EP1144401A2 - Derives de cyclohexenone de thiochromanoyl - Google Patents

Derives de cyclohexenone de thiochromanoyl

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Publication number
EP1144401A2
EP1144401A2 EP99963363A EP99963363A EP1144401A2 EP 1144401 A2 EP1144401 A2 EP 1144401A2 EP 99963363 A EP99963363 A EP 99963363A EP 99963363 A EP99963363 A EP 99963363A EP 1144401 A2 EP1144401 A2 EP 1144401A2
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EP
European Patent Office
Prior art keywords
alkyl
alkoxy
formula
cyano
methyl
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.)
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Application number
EP99963363A
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German (de)
English (en)
Other versions
EP1144401A3 (fr
Inventor
Klaus Langemann
Ernst Baumann
Wolfgang Von Deyn
Steffen Kudis
Guido Mayer
Ulf Misslitz
Ulf Neidlein
Matthias Witschel
Norbert Götz
Martina Otten
Karl-Otto Westphalen
Helmut Walter
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BASF SE
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BASF SE
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Publication of EP1144401A2 publication Critical patent/EP1144401A2/fr
Publication of EP1144401A3 publication Critical patent/EP1144401A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings

Definitions

  • the present invention relates to new thiochromanoylcyclohexenon derivatives of the formula I,
  • R 2 C ⁇ -C 6 -alkyl, C 6 haloalkyl, C ⁇ -C 6 alkoxy or Ci-C 6 haloalkoxy;
  • R 3 is hydrogen, halogen or Ci -C 6 alkyl
  • R 4 , R 5 is a radical mentioned under R 6 ;
  • C alkylcarbonyl C 1 -C 4 haloalkyl - carbonyl, C ⁇ -C 4 alkoxycarbonyl, C ⁇ -C 4 -Halogenalkoxycarbo- nyl, C ⁇ -C4-alkylsulfonyl, C ⁇ -C haloalkylsulfonyl,
  • Ci-C-haloalkylsulfonyl Ci-C-alkylcarbonyl, C 1 -C 4 alkoxycarbonyl and -C-C 4 haloalkoxycarbonyl;
  • R 7 is hydrogen or Ci-C 6 alkyl
  • R 8 are hydrogen, C 6 -alkyl, C 6 alkoxycarbonyl, cyano or Ci-C6 alkoxy;
  • R 9 is a radical mentioned under R 4 ;
  • Ci-Ce alkoxy C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, aminocarbonyl, N-Ci-C ⁇ -alkylaminocarbonyl or
  • R 10 is hydrogen, -CC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
  • R 11, R 12 is hydrogen, hydroxy, C ⁇ -C 6 -alkyl, C 6 -alkoxy, C 6 alkylthio, phenyl, phenyl -C 1 -C 4 alkyl or phenoxy, where the three last-mentioned substituents partially or can be completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkoxycarbonyl;
  • R 13 , R 14 are hydrogen, nitro, halogen, cyano, C 1 -C 6 -alkyl
  • Ci-C ⁇ -haloalkyl C ⁇ -C 6 -alkoxy, C ⁇ -C 6 -haloalkoxy, Ci-C ⁇ -alkylthio, C ⁇ -C 6 -haloalkylthio, Ci -C 6 -alkyl-sulfinyl, C ⁇ -C 6 -haloalkylsulfinyl, -C 6 alkyl sulfonyl,
  • R 13 , R 14 together form a methylidene group which can be substituted by one or two substituents from the following group: halogen, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 4 6 -haloalkoxy;
  • R 15 C ⁇ -C 6 -alkyl, C 6 haloalkyl, Ci-C ⁇ alkoxy or Ci-C6 haloalkoxy;
  • R 16 substituted (3-oxo-1-cyclohexen-2 -yl) carbonyl or substituted (1,3-dioxo-2-cyclohexyl) methylidene;
  • the invention also relates to processes for the preparation of compounds of the formula I, compositions which contain them and the use of these derivatives or compositions containing them for controlling harmful plants.
  • this invention is directed to new intermediates of the formula III, processes for their preparation and a process for the preparation of compounds of the formula X.
  • Cyclohexanediones which are linked via a carbonyl group to a dinuclear heterocycle, are known from the literature, for example from EP-A 283 261.
  • WO 97/09324 describes 2 -cyclohexane-1,3-dione-thiochromanoyl - and WO 97/30986 2 -cyclohexane-1,3-dione- (2 ', 3' -dihydrobenzodiothiine) derivatives.
  • the herbicidal properties of the compounds known hitherto and the tolerances to crop plants can only satisfy to a limited extent. It was therefore the object of this invention to find new, biologically, in particular herbicidally active, compounds with improved properties.
  • herbicidal compositions which contain the compounds I and have a very good herbicidal action.
  • processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
  • the compounds of the formula I can 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 agriculturally useful salts, the type of salt generally not being important. Generally they come
  • 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 come through as cations, with one to four hydrogen atoms passing through here if desired C ⁇ -C 4 alkyl, hydroxy-C ⁇ -C 4 alkyl, C 1 -C 4 -alkoxy-C ⁇ -C 4 alkyl, hydroxy-C ⁇ -C4-alkoxy-C ⁇ -C4 alkyl, phenyl or may be replaced by benzyl, preferably ammonium, dirnethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2 - (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) ammonium, Tri - methylbenzylammonium, further phosphon
  • 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 alkanoic acids, preferably formate, acetate , Propionate and butyrate.
  • Heterocyclyl which can be partially or completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • C-R 18, R 22 is hydrogen, C 1 4 alkyl or Ci-C4 alkoxycarbonyl
  • R 19 , R 21 , R 23 are hydrogen or C 1 -C 4 alkyl
  • R 20 is hydrogen, halogen, hydroxy, C ⁇ -C 6 alkyl
  • -C-C 6 haloalkyl di- (Ci-C ß -alkoxy) -methyl, (C ⁇ -C 6 -alkoxy) - (Ci -C 6 -alkylthio) -methyl, di- (C ⁇ -C 6 - alkylthio) methyl, -CC 6 alkoxy, -C 6 -haloalkoxy, Ci-C ⁇ -alkylthio, Ci-C ⁇ -haloalkylthio,
  • R 19 and R 20 or R 20 and R 23 together form a ⁇ bond or a Ci-Cs-alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl, from;
  • R 19 and R 23 together form a C ⁇ -C 4 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C 1 -C 4 alkoxycarbonyl, out;
  • R 20 and R 21 together form a -0- (CH) p -0-, -0- (CH 2 ) p -S-, -S- (CH 2 ) p -S-, -0- (CH) q - or -S - (CH 2 ) q chain, which can be substituted by one to three radicals from the following group: halogen, cyano, C 1 -C 4 alkyl, C 1 -C haloalkyl or Ci -C 4 - Alkoxycarbonyl;
  • R 20 and R 21 together with the carbon to which they are attached form a carbonyl group
  • Ci -C 6 alkylcarbonyl C 2 -C 6 alkenylcarbonyl, C 2 -C 6 alkynylcarbonyl, C 3 - C ⁇ cycloalkylcarbonyl, Ci-C ⁇ alkoxycarbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 - alkynyloxycarbonyl, Cj -C 6 alkylthiocarbonyl, Ci-C ⁇ -alkylaminocarbonyl, C 3 -C 6 -Alkenylaminocarbonyl,
  • alkyl, cycloalkyl or alkoxy radicals mentioned partially or completely halogenated can be and / or can carry one to three of the following groups: cyano, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, di - (C 1 -C 4 alkyl) amino, C
  • R 25 Cx-Ce alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C 6 cycloalkyl, where the four radicals mentioned can be partially or completely halogenated and / or one to three of the can carry the following groups: cyano, C 1 -C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C ⁇ -C 4 -alkylthio, C -C -haloalkylthio, C -C 4 -alkylcarbonyl, C 1 -C 4 - Alkoxycarbonyl or C ⁇ -C 4 haloalkoxycarbonyl;
  • R 26 , R 27 are hydrogen, hydroxy, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -alkoxy, C ⁇ -C 6 -alkylthio, phenyl, phenyl -C--C 4 -alkyl or phenoxy, the three latter substituents being partial or can be completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C alkyl, C 1 -C 4 halo alkyl, C ⁇ -C 4 alkoxy, C -C 4 haloalkoxy or C -C 4 alkoxycarbonyl;
  • R 28 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 6 -Cycloalkyl, C ⁇ -C 6 alkylcarbonyl, hydroxy, C ⁇ -C ⁇ alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, amino, C ⁇ -C 6 alkylamino, di- (C ⁇ -C 6 alkyl) amino or C ⁇ -C 6 -alkylcarbonylamino, where the alkyl, cycloalkyl or alkoxy radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following radicals: cyano, C ⁇ -C -alkoxycarbonyl, Cx -C 4 alkyl aminocarbonyl, di (C ⁇ -C 4
  • R 29 hydrogen f, C ⁇ -C 6 alkyl, C 3 - C 6 alkenyl or
  • Ha also represents the tautomeric forms Ha ', Ha''andHa''',
  • Ilb also represent the tautomeric forms Ilb 'Ilb''andIlb'''.
