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WO2000059911A2 - Derives tricycliques de dione de cyclohexane - Google Patents

Derives tricycliques de dione de cyclohexane Download PDF

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Publication number
WO2000059911A2
WO2000059911A2 PCT/EP2000/002565 EP0002565W WO0059911A2 WO 2000059911 A2 WO2000059911 A2 WO 2000059911A2 EP 0002565 W EP0002565 W EP 0002565W WO 0059911 A2 WO0059911 A2 WO 0059911A2
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alkyl
alkoxy
halogen
cyano
hydrogen
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German (de)
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WO2000059911A3 (fr
Inventor
Klaus Langemann
Ernst Baumann
Wolfgang Von Deyn
Steffen Kudis
Guido Mayer
Ulf Misslitz
Ulf Neidlein
Matthias Witschel
Thorsten Volk
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 WO2000059911A3 publication Critical patent/WO2000059911A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to new tricyclic cyclohexanedione derivatives with herbicidal activity, processes for the preparation of the tricyclic cyclohexanedione derivatives and intermediates for their preparation, compositions which contain them and the use of these derivatives or compositions comprising them for weed control.
  • Herbicidal tricyclic cyclohexanedione derivatives are known from the literature, for example from WO 97/19087.
  • the task was to find new tricyclic cyclohexanedione derivatives with improved properties.
  • R 1 is hydrogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl,
  • R 2 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C ⁇ -C 6 -haloalkyl, C ⁇ -C 6 -haloalkoxy, optionally with C ⁇ -C 3 -alkyl, halogen, cyano, nitro or C ⁇ -C 3 alkyl- sulfonyl-substituted phenyl or phenylsulfonyl optionally substituted with C ⁇ -C-alkyl, halogen, cyano or nitro;
  • R 3 , R 4 are hydrogen, C -C 6 alkyl, C -C 6 haloalkyl,
  • R 5 is hydrogen or C -C alkyl
  • R 6 is hydrogen, C ⁇ -C ⁇ alkyl or halogen
  • R 7 is hydrogen or Cx-C 6 alkyl
  • R 8 is C ⁇ -C 6 alkyl or Cx -C 6 alkoxy
  • R 9 substituted (3-oxo-1-cyclohexen-2 -yl) carbonyl or substituted (1, 3-dioxo-2-cyclohexyl) methylidene;
  • 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
  • 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, hydroxy-C ⁇ -C4 alkyl, Cx-C4 alkoxy-C ⁇ -C 4 - lkyl, hydroxy-C ⁇ -C4-alkoxy-C ⁇ -C4 alkyl, substituted phenyl or benzyl can be, preferably ammonium, dirnethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2 - (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) ammonium, tri-methylbenzylammonium , further phosphonium ions, s
  • 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 ⁇ -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 ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ - C 4 - haloalkoxy; Ri, R i5 hydrogen, C ⁇ -C 4 alkyl or C ⁇ -C 4 alkoxycarbonyl;
  • Ri 2 , R 14 , R 16 are hydrogen or C x -C 4 alkyl
  • R 3 is hydrogen, halogen, hydroxy, C ⁇ -C 6 alkyl
  • C ⁇ -C 6 -haloalkyl di- (C ⁇ -C 6 -alkoxy) -methyl, (C ⁇ -C ⁇ -alkoxy) - (C ⁇ -C 6 -alkylthio) -methyl, di- (C ⁇ -C 6 -alkylthio ) methyl, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy, C ⁇ -C 6 alkylthio, C ⁇ -C 6 haloalkylthio, C ⁇ -C 6 alkylsulfinyl, C -C 6 haloalkylsulfinyl, C ⁇ -C 6 -alkylsulfonyl, C ⁇ -C 6 -haloalkyl-sulfonyl, C ⁇ -C ⁇ -alkoxycarbonyl, C ⁇ -C 6 -haloalkoxy-carbony1;
  • R 12 and R X3 or R 12 and R 16 together form a ⁇ bond or a C ⁇ -C 5 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ - C 4 halo alkyl or C ⁇ -C 4 alkoxycarbonyl, from;
