoxyalkyl-, Alkoxy-, Halogenalkoxy-, Cycloalkoxy, Alkyl hio, Alkylsulfonyl-, Halogenalkylsulfonyl, Alkylcarbonyl-, Halogenalkylcarbonyl, Alkoxycarbonyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Alkenyloxy-, Alkinyloxy-Teile können geradkettig oder verzweigt sein. Sofern nicht anders angegeben tragen halogenierte Substituenten Vorzugs - weise ein bis fünf gleiche oder verschiedene Halogenatome. Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder Iod.The organic molecule parts mentioned for the substituents R i -R 16 represent collective terms for individual lists of the individual group members. All hydrocarbon chains, that is to say all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, cycloalkoxy, Alkyl hio, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenyl, cycloalkenyl, alkynyl, alkenyloxy, alkynyloxy parts can be straight-chain or branched. Unless otherwise stated, halogenated substituents preferably have one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
Ferner bedeuten beispielsweise:Furthermore, for example:
- C2-C4-Alkyl: Ethyl, n-Propyl, 1-Methylethyl, Butyl, 1-Methyl- propyl, 2-Methylpropyl oder 1 , 1-Dimethylethyl; Cι-C4-Alkyl, sowie die Alkylteile von z.B. Cι-C4-Alkylcarbonyl Heterocyclyl-Cι-C-alkyl, Phenyl-Cι~C4-alkyl und Hetaryl- Cι-C4~alkyl: C2-C4-Alkyl, wie voranstehend genannt sowie Methyl;- C 2 -C 4 alkyl: ethyl, n-propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl; Cι-C 4 alkyl, and the alkyl moieties of, for example, Cι-C 4 alkylcarbonyl heterocyclyl-Cι-C alkyl, phenyl-Cι ~ C4-alkyl and hetaryl Cι-C4 ~ alkyl: C 2 -C 4 - Alkyl, as mentioned above, and methyl;
C2-C6-Alkyl, sowie die Alkylteile von z.B. Cι-C6-Alkoxy-C2-C6- alkyl: C2-C4-Alkyl, wie voranstehend genannt, sowie Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2, 2-Dimethyl- propyl, 1-Ethylpropyl, Hexyl, 1, 1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methyl- pentyl, 4-Methylpentyl, 1, 1-Dirnethylbutyl, 1, 2-Dimethylbutyl, 1,3-Dimethylbutyl, 2, 2-Dimethylbutyl, 2, 3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Tri- methylpropyl, 1-Ethyl-l-methylpropyl oder l-Ethyl-3-methyl- propyl;C 2 -C 6 alkyl, and the alkyl parts of, for example, -C 6 alkoxy-C 2 -C 6 alkyl: C 2 -C 4 alkyl, as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-tri- methylpropyl, 1-ethyl-l-methylpropyl or l-ethyl-3-methylpropyl;
Ci-Ce-Alkyl, sowie die Alkylteile von z.B. Ci-Cβ-Alkoxy-Ci-Ce- alkyl und Cι-C6-Alkylcarbonyl : C2-C6-Alkyl, wie voranstehend genannt, sowie Methyl;Ci-Ce-alkyl, as well as the alkyl parts of, for example, Ci-Cβ-alkoxy-Ci-Ce alkyl and -CC 6 alkylcarbonyl: C 2 -C 6 alkyl, as mentioned above, and methyl;
Cι~C4-Halogenalkyl: einen Cι-C4-Alkylrest, wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Chlormethyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlor- difluormethyl, 2-Fluorethyl, 2-Chlorethyl, 2-Bromethyl, 2-Iodethyl, 2, 2-Difluorethyl, 2 , 2, 2-Trifluorethyl, 2-Chlor- 2-fluorethyl, 2-Chlor-2, 2-difluorethyl, 2 , 2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl, 2-Fluorpropyl, 3-Fluorpropyl, 2, 2-Difluorpropyl, 2, 3-Difluorpropyl, 2-Chlor- propyl, 3-Chlorpropyl, 2, 3-Dichlorpropyl, 2-Brompropyl, 3-Brompropyl, 3 ,3, 3-Trifluorpropyl, 3, 3 , 3-Trichlorpropyl, 2,2, 3,3, 3-Pentafluorpropyl, Heptafluorpropyl, l-(Fluor- methyl) -2-fluorethyl, 1- (Chlormethyl) -2-chlorethyl, l-(Brom- methyl) -2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brombutyl oder Nonafluorbutyl;Cι ~ C 4 -haloalkyl: a Cι-C 4 -alkyl radical as mentioned above which, chlorine, bromine / or iodine partially or fully substituted by fluorine, and is substituted, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloro propyl, 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2,2, 3,3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromomethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
Ci-Cβ-Halogenalkyl, sowie die Halogenalkylteile von Cι-C6- Halogenalkylcarbonyl : Cι-C4-Halogenalkyl wie voranstehend ge- nannt, sowie 5-Fluorpentyl, 5-Chlorpentyl, 5-Brompentyl,Ci-Cβ-haloalkyl, and the haloalkyl parts of Cι-C 6 - haloalkylcarbonyl: Cι-C 4 haloalkyl as mentioned above, and 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl,
5-Iodpentyl, Undecafluorpentyl, 6-Fluorhexyl, 6-Chlorhexyl, 6-Bromhexyl, 6-Iodhexyl oder Dodecafluorhexyl;5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorhexyl;
Cι~C4-Alkoxy, sowie die Alkoxyteile von Cι-C4-Alkoxycarbonyl: Methoxy, Ethoxy, Propoxy, 1-Methylethoxy, Butoxy, 1-Methyl - propoxy, 2-Methylpropoxy oder 1, 1-Dimethylethoxy; Ci-Cβ-Alkoxy, sowie die Alkoxyteile von Cι-C6-Alkoxy-Cι-C6_ alkyl, Cι-C6-Alkoxy-C2-C6-alkyl und Cι-C6~Alkoxycarbonyl : C1-C4-Alkoxy wie voranstehend genannt, sowie Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1, 1-Dimethyl- propoxy, 1, 2-Dimethylpropoxy, 2, 2-Dimethylpropoxy, 1-Ethyl- propoxy, Hexoxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methyl- pentoxy, 4-Methylpentoxy, 1, 1-Dimethylbutoxy, 1, 2-Dimethyl- butoxy, 1, 3-Dimethylbutoxy, 2, 2-Dimethylbutoxy, 2 , 3-Dimethyl- butoxy, 3,3-Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbutoxy, 1,1, 2-Trimethylpropoxy, 1, 2 ,2-Trimethylpropoxy,-C ~ C 4 alkoxy, and the alkoxy parts of -C -C 4 alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy; Ci-Cβ-alkoxy, and the alkoxy parts of -C-C6-alkoxy-Cι-C6 _ alkyl, Cι-C 6 -alkoxy-C 2 -C 6 -alkyl and Cι-C 6 ~ alkoxycarbonyl: C 1 -C 4 - Alkoxy as mentioned above, and pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 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-l-methylpropoxy oder l-Ethyl-2-methylpropoxy;1-ethyl-l-methylpropoxy or l-ethyl-2-methylpropoxy;
Cι-C4-Halogenalkoxy: einen Cι-C4-Alkoxyrest wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Fluormethoxy,Cι-C 4 -haloalkoxy: a Cι-C 4 alkoxy radical as mentioned above which is partially or fully substituted by fluorine, iodine, chlorine, bromine and / or substituted, eg fluoromethoxy,
Difluormethoxy, Trifluormethoxy, Chlordifluormethoxy, Bromdi - fluormethoxy, 2-Fluorethoxy, 2-Chlorethoxy, 2-Brom- ethoxy, 2-Iodethoxy, 2, 2-Difluorethoxy, 2, 2, 2-Trifluor- ethoxy, 2-Chlor-2-fluorethoxy, 2-Chlor-2, 2-difluorethoxy, 2, 2-Dichlor-2-fluorethoxy, 2, 2, 2-Trichlorethoxy, Pentafluorethoxy, 2-Fluorpropoxy, 3-Fluorpropoxy, 2-Chlorpropoxy, 3-Chlorpropoxy, 2-Brompropoxy, 3-Brompropoxy, 2,2-Difluor- propoxy, 2, 3-Difluorpropoxy, 2, 3-Dichlorpropoxy, 3,3,3-Tri- fluorpropoxy, 3, 3, 3-Trichlorpropoxy, 2, 2, 3, 3, 3-Pentafluor- propoxy, Heptafluorpropoxy, 1- (Fluormethyl) -2-fluorethoxy, 1- (Chlormethyl) -2-chlorethoxy, 1- (Brommethyl) -2-bromethoxy, 4-Fluorbutoxy, 4-Chlorbutoxy, 4-Brombutoxy oder Nonafluor- butoxy;Difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromdi - fluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2- Bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3, 3, 3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4- Bromobutoxy or nonafluorobutoxy;
Ci-Cδ-Halogenalkoxy: Cι-C4-Halogenalkoxy, wie voranstehend genannt, sowie z.B. 5-Fluorpentoxy, 5-Chlorpentoxy, 5-Brompen- toxy, 5-Iodpentoxy, Undecafluorpentoxy, 6-Fluorhexoxy, 6-Chlorhexoxy, 6-Bromhexoxy, 6-Iodhexoxy oder Dodecafluorhe- xoxy;Ci-C δ -haloalkoxy: Cι-C 4 -haloalkoxy, as mentioned above, as well as, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromogenoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6- Bromhexoxy, 6-iodohexoxy or dodecafluorhexoxy;
Ci-Cδ-Alkylthio: z.B. Methylthio, Ethylthio, Propylthio, 1-Methylethylthio, Butylthio, 1-Methylpropylthio, 2-Methyl- propylthio, 1, 1-Dimethylethylthio, Pentylthio, 1-Methylbutyl- thio, 2-Methylbutylthio, 3-Methylbutylthio, 2, 2-Dimethyl- propylthio, 1-Ethylpropylthio, Hexylthio, 1, 1-Dimethylpropyl- thio, 1,2-Dimethylpropylthio, 1-Methylpentylthio, 2-Methyl- pentylthio, 3-Methylpentylthio, 4-Methylpentylthio, 1, 1-Dimethylbutylthio, 1, 2-Dimethylbutylthio, 1, 3-Dimethyl- butylthio, 2, 2-Dimethylbutylthio, 2 , 3-Dimethylbutylthio, 3,3-Dimethylbutylthio, 1-Ethylbutylthio, 2-Ethylbutylthio, 1,1, 2-Trimethylpropylthio, 1, 2, 2-Trimethylpropylthio, 1-Ethyl-l-methylpropylthio oder l-Ethyl-2-methylpropylthio;Ci-C δ- alkylthio: e.g. methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3- Methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1, 2-trimethylpropylthio, 1, 2, 2-trimethylpropylthio, 1-ethyl-l-methylpropylthio or l-ethyl-2-methylpropylthio;
Cx-Ce-Alkylsulfonyl (Cι-C6-Alkyl-S (=0) 2~) : z.B. Methyl- sulfonyl, Ethylsulfonyl, Propylsulfonyl, 1-Methylethyl- sulfonyl, Butylsulfonyl, 1-Methylpropylsulfonyl, 2-Methyl- propylsulfonyl oder 1, 1-Dimethylethylsulfonyl, Pentyl - sulfonyl, 1-Methylbutylsulfonyl, 2-Methylbutylsulfonyl, 3-Methylbutylsulfonyl, 2, 2-Dimethylpropylsulfonyl, 1-Ethyl- propylsulfonyl, 1, 1-Dimethylpropylsulfonyl, 1, 2-Dimethyl- propylsulfonyl, Hexylsulfonyl, 1-Methylpentylsulfonyl, 2-Methylpentylsulfonyl, 3-Methylpentylsulfonyl, 4-Methyl - pentyls lfonyl , 1, 1-Dimethylbutylsulfonyl, 1, 2-Dimethylbutyl- sulfonyl, 1, 3-Dimethylbutylsulfonyl, 2 , 2-Dimethylbutyl - sulfonyl, 2 , 3-Dimethylbutylsulfonyl, 3 , 3-Dimethylbutylsulfonyl, 1-Ethylbutylsulfonyl, 2-Ethylbutylsulfonyl, 1, 1,2-Trimethylpropylsulfonyl, 1, 2, 2-Trimethylpropylsulfonyl, 1-Ethyl-l-methylpropylsulfonyl oder l-Ethyl-2-methylpropyl- sulfonyl;Cx-Ce-alkylsulfonyl (Cι-C 6 -alkyl-S (= 0) 2 ~): e.g. methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl or 1 , 1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-sulfonyl, 1, 2-sulfonyl -Methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl, 1, 3-dimethylbutylsulfonyl, 2, 2-dimethylbutylsulfonyl Dimethylbutylsulfonyl, 3, 3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1, 1,2-trimethylpropylsulfonyl, 1, 2, 2-trimethylpropylsulfonyl, 1-ethyl-l-methylpropylsulfonyl or 1-ethylpropylsulfonyl;