  • C ⁇ -C-alkyl as well as the alkyl parts of phenyl -C ⁇ -C 4 -alkyl and heterocyclyl -C ⁇ -C 4 -alkyl: e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1 , 1-dimethylethyl;
  • C ⁇ -C 6 alkyl and the alkyl parts of C ⁇ -C 6 -alkoxyimino-C ⁇ -C 6 - alkyl, N-C ⁇ -C 6 -alkoxy-N-C ⁇ -C 6 -alkylamino, N (C ⁇ -C 6 - Alkoxy) -N- (C ⁇ -C 6 -alkyl) -aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C ⁇ -C 6 -alkyl) -aminocarbonyl, (C 3 -C 6 -alkynyl) -N- (C ⁇ -C 6 -alkyl) -aminocarbonyl, N- (C ⁇ -C 6 -alkyl) -N-phenyla-minocarbonyl, N- (C ⁇ -C 6 -Alky1) -N- heterocyclylaminocarbonyl, phenyl-C ⁇ -C 6
  • C ⁇ -C 4 alkyl as mentioned above, and for example 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-trimethylpropyl, 1-ethyl-l-methylpropyl or l-ethyl-3-methylpropyl;
  • C ⁇ -C4-haloalkyl a C ⁇ -C 4 alkyl radical, as mentioned above, which is partially or completely
  • C ⁇ -C 6 -haloalkyl and the haloalkyl parts of N-C ⁇ -C6-haloalkylamino: C ⁇ -C-haloalkyl, as mentioned above, and for example 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6 -Fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorohexyl;
  • - C ⁇ -C 4 alkoxy eg methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy;
  • N-Ce-alkoxy and the alkoxy parts of N-C ⁇ -C 6 -alkoxyamino, di- (C ⁇ -C 6 -alkoxy) methyl, (C ⁇ -C 6 -alkoxy) (C ⁇ -C 6 -alkylthio) - methyl, C ⁇ -C 6 -alkoxyimino-C ⁇ -C 6 -alkyl, N-C ⁇ -C 6 -alkoxy- N-C ⁇ -C 6 -alkylamino, N- (C ⁇ -C 6 -alkoxy) -N- (C ⁇ -C 6 -alkyl) -aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C ⁇ -C 6 -alkoxy) -aminocarbonyl and N- (C 3 -C 6 -alkynyl) -N- (C ⁇ -C ⁇ -alkoxy) -aminocarbonyl
  • C ⁇ -C haloalkoxy a C ⁇ -C alkoxy radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxy, Difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromdi - fluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2- Chloro-2, 2-difluoroethoxy, 2,2-di-chloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2- Bromopropoxy, 3-brom
  • C ⁇ -C 6 -haloalkoxy C ⁇ -C 4 -haloalkoxy, as mentioned above, and for example 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
  • C ⁇ -C 4 alkylthio e.g. methylthio, ethylthio, propylthio,
  • C ⁇ -C 6 -alkoxy (C -C 6 -alkylthio) methyl: C ⁇ -C -alkylthio, as mentioned above, and for example pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutyl hio, 2, 2 -Dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, l-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-ethyl
  • C ⁇ -C-haloalkylthio a C ⁇ -C 4 -alkylthio radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2 -Fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2, 2-difluoroethylthio, 2, 2, 2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio,
  • C ⁇ -C 4 -haloalkylthio C ⁇ -C 4 -haloalkylthio, as mentioned above, and for example 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorhexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio;
  • C ⁇ -C 4 -haloalkylsulfinyl C ⁇ -C 4 -alkylsulfinyl, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethyl nyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2,2, 2-trichloroethylsulfinyl, 2-chloro-2-fluor
  • C ⁇ -C 6 -haloalkylsulfinyl C ⁇ -C -haloalkylsulfinyl as mentioned above, as well as 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexyl, 6-chlorohe- 6 , 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl, -
  • C ⁇ -C 4 haloalkylsulfonyl a C ⁇ -C 4 alkylsulfonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethyldifluoromethyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2, 2-difluoroethylsulfon
  • Cx - CQ -haloalkylsulfonyl C ⁇ -C -haloalkylsulfonyl as mentioned above, as well as 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorhexylsulfonyl, 6-bromhexylsulfonylylylsulfonyl;
  • C ⁇ -C 6 alkylamino e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1, 1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylam 2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1, 1-dimethylpropylamino, 1, 2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1, 1-dimethylbutylamino, 1 Dimethylbutylamino, 1, 3-dimethylbutylamino, 2, 2-dimethylbutylamino, 2, 3-dimethylbutylamino, 3, 3-dimethylbuty
  • Di- (C ⁇ -C 4 -alkyl) amino for example N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-di- (1-methylethyl) amino, N, N -Dibutylamino, N, N-di- (1-methylpropyl) amino, N, N-di- (2-methylpropyl) amino, N, N-di- (1, 1-dimethylethyl) amino, N-ethyl-N -methylamino, N-methyl-N-propylamino, N-methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N -Methyl-N- (2-methyl-propyl) amino, N- (1, 1-dimethylethyl) -N-methylamino, N-ethyl-N
  • Di- (C ⁇ -C 6 -alkyl) amino di- (C ⁇ -C 4 -alkyl) amino as mentioned above, and N, N-dipentylamino, N, N-dihexylamino, N-methyl-N-pentylamino, N- Ethyl-N-pentylamino, N-methyl-N-hexylamino or N-ethyl-N-hexylamino.