  • R i2 and R X6 together form a C ⁇ -C 4 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C haloalkyl or C ⁇ -C 4 alkoxycarbonyl, out;
  • R X3 and R X4 together form a -0- (CH 2 ) p -0-, -O- (CH 2 ) P -S-, -S- (CH 2 ) P -S-, -0- (CH 2 ) g - or -S- (CH 2 ) q chain, which can be substituted by one to three radicals from the following group: halogen, cyano, C ⁇ -C 4 -alkyl, C ⁇ -C -haloalkyl or C ⁇ -C 4 - Alkoxycarbonyl;
  • R i3 and R i4 together with the carbon to which they are attached form a carbonyl group
  • R 17 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 -alkoxyimino-C ⁇ -C 6 -alkyl where the alkyl, cycloalkyl or alkoxy radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy , C ⁇ -C 4 alkylthio, di- (C ⁇ -C 4 alkyl) amino,
  • C ⁇ -C 4 -alkylcarbonyl C ⁇ -C 4 -alkoxycarbonyl, C ⁇ -C -alkoxy-C ⁇ -C -alkoxycarbonyl, hydroxycarbonyl, C ⁇ -C 4 -alkylaminocarbonyl, di - (C x -C -alkyl) aminocarbonyl , Aminocarbonyl, C ⁇ -C 4 alkylcarbonyloxy or C 3 -C 6 cycloalkyl;
  • Heterocyclyl -C ⁇ -C 6 -alkenylcarbonyl where the phenyl or heterocyclyl radical of the 18 latter 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 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy;
  • C 3 -C ⁇ 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, C ⁇ -C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 haloalkylthio, C ⁇ -C 4 alkylcarbonyl, C ⁇ -C alkoxycarbonyl or Cx -C 4 haloalkoxycarbonyl; Phenyl, phenyl-C -C -alkyl, heterocyclyl or heterocyclic-C C-C 4 -alkyl, where the phenyl or heterocyclyl radical of the four last-mentioned substituents can be partially or completely halogenated and / or one to three of the following Can carry leftovers:
  • Ri 9 , R 20 are hydrogen, hydroxy, C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxy, C ⁇ -C 6 alkylthio, phenyl, phenyl -C ⁇ -C alkyl or phenoxy, the three latter substituents being partially or completely may be halogenated and / or may carry one to three of the following radicals: nitro, cyano, C ⁇ -C4-alkyl, C ⁇ -C4 halo-alkyl, C ⁇ -C4-alkoxy, C ⁇ -C4-haloalkoxy or Cx -C alkoxycarbonyl;
  • R 21 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C & haloalkynyl, C 3 -C 6 -Cycloalkyl, C ⁇ -C 6 alkylcarbonyl, hydroxy, C ⁇ -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C ⁇ alkynyloxy, amino, C ⁇ -C 6 alkylamino, di- (C ⁇ -C ⁇ - lkyl) amino or C ⁇ -C ⁇ 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 4 alkoxycarbonyl , C ⁇ -C -alkylaminocarbonyl, di-
  • R 22 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 and the alkyl parts of phenyl -C ⁇ -C 4 -alkyl and heterocyclyl -C ⁇ -C 4 -alkyl: for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1 , 1-dimethylethyl;
  • C ⁇ -C 6 alkyl and the alkyl parts of C ⁇ -C6-alkoxyimino-C ⁇ -C 6 - alkyl, N-C ⁇ -C 6 -alkoxy-N-C ⁇ -C 6 -alkylamino, N (C ⁇ -C 6 -alk - oxy) -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 -alkyl) -N-heterocyclylaminocarbonyl , Phenyl-
  • C ⁇ -C 4 -haloalkyl a C ⁇ -C-alkyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 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
  • C ⁇ -C 6 -haloalkyl and the haloalkyl parts of N-C ⁇ -C 6 -haloalkylamino: C ⁇ -C 4 -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 for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy;
  • N-C ⁇ -C 6 -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) -amino-carbonyl, N- (C 3 -C 6 -alkenyl) -N- (C ⁇ -C 6 -alkoxy) -aminocarbonyl and N- (C 3 -C 6 -alkynyl) -N- (C ⁇ -C 6 -alkoxy) -amin