Ci-Cβ-Halogenalkylsulfonyl: einen Cι-C6-Alkylsulfonylrest, wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also Fluormethylsulfonyl, Difluormethylsulfonyl, Trifluormethyl- sulfonyl, Chlordifluormethylsulfonyl, Bromdifluormethylsulfo- nyl, 2-Fluorethylsulfonyl, 2-Chlorethylsulfonyl, 2-Bromethyl- sulfonyl, 2-Iodethylsulfonyl, 2, 2-Difluorethylsulfonyl, 2, 2, 2-Trifluorethylsulfonyl, 2,2, 2-Trichlorethylsulfonyl, 2-Chlor-2-fluorethylsulfonyl, 2-Chlor-2 , 2-difluorethylsulfo- nyl, 2, 2-Dichlor-2-fluorethylsulfonyl, Pentafluorethyl - sulfonyl, 2-Fluorpropylsulfonyl, 3-Fluorpropylsulfonyl, 2-Chlorpropylsulfonyl, 3-Chlorpropylsulfonyl, 2-Brompropyl- sulfonyl, 3-Brompropylsulfonyl, 2, 2-Difluorpropylsulfonyl, 2, 3-Difluorpropylsulfonyl, 2, 3-Dichlorpropylsulfonyl, 3, 3, 3-Trifluorpropylsulfonyl, 3, 3,3-Trichlorpropylsulfonyl,Ci-Cβ-haloalkylsulfonyl: a -CC 6 alkylsulfonyl, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifonyl 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, 2,2, 2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2- Chloro-2, 2-difluoroethylsulfonyl, 2, 2-dichloro-2-fluoroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 2-bromopropylsulfonyl, 2, 2-difluoropropylsulfonyl, 2, 3-difluoropropylsulfonyl, 2, 3-dichloropropylsulfonyl, 3, 3, 3-trifluoropropylsulfonyl, 3, 3,3-trichloropropylsulfonyl,
2,2,3,3, 3-Pentafluorpropylsulfonyl, Heptafluorpropylsulfonyl, 1- (Fluormethyl)-2-fluorethylsulfonyl, 1- (Chlormethyl) -2-chlorethylsulfonyl, 1- (Brommethyl) -2-bromethylsul - fonyl, 4-Fluorbutylsulfonyl, 4-Chlorbutylsulfonyl, 4-Brombu- tylsulfonyl, Nonafluorbutylsulfonyl, 5-Fluorpentylsulfonyl, 5-Chlorpentylsulfonyl, 5-Brompentylsulfonyl, 5-Iodpentylsul - fonyl, 6-Fluorhexylsulfonyl, 6-Bromhexylsulfonyl, 6-Iodhexyl- sulfonyl oder Dodecafluorhexylsulfonyl;2,2,3,3, 3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1- (fluoromethyl) -2-fluoroethylsulfonyl, 1- (chloromethyl) -2-chloroethylsulfonyl, 1- (bromomethyl) -2-bromomethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorhexylsulfonyl, 6-bromhexylsulfonylylylsulfonyl;
C3-C6-Alkenyl: Prop-1-en-l-yl, Prop-2-en-l-yl, 1-Methyl- ethenyl, Buten-1-yl, Buten-2-yl, Buten-3-yl, 1-Methyl- prop-1-en-l-yl, 2-Methyl-prop-l-en-l-yl, l-Methyl-prop-2-en- 1-yl, 2-Methyl-prop-2-en-l-yl, Penten-1-yl, Penten-2-yl, Penten-3-yl, Penten-4-yl, 1-Methyl-but-l-en-l-yl, 2-Methyl- but-1-en-l-yl, 3-Methyl-but-l-en-l-yl, 1-Methyl- but-2-en-l-yl, 2-Methyl-but-2-en-l-yl, 3-Methyl- but-2-en-l-yl, l-Methyl-but-3-en-l-yl, 2-Methyl- but-3-en-l-yl, 3-Methyl-but-3-en-l-yl, 1, 1-Dimethyl- prop-2-en-l-yl, 1, 2-Dimethyl-prop-l-en-l-yl, 1, 2-Dimethyl- prop-2-en-l-yl, l-Ethyl-prop-l-en-2-yl, 1-Ethyl- prop-2-en-l-yl, Hex-1-en-l-yl, Hex-2-en-l-yl, Hex-3-en-l-yl, Hex-4-en-l-yl, Hex-5-en-1-yl, 1-Methyl-pent-l-en-l-yl, 2-Me- thyl-pent-1-en-l-yl, 3-Methyl-pent-l-en-l-yl, 4-Methyl- pent-1-en-l-yl, l-Methyl-pent-2-en-l-yl, 2-Methyl- pent-2-en-l-yl, 3-Methyl-pent-2-en-l-yl, 4-Methyl- pent-2-en-l-yl, l-Methyl-pent-3-en-l-yl, 2-Methyl- pent-3-en-l-yl, 3-Methyl-pent-3-en-l-yl, 4-Methyl- pent-3-en-l-yl, l-Methyl-pent-4-en-l-yl, 2-Methyl- pent-4-en-l-yl, 3-Methyl-pent-4-en-l-yl, 4-Methyl- pent-4-en-l-yl, 1, l-Dimethyl-but-2-en-l-yl, 1, 1-Dimethyl- but-3-en-l-yl, 1, 2-Dimethyl-but-l-en-l-yl, 1, 2-Dimethyl- but-2-en-l-yl, 1, 2-Dimethyl-but-3-en-l-yl, 1, 3-Dimethyl- but-1-en-l-yl, 1, 3-Dimethyl-but-2-en-l-yl, 1, 3-Dimethyl- but-3-en-l-yl, 2, 2-Dimethyl-but-3-en-l-yl, 2, 3-Dimethyl- but-1-en-l-yl, 2, 3-Dimethyl-but-2-en-l-yl, 2, 3-Dimethyl- but-3-en-l-yl, 3, 3-Dimethyl-but-l-en-l-yl, 3, 3-Dimethyl- but-2-en-l-yl, 1-Ethyl-but-l-en-l-yl, l-Ethyl-but-2-en-l-yl, l-Ethyl-but-3-en-l-yl, 2-Ethyl-but-l-en-l-yl, 2-Ethyl- but-2-en-l-yl, 2-Ethyl-but-3-en-l-yl, 1, 1, 2-Trimethyl- prop-2-en-l-yl, l-Ethyl-l-methyl-prop-2-en-l-yl, l-Ethyl-2-methyl-prop-l-en-l-yl oder l-Ethyl-2-methyl- prop-2-en-l-yl;C 3 -C 6 alkenyl: prop-1-en-l-yl, prop-2-en-l-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3- yl, 1-methyl-prop-1-en-l-yl, 2-methyl-prop-l-en-l-yl, l-methyl-prop-2-en- 1-yl, 2-methyl-prop-2-en-l-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methyl-but-l- en-l-yl, 2-methyl-but-1-en-l-yl, 3-methyl-but-l-en-l-yl, 1-methyl-but-2-en-l-yl, 2- Methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl, 2-methyl-but-3-en- l-yl, 3-methyl-but-3-en-l-yl, 1, 1-dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop-l-en-l-yl, 1, 2-dimethyl-prop-2-en-l-yl, l-ethyl-prop-l-en-2-yl, 1-ethyl-prop-2-en-l-yl, hex-1-en- l-yl, hex-2-en-l-yl, hex-3-en-l-yl, hex-4-en-l-yl, hex-5-en-1-yl, 1-methyl-pent l-en-l-yl, 2-methyl-pent-1-en-l-yl, 3-methyl-pent-l-en-l-yl, 4-methyl-pent-1-en-l- yl, l-methyl-pent-2-en-l-yl, 2-methyl-pent-2-en-l-yl, 3-methyl-pent-2-en-l-yl, 4-methyl-pent 2-en-1-yl, 1-methyl-pent-3-en-1-yl, 2-methyl-pent-3-en-1-yl, 3-methyl-pent-3-en-1-yl, 4-methyl-pent-3-en-l-yl, l-methyl-pent-4-en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl-pent-4- en-l-yl, 4-methyl-pent-4-en-l-yl, 1, l-dimethyl-but-2-en-l-yl, 1, 1-dimethyl-but-3-en-l- yl, 1, 2-dimethyl -but-1-en-1-yl, 1, 2-dimethyl-but-2-en-1-yl, 1, 2-dimethyl-but-3-en-1-yl, 1, 3-dimethyl-but -1-en-1-yl, 1, 3-dimethyl-but-2-en-1-yl, 1, 3-dimethyl-but-3-en-1-yl, 2, 2-dimethyl-but-3 -en-l-yl, 2,3-dimethylbut-1-en-l-yl, 2,3-dimethylbut-2-en-l-yl, 2,3-dimethylbut-3-ene -l-yl, 3,3-dimethyl-but-l-en-l-yl, 3,3-dimethyl-but-2-en-l-yl, 1-ethyl-but-l-en-l-yl , l-ethyl-but-2-en-l-yl, l-ethyl-but-3-en-l-yl, 2-ethyl-but-l-en-l-yl, 2-ethyl-but-2 -en-1-yl, 2-ethyl-but-3-en-1-yl, 1, 1, 2-trimethyl-prop-2-en-1-yl, 1-ethyl-1-methyl-prop-2 -en-1-yl, 1-ethyl-2-methyl-prop-1-en-1-yl or 1-ethyl-2-methyl-prop-2-en-1-yl;
C2-C.6-Alkenyl : C3-C6-Alkenyl wie voranstehend genannt , sowie Ethenyl ;C 2 -C. 6- alkenyl: C 3 -C 6 -alkenyl as mentioned above, and ethenyl;
C3-C6-Alkenyloxy: z . B . Prop-1-en-l-yloxy, Prop-2-en-l-yloxy, 1-Methylethenyloxy, Buten-1-yloxy, Buten-2-yloxy, Buten-3-yl - oxy, 1-Methyl-prop-l-en-l-yloxy, 2-Methyl-prop-l-en-l-yloxy, l-Methyl-prop-2-en-l-yloxy, 2-Methyl-prop-2-en-l-yloxy, Penten-1-yloxy, Penten-2-yloxy, Penten-3-yloxy, Penten-4-yl - oxy, 1-Methyl-but-l-en-l-yloxy, 2-Methyl-but-l-en-l-yloxy,C 3 -C 6 alkenyloxy: e.g. B. Prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, buten-1-yloxy, buten-2-yloxy, buten-3-yl-oxy, 1-methyl-prop- l-en-l-yloxy, 2-methyl-prop-l-en-l-yloxy, l-methyl-prop-2-en-l-yloxy, 2-methyl-prop-2-en-l-yloxy, Penten-1-yloxy, penten-2-yloxy, penten-3-yloxy, penten-4-yl - oxy, 1-methyl-but-l-en-l-yloxy, 2-methyl-but-l-en- l-yloxy,
3-Methyl-but-l-en-l-yloxy, l-Methyl-but-2-en-l-yloxy, 2-Me- thyl-but-2-en-l-yloxy, 3-Methyl-but-2-en-l-yloxy, 1-Methyl- but-3-en-l-yloxy, 2-Methyl-but-3-en-l-yloxy, 3-Methyl- but-3-en-l-yloxy, 1 , l-Dimethyl-prop-2-en-l-yloxy, 1 , 2-Dime- thyl-prop-1-en-l-yloxy, 1 , 2-Dimethyl-prop-2-en-l-yloxy, l-Ethyl-prop-l-en-2-yloxy, l-Ethyl-prop-2-en-l-yloxy, Hex-1-en-l-yloxy, Hex-2-en-l-yloxy, Hex-3-en-l-yloxy, Hex-4-en-l-yloxy, Hex-5-en-l-yloxy, 1-Methyl-pent-l-en-l-yl- oxy, 2-Methyl-pent-l-en-l-yloxy, 3-Methyl-pent-l-en-l-yloxy, 4-Methyl-pent-l-en-l-yloxy, l-Methyl-pent-2-en-l-yloxy, 2-Me- thyl-pent-2-en-l-yloxy, 3-Methyl-pent-2-en-l-yloxy, 4-Methyl- pent-2-en-l-yloxy, l-Methyl-pent-3-en-l-yloxy, 2-Methyl- pent-3-en-l-yloxy, 3-Methyl-pent-3-en-l-yloxy, 4-Methyl- pent-3-en-1-yloxy, l-Methyl-pent-4-en-l-yloxy, 2-Methyl- pent-4-en-l-yloxy, 3-Methyl-pent-4-en-l-yloxy, 4-Methyl- pent-4-en-l-yloxy, 1, l-Dimethyl-but-2-en-l-yloxy, 1,1-Dime- thyl-but-3-en-1-yloxy, 1, 2-Dimethyl-but-l-en-l-yloxy, 1,2-Di- methyl-but-2-en-l-yloxy, 1 , 2-Dimethyl-but-3-en-l-yloxy, 1, 3-Dirnethyl-but-1-en-1-yloxy, 1, 3-Dimethyl-but-2-en-l-yloxy, 1, 3-Dimethyl-but-3-en-l-yloxy, 2 ,2-Dimethyl-but-3-en-l-yloxy, 2, 3-Dimethyl-but-l-en-l-yloxy, 2, 3-Dimethyl-but-2-en-l-yloxy, 2, 3-Dimethyl-but-3-en-l-yloxy, 3 , 3-Dimethyl-but-l-en-l-yloxy, 3, 3-Dimethyl-but-2-en-l-yloxy, 1-Ethyl-but-l-en-l-yloxy, l-Ethyl-but-2-en-l-yloxy, l-Ethyl-but-3-en-l-yloxy, 2-Ethyl- but-1-en-l-yloxy, 2-Ethyl-but-2-en-l-yloxy, 2-Ethyl- but-3-en-l-yloxy, 1, 1, 2-Trimethyl-prop-2-en-l-yloxy, l-Ethyl-l-methyl-prop-2-en-l-yloxy, l-Ethyl-2-methyl- prop-1-en-l-yloxy oder l-Ethyl-2-methyl-prop-2-en-l- yloxy;3-methyl-but-l-en-l-yloxy, l-methyl-but-2-en-l-yloxy, 2-methyl-but-2-en-l-yloxy, 3-methyl-but- 2-en-l-yloxy, 1-methyl-but-3-en-l-yloxy, 2-methyl-but-3-en-l-yloxy, 3-methyl-but-3-en-l-yloxy, 1, l-dimethyl-prop-2-en-l-yloxy, 1, 2-dimethyl-prop-1-en-l-yloxy, 1, 2-dimethyl-prop-2-en-l-yloxy, l-ethyl-prop-l-en-2-yloxy, l-ethyl-prop-2-en-l-yloxy, hex-1-en-l-yloxy, hex-2-en-l-yloxy, hex 3-en-l-yloxy, Hex-4-en-l-yloxy, hex-5-en-l-yloxy, 1-methyl-pent-l-en-l-yloxy, 2-methyl-pent-l-en-l-yloxy, 3-methyl-pent-l-en-l-yloxy, 4-methyl-pent-l-en-l-yloxy, l-methyl-pent-2-en-l-yloxy, 2-methyl-pent- 2-en-l-yloxy, 3-methyl-pent-2-en-l-yloxy, 4-methyl-pent-2-en-l-yloxy, l-methyl-pent-3-en-l-yloxy, 2-methyl-pent-3-en-l-yloxy, 3-methyl-pent-3-en-l-yloxy, 4-methyl-pent-3-en-1-yloxy, l-methyl-pent-4- en-l-yloxy, 2-methyl-pent-4-en-l-yloxy, 3-methyl-pent-4-en-l-yloxy, 4-methyl-pent-4-en-l-yloxy, 1, l-dimethyl-but-2-en-l-yloxy, 1,1-dimethyl-but-3-en-1-yloxy, 1, 2-dimethyl-but-l-en-l-yloxy, 1, 2-dimethyl-but-2-en-1-yloxy, 1, 2-dimethyl-but-3-en-1-yloxy, 1, 3-dimethyl-but-1-en-1-yloxy, 1, 3-dimethyl-but-2-en-l-yloxy, 1, 3-dimethyl-but-3-en-l-yloxy, 2, 2-dimethyl-but-3-en-l-yloxy, 2, 3- Dimethyl-but-l-en-l-yloxy, 2, 3-dimethyl-but-2-en-l-yloxy, 2, 3-dimethyl-but-3-en-l-yloxy, 3, 3-dimethyl but-l-en-l-yloxy, 3, 3-dimethyl-but-2-en-l-yloxy, 1-ethyl-but-l-en-l-yloxy, l-ethyl-but-2-en- l-yloxy, l- Ethyl-but-3-en-l-yloxy, 2-ethyl-but-1-en-l-yloxy, 2-ethyl-but-2-en-l-yloxy, 2-ethyl-but-3-en- l-yloxy, 1, 1, 2-trimethyl-prop-2-en-l-yloxy, l-ethyl-l-methyl-prop-2-en-l-yloxy, l-ethyl-2-methyl-prop- 1-en-1-yloxy or 1-ethyl-2-methyl-prop-2-en-1-yloxy;