  • C ⁇ -C 4 ⁇ alkylcarbonyl for example methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl or 1, 1-dimethylethylcarbonyl;
  • C ⁇ -C 6 -alkylcarbonyl C ⁇ -C 4 -alkylcarbonyl, as mentioned above, and for example pentylcarbonyl, 1-methylbutylcarbonyl,
  • C ⁇ -C 4 haloalkylcarbonyl a C ⁇ -C 4 alkylcarbonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, Chlorofluoroacetyl, dichlorofluoracetyl, chlorodifluoroacetyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2, 2-difluoroethylcarbonyl, 2, 2, 2-trifluoroethylcarbonyl,
  • 2-chloro-2-fluoroethylcarbonyl 2-chloro-2, 2-difluoroethylcarbonyl, 2, 2-dichloro-2-fluoroethylcarbonyl, 2, 2, 2-trichloroethylcarbonyl, pentafluoroethylcarbonyl, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2, 2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2, 3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3, 3, 3-trifluoropropylcarbonyl, 3, 3, 3-trichloropropylcarbonyl, 2, 2, 3, 3, 3-pentafluoropropylcarbonyl, heptafluoropropylcarbonyl, 1- (
  • C ⁇ -C 6 -haloalkylcarbonyl a C ⁇ -C 4 -haloalkylcarbonyl radical as mentioned above, as well as 5-fluoropentylcarbonyl, 5-chloropentylcarbonyl, 5-bromopentylcarbonyl, perf luorpentyl-carbonyl, 6 -fluorhexylcarbonyl, 6-chlorohexylcarbonyl, 6-bromo- hexylcarbonyl or perfluorohexylcarbonyl;
  • Di- (C ⁇ -C 4 -alkyl) amino-C ⁇ -C 4 -alkoxycarbonyl i.e. for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylprooxycarbonyl or 1 -Dimethylethoxycarbonyl;
  • (C ⁇ -C 6 -alkoxy) carbonyl (C ⁇ -C 4 -alkoxy) carbonyl, as mentioned above, and for example pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1- Ethyl propoxycarbonyl, hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl,
  • - C ⁇ -C 4 -haloalkoxycarbonyl a C ⁇ -C 4 -alkoxycarbonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorodifluoromethoxyormyloxy, bromide carbonyl, 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl,
  • C ⁇ -C 6 -haloalkoxycarbonyl a C ⁇ -C 4 -haloalkoxycarbonyl radical as mentioned above, and 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6-fluoro-hexoxycarbonyl, 6 -chlorohexoxycarbonyl or 6-bromhexoxycarbonyl or ;
  • (C ⁇ -C 4 alkyl) carbonyloxy acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, 1-methylethylcarbonyloxy, butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy or 1, 1-dimethylethylcarbonyloxy;
  • (C ⁇ -C 4 -alkylamino) carbonyl for example methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, 1-methylethylaminocarbonyl, butylaminocarbonyl, 1-methylpropylaminocarbonyl, 2-methylpropylaminocarbonyl or 1, 1-dimethylethylaminocarbonyl;
  • (C ⁇ -C 6 ⁇ alkylamino) carbonyl (C ⁇ -C 4 -alkylamino) carbonyl, as mentioned above, and for example pentylaminocarbonyl, 1-methylbutylaminocarbonyl, 2-methylbutylaminocarbonyl, 3-methylbutylaminocarbonyl, 2, 2-dimethylpropylaminocarbonyl, 1-ethylpropylaminocarbonyl, hexylaminocarbonyl, 1, 1-dimethylpropylaaminocarbonyl, 1, 2-dimethylpropylaminocarbonyl, 1-methylpentylaminocarbonyl, 2-methylpentylaminocarbonyl, 3-methylpentylaminocarbonyl, 4-methylpentylaminocarbonyl, 1, 1-dimethyl , 2-dimethylbutylaminocarbonyl, 1,3-dimethylbutylaminocarbonyl, 2, 2-dimethylbutylaminocarbonyl,
  • Di- (C ⁇ -C alkyl) aminocarbonyl e.g. N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N, N-di- (1-methylethyl) aminocarbonyl, N, N-dipropylaminocarbonyl, N, N-dibutylaminocarbonyl, N, N-di- (1- methylpropyl) aminocarbonyl, N, N-di- (2-methylpropyl) aminocarbonyl, N, N-di- (1, 1-dimethylethyl) aminocarbonyl, N-ethyl-N-methylaminocarbonyl, N-methyl-N -propyla- minocarbonyl, N-methyl-N- (1-methylethyl) -aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N- (1-methylpropyl) -amino-carbony
  • Di- (C ⁇ -C 6 -alkyl) -aminocarbonyl Di- (C ⁇ -C 4 -alkyl) -aminocarbonyl, as mentioned above, and for example N-methyl-N-pentylaminocarbonyl, N-methyl-N- (1-methylbutyl ) -aminocarbonyl, N-methyl-N- (2-methylbutyl) -aminocarbonyl, N-methyl-N- (3-methylbutyl) -aminocarbonyl, N-methyl-N- (2, 2-dimethylpropyl) -aminocarbonyl, N- Methyl-N- (1-ethyl-propyl) -aminocarbonyl, N-methyl-N-hexylaminocarbonyl, N-methyl-N- (1, 1-dimethylpropyl) -aminocarbonyl, N-methyl-N-N-
  • Di- (C ⁇ -C 6 -alkyl) -aminothiocarbonyl e.g. N, N-dimethylamino-thiocarbonyl, N, N-diethylaminothiocarbonyl, N, N-di- (1-methylethyl) aminothiocarbonyl, N, N-dipropylaminothiocarbonyl, N, N -Dibutylaminothiocarbonyl, N, N-di- (1-methylpropyl) -amino-thiocarbonyl, N, N-di- (2-methylpropyl) -aminothiocarbonyl,
  • C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkoxy C ⁇ -C 4 -alkoxy, and the alkoxyalkoxy parts of C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkoxycarbonyl: C ⁇ -C 4 -alkoxy, as mentioned above, substituted C ⁇ -C 4 - Alkoxy, for example for Methoxymethoxy, ethoxymethoxy, propoxymethoxy, (1-methylethoxy) methoxy, butoxymethoxy, (l-methylpropoxy) methoxy, (2-methylpropoxy) methoxy, (1, 1-dimethylethoxy) methoxy, 2- (methoxy) ethoxy, 2- ( Ethoxy) ethoxy, 2- (propoxy) ethoxy, 2- (1-methylethoxy) ethoxy, 2- (butoxy) ethoxy, 2- (l-methylpropoxy) ethoxy, 2- (2-methylpropoxy) ethoxy, 2- ( 1,
  • C 3 -C 6 alkenyl and the alkenyl parts of C 3 -C 6 alkenyl carbonyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkenylaminocarbonyl, N- (C 3 -C 6 alkenyl) -N- (C ⁇ -C 6 ) alkyl-aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C ⁇ -C 6 -alkoxy) amino-carbonyl: for example prop-2 -en-1-yl, but-1-en-4-yl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, 2-butene-1 -yl, l-penten-3-yl, l-penten-4-yl, 2-penten-4-yl, 1-methyl-but-2-en-l-yl, 2-methyl-but-2-ene
  • C 3 -Ce haloalkenyl a C 3 -C 6 alkenyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroallyl, 3-chloroallyl, 2, 3-dichlorallyl, 3, 3-dichlorallyl, 2,3,3-trichlorallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromoallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromoallyl or 2,3-dibromobut-2-enyl;
  • C 3 -C 6 alkynyl and the alkynyl parts of C 3 -C 6 ⁇ alkynylcarbonyl, C 3 -C 6 alkynyloxy, CC 5 alkynyloxycarbonyl, C 3 -C 6 alkynylaminocarbonyl, N- (C 3 -C 6 -alkynyl) -N- (C ⁇ -C 6 -alkyl) -aminocarbonyl, N- (C 3 -C 6 -alkynyl) -N- (C ⁇ -C 6 -alkoxy-aminocarbonyl: eg propargyl, but-l -in-3-yl, but-1-in-4-yl, but-2-in-1-yl, pent-1-in-3-yl, pent-1-in-4-yl, pent-1 -in-5-yl, pent-2-yn-l-yl, pent-2-yn-4-yl, pen