  • C ⁇ -C ⁇ -haloalkoxy C ⁇ -C 4 -haloalkoxy, as mentioned above, and for example 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorhexoxy, 6-chlorohexoxy, 6- Bromhexoxy, 6-iodohexoxy or dodecafluorohexoxy;
  • C ⁇ -C 4 alkylthio for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1, 1-dimethylethylthio;
  • C ⁇ -C 6 -alkoxy C ⁇ -C ⁇ - alkylthio methyl: C ⁇ -C -alkylthio, as mentioned above, and for example 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,
  • C ⁇ -C 4 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-tri- chloroethylthio, 2-chloro-2-fluoroethylthio,
  • C ⁇ -C 6 -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, bromodifluoromethylsulfinyl , 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2, 2, 2-trifluoroethylsulfinyl, 2, 2, 2-trichloroethylsulfinyl,
  • 2-chloro-2-fluoroethylsulfinyl 2-chloro-2, 2-difluoroethylsulfinyl - nyl, 2, 2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl nyl, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 2, 2-difluoropropylsulfinyl, 2, 3-difluoropropylsulfinyl, 2, 3, 3-dichloromethyl 3-trifluoropropylsulfinyl, 3, 3, 3-trichloropropylsulfinyl, 2, 2, 3, 3, 3-
  • C ⁇ -C 6 -haloalkylsulfinyl C ⁇ -C 4 -haloalkylsulfinyl as mentioned above, as well as 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopen-ylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorosulfinyl 6-bromohexyls finyl, 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
  • C ⁇ -C 6 -haloalkylsulfonyl C ⁇ -C -haloalkylsulfonyl as mentioned above, and 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromhexylsulfonylylylsulfonyl;
  • C ⁇ -C 6 -alkylamino for example methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1, 1-dimethylethylamino, pentylamino,
  • 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 -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, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl,
  • 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-difluoroe
  • C ⁇ -C 6 -haloalkylcarbonyl a C ⁇ -C 4 -haloalkylcarbonyl radical as mentioned above, and 5-fluoropentylcarbonyl, 5-chloropentylcarbonyl, 5 -bromopentylcarbonyl, perfluoropentylcarbonyl, 6-fluorhexylcarbonyl, 6 -chlorohexylcarbonyl, 6-bromo- hexylcarbonyl or perfluorohexylcarbonyl;
  • C ⁇ -C 4 -alkoxycarbonyl and the alkoxycarbonyl parts of di- (C ⁇ -C 4 -alkyl) amino-C ⁇ -C 4 -alkoxycarbonyl, i.e. for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1- Methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1, 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-dimethyl-propoxycarbonyl, 1- Ethylpropoxycarbonyl, Hexoxycarbonyl, 1, 1-Dirnethylpropoxycarbonyl, 1, 2-Dimethylpropoxycarbonyl, 1-Methylpentoxycarbonyl, 2-Methylpentoxycarbonyl, 3-Methyl-pentoxycarbonyl, 4-Methylpentoxycarbonyl, 1, 1-Dimethylbutoxycarbonyl, 1,2-Dimethylbutoxycarbonony1, 1 3-dimethylbutoxycarbonyl, 2, 2-dimethylbutoxycarbonyl, 2, 3-dimethylbutoxycarbonyl, 3, 3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-eth
  • 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, chlorodifluoromethoxycarbonyl, bromodifluoryl, bromodifluoro 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-iodoethoxycarbonyl, 2, 2-difluoroethoxycarbonyl, 2,2, 2-trifluoroethoxycarbonyl, 2-chloro-2-fluoroethoxycarbonyl, 2-chloro-2, 2-difluoroethoxycarbonyl, 2,2-dichloro-2-fluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbony
  • Cx-Cg-halooxycarbonyl a C ⁇ -C 4 halooxycarbonyl radical as mentioned above, and 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6-fluorohexoxycarbonyl, 6-chlorohexoxycarbonyl or 6-bromhexoxycarbonyl;