C3-C6-Alkinyl: Prop-1-in-l-yl, Prop-2-in-l-yl, But-1-in-l-yl, But-l-in-3-yl, But-l-in-4-yl, But-2-in-l-yl, Pent-1-in-l-yl, Pent-l-in-3-yl, Pent-l-in-4-yl, Pent-l-in-5-yl, Pent-2-in-l-yl, Pent-2-in-4-yl, Pent-2-in-5-yl, 3-Methyl-but-l-in-3-yl, 3-Methyl-but-l-in-4-yl, Hex-1-in-l-yl, Hex-l-in-3-yl, Hex-l-in-4-yl, Hex-l-in-5-yl, Hex-l-in-6-yl, Hex-2-in-l-yl, Hex-2-in-4-yl, Hex-2-in-5-yl, Hex-2-in-6-yl, Hex-3-in-l-yl, Hex-3-in-2-yl, 3-Methyl- pent-1-in-l-yl, 3-Methyl-pent-l-in-3-yl, 3-Methyl- pent-l-in-4-yl, 3-Methyl-pent-l-in-5-yl, -Methyl- pent-1-in-l-yl, 4-Methyl-pent-2-in-4-yl oder 4-Methyl- pent-2-in-5-yl;C 3 -C 6 alkynyl: prop-1-in-1-yl, prop-2-in-1-yl, but-1-in-1-yl, but-1-in-3-yl, but- l-in-4-yl, but-2-in-l-yl, pent-1-in-l-yl, pent-l-in-3-yl, pent-l-in-4-yl, pent l-in-5-yl, pent-2-in-l-yl, pent-2-in-4-yl, pent-2-in-5-yl, 3-methyl-but-l-in-3- yl, 3-methyl-but-l-in-4-yl, hex-1-in-l-yl, hex-l-in-3-yl, hex-l-in-4-yl, hex-l- in-5-yl, hex-1-in-6-yl, hex-2-in-1-yl, hex-2-in-4-yl, hex-2-in-5-yl, hex-2- in-6-yl, hex-3-in-1-yl, hex-3-in-2-yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-yl 3-yl, 3-methyl-pent-l-in-4-yl, 3-methyl-pent-1-in-5-yl, -methyl-pent-1-in-1-yl, 4-methyl-pent -2-in-4-yl or 4-methylpent-2-in-5-yl;
C2-C6-Alkinyl: C3-C6-Alkinyl, wie voranstehend genannt, sowie Ethinyl :C 2 -C 6 alkynyl: C 3 -C 6 alkynyl, as mentioned above, and ethynyl:
Cs-Cβ-Alkinyloxy: z.B. Prop-1-in-l-yloxy, Prop-2-in-l-yloxy, But-1-in-l-yloxy, But-l-in-3-yloxy, But-l-in-4-yloxy, But-2-in-l-yloxy, Pent-1-in-l-yloxy, Pent-l-in-3-yloxy, Pent-l-in-4-yloxy, Pent-l-in-5-yloxy, Pent-2-in-l-yloxy, Pent-2-in-4-yloxy, Pent-2-in-5-yloxy, 3-Methyl-but-l-in- 3-yloxy, 3-Methyl-but-l-in-4-yloxy, Hex-1-in-l-yloxy, Hex-l-in-3-yloxy, Hex-l-in-4-yloxy, Hex-l-in-5-yloxy, Hex-l-in-6-yloxy, Hex-2-in-l-yloxy, Hex-2-in-4-yloxy, Hex-2-in-5-yloxy, Hex-2-in-6-yloxy, Hex-3-in-l-yloxy, Hex-3-in-2-yloxy, 3-Methylpent-l-in-l-yloxy, 3-Methyl- pent-l-in-3-yloxy, 3-Methyl-pent-l-in-4-yloxy, 3-Methyl- pent-l-in-5-yloxy, 4-Methyl-pent-l-in-l-yloxy, 4-Methyl- pent-2-in-4-yloxy oder 4-Methylpent-2-in-5-yloxy;Cs-Cβ-alkynyloxy: for example prop-1-in-1-yloxy, prop-2-in-1-yloxy, but-1-in-1-yloxy, but-1-in-3-yloxy, but-1 -in-4-yloxy, but-2-in-1-yloxy, pent-1-in-1-yloxy, pent-1-in-3-yloxy, pent-1-in-4-yloxy, pent-1 -in-5-yloxy, pent-2-in-1-yloxy, pent-2-in-4-yloxy, pent-2-in-5-yloxy, 3-methyl-but-l-in-3-yloxy , 3-methyl-but-1-in-4-yloxy, hex-1-in-1-yloxy, hex-1-in-3-yloxy, hex-1-in-4-yloxy, hex-1-in -5-yloxy, hex-1-in-6-yloxy, hex-2-in-1-yloxy, hex-2-in-4-yloxy, Hex-2-in-5-yloxy, hex-2-in-6-yloxy, hex-3-in-l-yloxy, hex-3-in-2-yloxy, 3-methylpent-l-in-l- yloxy, 3-methyl-pent-l-in-3-yloxy, 3-methyl-pent-l-in-4-yloxy, 3-methyl-pent-l-in-5-yloxy, 4-methyl-pent- 1-in-1-yloxy, 4-methylpent-2-in-4-yloxy or 4-methylpent-2-in-5-yloxy;
C3-C6-Cycloalkyl: Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl ;C 3 -C 6 cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
C3-C6-Cycloalkoxy: Cyclopropoxy, Cyclobutoxy, Cyclopentoxy oder Cyclo exoxy;C 3 -C 6 cycloalkoxy: cyclopropoxy, cyclobutoxy, cyclopentoxy or cycloexoxy;
C3-C6-Cycloalkenyl: Cyclopropen-1-yl, Cyclobuten-1-yl, Cyclo- buten-3-yl, Cyclopenten-1-yl, Cyclopenten-3-yl, Cyclo- hexen-1-yl, Cyclohexen-3-yl oder Cyclohexen-4-yl;C 3 -C 6 cycloalkenyl: cyclopropen-1-yl, cyclobuten-1-yl, cyclobutenen-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexene 3-yl or cyclohexen-4-yl;
Heterocyclyl, sowie die Heteroxycyclylreste in Hetero- cyclyloxy und Heterocyclyl-Cι-C4-alkyl : drei- bis siebenglie- drige, gesättigte oder partiell ungesättigte mono- oder poly- cyclische Heterocyclen, die ein bis drei Heteroatome ausgewählt aus einer Gruppe bestehend aus Sauerstoff, Stickstoff und Schwefel enthalten, wie Oxiranyl, 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydro- thienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-Isoxazolidinyl, 4-Isoxazolidinyl, 5-Isoxazolidinyl, 3-Isothiazolidinyl, 4-Isothiazolidinyl, 5-Isothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxa- zolidinyl, 5-Oxazolidinyl, 2-Thiazolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-Imidazolidinyl, 4-Imidazolidinyl, 1, 2, 4-Oxadiazolidin-3-yl, 1, 2, 4-Oxadiazolidin-5-yl,Heterocyclyl, as well as the heteroxycyclyl residues in heterocyclic and heterocyclyl -CC 4 -alkyl: three- to seven-membered, saturated or partially unsaturated mono- or poly-cyclic heterocycles, the one to three heteroatoms selected from a group consisting of oxygen , Contain nitrogen and sulfur, such as oxiranyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidiazinyl , 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl , 4-imidazolidinyl, 1, 2, 4-oxadiazolidin-3-yl, 1, 2, 4-oxadiazolidin-5-yl,
1,2, 4-Thiadiazolidin-3-yl, 1,2, 4-Thiadiazolidin-5-yl, l,2,4-Triazolidin-3-yl, 1, 3, 4-Oxadiazolidin-2-yl, 1,3,4-Thia- diazolidin-2-yl, 1, 3, 4-Triazolidin-2-yl, 2,3-Dihydro- furan-2-yl, 2, 3-Dihydrofuran-3-yl, 2, 3-Dihydrofuran-4-yl, 2,3-Dihydrofuran-5-yl, 2, 5-Dihydrofuran-2-yl, 2,5-Dihydro- furan-3-yl, 2, 3-Dihydrothien-2-yl, 2, 3-Dihydrothien-3-yl, 2,3-Dihydrothien-4-yl, 2, 3-Dihydrothien-5-yl, 2,5-Dihydro- thien-2-yl, 2, 5-Dihydrothien-3-yl, 2, 3-Dihydropyrrol-2-yl, 2,3-Dihydropyrrol-3-yl, 2, 3-Dihydropyrrol-4-yl, 2,3-Dihydro- pyrrol-5-yl, 2, 5-Dihydropyrrol-2-yl, 2, 5-Dihydropyrrol-3-yl, 2,3-Dihydroisoxazol-3-yl, 2, 3-Dihydroisoxazol-4-yl, 2,3-Dihy- droisoxazol-5-yl, 4, 5-Dihydroisoxazol-3-yl, 4, 5-Dihydroisoxa- zol-4-yl, 4, 5-Dihydroisoxazol-5-yl, 2, 5-Dihydroisoxazol-3-yl, 2,5-Dihydroisoxazol-4-yl, 2 , 5-Dihydroxazol-5-yl, 2,3-Dihy- droisothiazol-3-yl, 2, 3-Dihydroisothiazol-4-yl, 2 , 3-Dihydroi- sothiazol-5-yl, 4, 5-Dihydroisothiazol-3-yl, 4 , 5-Dihydroiso- thiazol-4-yl, 4, 5-Dihydroisothiazol-5-yl, 2 , 5-Dihydroisothia- zol-3-yl, 2, 5-Dihydroisothiazol-4-yl, 2, 5-Dihydroisothia- zol-5-yl, 2,3-Dihydropyrazol-3-yl, 2, 3-Dihydropyrazol- 4-yl, 2,3-Dihydropyrazol-5-yl, 4, 5-Dihydropyrazol-3-yl, 4 , 5-Dihydropyrazol-4-yl , 4 , 5-Dihydropyrazol-5-yl, 2, 5-Dihydropyrazol-3-yl, 2, 5-Dihydropyrazol-4-yl,1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl 1,1 3,4-thia-diazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3- Dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2, 3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2- yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazole 3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl, 2,5- Dihydroxazol-5-yl, 2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, 4,5-dihydroisothiazol-3-yl, 4, 5-dihydroisothiazol-4-yl, 4, 5 Dihydroisothiazol-5-yl, 2,5-dihydroisothia zol-3-yl, 2, 5-dihydroisothiazol-4-yl, 2, 5-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-3-yl, 2, 3-dihydropyrazol-4-yl, 2, 3-dihydropyrazol-5-yl, 4, 5-dihydropyrazol-3-yl, 4, 5-dihydropyrazol-4-yl, 4, 5-dihydropyrazol-5-yl, 2, 5-dihydropyrazol-3-yl, 2, 5-dihydropyrazol-4-yl,
2, 5-Dihydropyrazol-5-yl, 2, 3-Dihydrooxazol-2-yl, 2,3-Dihydro- oxazol-4-yl, 2 , 3-Dihydrooxazol-5-yl, 4, 5-Dihydrooxazol-2-yl, 4, 5-Dihydrooxazol-4-yl, 4, 5-Dihydrooxazol-5-yl, 2,5-Dihydro- oxazol-2-yl, 2, 5-Dihydrooxazol-4-yl, 2, 5-Dihydrooxazol-5-yl, 2, 3-Dihydrothiazol-2-yl, 2, 3-Dihydrothiazol-4-yl, 2,3-Dihy- drothiazol-5-yl, 4, 5-Dihydrothiazol-2-yl, 4 , 5-Dihydrothia- zol-4-yl, 4, 5-Dihydrothiazol-5-yl, 2, 5-Dihydrothiazol-2-yl, 2, 5-Dihydrothiazol-4-yl, 2, 5-Dihydrothiazol-5-yl, 2,3-Dihy- droimidazol-2-yl, 2, 3-Dihydroimidazol-4-yl, 2, 3-Dihydroimida- zol-5-yl, 4 , 5-Dihydroimidazol-2-yl, 4, 5-Dihydroimidazol-4-yl, 4, 5-Dihydroimidazol-5-yl, 2 , 5-Dihydroimidazol-2-yl, 2,5-Dihy- droimidazol-4-yl, 2 , 5-Dihydroimidazol-5-yl, 2-Morpholinyl, 3-Morpholinyl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperidinyl, 3-Tetrahydropyridazinyl, 4-Tetrahydropyridazinyl, 2-Tetra- hydropyrimidinyl, 4-Tetrahydropyrimidinyl, 5-Tetrahydro- pyrimidinyl, 2-Tetrahydropyrazinyl, 1, 3, 5-Tetrahydrotria- zin-2-yl, 1, 2, 4-Tetrahydrotriazin-3-yl, 1,3-Dihydro- oxazin-2-yl, 2-Tetrahydropyranyl, 3-Tetrahydropyranyl, 4-Tetrahydropyranyl, 2-Tetrahydrothiopyranyl, 3-Tetrahydro- thiopyranyl, 4-Tetrahydrothiopyranyl, 1, 3-Dioxolan-2-yl,2, 5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2- yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazole 5-yl, 2, 3-dihydrothiazol-2-yl, 2, 3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4, 5-dihydrothiazol-2-yl, 4, 5- Dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2, 3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4- yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3- Morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropydrazine zin-2-y l, 1, 2, 4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydro-thiopyranyl, 4- Tetrahydrothiopyranyl, 1, 3-dioxolan-2-yl,