  • C -C 6 alkynyl and the alkynyl parts of C -C 6 alkynylcarbonyl: C 3 -C 6 alkynyl, as mentioned above, and ethynyl;
  • C 3 -C 6 haloalkynyl a C 3 -C 6 alkynyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 1,1-difluoroprop-2- in-l-yl, 3-iodo-prop-2-in-l-yl, 4-fluorobut-2-in-l-yl, 4-chlorobut-2-in-l-yl, 1, 1-difluorobut- 2-in-l-yl, 4-iodobut-3-in-l-yl, 5-fluoropent-3-in-l-yl, 5-iodo-pent-4-in-l-yl, 6- Fluoro-hex-4-in-1-yl or 6-iodo-hex-5-in-1-yl;
  • C 2 -C 6 -alkenediyl ethene-1, 1-diyl, ethene-1, 2 -diyl, 1 - propene-1, 1-diyl, 1 - propene-1, 2 -diyl, 1-propen-1, 3-diyl, 2-propen-1, 1-diyl, 2-propen-1, 2-diyl, 2-propen-1, 3-diyl,
  • C 2 -C 6 -alkindiyl ethine-1,2-diyl, 1,3-propin-1,3-diyl, 2-propyne-1,1-diyl, 2-propyne-1,3-diyl, 1-butyne 1,3-diyl, 1-butyne-1,4-diyl, 2-butyne-1,1-diyl, 2-butyne-1,4-diyl, 1-methyl-2-propyne-1,1-diyl, 1-methyl -2-propyne-1,3-diyl, 1-pentyn-1,3-diyl, 1-pentyn-1,4-diyl, 1-pentyn-1,5-diyl, 2-pentyn-1, 1-diyl, 2-pentyn-1, 4 -diyl, 2 -pentin-1, 5-diyl, 3-pentyn-1, 1-diyl,
  • Heterocyclyl and also heterocyclyl parts of heterocyclylcarbonyl, heterocyclyl-C ⁇ -Cg-alkyl, heterocyclyloxycarbonyl,
  • 5-membered rings with two heteroatoms such as tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydroisoxazol-3-yl, tetrahydroisoxazol-4-yl, tetrahydroisoxazol-5-yl, 1,2-oxathiol 3-yl, 1,2-oxathiolan-4-yl, 1,2-oxathiolan-5-yl, tetrahydroisothiazol-3-yl, tetrahydroisothiazol-4-yl, tetrahydroisothiazol-5-yl, 1,2- Dithiolan-3-yl, 1,2-dithiolan-4-yl, tetrahydroimidazol-2-yl, tetrahydro-imidazol-4-yl, tetrahydrooxazol-2-yl, tetrahydrooxazol-4
  • 5-membered rings with three heteroatoms such as l, 2,3- ⁇ 2 -oxadiazolin-4-yl, 1, 2, 3- ⁇ 2 -oxadiazolin-5-yl, 1, 2, 4- ⁇ 4 -oxadiazolin -3-yl, 1, 2, 4- ⁇ 4 -oxadiazolin-5-yl, 1,2, 4- ⁇ 2 -oxadiazolin-3-yl, 1,2, 4- ⁇ 2 -oxadiazolin-5-yl, 1,2, - ⁇ 3 -oxadiazolin-3-yl, 1, 2, 4- ⁇ 3 -oxadiazolin-5-yl, 1, 3, 4- ⁇ 2 -oxadiazolin-2-yl, 1,3, 4- ⁇ 2 -Oxadiazolin-5-yl, 1, 3, 4- ⁇ 3 -Oxadiazolin-2-yl, 1, 3, 4-oxadiazolin-2-yl, l, 2,4- ⁇ 4 -Thiadiazolin-3-yl , 1,2, 4- ⁇ -thiadiazoline-5-yl, 1,
  • 6-membered rings with a hetero atom such as: Tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, Tetra-hydrothiopyran-4-yl, 2H-3, 4-dihydropyran-6-yl, 2H-3, 4-dihydropyran-5-yl, 2H-3, 4-dihydropyran-4-yl, 2H-3, 4- Dihydropyran-3-yl, 2H-3, 4-dihydropyran-2-yl, 2H-3, 4-dihydropyran-6-yl, 2H-3, 4-dihydrothiopyran-5-yl, 2H-3, 4-dihydrothiopyran 4-yl, 2H-3, 4-
  • 6-membered rings with two heteroatoms e.g.
  • 1,2,3, 6-tetrahydropyridazin-4-yl 4H-5, 6-dihydro-l, 3-oxazin-2-yl, 4H-5, 6-dihydro-l, 3-oxazin-4- yl, 4H-5,6-dihydro-1, 3-oxazin-5-yl, 4H-5, 6-dihydro-l, 3-oxazin-6-yl, 4H-5, 6-dihydro-l, 3-thiazin-2-yl, 4H-5, 6-dihydro-l, 3-thiazin-4-yl, 4H-5, 6-dihydro-l, 3-thiazin-5-yl, 4H-5, 6-dihydro-1,3-thiazin-6-yl, 3,4,5-6-tetrahydropyrimidin-2-yl, 3,4,5,6-tetrahydropyrimidin-4-yl, 3,4,5,6- Tetrahydro-pyrimidin-5-yl, 3, 4, 5, 6-tetrahydropyr
  • 6-membered rings with three heteroatoms e.g. 1,3,5-triazine-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl or 1,2,4-triazin-6-yl;
  • 6-membered rings with four heteroatoms e.g. 1,2,4,5-tetrazin-3-yl;
  • N-linked heterocyclyl a saturated, partially saturated or unsaturated 5- or 6-membered N-linked heterocyclic ring, the at least one nitrogen and optionally one to three identical or different hetero atoms, selected from the following group: oxygen, sulfur or nitrogen contains, e.g.
  • N-linked 5-membered rings with a hetero atom such as:
  • N-linked 5-membered rings with two heteroatoms e.g. Tetrahydropyrazol-1-yl, tetrahydroisoxazol-2-yl, tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl, tetrahydrooxazol-3-yl, tetrahydrothiazol-3-yl, 4, 5-dihydro-l zol-l-yl, 2,5-dihydro-lH-pyrazol-l-yl, 2,3-dihydro-lH-pyrazol-l-yl, 2,5-dihydroisoxazol-2-yl, 2,3- Dihydroisoxazol-2-yl, 2,5-dihydroisothiazol-2-yl, 2,3-dihydroisoxazol-2-yl, 4,5-dihydro-lH-imidazol-l-yl,
  • N-linked 5-membered rings having three hetero atoms such as 1,2, 4- ⁇ 4 -Oxadiazolin-2-yl, 1,2, 4- ⁇ 2 -Oxadiazolin-yl-4, 1,2, 4- ⁇ 3 -oxadiazolin-2-yl, 1, 3, 4- ⁇ 2 -oxadiazolin-4-yl, 1, 2, 4- ⁇ 5 -thiadiazolin-2-yl, 1, 2, 4- ⁇ 3 -thiadiazolin-2 -yl, 1, 2, 4- ⁇ 2 -thiadiazolin-4-yl, 1,3, 4- ⁇ 2 -thiadiazolin-4-yl, l, 2,3- ⁇ 2 -triazolin-l-yl, 1, 2, 4- ⁇ 2 -triazolin-l-yl, l, 2,4- ⁇ 2 -triazolin-4-yl, 1, 2, 4- ⁇ 3 -triazolin-l-yl, 1,2,4- ⁇ 1 - triazolin-4-yl, 1, 2, 3-triazol-l-yl or 1, 2, 4-
  • N-linked 5-membered rings with four heteroatoms e.g. Tetrazol-1-yl
  • N-linked 6-membered rings with a hetero atom e.g. :
  • Piperidin-1-yl 1, 2, 3, 4-tetrahydropyridin-l-yl, 1,2,5,6-tetrahydropyridin-1-yl, 1, 4-dihydropyridin-l-yl or 1, 2- Dihydropyridin-l-yl; N-linked 6-membered rings with two heteroatoms, such as hexahydropyrimidin-1-yl, hexahydropyrazin-1-yl, hexahydropyridazin-1-yl, tetrahydro-1, 3-oxazine-3-yl, tetrahydro-1, 3-thiazin-3-yl , Tetrahydro-1,4-thiazin-4-yl, tetrahydro-1,4-oxazin-4-yl, tetrahydro-1,2-oxazin-2-yl, 2H-5,6-dihydro-l , 2-oxazin-2-yl,
  • the variables preferably have the following meanings, in each case individually or in combination: A C ⁇ -Ce-alkanediyl or C 2 -C. 6 -alkenediyl, where the radicals mentioned can carry one or two substituents from the following group: cyano, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -alkylthio, C ⁇ -C- ⁇ -alkylcarbonyl or C ⁇ -C 4 -alkoxycarbonyl; preferably C ⁇ -C 4 -alkanediyl, such as methane-1, 1-diyl, ethane-1, 1-diyl or ethane-1, 2-diyl, or C 2 -C 4 -alkenediyl, such as ethene-1, 1-diyl , Ethene-1,2-diyl, 1-methyl-ethene-1,2-diyl
  • N-linked heterocyclyl such as pyrazol-1-yl, imidazol-1-yl, 1, 2, 4-triazol-1-yl, pyrrolidin-1-yl, tetrahydroisoxazol-2-yl or morpholin-4-yl; particularly preferably cyano, nitro, OR 4 , S0 2 R 6 , 0NR 6 R 7 , P (0) R 1: L R 12 , P (S) R 1: L R 12 , COR 6 or C0 2 R 6 ;
  • R 2 is C 1 -C 4 alkyl, such as methyl, ethyl, propyl or 1-methylethyl;
  • R 3 is hydrogen, halogen, such as fluorine, chlorine or bromine, or C ⁇ -C-alkyl, such as methyl or ethyl; particularly preferably hydrogen, chlorine or methyl; particularly preferably hydrogen;
  • n 0, 1 or 2; preferably 2;
  • n 0, 1, 2, 3 or 4; preferably 0.1 or 2; particularly preferably 0;