  • (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-ethyl-propylaminocarbonyl, hexylaminocarbonyl, 1, 1-dimethylpropylaaminocarbonyl, 1, 2-dimethylpropylaminocarbonyl, 1-methylpentylaminocarbonyl, 2-methylpentylaminocarbonyl, 3-methylpentylaminocarbonyl, 4-methylpentylaminocarbonyl, 1, 1-dimethyl 1, 2-dimethylbutylaminocarbonyl, 1,3-dimethylbutylaminocarbonyl, 2, 2-dimethylbutylaminocarbonyl,
  • Di- (C ⁇ -C 4 -alkyl) -aminocarbonyl for example 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
  • 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-dimethyl-propyl) -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 alkenylcarbonyl, 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 ) alkylaminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C ⁇ -C 6 -alkoxy) aminocarbonyl: eg prop-2-ene -l-yl, but-l-en-4-yl, 1-methyl-prop-2-en-l-yl, 2-methyl-prop-2-en-l-yl, 2-butene-l-yl , l-penten-3-yl, l-penten-4-yl, 2-penten-4-yl, 1-methyl-but-2-en-l-yl, 2-
  • 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 -Cg alkynylcarbonyl, C 3 -C 6 alkynyloxy, C 3 -C 6 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 ⁇ -C6 alkoxy aminocarbonyl: for example, propargyl, but- l-in-3-yl, but-l-in-4-yl, but-2-in-l-yl, pent-l-in-3-yl, pent-l-in-4-yl, pent 1-in-5-yl, pent-2-in-1-yl, pent-2-in-4-yl, pent-2-in-5-yl, 3-methyl
  • 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;
  • 6-link rings such as:
  • a bicyclic ring system can be formed with a fused-on phenyl ring or with a C 3 -C 6 carbocycle or with a further 5- to 6-membered heterocycle.
  • 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 such as: Tetrahydropyrrol-1-yl, 2,3-dihydro-lH-pyrrol-l-yl, 2,5-di-hydro-lH-pyrrol-1-yl, pyrrol-1-yl, tetrahydropyrazol-1-yl, tetrahydroisoxazole 2-yl, tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl, tetrahydrooxazol-3-yl, tetrahydrothiazol-3-yl, 4,5-dihydro-lH-pyrazol-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- Di
  • N-linked 6-membered rings such as:
  • Piperidin-1-yl 1, 2, 3, 4-tetrahydropyridin-l-yl, 1,2,5,6-tetrahydropyridin-1-yl, 1, 4-dihydropyridin-l-yl, 1,2- Dihydropyridin-1-yl, hexahydropyrimidin-1-yl, hexahydropyrazin-1-yl, hexahydropyridazin-1-yl, tetrahydro-1, 3-oxazin-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 1, 2-oxazin-2-yl, 2H-5, 6-dihydro-l, 2-thiazin-2-yl, 2H-3, 6-dihydr
  • Phthalimide tetrahydrophthalimide, succinimide, maleimide or glutarimide
  • Tricyclic cyclohexanedione derivatives of the formula III are preferred
  • Tricyclic cyclohexanedione derivatives of the formula IV are also preferred
  • the variables preferably have the following meanings, in each case individually or in combination: Ri is hydrogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl,
  • R 2 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkyl, C ⁇ -C ⁇ -haloalkoxy, optionally with C terrorism dilemma-C 3 alkyl, halogen, cyano, nitro or C ⁇ -C 3 alkyl sulfonyl substituted phenyl or phenyl sulfonyl optionally substituted with C ⁇ -C 3 alkyl, halogen, cyano or nitro;
  • R 3 , R 4 are hydrogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -alkoxy, C ⁇ -C 6 -alkylthio, C ⁇ -C 6 -alkylsulfonyl, C 2 -C 6 -alkoxyalkyl, C ⁇ -C 6 -alkoxycarbonyl, C ⁇ -C ⁇ alkylcarbonyl, halogen, optionally with C ⁇ -C 3 alkyl, halogen, cyano or
  • R 5 is hydrogen
  • R 6 is hydrogen, C ⁇ -C 3 alkyl or halogen
  • N-linked heterocyclyl which 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 or C ⁇ -C 4 haloalkoxy; preferably hydroxy, mercapto, halogen, OR i "7 , SR i7 , S0 2 R i8 , OS0 2 R i8 , NR 2i R 22 , ONR 18 R i8 or N-linked heterocyclyl, which can be partially or completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C 4 alkyl,