1, 3-Dioxolan-4-yl, 1, 3-Dithiolan-2-yl, 1, 3-Dithiolan-4-yl, 1, 3-Dioxan-2-yl, 1, 3-Dioxan-4-yl, 1, 3-Dioxan-5-yl, 1,3-Di- thian-2-yl, 1, 3-Dithian-4-yl, 1, 3-Dithian-5-yl, 3,4,5,6- Tetrahydropyridin-2-yl, 4H-1, 3-Thiazin-2-yl, 4H-3, 1-Benzo- thiazin-2-yl, 1, l-Dioxo-2, 3 , 4, 5-tetrahydrothien-2-yl, 2H-1, 4-Benzothiazin-3-yl, 2H-1, 4-Benzoxazin-3-yl oder 1, 3-Dihydrooxazin-2-yl;1, 3-dioxolan-4-yl, 1, 3-dithiolan-2-yl, 1, 3-dithiolan-4-yl, 1, 3-dioxan-2-yl, 1, 3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,3-diethian-2-yl, 1,3-dithian-4-yl, 1,3-dithian-5-yl, 3,4,5,6- Tetrahydropyridin-2-yl, 4H-1, 3-thiazin-2-yl, 4H-3, 1-benzothiazin-2-yl, 1, l-dioxo-2, 3, 4, 5-tetrahydrothien-2- yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl or 1,3-dihydrooxazin-2-yl;
Hetaryl, sowie die Hetarylreste in Hetaryloxy und Hetaryl- Cι-C4~alkyl: aromatische mono- oder polycyclische Reste, welche neben Kohlenstoffringgliedern zusätzlich ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Sauerstoff- oder ein Schwefelatom oder ein Sauerstoff- oder ein Schwefelatom enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-Isoxazolyl, 4-Isoxazolyl, 5-Isoxazolyl, 3-Isothiazolyl, 4-Isothiazolyl, 5-Isothiazolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-Oxa- zolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazolyl, 2-Imidazolyl, 4-Imidazolyl, 1, 2, 4-Oxadiazol- 3-yl, 1,2, 4-Oxadiazol-5-yl, 1, 2, 4-Thiadiazol-3-yl,Hetaryl, as well as the hetaryl residues in hetaryloxy and hetaryl -CC-C 4 ~ alkyl: aromatic mono- or polycyclic residues which, in addition to carbon ring members, also contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one May contain sulfur atom, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5 -Isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1 , 2, 4-oxadiazol-3-yl, 1,2, 4-oxadiazol-5-yl, 1, 2, 4-thiadiazol-3-yl,
1, 2, 4-Thiadiazol-5-yl, 1, 2, 4-Triazol-3-yl, 1, 3, 4-Oxadiazol- 2-yl, 1, 3, 4-Thiadiazol-2-yl, 1, 3 , 4-Triazol-2-yl, 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl, 2-Pyrazinyl, 1,3, 5-Triazin-2-yl, 1, 2, 4-Triazin-3-yl, 1, 2, 4, 5-Tetrazin- 3-yl, sowie die entsprechenden benzokondensierten Derivate;1, 2, 4-thiadiazol-5-yl, 1, 2, 4-triazol-3-yl, 1, 3, 4-oxadiazol-2-yl, 1, 3, 4-thiadiazol-2-yl, 1, 3, 4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3, 5-triazin-2-yl, 1, 2, 4- Triazin-3-yl, 1, 2, 4, 5-tetrazin-3-yl, and the corresponding benzo-condensed derivatives;
C2-C6-Alkandiyl : z.B. Ethan-1, 2-diyl, Propan-1, 3-diyl, Butan-1, 4-diyl, Pentan-1, 5-diyl oder Hexan-1, 6-diyl;C 2 -C 6 alkanediyl: for example ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl or hexane-1, 6-diyl;
cyclisches Ringsystem mit 3 - 14 Ringatomen: C3-C8-Cycloalkyl, insbesondere C3-C6-Cycloalkyl wie zuvor genannt, fernercyclic ring system with 3-14 ring atoms: C 3 -C 8 cycloalkyl, in particular C 3 -C6 cycloalkyl as mentioned above, furthermore
Cycloheptyl oder Cyclooctyl; C3-Cβ-Cycloalkenyl wie zuvor genannt; bi- oder tricyclische carbocyclische oder heterocycli- sche Ringsysteme mit bis zu 14 Ringatomen, wobei die Ring- systeme gesättigt oder ungesättigt sein und eine, zwei oder drei Doppelbindungen enthalten können, und im Falle der heterocyclischen Ringe die Heteroatome ausgewählt sind aus Stickstoff, Schwefel und/oder Sauerstoff. Carbocyclische bi- oder tricyclische Ringsysteme sind z.B. Adamantyl, Norbornyl, Camphyl oder Camphenyl. Die bi- oder tricyclischen Ring- Systeme können ggf. durch Ci-Cβ-Alkyl, Ci-Cβ-Alkoxy,Cycloheptyl or cyclooctyl; C 3 -Cβ-cycloalkenyl as mentioned above; bi- or tricyclic carbocyclic or heterocyclic ring systems with up to 14 ring atoms, where the ring systems can be saturated or unsaturated and can contain one, two or three double bonds, and in the case of heterocyclic rings the heteroatoms are selected from nitrogen, sulfur and / or oxygen. Carbocyclic bi- or tricyclic ring systems are for example adamantyl, norbornyl, camphyl or camphenyl. The bi- or tricyclic ring systems can optionally be substituted by Ci-Cβ-alkyl, Ci-Cβ-alkoxy,
Ci-Cβ-Halogenalkyl, Cι-C6-Halogenalkoxy oder Halogen ein- oder mehrfach substituiert sein.Ci-Cβ-haloalkyl, -CC 6 -haloalkoxy or halogen be substituted one or more times.
Ci-Cδ-Alkyl, das durch ein cyclisches Ringsystem mit 3 - 14 Ringatomen substituiert ist: eine geradkettige oder verzweigte Ci-Cβ-Alkylgruppe, die durch die zuvor genannten C3-C6-Cycloalkyl-, C3-C6-Cycloalkenylgruppen oder carbo- cyclischen oder heterocyclischen Ringsysteme mit bis zu 14 Ringatomen substituiert ist. Beispielhaft seien genannt: Cy- clopropyl-methyl, 1-Cyclopropyl-ethyl, 2-Cyclopropyl-ethyl,Ci-C δ -alkyl which is substituted by a cyclic ring system with 3 - 14 ring atoms: a straight-chain or branched Ci-Cβ-alkyl group which is characterized by the aforementioned C 3 -C 6 cycloalkyl, C 3 -C 6 - Cycloalkenyl groups or carbocyclic or heterocyclic ring systems with up to 14 ring atoms is substituted. Examples include: cyclopropyl-methyl, 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl,
1-Methyl-l-cyclopropyl-ethyl, Adamantyl-methyl, Norbornyl-me- thyl, Camphyl-methyl oder Camphenyl-methyl. Diese Ringsysteme können ggf. durch C^-Cö-Alkyl, Cι-C6-Alkoxy, Cχ-C6-Halogen- alkyl, Cι-C6-Halogenalkoxy oder Halogen ein- oder mehrfach substituiert sein.1-methyl-1-cyclopropyl-ethyl, adamantyl-methyl, norbornyl-methyl, camphyl-methyl or camphenyl-methyl. These ring systems optionally may be prepared by C ^ -C ö -alkyl, C 6 alkoxy, Cχ-C6-halo-alkyl, Cι-C -haloalkoxy or halogen or mono- 6 be substituted multiple times.
Alle Phenyl-, Hetaryl- und Heterocyclylringe sind vorzugsweise unsubstituiert oder tragen ein bis drei Halogenatome und/oder einen oder zwei Reste aus folgender Gruppe: Nitro, Cyano, Methyl, Trifluormethyl, Methoxy, Trifluormethoxy oder Methoxycarbonyl.All phenyl, hetaryl and heterocyclyl rings are preferably unsubstituted or carry one to three halogen atoms and / or one or two radicals from the following group: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.
In Hinblick auf die Verwendung der erfindungsgemäßen Verbindungen der Formel I als Herbizide haben die Variablen vorzugsweise folgende Bedeutungen, und zwar jeweils für sich allein oder in Kom- bination miteinander: Ri Nitro, Halogen, Cyano, Rhodano, Ci-Cδ-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkoxy-Cι-C6-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, -OR6 oder -S(0)nR8; insbesondere Nitro, Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy; bevorzugt Chlor, Methyl oder Methoxy.With regard to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the following meanings, in each case individually or in combination with one another: Ri is nitro, halogen, cyano, thiocyanato, Ci-C δ -alkyl, C 6 haloalkyl, Cι-C 6 -alkoxy-Cι-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 -Alkynyl, -OR 6 or -S (0) n R 8 ; in particular nitro, fluorine, chlorine, bromine, methyl, ethyl, methoxy; preferably chlorine, methyl or methoxy.
R2 Wasserstoff, Nitro, Halogen, Cyano, Rhodano, Cι-C6-Alkyl, Cι-C6-Halogenalkyl, Ci-Cβ-Alko- xy-Cι-C6-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, -OR6 oder besonders bevorzugt Wasserstoff, Nitro, Halogen, wie z.B. Fluor, Chlor oder Brom, Ci-Cβ-Alkyl, Ci-Cβ-Halogenalkyl, -OR6 oder -S0R8; insbesondere Nitro, Halogen wie z.B. Fluor, Chlor oder Brom, Cι-C6-Alkyl, Cι-C6-Halogenalkyl, -OR6 oder S02R8; bevorzugt -S02-R8, wobei R8 Ci-Cβ-Alkyl bedeutet, insbesondere Methyl oder Ethyl. Der Substituent R2 steht bevorzugt an 4- oder 5-Stellung des Phenylringes, insbesondere in 4-Stellung, d.h. in para-Position zur Py- razolcarbonylgruppe .R2 is hydrogen, nitro, halogen, cyano, thiocyanato, Cι-C 6 -alkyl, C 6 haloalkyl, Ci-Cβ-alcohol xy-Cι-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -OR 6 or particularly preferably hydrogen, nitro, halogen, such as fluorine, chlorine or bromine, Ci-Cβ-alkyl, Ci-Cβ-haloalkyl, -OR 6 or -S0R 8 ; in particular nitro, halo such as fluorine, chlorine or bromine, Cι-C 6 -alkyl, C 6 haloalkyl, -OR 6, or S0 2 R 8; preferably -S0 2 -R 8 , where R 8 is Ci-Cβ-alkyl, especially methyl or ethyl. The substituent R 2 is preferably in the 4- or 5-position of the phenyl ring, in particular in the 4-position, ie in the para-position to the pyrazole carbonyl group.