  • R 4 , R 5 is a radical mentioned under R 6 ; Hydrogen, C ⁇ -C 4 -alkylcarbonyl, C ⁇ -C 4 -haloalkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl, C ⁇ -C -haloalkoxycarbonyl, C ⁇ -C 4 -alkylsulfonyl, C ⁇ -C 4 -haloalkylsulfonyl, P (0 ) Rii i or P (S) R 11 R 12 ; preferably C ⁇ -C 4 alkylcarbonyl, C ⁇ -C 4 haloalkylcarbonyl, C ⁇ -C 4 alkylsulfonyl or C ⁇ -C 4 haloalkylsulfonyl;
  • R 6 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, where the three radicals mentioned can be partially or completely halogenated and / or one to three of the following
  • Groups can carry: cyano, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C -C 4 -alkylsulfonyl, C ⁇ -C 4 -haloalkylsulfonyl, C -C 4 -alkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl and C ⁇ - C 4 haloalkoxycarbonyl;
  • C ⁇ -C 4 alkyl preferably C ⁇ -C 4 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, where the three radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy or Cx-C 4 alkoxycarbonyl;
  • R 7 is hydrogen or C ⁇ -C 4 alkyl, such as methyl or ethyl
  • R 8 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxycarbonyl or
  • Cx -C 6 alkoxy preferably hydrogen, C ⁇ -C 4 alkyl or C ⁇ -C alkoxy;
  • R 9 is C ⁇ -C 6 alkyl, C 3 -C 5 alkenyl, C 3 -C 6 alkynyl, C ⁇ -C 4 alkylcarbonyl, C ⁇ -C 6 alkoxy, C 3 -C 6 alkenyloxy or
  • R 10 is hydrogen, C -C 6 alkyl, C 3 -C 6 alkenyl or
  • R 11 , R 12 are hydroxy, C ⁇ -C 6 alkyl or C ⁇ -C 6 alkoxy;
  • R 13 , R 14 are hydrogen, C ⁇ -C 6 alkyl or C ⁇ -C 6 haloalkyl; preferably hydrogen or C ⁇ -C 6 alkyl, such as methyl, ethyl or propyl;
  • R 13, R 14 together form a methylidene group which may be substituted by one or two substituents from the following group: halogen, cyano, C ⁇ -C6 alkyl, C ⁇ -C6-halo-alkyl, C ⁇ -C6 alkoxy, or C ⁇ -C 6 haloalkoxy;
  • R 13 , R 14 preferably (R 13 , R 14 ) hydrogen, C ⁇ -C-alkyl such as methyl, ethyl or n-propyl or C ⁇ -C 4 -haloalkyl such as chloromethyl, fluoromethyl or trifluoromethyl; particularly preferably hydrogen, methyl or ethyl;
  • R 18 , R 22 are hydrogen or C ⁇ -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 19 , R 21 , R 23 are hydrogen or C ⁇ -C alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 20 is hydrogen, hydroxy, C ⁇ -C 6 -alkyl, di- (C ⁇ -C 6 -alk-oxy) -methyl, (C ⁇ -C 6 -alkoxy) - (C ⁇ -C 6 -alkylthio) -methyl, di- (C ⁇ -C 6 alkylthio) methyl, C ⁇ -C 6 alkylthio,
  • R 19 and R 20 or R 20 and R 23 together form a ⁇ bond or a C 3 -Cs alkyl chain, which have up to three radicals from the following
  • Group can carry: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C1-C4 alkoxycarbonyl, from;
  • R 19 and R 23 together form a C ⁇ -C 4 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C 1 -C 4 alkyl, C ⁇ -C 4 haloalkyl or C ⁇ -C 4 - Alkoxycarbonyl, from;
  • R 20 and R 21 together form a -0- (CH 2 ) p -0-, -0- (CH 2 ) p -S- or -S- (CH 2 ) p -S chain, which is represented by one to three Radicals from the following group can be substituted: halogen, cyano, C 1 -C 4 alkyl, C ⁇ -C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl; preferably R 20 and R 21 together form a -O- (CH) p -0-, -0- (CH 2 ) p -S- or -S- (CH 2 ) p -S chain, which is represented by one to three the radicals from the following groups can be substituted: C ⁇ -C 4 haloalkyl or C ⁇ -C 4 alkoxycarbonyl;
  • R 20 and R 21 together with the carbon to which they are attached form a carbonyl group
  • R 24 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl,
  • C ⁇ -C 6 alkyl preferably C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C ⁇ -C 6 alkylcarbonyl, C ⁇ -C 6 alkoxycarbonyl, C ⁇ -C 6 alkyl - aminocarbonyl or N, N -Di (Cx-C ß -alkyl) aminocarbonyl, where- said alkyl or alkoxy radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C -alkoxy, C ⁇ -C 4 -alkylthio or C ⁇ -C 4 -alkoxycarbonyl, -
  • R 26 , R 27 hydroxy, C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxy, phenyl, phenyl -C ⁇ -C 4 alkyl or phenoxy, where the latter three substituents can be partially or completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C 4 -alkyl, C ⁇ -C 4 -haloalkyl, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy or C ⁇ -C 4 -alkoxycarbonyl;
  • R 28 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl,
  • Di- (C ⁇ -C 6 -alkyl) amino where the alkyl, cycloalkyl or alkoxy radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following radicals: cyano, C ⁇ -C 4 alkoxycarbonyl , C ⁇ -C 4 alkylaminocarbonyl, di (C ⁇ -C 4 alkyl) aminocarbonyl or C 3 -C 6 cycloalkyl;
  • R 29 is C ⁇ -C 6 alkyl or C 3 -C 6 alkenyl
  • R 4 C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, where the three radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C -alkoxy, C ⁇ -C4 -halogen- alkoxy, C ⁇ -C-alkylsulfonyl, C -C 4 -haloalkylsulfonyl,
  • R 17 halogen, OR 24 , SR 24 , S0 2 R 25 , OS0 2 R 25 , NR 28 R 29 , ONR 25 R 25 or N-linked heterocyclyl, which can be partially or completely halogenated and / or one to three of the following Residues can carry: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy;
  • R 18 , R 22 are hydrogen or Cx -C -alkyl
  • R 19 , R 21 , R 23 are hydrogen or Cx -C 4 alkyl
  • R 20 is hydrogen, hydroxy, C ⁇ -C 3 -alkyl, di- (C ⁇ -C 6 -alk-oxy) -methyl, (C ⁇ -C 6 -alkoxy) - (C ⁇ -C 6 -alkylthio) -methyl, di- (C ⁇ -C 6 -alkylthio) methyl, C ⁇ -C 6 alkylthio, C ⁇ -C 6 haloalkylthio, C -C ö alkylsulfonyl or Cx-C6 haloalkylsulfonyl; in particular hydrogen, hydroxy or C ⁇ -C 6 alkyl;
  • R 19 and R 23 together form a C ⁇ -C 4 alkyl chain which can carry one to three radicals from the following group: halogen, C ⁇ -C 4 alkyl or cx -C 4 haloalkyl;
  • R 19 and R 23 together form a methylene bridge which can carry one or two radicals from the following group: halogen, C ⁇ -C alkyl or C ⁇ -C 2 haloalkyl;
  • R 20 and R 21 together with the carbon to which they are attached form a carbonyl group
  • R 18 , R 22 are hydrogen or Cx -C 4 alkyl
  • R 19 , R 21 , R 23 are hydrogen or C ⁇ -C 4 alkyl
  • R 20 is hydrogen, hydroxy, C ⁇ -C 6 -alkyl, di- (Ci-Ce-alk-oxy) -methyl, (C ⁇ -C 6 -alkoxy) - (C ⁇ -C 6 -alkylthio) -methyl, di- ( C ⁇ -C 6 -alkylthio) methyl, C -C 6 -alkylthio, C ⁇ -C 6 -haloalkylthio, C ⁇ -C 6 -alkylsulfonyl or Cx-C 6 -haloalkylsulfonyl; in particular hydrogen, hydroxy or C ⁇ -C 6 alkyl;
  • R 20 and R 21 together with the carbon to which they are attached form a carbonyl group