  • Ri, Ri 5 is hydrogen or C ⁇ -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R i2 , R 4 , R i6 hydrogen or C ⁇ -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 3 is hydrogen, hydroxy, C ⁇ -C6-alkyl, di- (C ⁇ -C 6 -alk-oxy) -methyl, (C ⁇ -Ce -alkoxy) - (C ⁇ -C 6 -alkylthio) -methyl, di- (C ⁇ -C 6 -alkylthio) methyl, C ⁇ -C 6 alkylthio, Cx-C6 -Halogenalky1thio, C-C6 alkylsulfinyl, C ⁇ -C 6 "haloalkylsulfinyl, alkylsulfonyl or C ⁇ -C ⁇
  • Radicals can be substituted by one to three C ⁇ -C 4 alkyl radicals
  • R i2 and R 13 or R 12 and R i6 together form a ⁇ bond or a C 3 -C 5 alkyl chain which have up to three residues from the following
  • Group can carry: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C ⁇ -C 4 alkoxycarbonyl, from;
  • Ri 2 and R 16 together form a C ⁇ -C 4 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C ⁇ -C 4 alkoxycarbonyl , out;
  • R 3 and Rl 4 together form a -0- (CH 2 ) p -0-, -0- (CH 2 ) p -S- or -S- (CH 2 ) P -S chain, which by one to three Residues from the following group can be substituted: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C ⁇ - ⁇ alkoxycarbonyl; preferably R 13 and R i4 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: Cx-C 4 haloalkyl or C ⁇ -C 4 alkoxycarbonyl;
  • R i3 and R i4 together with the carbon to which they are attached form a carbonyl group; C ⁇ -C ⁇ 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 alkylaminocarbonyl or N, N-di (C ⁇ -C 6 -alkyl) aminocarbonyl, where the alkyl or alkoxy radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy, C ⁇ -C 4 alkylthio or C ⁇ -C 4 alkoxycarbonyl;
  • R 18 is C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 cycloalkyl, 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, C ⁇ -C 4 alkylthio, C ⁇ -C alkylcarbonyl or C ⁇ -C 4 alkoxycarbonyl;
  • R i9 , R 20 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, Cx -C 4 -haloalkyl, C ⁇ -C -alkoxy, C ⁇ -C 4 -haloalkoxy or Cx-C 4 -alkoxycarbonyl;
  • R 2i 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 -alkoxycarbonyl, C ⁇ -C 4 alkylaminocarbonyl, di- (C ⁇ -C 4 alkyl) aminocarbonyl or C 3 -C 6 cycloalkyl;
  • R 22 is C ⁇ -C ⁇ alkyl or C 3 -C 6 alkenyl
  • R is methyl, ethyl, halogen, methoxy, methylthio, methylsulfonyl, nitro, cyano;
  • R 2 is methyl, ethyl, optionally with halogen, cyano,
  • R 3 , R 4 are hydrogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -alkylcarbonyl, phenyl optionally substituted by halogen, cyano, nitro,
  • R 5 is hydrogen
  • R 6 is hydrogen, methyl, chlorine
  • R i ° halogen OR i7 , SR 17 , S0 2 R l8 , OS0 2 R i8 , NR 2i R 22 , ONR l8 Ri 8 or N-linked heterocyclyl, which can be partially or completely halogenated and / or one to three of the can carry the following radicals: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C haloalkyl, C ⁇ -C alkoxy or C ⁇ -C 4 haloalkoxy;
  • R i5 hydrogen or C ⁇ -C 4 alkyl
  • R 12 , R i , R 6 are hydrogen or Cx-C 4 alkyl
  • R i3 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,
  • Ri and R i6 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 c ⁇ -C 4 haloalkyl;
  • R i2 and R 16 together form a methylene bridge which can carry one or two radicals from the following group: halogen, C ⁇ -C 2 alkyl or C ⁇ -C 2 haloalkyl;
  • R 13 and R i4 together with the carbon to which they are attached form a carbonyl group
  • the compounds of the formula Ia are also extremely preferred.