R3 Wasserstoff, Halogen, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, Ci-Cβ-Alkoxy, C2-C6-Alkenyl oder C2-C6-Alkinyl; besonders bevorzugt Wasserstoff, Halogen wie z.B.R 3 is hydrogen, halogen, Ci-Cβ-alkyl, -C-C 6 haloalkyl, Ci-Cβ-alkoxy, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl; particularly preferably hydrogen, halogen such as
Fluor, Chlor oder Brom, Cι-C4-Alkyl wie z.B. Methyl oder Ethyl, Cι-C-Halogenalkyl wie z.B. Trifluormethyl, Cι-C4-Alkoxy wie z.B. Methoxy oder Ethoxy, Allyl oder Propargyl; insbesondere bevorzugt Wasserstoff oder Methyl;Fluorine, chlorine or bromine, -C 4 alkyl such as methyl or ethyl, -C -C haloalkyl such as trifluoromethyl, -C 4 alkoxy such as methoxy or ethoxy, allyl or propargyl; particularly preferably hydrogen or methyl;
R4 Wasserstoff, Nitro, Halogen, Cyano, Rhodano,R 4 is hydrogen, nitro, halogen, cyano, rhodano,
Cι-C6-Alkyl, Cι-C6-Halogenalkyl, C3-C6-Cycloalkyl, C-C6-Alkenyl, C4-C6-Cycloalkenyl, C2-C6-Alkinyl, Cι-C6-Alkylthio, Cι-C6-Halogenalkoxy, -COR12, -C02R12,Cι-C 6 -alkyl, C 6 haloalkyl, C 3 -C 6 cycloalkyl, CC 6 alkenyl, C 4 -C 6 cycloalkenyl, C 2 -C 6 alkynyl, Cι-C 6 alkylthio, -C-C 6 haloalkoxy, -COR 12 , -C0 2 R 12 ,
-COSR12, -CONR12R13, -C(R1 )=NR15, -PO(OR12) (OR13) , C1-C4-Alkyl, das einen Rest aus folgender Gruppe trägt: -COR12, -C02R12, -COSR12, -CONR12R13 oder -C (R14) ^NR*; Heterocyclyl, Heterocyclyl-Cι-C-alkyl, Phenyl, Phe- nyl-Cι-C4-alkyl, Hetaryl oder Hetaryl-Cι-C4-alkyl, wobei die sechs letztgenannten Reste ihrerseits substituiert sein können durch ein bis drei Halogenatome und/ oder einen bis drei Reste aus folgender Gruppe tragen können: Nitro, Cyano, C1-C4-Alkyl, Cι-C4-Halogenalkyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C4-Alkylcarbonyl oder Cι-C-Alkoxycarbonyl; insbesondere Wasserstoff. R5 Wasserstoff, Nitro, Halogen, Cyano, Rhodano,-COSR 12 , -CONR 12 R 13 , -C (R 1 ) = NR 15 , -PO (OR 12 ) (OR 13 ), C 1 -C 4 alkyl, which carries a radical from the following group: -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 12 R 13 or -C (R 14 ) ^ NR *; Heterocyclyl, heterocyclyl -CC-C-alkyl, phenyl, phenyl -CC-C 4 -alkyl, hetaryl or hetaryl -CC-C 4 -alkyl, where the last six radicals in turn can be substituted by one to three halogen atoms and / or may carry one to three radicals from the following group: nitro, cyano, C 1 -C 4 -alkyl, C 4 haloalkyl, Cι-C 4 -alkoxy, C 4 haloalkoxy, Cι-C 4 alkylcarbonyl or -CC alkoxycarbonyl; especially hydrogen. R 5 hydrogen, nitro, halogen, cyano, rhodano,
Cι-C6-Alkyl, Cι-C6-Halogenalkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C4-C6-Cycloalkenyl, C2-C6-Alkinyl, Cx-Cö-Alkylthio, Cι-C6-Halogenalkoxy, -COR12, -C0R12, -COSR12, -CONR12R13, -C (R14) =NR15, -PO (OR12) (OR13) ,Cι-C 6 -alkyl, C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 4 -C 6 cycloalkenyl, C 2 -C 6 alkynyl, Cx-C ö -Alkylthio, -C-C 6 -haloalkoxy, -COR 12 , -C0R 12 , -COSR 12 , -CONR 12 R 13 , -C (R 14 ) = NR 15 , -PO (OR 12 ) (OR 13 ),
Cι-C4-Alkyl, das einen Rest aus folgender Gruppe trägt: -COR12, -C02R12, -COSR12, -CONR12R13 oder -C (R14) =NR15; Heterocyclyl, Heterocyclyl-Cχ-C4-alkyl, Phenyl, Phe- nyl-Cι-C4-alkyl, Hetaryl oder Hetaryl-Cι-C4-alkyl, wo- bei die sechs letztgenannten Reste ihrerseits substituiert sein können durch ein bis drei Halogenatome und/ oder einen bis drei Reste aus folgender Gruppe tragen können: Nitro, Cyano, Cι~C-Alkyl, Cι-C4-Halogenalkyl, Cι-C4-Alkoxy, Cχ-C4-Halogenalkoxy, Cι-C4~Alkylcarbonyl oder Cι-C4-Alkoxycarbonyl; besonders bevorzugt Wasserstoff, Halogen, Cyano, Rhodano, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, -COR12, -C02R12, -COSR12, -CONR12R13 oder -PO(OR12) (OR13) ; insbesondere Wasserstoff.C 1 -C 4 alkyl which carries a radical from the following group: -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 12 R 13 or -C (R 14 ) = NR 15 ; Heterocyclyl, heterocyclyl-Cχ-C 4 -alkyl, phenyl, phenyl-Cι-C 4 -alkyl, hetaryl or hetaryl-Cι-C 4 -alkyl, where the latter six radicals in turn can be substituted by one to three halogen atoms / or may carry one to three and radicals from the following group: nitro, cyano, ~ C alkyl, Cι-C4-haloalkyl, Cι-C4-alkoxy, Cχ-C4-haloalkoxy, Cι-C 4 ~ Alkylcarbonyl or -CC 4 alkoxycarbonyl; particularly preferably hydrogen, halogen, cyano, rhodano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 12 R 13 or -PO (OR 12 ) ( OR 13 ); especially hydrogen.
R6 Wasserstoff, Methyl; insbesondere Wasserstoff.R6 is hydrogen, methyl; especially hydrogen.
R7 Cyclopropyl, Cyclopentyl, Cyclohexyl, Adamantyl,R 7 cyclopropyl, cyclopentyl, cyclohexyl, adamantyl,
Norbornyl, Camphyl oder Camphenyl, die unsubstituiert oder ein- oder zweifach substituiert sind durch Ci-Cβ-Alkyl, insbesondere Methyl.Norbornyl, camphyl or camphenyl, which are unsubstituted or mono- or disubstituted by Ci-Cβ-alkyl, especially methyl.
R8 Ci-Cö-Alkyl, insbesondere Methyl, Ethyl;R 8 Ci-C ö alkyl, especially methyl, ethyl;
R9 Wasserstoff, Cι-C6-Alkyl;R 9 is hydrogen, -CC 6 alkyl;
RIO Wasserstoff, Ci-Cβ-Alkyl;RIO hydrogen, Ci-Cβ-alkyl;
R 1 Ci-Cδ-Alkyl, Ci-Cβ-Alkoxy;R 1 Ci-C δ alkyl, Ci-Cβ-alkoxy;
R12 Wasserstoff, Ci-Cβ-Alkyl; R 12 is hydrogen, Ci-Cβ-alkyl;
R 3 Wasserstoff, Cχ-C6-Alkyl;R 3 is hydrogen, Cχ-C 6 alkyl;
R14 Wasserstoff, Cι-C6-Alkyl; R 14 is hydrogen, -CC 6 alkyl;
Ri5 Wasserstoff, Cχ-C6-Alkyl, Cι-C6-Alkoxy.Ri5 hydrogen, Cχ-C 6 alkyl, -CC 6 alkoxy.
R16 Hydroxy. Besonders bevorzugt sind in diesem Sinne Verbindungen der Formel' I, wobei R1 - R15 jeweils unabhängig voneinander folgende Bedeutungen haben:R 16 hydroxy. In this sense, particular preference is given to compounds of the formula I, where R 1 -R 15 each independently have the following meanings:
Ri Chlor, Methyl, Methoxy;Ri chlorine, methyl, methoxy;
R2 Methylsulfonyl, Ethylsulfonyl;R 2 methylsulfonyl, ethylsulfonyl;
*3 Wasserstoff,* 3 hydrogen,
R4 Wasserstoff,R 4 is hydrogen,
R5 Wasserstoff,R 5 is hydrogen,
R6 Wasserstoff,R 6 is hydrogen,
R7 Cyclopropyl, Cyclopentyl, Adamantyl, Norbornyl, Camphyl oder Camphenyl, die unsubstituiert oder ein- oder zweifach substituiert sind durch Methyl.R 7 cyclopropyl, cyclopentyl, adamantyl, norbornyl, camphyl or camphenyl, which are unsubstituted or mono- or disubstituted by methyl.
Besonders bevorzugt sind Verbindungen der Formel I mit folgenden Resten R1 - R7, bzw. einer oder mehreren Kombinationen a) - g) derartiger Reste:Compounds of the formula I with the following radicals R 1 -R 7 or one or more combinations a) -g) of such radicals are particularly preferred:
a) R1 = Cι-C6 -Alkyl; Halogen; Cχ-C6 -Alkoxy.a) R 1 = -C 6 alkyl; Halogen; Cχ-C 6 alkoxy.
b) R2 = Ci-Cß-Alkylsulfonyl; wobei R2 vorzugsweise in para-Stel- lung zur Pyrazolylcarbonylgruppe am Phenylring steht.b) R 2 = Ci-C ß- alkylsulfonyl; where R 2 is preferably in the para position to the pyrazolylcarbonyl group on the phenyl ring.
c) R3 = R4 = Wasserstoffc) R 3 = R 4 = hydrogen
d) R5 = Wasserstoff oder Cι-C6 -Alkyld) R 5 = hydrogen or -CC 6 alkyl
e) R6 = Wasserstoffe) R 6 = hydrogen
f) R7 = Cyclopropyl, Cyclopentyl.f) R 7 = cyclopropyl, cyclopentyl.
<?) R16 = Hydroxy oder Phenyl-Sulfonyloxy<?) R 16 = hydroxy or phenylsulfonyloxy
Bevorzugte Ausführungsformen sind die folgenden Verbindungen der Formeln Ial - Ia6 : Preferred embodiments are the following compounds of the formulas Ial-Ia6:
Tabelle 1Table 1
Bevorzugt sind ferner Verbindungen Ia2, insbesondere die Verbindungen Ia2.001-Ia2.018, die sich von den entsprechenden Verbindungen lal .001-Ial .018 dadurch unterscheiden, daß R5 in For- mel I für Methoxy steht:Also preferred are compounds Ia2, in particular the compounds Ia2.001-Ia2.018, which differ from the corresponding compounds Ial .001-Ial .018 in that R 5 in formula I is methoxy:
Bevorzugt sind ferner Verbindungen Ia3, insbesondere die Verbindungen Ia3.001-la3.018, die sich von den entsprechenden Verbindungen lal .001-Ial.018 dadurch unterscheiden, daß R5 in Formel I für Methyl steht: Also preferred are compounds Ia3, in particular the compounds Ia3.001-la3.018, which differ from the corresponding compounds Ial .001-Ial.018 in that R 5 in formula I is methyl:
Bevorzugt sind ferner Verbindungen Ia4, insbesondere dieCompounds Ia4, in particular those, are also preferred
Verbindungen Ia4.001-Ia4.018, die sich von den entsprechenden Verbindungen lal .001-Ial.018 dadurch unterscheiden, daß R5 in Formel I für Ethyl steht:Compounds Ia4.001-Ia4.018, which differ from the corresponding compounds Ial .001-Ial.018 in that R 5 in formula I is ethyl:
Bevorzugt sind ferner Verbindungen Ia5, insbesondere die Verbindungen Ia5.001-Ia5.018, die sich von den entsprechendenAlso preferred are compounds Ia5, in particular compounds Ia5.001-Ia5.018, which differ from the corresponding ones
Verbindungen lal .001-Ial.018 dadurch unterscheiden, daß R5 in Formel I für Cyano steht:Distinguish compounds lal .001-Ial.018 in that R 5 in formula I is cyano:
Bevorzugt sind ferner Verbindungen Ia6, insbesondere die Verbindungen Ia6.001-Ia6.018, die sich von den entsprechenden Verbindungen lal .001-Ial.018 dadurch unterscheiden, daß R5 in Formel I für i-Propyl steht: Also preferred are compounds Ia6, in particular the compounds Ia6.001-Ia6.018, which differ from the corresponding compounds Ial .001-Ial.018 in that R 5 in formula I is i-propyl:
Die Verbindungen der Formel I werden im wesentlichen nach den in WO 98/50366 beschriebenen Verfahren hergestellt.The compounds of the formula I are essentially prepared by the processes described in WO 98/50366.
Besonders eignet sich ein Verfahren, das dadurch gekennzeichnet ist, daß man ein Pyrazol der Formel IIA method is particularly suitable which is characterized in that a pyrazole of the formula II
R7 mit einer Carbonsäure III oder einem aktivierten Derivat davonR 7 with a carboxylic acid III or an activated derivative thereof
wobei die Variablen R1 bis R5 die unter Anspruch 1 genannten Bedeutungen haben und L1 für Hydroxy oder eine nucleophil verdräng- bare Abgangsgruppe (z.B. Halogen, Anhydrid) steht, acyliert und das Acylierungsprodukt gegebenenfalls in Gegenwart eines Katalysators zu den Verbindungen I umlagert.where the variables R 1 to R 5 have the meanings given in claim 1 and L 1 represents hydroxyl or a nucleophilically displaceable leaving group (for example halogen, anhydride), acylated and the acylation product rearranged to the compounds I, if appropriate in the presence of a catalyst.
Verbindungen der Formel II sind literaturbekannt oder können käuflich erworben werden. Alternativ können Verbindungen der For- mel II nach dem in DE 19910505 beschriebenen Verfahren hergestellt werden.Compounds of the formula II are known from the literature or can be purchased. Alternatively, compounds of the formula II can be prepared by the process described in DE 19910505.
Verbindungen der Formel III sind unter anderem aus WO 98/50366 und den dort angegebenen Literaturangaben bekannt. Im folgenden Reaktions Schema wird ein Syntheseweg zur Herstellung von Verbindungen I ausgehend von Verbindungen A über die Zwischenverbindungen B, C und D beispielhaf t für R1 = Methoxy, R2=Methylsulfonyl , R3=R4=R5=R6=H, R7=Cyclopropyl beschrieben (Kt -Bu = Kalium - tert .butylat; n-Buli = n-Butyl - lithium ; ACOH = Essigsäure; DME = Dimethylethoxyethan) .Compounds of the formula III are known, inter alia, from WO 98/50366 and the references given therein. In the following reaction scheme, a synthetic route for the preparation of compounds I starting from compounds A via the intermediate compounds B, C and D is exemplary for R 1 = methoxy, R 2 = methylsulfonyl, R 3 = R 4 = R 5 = R 6 = H , R 7 = cyclopropyl (Kt -Bu = potassium - tert.butylate; n-Buli = n-butyl - lithium; ACOH = acetic acid; DME = dimethylethoxyethane).
II
Die Verbindungen I können in Form ihrer landwirtschaftlich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes im allgemeinen nicht ankommt. Üblicherweise werden die Salze von solchen Basen in Betracht kommen, welche die herbizide Wirkung von I nicht negativ beeinträchtigen.The compounds I can be in the form of their agriculturally useful salts, the type of salt generally not being important. Usually the salts of such bases will be considered which do not adversely affect the herbicidal activity of I.