  • R 3 is hydrogen
  • X CR 13 R 14 , C 0 or S0 2 ; particularly preferably CR 13 R 14 or S0 2, particularly preferably CR 13 R 14 ; also particularly preferred S0;
  • R 4 C ⁇ -C 6 alkyl, which can be partially or fully halogenated
  • R 5 is C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or heterocyclyl; particularly preferably Cx-C ß- alkyl or C 3 -C 6 -alkenyl; particularly preferably Cx -C 6 alkyl;
  • R 6 C ⁇ -C 6 alkyl or C 3 -C 6 alkenyl, where the two radicals mentioned can be partially or completely halogenated; particularly preferably C ⁇ -C 6 alkyl or C 3 -C 6 alkenyl; particularly preferably C ⁇ -C 6 alkyl;
  • R 9 is C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C x -C 4 haloalkyl carbonyl;
  • R 10 C ⁇ -C 6 alkyl or C 3 -C 6 alkenyl
  • R 18 , R 19 , R 20 , R 21 , R 22 , R 23 are hydrogen or C ⁇ -C 4 alkyl; particularly preferably hydrogen or methyl; or R 20 and R 21 together with the carbon to which they are attached form a carbonyl group.
  • the compounds of the formula Ia are also extremely preferred.
  • the compounds of the formula Ia2 in particular the compounds Ia2.1 to Ia2.285, which differ from the compounds Ial.l to Ial.285 in that R 20 and R 21 are methyl.
  • the compounds of the formula Ia5 in particular the compounds IaS.l to Ia5.285, which differ from the compounds Ial.l to Ial.285 in that R 18 , R 19 , R 22 and R 23 are methyl and that R 20 and R 21 form a carbonyl group with the carbon to which they are attached.
  • the compounds of the formula Ia7 in particular the compounds Ia7.1 to Ia7.285, which differ from the compounds Ial.l to Ial.285, in that R 19 and R 23 together form an ethylene bridge.
  • the thiochromanoylcyclohexenone derivatives of the formula I can be obtained in various ways, for example by the following processes:
  • L 1 is a nucleophilically displaceable leaving group such as halo gen ⁇ for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or Trif luoracetat etc.
  • halo gen ⁇ for example bromine or chlorine
  • hetaryl for example imidazolyl or pyridyl
  • carboxylate for example acetate or Trif luoracetat etc.
  • the activated purple benzoic acid can be used directly, as in the case of the benzoyl halides or generated in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine / azodicarbonyl acid esters, 2-pyridine disulfide / triphenylphosphine, carbonyldimidazole etc.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently used in equimolar amounts.
  • a slight excess of the auxiliary base e.g. Under certain circumstances, 1.2 to 1.5 molar equivalents, based on purple or Illb, can be advantageous.
  • Tertiary alkyl amines, pyridine or alkali metal carbonates are suitable as auxiliary bases.
  • a solvent e.g. chlorinated hydrocarbons such as methylene chloride or 1, 2-dichloroethane, aromatic hydrocarbons such as toluene, xylene or chlorobenzene, ethers such as diethyl ether, methyl tert. butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof.
  • chlorinated hydrocarbons such as methylene chloride or 1, 2-dichloroethane
  • aromatic hydrocarbons such as toluene, xylene or chlorobenzene
  • ethers such as diethyl ether, methyl tert. butyl ether, tetrahydrofuran
  • benzoyl halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10 ° C. when this reactant is added. The mixture is then stirred at 20-100 ° C., preferably at 25-50 ° C., until the reaction is complete. The processing takes place in the usual way, e.g. the reaction mixture is poured onto water and the product of value is extracted. Methylene chloride, diethyl ether and ethyl acetate are particularly suitable as solvents for this. After drying the organic phase and removing the solvent, the crude ester can be used for rearrangement without further purification.
  • the rearrangement of the esters to the compounds of the formula I is advantageously carried out at from 20 to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.
  • solvent e.g. Acetonitrile, methylene chloride, 1, 2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used.
  • Preferred solvents are acetonitrile and dioxane.
  • Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali carbonates such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester. Triethylamine or alkali carbonates are preferred used, preferably in double equimolar ratio with respect to the ester.
  • Inorganic cyanides such as sodium cyanide or potassium cyanide and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide are suitable as cyano compounds. They are used in an amount of 1 to 50 mole percent, based on the ester. Preferably acetone cyanohydrin or trimethylsilyl cyanide, e.g. in an amount of 5 to 15, preferably about 10 mole percent, based on the ester.
  • the reaction mixture is e.g. with dilute mineral acid, such as
  • hydrochloric acid or sulfuric acid acidified, with an organic solvent, e.g. Extracted methylene chloride or ethyl acetate.
  • the organic extract can be mixed with 5-10% alkali carbonate solution, e.g. Sodium carbonate or potassium carbonate solution are extracted.
  • the aqueous phase is acidified and the precipitate that forms is filtered off with suction and / or extracted with methylene chloride or ethyl acetate, dried and concentrated.
  • halogenating agents examples include phosgene, diphosgene, triphosgene, thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, mesyl chloride, chloromethylene-N, N-dimethylammonium chloride, oxalyl bromide, phosphorus oxybromide etc.
  • L 2 stands for a nucleophilically displaceable leaving group, such as halogen, for. B. chlorine or bromine, hetaryl, e.g. B. imidazolyl, carboxylate, e.g. B. acetate, or sulfonate, e.g. B. mesylate or triflate etc.
  • halogen for. B. chlorine or bromine
  • hetaryl e.g. B. imidazolyl
  • carboxylate e.g. B. acetate
  • sulfonate e.g. B. mesylate or triflate etc.
  • the compounds of formula V ⁇ , Vß, V ⁇ or V ⁇ can be used directly, such as. B. in the case of carboxylic acid halides or generated in situ, for. B. activated carboxylic acids (with carboxylic acid and dicyclohexylcarbodiimide etc.).
  • Suitable oxidizing agents are m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen peroxide, if appropriate in the presence of a catalyst such as tungstate.