  • Li stands for a nucleophilically displaceable leaving group, such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate etc.
  • halogen for example bromine or chlorine
  • hetaryl for example imidazolyl or pyridyl
  • carboxylate for example acetate or trifluoroacetate etc.
  • the activated benzoic acid Va can be used directly, as in the case of the benzoyl halides, or generated in situ, e.g. with dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2-pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently used in equimolar amounts.
  • a slight excess of the auxiliary base e.g. Under certain circumstances, 1.2 to 1.5 molar equivalents, based on Va or Vb, can be advantageous.
  • Suitable auxiliary bases are tertiary alkylammes, pyridine or alkali metal carbonates.
  • 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 become.
  • 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 the 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.
  • a solvent for example, acetonitrile, methylene chloride, 1, 2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used as solvents.
  • 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 carbonate are preferably used, preferably in a 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. acidified with dilute mineral acid such as 5% hydrochloric acid or sulfuric acid, 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 can be extracted.
  • the aqueous phase is acidified and the precipitate formed is suction filtered and / or extracted with methylene chloride or ethyl acetate, dried and concentrated.
  • Suitable halogenating agents are, for example, 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 A ⁇ , Aß, A ⁇ or A ⁇ 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 compounds of the formula V are prepared by oxidation of the compounds of the formula XIII using oxidizing agents:
  • T is C ⁇ -C -alkoxy and the other substituents have the meaning described above.
  • Suitable oxidizing agents are, for example, m-chloroperbenzoic acid, peroxyacetic acid or hydrogen peroxide, if appropriate in the presence of a catalyst such as tungsten.
  • Compounds of the formula Xllla are prepared by dipolar cycloaddition of compounds of the formula XIV in the presence of an oxidizing agent (see, for example, Kim, JN et.al. Synth. Commun. 1990, 20, 1373; Hassner, A. et. Al. Synthesis 1989, 57; Kellabennani, AE et al. Tetrahedron 1995, 51, 10923),
  • T is C ⁇ -C -alkoxy and the other substituents have the meanings described above.
  • oxidizing agents come e.g. Chloramine T or sodium hypochlorite are used.
  • T is C ⁇ -C 4 alkoxy and the other substituents have the meaning described above.
  • the oximes XIV are prepared using generally known methods from the aldehydes XVI (see March, J. Advanced Organic Chemistry, 4th Ed., Wiley and Sons 1992, pp. 906 ff.).
  • T is C ⁇ -C -alkoxy and the other substituents have the meaning described above.
  • the hydrazone XV is represented by generally known methods from the aldehydes XVI (see March, J. Advanced Organic Chemistry, 4th Ed., Wiley, 1992, pp. 904 ff.).
  • T is C ⁇ -C 4 alkoxy and the other substituents have the meaning described above.
  • Compounds of the formula XVI are prepared by nucleophilic aromatic substitution of compounds of the formula XVII with substituted allyl thiols in polar solvents in the presence of bases.
  • Tertiary amines such as triethylamine or pydridine or alkali metal carbonates such as lithium carbonate or sodium carbonate can be used as bases.
  • Methanol, ethanol, dimethylformamide or N-methyl-pyrrolidone are suitable as solvents.
  • aldehydes of the formula XVII are known from, for example, WO 98/31681.
  • Hydroxylammonium chloride (4.48 g, 64.5) is added to a solution of the methyl ester from stage a) (15.85 g, 58.6 mmol) and Na CO 3 (3.5 g, 33 mmol) in ethanol (200 ml) mmol) was added and the mixture was stirred at RT over the weekend. Water (200 ml) is added and the mixture is stirred for a further hour before the mixture is concentrated on a rotary evaporator. The residue is taken up in water / ethyl acetate, the organic phase is dried over Na 2 S0 4 and the solvent is removed. The oxime is obtained quantitatively as a light syrup.