Als basische Salze eignen sich besonders diejenigen der Alkalimetalle, vorzugsweise die Lithium, Natrium- und Kaliumsalze, die der Erdalkalimetalle, vorzugsweise Calcium-, Magnesium-, und Bariumsalze und die der Übergangsmetalle, vorzugsweise Mangan-, Kupfer-, Zink- und Eisensalze, Ammoniumsalze, sowie Ammoniumsalze, die ein bis vier Cχ-C4-Alkyl, Hydroxy-Cι-C4-alkylsub- stituenten, einen Phenyl- oder Benzylsubstituenten tragen können, vorzugsweise Diethylammonium-, Diisopropylammonium-, Tetramethyl - ammonium-, Tetrabutylammonium- , Trimethylbenzylammonium-, und Trimethyl- (2-hydroxyethyl) -ammoniumsalze, die Phosphoniumsalze, die Sulfoniumsalze, vorzugsweise Tri- (Cι-C4~alkyl) sulfoniumsalze, und die Sulfoxoniumsalze, vorzugsweise Tri- (Cι-C4-alkyl) - sulfoxoniumsalze .Particularly suitable basic salts are those of the alkali metals, preferably the lithium, sodium and potassium salts, those of the alkaline earth metals, preferably calcium, magnesium and barium salts and those of the transition metals, preferably manganese, copper, zinc and iron salts, ammonium salts , and ammonium salts which can carry one to four Cχ-C 4 alkyl, hydroxy-Cι-C 4 alkyl substituents, a phenyl or benzyl substituent, preferably diethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium -, And trimethyl (2-hydroxyethyl) ammonium salts, the phosphonium salts, the sulfonium salts, preferably tri- (C 4 -C 4 -alkyl) sulfonium salts, and the sulfoxonium salts, preferably tri- (C 1 -C 4 alkyl) sulfoxonium salts.
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Sie können ferner als Wachstums - regulatoren für Pflanzen (Schadpflanzen, Kultur- und Nutzpflanzen) eingesetzt werden. Die die Verbindungen I enthaltenden herbiziden Mittel bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schadgräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf.The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. They can also be used as growth regulators for plants (harmful plants, crops and useful plants). The herbicidal compositions containing the compounds I control vegetation on nonculture areas very good, especially with high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I bzw. sie enthaltende Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen:Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) , Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum,Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum,
(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) , Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.ru- stica) , Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifo- lium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersica, Musus spec, manus spec, Medicinal specimen, Malus spec. Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seea cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
Darüber hinaus können die Verbindungen I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden.In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
Die Applikation der herbiziden Mittel bzw. der Wirkstoffe kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirk- Stoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by) . Die Verbindungen I bzw. die sie enthaltenden herbiziden Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Oldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active substances are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active compounds grow more rapidly on the leaves below unwanted plants or the uncovered floor area (post-directed, lay-by). The compounds I or the herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules , Dusting, scattering or pouring. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Als inerte Zusatzstoffe kommen im Wesentlichen in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kero- sin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromati- sehe Kohlenwasserstoffe, z.B. Paraffin, Tetrahydronaphthalin, al- kylierte Naphthaline oder deren Derivate, alkylierte Benzole oder deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Ketone wie Cyclohexanon oder stark polare Lösungsmittel, z. B. Amine wie N-Methylpyrrolidon oder Wasser.The following are essentially considered as inert additives: mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Oldispersionen können die Verbindungen I als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oldispersions, the compounds I as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxy- ethylenoctylp enolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether, Alkyl - arylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethyleno- xid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether oder Polyoxypropylenalkylether, Laurylalkoholpolyglykolether- acetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht.The surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylp enol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, alkylphenol, alkylphenol Alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether. acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose.
Pulver-, Streu- und Stäubemittel können durch Mischen oder ge- meinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe herge- stellt werden. Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harn- Stoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urine and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
Die Konzentrationen der Wirkstoffe I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Die Formulierungen enthalten im allgemeinen 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, mindestens eines Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. The formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Die erfindungsgemäßen Verbindungen I können beispielsweise wie folgt formuliert werden:The compounds I according to the invention can be formulated, for example, as follows:
I 20 Gewichtsteile einer Verbindung I werden in einer Mischung gelöst, die aus 80 Gewichtsteilen alkyliertem Benzol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylen- oxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100.000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew. % des Wirkstoffs enthält.I 20 parts by weight of a compound I are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 Moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
II 20 Gewichtsteile einer Verbindung I werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctylphenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylen- oxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100.000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew. % des Wirkstoffs enthält.II 20 parts by weight of a compound I are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil , By pouring and finely distributing the solution in 100,000 parts by weight of water an aqueous dispersion containing 0.02% by weight of the active ingredient.
III 20 Gewichtsteile einer Verbindung I werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanon, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew. % des Wirkstoffs enthält.III 20 parts by weight of a compound I are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
IV 20 Gewichtsteile eines Wirkstoffes der Formel I werden mit 3 Gewichtsteilen des Natriumsalzes der Diisobutylnaphthalin- sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einerIV 20 parts by weight of an active ingredient of the formula I are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulphonic acid and 17 parts by weight of the sodium salt
Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20 000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew. % des Wirkstoffs enthält.Lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
V 3 Gewichtsteile eines Wirkstoffes der Formel I werden mit 97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew. % des Wirkstoffs enthält.V 3 parts by weight of an active ingredient of the formula I are mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3% by weight of the active ingredient.
VI 20 Gewichtsteile einer Verbindung I werden mit 2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichtsteilen Natrium- salz eines Phenol-Harnstoff-Formaldehyd-Kondensates und 68 Gewichtsteilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.VI 20 parts by weight of a compound I are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
VII 1 Gewichtsteil einer Verbindung I wird in einer Mischung ge- löst, die aus 70 Gewichtsteilen Cyclohexanon, 20 Gewichtsteilen ethoxyliertem Isooctylphenol und 10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Man erhält ein stabiles Emulsionskonzentrat.VII 1 part by weight of a compound I is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.
VIII 1 Gewichtsteil einer Verbindung I wird in einer Mischung gelöst, die aus 80 Gewichtsteilen Cyclohexanon und 20 Gewichtsteilen Wettol ® EM 31 (nicht ionischer Emulgator auf der Basis von ethoxyliertem Ricinusöl) . Man erhält ein stabiles Emulsionskonzentrat. Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die Verbindungen I mit zahlreichen Vertretern anderer herbizider oder wachstumsregulierender Wirkstoff - gruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1, 2, 4-Thiadiazole, 1, 3, 4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Aminotriazole, Anilide, (Het) -Aryloxyalkansäure und deren Derivate, Benzoesäure und deren Derivate, Benzothiadiazinone, 2-Aroyl-l, 3-cyclohexan- dione, Hetaryl-Aryl-Ketone, Benzylisoxazolidinone, Me- ta-CF3-phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracetanilide, Cyclohexan-1, 3-dionderivate, Diazine, Dichlorpropionsäure und deren Derivate, Dihydrobenzofurane, Dihydrofuran-3-one, Dinitroaniline, Dinitrophenole, Diphenyl- ether, Dipyridyle, Halogencarbonsäuren und deren Derivate, Harn- Stoffe, 3-Phenyluracile, Imidazole, Imidazolinone, N-Phe- nyl-3,4, 5, 6-tetrahydrophthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- oder Heteroaryloxyphenoxypropionsäureester, Phenylessig- säure und deren Derivate, Phenylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincarbonsäure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonylharnstoffe, Triazine, Triazinone, Triazolinone, Triazolcarboxamide, Uracile in Betracht.VIII 1 part by weight of a compound I is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (non-ionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained. To broaden the spectrum of activity and to achieve synergistic effects, the compounds I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1, 2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2-aroyl come as mixing partners -l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzene , Dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, urine substances, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5, 6-tetrahydrophthalimides, Oxadiazoles, oxiranes, phenols, aryloxy- or heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acids and their derivatives, pyrimide yl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils.
Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, beispielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden.It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
Die Aufwandmengen an Wirkstoff betragen je nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0.001 bis 3.0, vorzugsweise 0.01 bis 1.0 kg/ha aktive Substanz (a. S.)Depending on the control target, the season, the target plants and the growth stage, the active compound application rates are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see also)
Beispiel 1example 1
(5-Methoxy-l-cyclopropyl-lH-pyrazol-4-yl) - (4-methyl- sulfonyl-2-methoxy-3-vinyl-phenyl) -methanon(5-methoxy-1-cyclopropyl-1H-pyrazol-4-yl) - (4-methylsulfonyl-2-methoxy-3-vinylphenyl) methanone
a) 2-Methoxy-6-methylsulfanyl-benzaldehyda) 2-methoxy-6-methylsulfanyl-benzaldehyde
Zu einer Lösung von 2-Chlor-6-methoxybenzaldehyd (20 g, 0.12 mol) in NMP (12.2 g, 0.18 mol) wurde bei 0 °C portionsweise NaSMe (12.2 g, 0.18 mol) gegeben. Die Lösung rührte bei 0 °C 3 h und färbte sich schwarz. Anschließend wurde in ca. 2 1 Eiswasser einge- rührt, mit 10%iger HC1 auf pH = 3 angesäuert und der Niederschlag abgesaugt.NaSMe (12.2 g, 0.18 mol) was added in portions at 0 ° C. to a solution of 2-chloro-6-methoxybenzaldehyde (20 g, 0.12 mol) in NMP (12.2 g, 0.18 mol). The solution stirred at 0 ° C for 3 h and turned black. Subsequently, ice water was poured into approx. stirred, acidified to pH = 3 with 10% HC1 and the precipitate was suction filtered.
Ausbeute: 13.6 g (65%). 1H-NMR(270MHz, CDC13) : 2.4 (s, 3H) ; 3.9 (s, 3H) ; 6.8 (d, 1H) ; 6.95 (d, 1H) ; 7.42 (d, 1H) ; 10.6 (s, 1H) .Yield: 13.6 g (65%). 1 H NMR (270 MHz, CDC1 3 ): 2.4 (s, 3H); 3.9 (s, 3H); 6.8 (d, 1H); 6.95 (d. 1H); 7.42 (d, 1H); 10.6 (s, 1H).
b) 3-Brom-2-methoxy-6-methylsulfanyl-benzaldehydb) 3-bromo-2-methoxy-6-methylsulfanyl-benzaldehyde
Zu einer Lösung von 2-Methoxy-6-methylsulfanyl-benzaldehyd (22 g, 0.12 mol) in Dioxan (500 ml) wurde Brom (28.8 g, 0.18 mol) (in Dioxan (500 ml) gelöst) getropft und bei 50 ° C über 6 h gerührt. Die Mischung wurde dann eingeengt, in CH2C12 aufgenommen, mit H20 gewaschen, über MgS04 getrocknet und eingeengt. Der Feststoff wurde aus Diisopropylether umkristallisiert.Bromine (28.8 g, 0.18 mol) (dissolved in dioxane (500 ml)) was added dropwise to a solution of 2-methoxy-6-methylsulfanyl-benzaldehyde (22 g, 0.12 mol) in dioxane (500 ml) and at 50 ° C. stirred for 6 h. The mixture was then concentrated, taken up in CH 2 C1 2 , washed with H 2 0, dried over MgS0 4 and concentrated. The solid was recrystallized from diisopropyl ether.
Ausbeute: 17.5 g (56%). 1H-NMR(270MHz, CDCI3) : 2.40 (s, 3H) ; 3.90 (s, 3H) ; 6.72 (d, 1H) ; 6.85 (d, 1H) ; 7.42 (m, 1H) ; 10.6 (s, 1H) .Yield: 17.5 g (56%). 1 H NMR (270 MHz, CDCI 3 ): 2.40 (s, 3H); 3.90 (s, 3H); 6.72 (d, 1H); 6.85 (d. 1H); 7.42 (m, 1H); 10.6 (s, 1H).
c) l-Brom-2-methoxy-4-methylsulfanyl-3-vinyl-benzolc) l-bromo-2-methoxy-4-methylsulfanyl-3-vinyl-benzene
Zu einer Lösung von Methytriphenylphosphoniumbromid (19.7 g, 55.4 mmol) in THF (180 ml) wurde bei 0 °C K-t-Bu (6.2 g, 55.4 mmol) gegeben. Anschließend wurde bei -10 bis -5 °C 3-Brom-2-methoxy-6-methylsulfanyl-benzaldehyd (12 g, 46 mmol) ge- löst in THF (180 ml) zugegeben und 7 h bei RT über Nacht gerührt. Die Mischung wurde filtriert, die Lösung mit H20 (200 ml) und MTBE (200 ml) versetzt und anschließend mit MTBE (200 ml) extrahiert. Die vereinigten org. Phasen wurden über MgSÜ4 getrocknet und eingeengt. Chromatographie (Cyclohexan -> Cyclohexan/EtOAc 9:1) lie- ferte l-Brom-2-methoxy-4-methylsulfonyl-3-vinyl-benzol .Kt-Bu (6.2 g, 55.4 mmol) was added to a solution of methyltriphenylphosphonium bromide (19.7 g, 55.4 mmol) in THF (180 ml) at 0 ° C. Then 3-bromo-2-methoxy-6-methylsulfanyl-benzaldehyde (12 g, 46 mmol) dissolved in THF (180 ml) was added at -10 to -5 ° C. and the mixture was stirred at RT overnight for 7 h. The mixture was filtered, the solution was mixed with H 2 0 (200 ml) and MTBE (200 ml) and then extracted with MTBE (200 ml). The united org. Phases were dried over MgSÜ 4 and concentrated. Chromatography (cyclohexane -> cyclohexane / EtOAc 9: 1) provided l-bromo-2-methoxy-4-methylsulfonyl-3-vinyl-benzene.