  • the starting compounds are generally used in an equimolar ratio. However, it can also be advantageous to use one or the other component in excess.
  • reactants and the base are expediently used in equimolar amounts.
  • Suitable bases are tertiary alkyl amines such as triethylamine, aromatic amines such as pyridine, alkali metal carbonates, e.g. Sodium carbonate or potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, alkali metal alcoholates such as sodium methoxide, sodium ethanolate, potassium tert. - butanolate or alkali metal hydrides, e.g. Sodium hydride. Triethylamine or pyridine are preferably used.
  • solvents examples include chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons e.g. Toluene, xylene or chlorobenzene, ethers such as diethyl ether, methyl tert. butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate, or mixtures thereof.
  • chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane
  • aromatic hydrocarbons e.g. Toluene, xylene or chlorobenzene
  • ethers such as diethyl ether, methyl tert. butyl ether, tetrahydrofuran or dioxane
  • polar aprotic solvents such as acetonitrile, dimethyl
  • reaction temperature is in the range from 0 ° C. to the boiling point of the reaction mixture.
  • the product can be worked up in a manner known per se.
  • compounds Ia, Ib or mixtures thereof can be formed in processes B to D.
  • the latter can be separated using classic separation methods, e.g. Crystallization, chromatography, etc., are separated.
  • cyclohexanediones of the formula IV used as starting materials are known or can be prepared by processes known per se (e.g. EP-A 71 707, EP-A 142 741, EP-A 243 313, US 4,249,937, WO 92/13821).
  • alkylating agents V ⁇ sulfonylating agents Vß, phosphonylating agents V ⁇ and V ⁇
  • compounds Vl ⁇ , Vlß, Vl ⁇ , Vl ⁇ , Vl ⁇ and Vl ⁇ are known or can be prepared in analogy to known processes.
  • R 1 Cyano, Rhodano, Nitro, OR 4 , SR 5 , SOR 6 , S0 2 R 6 , ONR 6 R 7 , ON CR 6 R 8 , NR 9 R 10 , P (0) R 1] -R 12 , P (S) R 11 R 12 , COR 6 , CO 2 R 6 , phenyl, heterocyclyl or N-linked heterocyclyl, where the last three radicals in turn can be partially or completely halogenated and / or can carry one to three substituents from the following group : Nitro, cyano, C -C 4 alkyl, C -C 4 haloalkyl, C ⁇ -C alkoxy, C -C haloalkoxy or C ⁇ -C 4 alkoxycarbonyl; R 2 is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C -C 6 alkoxy or
  • R 3 is hydrogen, halogen or C ⁇ -C 6 alkyl
  • n 0, 1, 2, 3 or 4;
  • R 4 , R 5 is a radical mentioned under R 6 ;
  • Substituents can be partially or completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C alkyl, C ⁇ -C haloalkyl, C -C 4 alkoxy, C ⁇ -C 4 haloalkoxy or C ⁇ -C 4 alkoxycarbonyl,
  • R 6 C -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or
  • C -C 6 cycloalkyl where the four radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy, Cx -C haloalkoxy, Cx -C 4 - Alkylthio,
  • R 7 is hydrogen or C -C 6 alkyl
  • R 8 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxycarbonyl, cyano or C -C6 alkoxy;
  • R 9 is a radical mentioned under R 4 ;
  • R 10 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
  • R 11 , R 12 are hydrogen, hydroxy, C -C 6 alkyl, Cx -C 6 alkoxy,
  • R 13 , R 14 are hydrogen, nitro, halogen, cyano, C -C 6 alkyl
  • C -C 6 haloalkyl C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy, C ⁇ -C 6 alkylthio, C x -C 6 haloalkylthio, C -C 6 alkyl - sulfinyl, C ⁇ -C 6 - Haloalkylsulfinyl, C -C 6 alkylsulfonyl, C -C ⁇ -haloalkylsulfonyl, N-C ⁇ -C 6 alkylamino,
  • R 13 , R 14 together form a methylidene group, which can be substituted by one or two substituents from the following group: halogen, cyano, C ⁇ -C 6 alkyl, C -C 6 haloalkyl, C ⁇ -C 6 alkoxy or C - C 6 haloalkoxy;
  • R 15 is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C -C 6 alkoxy or C ⁇ -C ⁇ haloalkoxy;
  • R 30 is hydroxy or a hydrolyzable residue;
  • residues which can be hydrolyzed are alkoxy, phenoxy, alkylthio, phenylthio residues, which may optionally be substituted, halides, hetaryl residues, which are bonded via nitrogen, amino, imino residues, which may optionally be substituted, etc.
  • Carboxylic acids of the formula IIIb are likewise preferred
  • Carboxylic acid esters of the formula IIIc are also preferred.
  • halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.
  • the carboxylic acid esters of the formula IIIc can be obtained in various ways, for example by the following processes:
  • Suitable oxidizing agents are m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen oxide, if appropriate in the presence of a catalyst such as tungstate.
  • organometallic reagents such as Grignard, organolithium or organozinc compounds, or CH-acidic compounds such as aldehydes, ketones, carboxylic acid derivatives (esters, amides etc.), nitriles, sulfones, 1,3-dithio compounds, diketones, dicarboxylic acid ester derivatives, ketocarboxylic acid derivatives,
  • CH-acidic bases such as alkali or alkaline earth metal hydroxides e.g. Sodium hydroxide or potassium hydroxide, alkali or alkaline earth carbonates, e.g. Sodium carbonate or potassium carbonate, alkali or alkaline earth hydrogen carbonates e.g. Sodium bicarbonate or potassium bicarbonate, alkali or alkaline earth alcoholates, e.g. Sodium methoxide, sodium methoxide or potassium tert-butoxide, alkali or alkaline earth hydrides, e.g. Sodium hydride, or organometallic bases such as butyllithium.
  • alkali or alkaline earth metal hydroxides e.g. Sodium hydroxide or potassium hydroxide
  • alkali or alkaline earth carbonates e.g. Sodium carbonate or potassium carbonate
  • alkali or alkaline earth hydrogen carbonates e.g. Sodium bicarbonate or potassium bicarbonate
  • halides of the formula VII can be obtained by halogenating the corresponding alkyl compounds X in the presence of a radical initiator or by means of radiation.
  • Suitable halogenating agents are, for example, chlorine, bromine, N-chloramine, N-chlorosuccinimide, N-bromosuccinimide, etc.
  • radical initiators i.a. Benzoyl peroxide or azobisisobutyronitrile.
  • suitable radiation sources such as UV-Hg low-pressure or Hg high-pressure lamps.
  • Suitable halogenating agents are phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide, phosgene, carbonic acid bromide, oxalyl chloride, oxalyl bromide, and binary systems such as carbon tetrachloride / triphenylphosphine or tetrabromomethane / triphenylphosphine, etc.
  • aldehydes or ketones of the formula VIII can be obtained in a manner known per se by oxidation of corresponding compounds of the formula XI.
  • Suitable oxidizing agents include Hydrogen peroxide, chromic acid, potassium permanganate, pyridinium dichromate, cerammonium nitrate, N-methylmorpholine-N-oxide or tetramethylmorpholine-N-oxide (cf. J. March, "Advanced Organic Chemistry", 4th edition, p. 1158 ff., Wiley-Interscience Publication , 1992).
  • Chlorine or bromine are particularly suitable as halogenating agents.
  • the alcohols of the formula XI can be obtained in a manner known per se by reacting corresponding aldehydes or ketones with carbon nucleophiles.
  • Suitable carbon nucleophiles are, for example, organometallic reagents such as Grignard compounds, organolithium or organozinc compounds, but also hydrides (or reducing agents such as lithium aluminum hydride, boranate etc. or “hydride-generating systems”, such as reductions with hydrogen over catalyst) illustrated below as an example.