Ausbeute: 4.67 g (39%). 1H-NMR(270MHz , CDCI3) : 2.40 (s, 3H) ; 3.70 (S, 3H) ; 5.62 (dd, 1H) ; 5.90 (dd, 1H) ; 6.70-6.90 (m, 2H) ; 7.40 (S, 1H) .Yield: 4.67 g (39%). 1 H NMR (270 MHz, CDCI 3 ): 2.40 (s, 3H); 3.70 (S, 3H); 5.62 (dd, 1H); 5.90 (dd, 1H); 6.70-6.90 (m, 2H); 7.40 (S, 1H).
d) 2-Methoxy-4-methylsulfanyl-3-vinyl-benzoesäured) 2-methoxy-4-methylsulfanyl-3-vinyl-benzoic acid
Zu einer Lösung von l-Brom-2-methoxy-4-methylsulfanyl-3-vinyl- benzol (7 g, 31.3 mmol) in THF (300 ml) wurde bei -100 °C n-BuLi (25 ml, 15%ig in n-Hexan, 4.1 mmol) gegeben und 20 min. bei -100 °C nachgerührt. Anschließend wurde bei -100 °C C02 eingeleitet (exoterme Reaktion auf -60 °C) . Dann wurde noch 1 h bei -80 bis -90 °C nachgerührt und bei -40 °C NaOH (100 ml) zugetropft. Die Lösung wurde in EtOAc (400 ml) eingerührt, 3 x mit 5%iger NaOH extrahiert, mit 10%iger HC1 angesäuert auf pH = 1. Die H20-Phase wurde mit EtOAc (300 ml) extrahiert, die vereinigten org. Phasen über MgS04 getrocknet und eingeengt.To a solution of l-bromo-2-methoxy-4-methylsulfanyl-3-vinylbenzene (7 g, 31.3 mmol) in THF (300 ml) was added n-BuLi (25 ml, 15%) at -100 ° C in n-hexane, 4.1 mmol) and 20 min. stirred at -100 ° C. Then C0 2 was introduced at -100 ° C (exotic reaction to -60 ° C). The mixture was then stirred for a further 1 h at -80 to -90 ° C. and NaOH (100 ml) was added dropwise at -40 ° C. The solution was stirred into EtOAc (400 ml), extracted 3 × with 5% NaOH, acidified to pH = 1 with 10% HC1. The H 2 0 phase was extracted with EtOAc (300 ml), the combined org. Phases dried over MgS0 4 and concentrated.
Ausbeute: 6.8 g (98%). 1H-NMR(270MHz, CDC13) : 1.90 (s, 3H) ; 2.42 (s, 3H) ; 3.62 (s, 3H) ; 5.50-5.80 (m, 2H) ; 6.58-6.65 (m, IH) ; 7.1 (d, IH); 7.6 (d, IH) .Yield: 6.8 g (98%). 1 H NMR (270 MHz, CDC1 3 ): 1.90 (s, 3H); 2.42 (s, 3H); 3.62 (s, 3H); 5.50-5.80 (m, 2H); 6.58-6.65 (m, IH); 7.1 (d, IH); 7.6 (d, IH).
e) 4-Methylsulfonyl-2-methoxy-3-vinyl-benzoesäuree) 4-methylsulfonyl-2-methoxy-3-vinyl-benzoic acid
Zu einer Lösung von 2-Methoxy-4-methylsulfanyl-3-vinyl-benzoe- säure (6.8 g, 30 mmol) in AcOH (130 ml) wurde NaW0 (kat.) gegeben, H2O2 (8.6 ml, 76 mmol) zugetropft und 5 h bei Raumtemperatur gerührt. Die Lösung wurde eingeengt, in Methylenchlorid aufgenommen, über Magnesiumsulfat getrocknet und eingeengt.NaOH (cat.) Was added to a solution of 2-methoxy-4-methylsulfanyl-3-vinylbenzoic acid (6.8 g, 30 mmol) in AcOH (130 ml), H 2 O 2 (8.6 ml, 76 mmol ) added dropwise and stirred for 5 h at room temperature. The solution was concentrated, taken up in methylene chloride, dried over magnesium sulfate and concentrated.
Ausbeute: 4.8 g (61%) . iH-NMR (270MHz, CDCI3) : 3.20 (s, 3H) ; 3.70 (s, 3H) ; 5.65-5.90 (m, 2H) ; 7.0-7.20 (m, IH) ; 7.65-7.95 (m, 2H) .Yield: 4.8 g (61%). i H-NMR (270 MHz, CDCI 3 ): 3.20 (s, 3H); 3.70 (s, 3H); 5.65-5.90 (m, 2H); 7.0-7.20 (m, IH); 7.65-7.95 (m, 2H).
f) 5-Hydroxy-l-cyclopropyl-lH-pyrazol-4-yl)- (4-methyl- sulfonyl-2-methoxy-3-vinyl-phenyl) -methanonf) 5-Hydroxy-1-cyclopropyl-1H-pyrazol-4-yl) - (4-methylsulfonyl-2-methoxy-3-vinylphenyl) methanone
Zu einer Lösung von 4-Methylsulfonyl-2-methoxy-3-vinyl-benzoe- säure (1.6 g, 6 mmol) in Toluol (60 ml) wurde S0C12 (1.2 g, 10 mmol) gegeben und 2 h auf Rückfluß erhitzt. Anschließend wurde eingeengt und das Produkt zu einer Lösung von N-Cyclopropylpyra- zolon (6 mmol), K2C03 (1.6 g, 11.6 mmol) in DME (30 ml) gegeben und bei RT über Nacht gerührt. Anschließend wurde 2 h auf Rückfluß erhitzt, die Mischung eingeengt und in H20 gelöst. Die H20- Phase wurde 3 x mit CH2C12 extrahiert, die vereinigten org. Phasen wurden über MgSÜ4 getrocknet und eingeengt.SO 4 (1.2 g, 10 mmol) was added to a solution of 4-methylsulfonyl-2-methoxy-3-vinyl-benzoic acid (1.6 g, 6 mmol) in toluene (60 ml) and the mixture was heated under reflux for 2 h. The mixture was then concentrated and the product was added to a solution of N-cyclopropylpyrazolone (6 mmol), K 2 CO 3 (1.6 g, 11.6 mmol) in DME (30 ml) and stirred at RT overnight. The mixture was then heated to reflux for 2 h, the mixture was concentrated and dissolved in H 2 0. The H 2 0 phase was extracted 3 times with CH 2 C1 2 , the combined org. Phases were dried over MgSÜ4 and concentrated.
Beispiel 2Example 2
In gleicher Weise wie in Beispiel 1 beschrieben können die fol- genden Verbindungen erhalten werden:The following compounds can be obtained in the same way as described in Example 1:
Tabelle 2 . 1 Table 2. 1
1) Verbindung I mit R16 = 4 -Methylphenyl -sulfonyloxy 1) Compound I with R 16 = 4 -methylphenylsulfonyloxy
30 Beispiel 330 Example 3
Zu gleicher Weise wie in Beispiel 1 beschrieben, können die fol' genden Verbindungen hergestellt werden:The following compounds can be prepared in the same manner as described in Example 1:
45 Tabelle 3.145 Table 3.1
10 10
Beispiel 4Example 4
15 Die herbizide Wirkung der Verbindungen der Formel I ließ sich durch Gewächshausversuch zeigen:15 The herbicidal activity of the compounds of the formula I was demonstrated by greenhouse tests:
Als Kulturgefäße dienten Plastiktöpfe mit lehmigem Sand mit etwa 3,0% Humus als Substrat. Die Samen der Testpflanzen wurden nach 2 Arten getrennt eingesät.Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to 2 types.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um " Keimung und Wachstum zu fördern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Test- pflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde. 30In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote "germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients. 30
Zum Zweck der Nachauflaufbehandlung wurden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen wurden dafür entweder di - " rekt gesät und in den gleichen Gefäßen aufgezogen oder sie wurden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefäße verpflanzt.For the purpose of post-emergence treatment, depending on the growth habit, the test plants were first grown to a height of 3 to 15 cm and then treated with the active ingredients suspended or emulsified in water. The test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 - 25°CThe plants became species-specific at temperatures of 10 - 25 ° C
40 bzw. 20 - 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.40 or 20 - 35 ° C kept. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
45 Bewertet wird nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf .45 Evaluation is based on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
Die in den Gewächshausversuchen verwendeten Pflanzen setzen sich vorzugsweise aus folgenden Arten zusammen:The plants used in the greenhouse experiments are preferably composed of the following types:
10 Code Deutscher Name Englischer Name10 Code German name English name
AMARE Fuchsschwanz, pigweed zurückgekrümmterAMARE foxtail, pigweed curved back
CHEAL Weißer Gänsefuß lambsquarters ECHCG Hühnerhirse barnyardgrass 15 POLPE Flohknöterich ladysthumb SETVI Grüne Borstenhirse green foxtail SINAL Weißer Senf white mustard SOLNI Schwarzer Nachtblack nightshade schattenCHEAL white goose foot lambsquarters ECHCG chicken millet barnyardgrass 15 POLPE knotweed ladysthumb SETVI green bristle millet green foxtail SINAL white mustard white mustard SOLNI black night black nightshade shade
2020
Im Vorauflaufverfahren werden mit den erfindungsgemäßen Verbindungen I bei 0.25 kg/ha a. S. (aktive Substanz) Schadgräser bzw. breitblättrige Pflanzen sehr gut bekämpft. Die erfindungs- 25 gemäßen Verbindungen verfügen somit über eine ausgeprägte herbizide Wirkung.In the pre-emergence process with the compounds I according to the invention at 0.25 kg / ha a. S. (active substance) combats harmful grasses or broad-leaved plants very well. The compounds of invention 25 proper thus have a strong herbicidal action.
Tabelle 4.1Table 4.1
_0 Herbizide Aktivität bei Nachauflaufanwendung im Gewächshaus (Aufwandmenge: 0,25 kg/ha aktive Substanz)_ 0 herbicidal activity in post-emergence applications in the greenhouse (application rate: 0.25 kg / ha of active substance)
3535
4040
4545

Claims

Patentansprüche claims
1. Pyrazole der Formel I1. pyrazoles of the formula I.
in der die Reste folgende Bedeutungen haben: in which the residues have the following meanings:
R1 Wasserstoff, Nitro, Halogen, Cyano, Rhodano,R 1 is hydrogen, nitro, halogen, cyano, rhodano,
Ci-Cδ-Alkyl, Ci-Cε-Alkoxy, Ci-Cβ-Halogenalkyl, Cι-C6-Alkylthio, Cι-C6-Alkoxy-Cι-C6-alkyl, C2-C6-Al- kenyl, C2-C6-Alkinyl, -S(0)nR8, -S02OR9, -S02NR9R10, -NR10SO2Rι:L, -NRiOCOR11, -PO (OR12) (OR13) ;Ci-C δ- alkyl, Ci-Cε-alkoxy, Ci-Cβ-haloalkyl, Cι-C 6 -alkylthio, Cι-C 6 -alkoxy-Cι-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 alkynyl, -S (0) n R 8 , -S0 2 OR 9 , -S0 2 NR 9 R 10 , -NR 10 SO 2 R ι: L , -NR iO COR 11 , -PO ( OR 12 ) (OR 13 );
R2 Wasserstoff, Ci-Cβ-Alkyl, Cι-C6-Alkoxy, Cι-C6-Al- kylthio, C2-C6-Alkenyl, C2-C6-Alkinyl, Halogen, Nitro, -S(0)nR8, -S02OR9, -S02NR9R °, -NR10SO2Rι:L, -NR^COR11, -PO(OR12) (OR13) ;R 2 is hydrogen, Ci-Cβ-alkyl, Cι-C 6 -alkoxy, C 6 alkylthio -Al-, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogen, nitro, -S (0) n R 8 , -S0 2 OR 9 , -S0 2 NR 9 R °, -NR 10 SO 2 R ι: L , -NR ^ COR 11 , -PO (OR 12 ) (OR 13 );
R3 Wasserstoff, Halogen, Ci-Cβ-Alkyl, Ci-Cδ-Halogenal- kyl, Cχ-C6-Alkoxy, C2-C6-Alkenyl oder C2-C6-Alkinyl;R 3 is hydrogen, halogen, Ci-Cβ-alkyl, Ci-C δ -haloalkyl, Cχ-C 6 alkoxy, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl;
R4, R5 Wasserstoff, Nitro, Halogen, Cyano, Rhodano,R 4 , R 5 hydrogen, nitro, halogen, cyano, rhodano,
Cι-C6-Alkyl, Ci-Cβ-Halogenalkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C4-C6-Cycloalkenyl, C2-C6-Alkinyl, Ci-Cβ-Alkylthio, Ci-Cö-Halogenalkoxy, -COR12, -C02R12, -COSR12, -CONR1 R13, -C (R14) =NR15,-C-C 6 alkyl, Ci-Cβ-haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 4 -C 6 cycloalkenyl, C 2 -C 6 alkynyl, Ci-Cβ-alkylthio , Ci-C ö -haloalkoxy, -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 1 R 13 , -C (R 14 ) = NR 15 ,
-PO(OR12) (OR13) , Cx-C4-Alkyl, das einen Rest aus folgender Gruppe trägt: -COR12, -C02R12, -COSR12, -CONR12R13 oder -C (R14) =NR15; Heterocyclyl, Hetero- cyclyl-Cι-C4-alkyl, Phenyl, Phenyl-Cι-C4-alkyl, He' taryl oder Hetaryl-Cι-C -alkyl, wobei die sechs letztgenannten Reste substituiert sein können;-PO (OR 12 ) (OR 13 ), C x -C 4 alkyl which carries a radical from the following group: -COR 12 , -C0 2 R 12 , -COSR 12 , -CONR 12 R 13 or -C ( R 14 ) = NR 15 ; Heterocyclyl, heterocyclic -CC 4 -alkyl, phenyl, phenyl -CC 4 -alkyl, He 'taryl or hetaryl -CC-C alkyl, where the latter six radicals can be substituted;
oderor
R4 un(j R5 bilden gemeinsam eine C2-C6-Alkandiylkette, die ein- bis vierfach durch C!-C4-Alkyl substituiert sein kann und/oder durch Sauerstoff oder Schwefel oder einen gegebenenfalls C1-C4-Alkyl substituierten Stickstoff unterbrochen sein kann;R4 and ( R5 together form a C 2 -C 6 alkanediyl chain which can be substituted one to four times by C ! -C 4 alkyl and / or by oxygen or sulfur or an optionally C 1 -C 4 alkyl substituted nitrogen may be interrupted;
R6 Wasserstoff, Halogen, Ci-Cβ-Alkyl, Ci-Ce-Alkoxy, C3-C8-Cycloalkyl;R 6 is hydrogen, halogen, Ci-Cβ-alkyl, Ci-Ce-alkoxy, C 3 -C 8 cycloalkyl;
R7 cyclisches Ringsystem mit 3 - 14 Ringatomen, das gegebenenfalls substituiert ist durch Cι-C6-Alkyl, Ci-Cδ-Alkoxy, Ci-Ce-Halogenalkyl, Ci-Cβ-Halogenal- koxy, Halogen; oder Cι-C6-Alkyl, das durch ein cyclisches Ringsystem substituiert ist;R 7 cyclic ring system with 3 - 14 ring atoms, which is optionally substituted by -CC 6 alkyl, Ci-C δ alkoxy, Ci-Ce-haloalkyl, Ci-Cβ-haloalkoxy, halogen; or -CC 6 alkyl which is substituted by a cyclic ring system;
n 0, 1 oder 2;n 0, 1 or 2;
R8 Cι-C6-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkoxy- C2-C6-alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl;R 8 -C-C 6 alkyl, -C-C 6 haloalkyl, -C-C 6 alkoxy- C 2 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R9 Wasserstoff, Cι-C6-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkoxy-C2-C6-alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl;R 9 are hydrogen, C 6 -alkyl, C 6 haloalkyl, Cι-C 6 -alkoxy-C 2 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R10 Wasserstoff oder Cι-C6-Alkyl;R 10 is hydrogen or -CC 6 alkyl;
R11 Ci-Cβ-Alkyl oder Ci-Ce-Halogenalkyl;R 11 Ci-Cβ-alkyl or Ci-Ce-haloalkyl;
R12 Wasserstoff, Ci-Cβ-Alkyl, C3-Ce-Cycloalkyl,R 12 is hydrogen, Ci-Cβ-alkyl, C 3 -Ce cycloalkyl,
Cχ-C6-Halogenalkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, Phenyl oder Benzyl, wobei die beiden letztgenannten Reste partiell oder vollständig halogeniert sein können und/oder einen bis drei Reste aus der folgenden Gruppe tragen können:Cχ-C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, phenyl or benzyl, where the latter two radicals can be partially or completely halogenated and / or carry one to three radicals from the following group can:
Nitro, Cyano, Cι-C4-Alkyl, Cι-C4-Halogenalkyl, Cχ-C4-Alkoxy, Cχ-C4~Halogenalkoxy, Cι-C4-Alkylcarbo- nyl oder Cι-C4~Alkoxycarbonyl;Nitro, cyano, C4 alkyl, Cι-C4-haloalkyl, Cχ-C4-alkoxy, Cχ-C ~ 4 haloalkoxy, Cι-C 4 -Alkylcarbo- nyl or Cι-C ~ 4 alkoxycarbonyl;
R13 Wasserstoff , Ci-Cβ-Alkyl , C3-C6-Alkenyl oderR 13 is hydrogen, Ci-Cβ-alkyl, C 3 -C 6 alkenyl or
C3-C6-Alkinyl ;C 3 -C 6 alkynyl;
oderor
R12 und R13 bilden gemeinsam eine C2-C6-Alkandiylkette, die ein- bis vierfach durch Cι-C-Alkyl substituiert sein kann und/oder durch Sauerstoff oder Schwefel oder einen gegebenenfalls Cι-C4-Alkyl substituier- ten Stickstoff unterbrochen sein kann;R 12 and R 13 together form a C 2 -C 6 alkanediyl chain which can be substituted one to four times by C 1 -C 4 alkyl and / or substituted by oxygen or sulfur or an optionally C 1 -C 4 alkyl nitrogen may be interrupted;
R14 Wasserstoff, Ci-Cβ-Alkyl, Ci-Ce-Halogenalkyl,R 14 is hydrogen, Ci-Cβ-alkyl, Ci-Ce-haloalkyl,
Ci-Cβ-Alkoxy, Cι-C6-Alkoxycarbonyl, C3-Ce-Cycloal- kyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Phenyl oder Benzyl, wobei die beiden letztgenannten Reste partiell oder vollständig halogeniert sein können und/ oder einen bis drei Reste aus der folgenden Gruppe tragen können:Ci-Cβ-alkoxy, -C-C 6 alkoxycarbonyl, C 3 -Ce cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl or benzyl, the latter two radicals being partial or complete can be halogenated and / or can carry one to three radicals from the following group:
Nitro, Cyano, Cι~C4-Alkyl, Cι-C4-Halogenalkyl, C1-C4-Alkoxy, Cι~C4-Halogenalkoxy, Cι-C -Alkylcarbo- nyl oder Cι-C4-Alkoxycarbonyl;Nitro, cyano, ~ C 4 -alkyl, C 4 haloalkyl, C 1 -C 4 alkoxy, Cι ~ C4 haloalkoxy, Cι-C -Alkylcarbo- nyl or Cι-C 4 alkoxycarbonyl;
R15 Cι-C6-Alkyl, Cι-C6-Halogenalkyl, C3-C6-Cycloalkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, Cι-C6-Alkoxy, Cι-C6-Halogenalkoxy, C3-Ce-Cycloalkoxy, C3-Cβ-Alke- nyloxy, C3-C6~Alkinyloxy, Phenyl, Benzyl oder Ben- zyloxy, wobei die drei letztgenannten Reste partiell oder vollständig halogeniert sein können und/ oder einen bis drei Reste aus der folgenden Gruppe tragen können:R 15 -C-C 6 alkyl, -C-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Cι-C 6 alkoxy, Cι-C 6 -haloalkoxy, C 3 -Ce-cycloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, phenyl, benzyl or benzyloxy, where the latter three radicals can be partially or completely halogenated and / or one can carry up to three residues from the following group:
Nitro, Cyano, C1-C4-Alkyl, Cι-C4-Halogenalkyl, C1-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C4-Alkylcarbo- nyl oder Cι~C4-Alkoxycarbonyl;Nitro, cyano, C1-C 4 -alkyl, C 4 haloalkyl, C 1 -C 4 -alkoxy, C 4 haloalkoxy, Cι-C 4 -Alkylcarbo- nyl or Cι ~ C 4 alkoxycarbonyl;
R16 Hydroxy, Cι-C6 -Alkoxy, C3-C6-Alkenyloxy,R 16 hydroxy, -CC 6 alkoxy, C 3 -C 6 alkenyloxy,
Ci-Ce-Alkylsulfonyloxy, Cι-C6-Alkylcarbonyloxy, Phenyl -C1-C4-alkoxy, Phenylcarbonyloxy, Phenylcar- bonyl-Cι-C4 -alkoxy, Phenylsulfonyloxy, wobei derCi-Ce-alkylsulfonyloxy, -C-C 6 alkylcarbonyloxy, phenyl -C1-C4-alkoxy, phenylcarbonyloxy, phenylcarbonyl-Cι-C 4 alkoxy, phenylsulfonyloxy, the
Phenylrest der vier letztgenannten Substituenten partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Nitro, Cyano, C1-C4 -Alkyl, Cι-C4-Halogen- alkyl, Cι-C4-Alkoxy oder Cι-C4-Halogenalkoxy;Cι-C nitro, cyano, C 1 -C 4 alkyl, halo-4 alkyl, Cι-C4-alkoxy or: may be phenyl radical of the four last-mentioned substituents partially or fully halogenated and / or may carry one to three of the following groups -C-C 4 haloalkoxy;
sowie deren Tautomere und landwirtschaftlich brauchbaren Salze.as well as their tautomers and agriculturally useful salts.
2. Pyrazole nach Anspruch 1, wobei R7 folgende Bedeutungen hat: C3-Ci4-Cycloalkyl, C3-Ci4-Cycloalkenyl oder ein carbocycli- sches bi- oder tricyclisches System ausgewählt aus der Gruppe Adamantyl, Camphyl, Camphenyl oder Norbornyl.2. pyrazoles according to claim 1, wherein R 7 has the following meanings: C 3 -Ci 4 -cycloalkyl, C3-Ci 4 -cycloalkenyl or a carbocyclic bi- or tricyclic system selected from the group adamantyl, camphyl, camphenyl or norbornyl.
3. Pyrazole nach Anspruch 2, wobei R7 folgende Bedeutungen hat: Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl . 3. pyrazoles according to claim 2, wherein R 7 has the following meanings: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
4. Pyrazole nach einem der Ansprüche 1 - 3, wobei R2 in 4-Stel- lung des Phenylringes steht und folgende Bedeutung hat: -S02R8, -S02OR9 und R9 und R8 jeweils Cι-C6-Alkyl bedeuten.4. pyrazoles according to any one of claims 1-3, wherein R 2 is in the 4-position of the phenyl ring and has the following meaning: -S0 2 R 8 , -S0 2 OR 9 and R 9 and R 8 each -C-C 6 -Alkyl mean.
5 5. Pyrazole nach einem der Ansprüche 1 - 4, wobei R3 Wasserstoff oder Ci-Cβ-Alkyl bedeutet.5 5. pyrazoles according to any one of claims 1-4, wherein R 3 is hydrogen or Ci-Cβ-alkyl.
6. Pyrazole nach einem der Ansprüche 1 - 5, wobei R4 Wasserstoff oder Ci-Cβ-Alkyl bedeutet.6. pyrazoles according to any one of claims 1-5, wherein R 4 is hydrogen or Ci-Cβ-alkyl.
1010
7. Pyrazole nach einem der Ansprüche 1 - 6 wobei R5 Wasserstoff, Cι-C6-Alkyl, Cι-C6-Alkoxy oder Cyano bedeutet.7. pyrazoles according to any one of claims 1-6 wherein R 5 is hydrogen, -CC 6 alkyl, -C-C 6 alkoxy or cyano.
8. Pyrazole nach einem der Ansprüche 1 - 7, wobei R3, R4 und R5 15 jeweils gleich sind und Wasserstoff bedeuten.8. pyrazoles according to any one of claims 1-7, wherein R 3 , R 4 and R 5 15 are each the same and are hydrogen.
9. Pyrazole nach einem der Ansprüche 1 - 8, wobei R1 Halogen, Ci-Cε-Alkoxy oder Cι-C6-Alkyl bedeutet.9. pyrazoles according to any one of claims 1-8, wherein R 1 is halogen, Ci-Cε-alkoxy or -CC 6 alkyl.
20 10. Pyrazole nach einem der Ansprüche 1 - 9, wobei R16 Hydroxy bedeutet.20 10. Pyrazole according to any one of claims 1-9, wherein R 16 is hydroxy.
11. Verfahren zur Herstellung von Pyrazolen gemäß den Ansprüchen 1 - 10, dadurch gekennzeichnet, daß man ein Pyrazol der For- 25 mel II11. A process for the preparation of pyrazoles according to claims 1-10, characterized in that a pyrazole of formula 25 mel II
mit einer Carbonsäure III oder einem aktivierten Derivat davon with a carboxylic acid III or an activated derivative thereof
wobei die Variablen R1 bis R7 die unter Anspruch 1 genannten Bedeutungen haben und L1 für Hydroxy oder eine nucleophil verdrängbare Abgangsgruppe steht, acyliert und das Acylie- 45 rungsprodukt gegebenenfalls in Gegenwart eines Katalysators zu den Verbindungen I umlagert. where the variables R 1 to R 7 have the meanings given in Claim 1 and L 1 represents hydroxy or a nucleophilically displaceable leaving group, acylated and the acylation product rearranged to the compounds I, if appropriate in the presence of a catalyst.
12. Mittel, enthaltend eine herbizid wirksame Menge mindestens eines Pyrazols der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I gemäß den Ansprüchen 1 - 10 und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmit-12. Agent containing a herbicidally effective amount of at least one pyrazole of the formula I or an agriculturally useful salt of I according to claims 1-10 and auxiliaries customary for the formulation of crop protection agents.
13. Verfahren zur Herstellung von herbizid wirksamen Mitteln gemäß Anspruch 11, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines Pyrazols der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I gemäß den Ansprüchen 1 - 10 und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel mischt.13. A process for the preparation of herbicidally active agents according to claim 11, characterized in that mixing a herbicidally effective amount of at least one pyrazole of the formula I or an agriculturally useful salt of I according to claims 1-10 and auxiliaries customary for the formulation of crop protection agents ,
14. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, da- durch gekennzeichnet, daß man eine herbizid wirksame14. A process for combating undesirable plant growth, characterized in that a herbicidally active
Menge mindestens eines Pyrazols der Formel I oder eines landwirtschaftlich brauchbaren Salzes hiervon gemäß den Ansprüchen 1 - 9 auf Pflanzen, deren Lebensraum und/oder auf Samen einwirken läßt.Amount of at least one pyrazole of the formula I or an agriculturally useful salt thereof according to claims 1-9 on plants, their habitat and / or on seeds.
15. Verwendung der Pyrazole der Formel I und deren landwirtschaftlich brauchbaren Salze gemäß den Ansprüchen 1 - 9 als Herbizide. 15. Use of the pyrazoles of the formula I and their agriculturally useful salts according to claims 1-9 as herbicides.
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IL85659A (en) 1987-03-17 1992-03-29 Nissan Chemical Ind Ltd 4-benzoylpyrazole derivatives,method for their preparation and herbicidal compositions containing them
ZA982449B (en) 1997-03-24 1999-09-23 Dow Agrosciences Llc Process for preparing 1-Alkyl-4-(2-chloro-3-alkoxy-4-alkylsulfonylbenzoyl)-5-hydroxypyrazole and related compounds.
DE59811763D1 (en) * 1997-05-07 2004-09-09 Basf Ag SUBSTITUTED 4- (3-ALKENYL-BENZOYL) -PYRAZOLE
AU731305B2 (en) 1997-05-23 2001-03-29 Dow Agrosciences Llc 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides
EP0990649B1 (en) 1997-06-12 2004-05-12 Nippon Soda Co., Ltd. Benzoylpyrazole derivatives having specified substituents and herbicides
US5807806A (en) * 1997-06-12 1998-09-15 Nippon Soda Co., Ltd. Benzoylpyrazole derivatives having specific substituents and herbicide

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