  • Barium permanganate (Ba (Mn0 4 ) 2 ; see H. Firouzabadi et. Al., Tetrahedron 46, 6869 (1990)), silver nitrate (AgN0 3 ; see E. Ghera et. Al., Synthesis 504 (1984)), potassium dichromate (K 2 Cr 2 0 7 ; see E. Santaniello, Tetrahedron Lett. 4581 (1979)), bis - (p-methoxyphenyl) selenium oxide (see K. Ariyoshi et. Al., Chem Lett. 6, 891 (1984)) or isopropyl nitrite (see S. Kuriatkowski et. Al., Tetrahedron Lett. 2093 (1990)).
  • protective groups for certain functionalities in the synthesis variants described above, if the functionalities are not compatible with the required reaction conditions.
  • the choice of the protective groups depends both on the reaction conditions and on the molecular structure. Protecting groups, their introduction and splitting off are generally known from the literature (cf. TW Greene et. Al., "Protective Groups in Organic Synthesis", 2 nd Ed., Wiley-New York, 1991) and can be used analogously to processes known from the literature .
  • the reaction temperatures are generally between -100 ° C and the reflux temperature of the reaction mixture.
  • Solvents or solvent mixtures adapted to the reaction conditions are generally used.
  • the reactants are usually used in a stoichiometric ratio. However, it can also be advantageous to use one or the other reactants in excess or deficit.
  • Halogenating agents include N-bromosuccinimide, N-chlorosuccinid, bromine or chlorine. They are generally used in a three-fold excess based on the starting material. However, it can also be advantageous to use a larger or smaller excess.
  • inert solvents such as halogenated hydrocarbons, e.g. Dichloromethane, trichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene etc. or aromatics such as benzene, toluene or xylene. It can also be an advantage
  • the reaction temperatures of the first stage are usually between -80 ° C and reflux temperature of the reaction mixture. Is preferably carried out at temperatures from -80 ° C to room temperature, in particular at -80 ° C to 0 ° C.
  • Suitable reducing agents are alanates such as lithium alanate,
  • the reducing agent is generally used in equimolar amounts. However, it can also be advantageous to use an excess or deficit.
  • Suitable solvents for the second reaction stage are in particular solvents such as ethers, e.g. Diethyl ether, methyl tert. -butyl ether or 1,4-dioxane, or dipolar solvents such as dimethylformamide, diethylforma id, dimethyl sulfoxide, N-methylpyrrolidone. But alcohols such as methanol, ethanol etc. can also be used.
  • the reaction is generally carried out at 0 ° C. to the reflux temperature of the reaction mixture, preferably at 0 to 100 ° C., in particular at 10 to 40 ° C.
  • the compounds of the formula XIII are prepared from the corresponding cyclohexanone derivatives by methods known per se by reaction with dithiols (cf. TW Greene, et al. In “Protective Groups in Organic Synthesis", 2nd edition, p. 201 -203, Wiley, New York, 1991).
  • Step c) 4, 4, 8 -trimethyl-1, l-dioxothiochroman-7-carboxylic acid methyl ester
  • methyl 2-methyl-3-oxocyclohexanecarboxylate prepared according to Gupla et al. J. Sei. Ind. Res. B, 1962, 21, 219
  • 200 ml of methylene chloride was initially added 41.0 g (436 mmol) of 1,2-dimercaptoethane and then 6.8 ml of boron trifluoride etherate were added dropwise and the mixture was stirred at room temperature overnight.
  • 200 ml of 2N sodium hydroxide solution were added, the phases were separated, the organic phase was dried over sodium sulfate and the solvent was removed. Yield: 56.7 g (yellow oil)
  • Spatula tip sodium tungstate 208 g (1830 mmol) of 30% hydrogen peroxide solution were added dropwise at 50 to 60 ° C. and the mixture was stirred at 50 ° C. for a further 3 hours. Then the mixture was poured into water and the resulting precipitate was filtered off with suction. The product was washed successively with sodium bisulfite solution and water and dried in vacuo.
  • the compounds of formula I and their agriculturally useful salts are suitable both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions which contain compounds of the formula I control vegetation very well on non-cultivated areas, especially when high amounts are applied. 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 of the formula I or herbicidal compositions comprising 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 of the formula I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the compounds of the formula I or the herbicidal compositions comprising them can be prepared, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oldispersions, pastes, dusts, sprinkling agents or granules Spraying, atomizing, dusting, scattering or pouring can be used.
  • 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.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
  • Mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and water.
  • Paraffin Paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
  • ketones such as cyclo
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oldispersions the thiochromanoylcyclohexenone derivatives of the formula I as such or dissolved in an oil or solvent, 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.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylpheny
  • 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, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within a wide range.
  • the formulations contain from about 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 following formulation examples illustrate the preparation of such preparations:
  • Benzene 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide in 1 mole 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 in 1 mole of castor oil.
  • an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • Wettol R EM 31 nonionic emulsifier based on ethoxylated castor oil ".
  • the compounds of the formula I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with 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 hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the application rates of the compound of the formula I are, depending on the control target, the season, the target plants and the growth stage, 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.).
  • the thiochromanoylcyclohexenone derivatives of the formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • Plastic flower 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 species.
  • 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 clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and a few days before of the treatment transplanted into the test vessels.
  • the application rate for post-emergence treatment was 0.25 and 0.125 kg / ha aS (active substance).
  • the plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C.
  • 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 was carried out 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 composed of the following types:
  • compound 2.13 had a very good post-emergence effect against the harmful plants Avena fatua, Galium aparine, Polygonum persicaria and Sinapis alba. Furthermore, compound 2.25 showed a very good action against the weeds Chenopodium album, Polygonum persicaria and Sinapis alba with simultaneous tolerance in the crop plant Triticum aestivum.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)

Abstract

L'invention concerne des dérivés de cyclohexénone de thiochromanoyl de la formule (I) où les variables ont la signification suivante: représente éventuellement une chaîne alkyle saturée ou non saturée; R<1? représente cyano, rhodano, nitro, OR?4>, SR<5>, SOR<6>, SO2R<6>, ONR<6>NR<7>, ON=CR<6>R<8>, NR<9>R<10>, P(O)R<11>R<12>, P(S)R<11>R<12>, CO2R<6>, ou bien du phényle ou hétérocyclyle éventuellement substitué; R<2> représente alkyle, halogènalkyle, alcoxy ou halogènalcoxy; R<3> représente de l'hydrogène, alkyle ou halogène; X représente de l'oxygène, soufre, S=O, S(=O)2, CR<13>R<14>, C=O ou C=NR<15>; m vaut 0, 1 ou 2; n vaut 0, 1, 2, 3 ou 4; R<16> représente (3-Oxo-1-cyclohexen-2-yl)-carbonyle substitué ou (1, 3-Dioxo-2-cyclohexyl)-méthylidène substitué. L'invention concerne également leurs sels utilisables dans l'agriculture; les produits intermédiaires et le procédé de production des dérivés de cyclohexénone de thiochromanoyl; les produits les contenant ainsi que l'utilisation de ces dérivés ou les produits les contenant et destinés à lutter contre les plantes indésirables.
EP99963363A 1998-12-15 1999-12-02 Derives de cyclohexenone de thiochromanoyl Withdrawn EP1144401A3 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19857898 1998-12-15
DE19857898 1998-12-15
PCT/EP1999/009395 WO2000035903A2 (fr) 1998-12-15 1999-12-02 Derives de cyclohexenone de thiochromanoyl

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DE19532311A1 (de) * 1995-09-01 1997-03-06 Basf Ag Benzoylderivate
SK282671B6 (sk) * 1996-02-24 2002-11-06 Basf Aktiengesellschaft Hetaryolderiváty, spôsob ich prípravy, medziprodukty na ich prípravu, herbicídne prostriedky s ich obsahom a ich použitie

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EP1144401A3 (fr) 2002-09-11
JP2002532489A (ja) 2002-10-02

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