  • step d) The acid from step d) (4.4 g, 16.3 mmol) was dissolved in 30 ml of glacial acetic acid and a spatula tip of sodium tungstate was added. Thereafter, perhydrol (4.16 g, 36.7 mmol) was added dropwise at 50 ° C. and the mixture was stirred at 50 ° C. for a further 4 h. The mixture was stirred into ice water and extracted with ethyl acetate. The organic phase was washed with water, dried over sodium sulfate and concentrated.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the I-containing 1C herbicides control vegetation very well on nonculture areas, especially at high application rates. In crops such as wheat, rice, maize, soybeans and cotton, they work against weeds and grass weeds without causing any significant damage to crops. 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 are considered
  • Triticum aestivum Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
  • the compounds I can also be used in crops which are tolerant by breeding including genetic engineering methods the 5 action of herbicides are used.
  • the herbicidal compositions or the active compounds can be applied in the pre-emergence or in the post-emergence. If the active ingredients 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 hit wherever 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 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, furthermore 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, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the tricyclic cyclohexanedione derivatives 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 and fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, arylphenyl,
  • 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 earths such as silica, 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.
  • mineral earths such as silica, 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 s
  • 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 compound no. 49.1 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.
  • VIII 1 part by weight of compound 49.1 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20
  • Wettol ® EM 31 non-ionic emulsifier based on ethoxylated castor oil. A stable emulsion concentrate is obtained.
  • the tricyclic cyclohexanedione derivatives can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • 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 served as the 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 were first grown to a height of 3 to 15 cm, depending on the growth habit, 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 application rate for post-emergence treatment was 0.5 or 0.25 kg / ha a. S.
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • 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:

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des dérivés tricycliques de dione de cyclohexane de la formule (I) dans laquelle les substituants ont la signification suivante: R1 désigne hydrogène, alkyle C¿1?-C6, haloalkyle C1-C6, alcoxy C1-C6, haloalcoxy C1-C6, alkylthio C1-C6, haloalkylthio C1-C6, alkylsulfinyle C1-C6, haloalkylsulfinyle C1-C6, alkylsulfonyle C1-C6, haloalkylsulfonyle C1-C6, halogène, cyano ou nitro; X désigne O ou NR?2; R2¿ désigne hydrogène, alkyle C¿1?-C6, alcoxy C1-C6, haloalkyle C1-C6, haloalcoxy C1-C6, phényle éventuellement substitué par alkyle C1-C3, halogène, cyano, nitro ou alkylsulfonyle C1-C3 ou phénylsulfonyle éventuellement substitué par alkyle C1-C3, halogène, cyano ou nitro; R?3,R4¿ désignent hydrogène, alkyle C¿1?-C6, haloalkyle C1-C6, alcoxy C1-C6, haloalcoxy C1-C6, alkylthio C1-C6, haloalkylthio C1-C6, alkylsulfinyle C1-C6, haloalkylsulfinyle C1-C6, alkylsulfonyle C1-C6, haloalkylsulfonyle C1-C6, NR?7R8¿, alcoxyalkyle C¿2?-C6, alcoxycarbonyle C1-C6, alkylcarbonyle C1-C6, halogène, cyano, nitro, phényle éventuellement substitué par alkyle C1-C3, halogène, cyano ou nitro; R?5¿ désigne hydrogène, alkyle C¿1?-C4; R?6¿ désigne hydrogène, alkyle C¿1?-C6 ou halogène; R?7¿ désigne hydrogène ou alkyle C¿1?-C6; R?8¿ désigne alkyle C¿1?C6 ou alcoxy C1-C6; 1 vaut 0,1 ou 2; n vaut 1 ou 2; R?9¿ désigne (3-oxo-1-cyclohexène-2-yle)carbonyle substitué ou (1,3-dioxo-2-cyclohexyle)-méthylidène. L'invention concerne en outre les sels utilisables sur le plan agricole des composés (I), des procédés permettant de préparer les dérivés tricycliques de dione de cyclohexane, ainsi que des produits intermédiaires utilisés pour les préparer, des agents les contenant et l'utilisation de ces dérivés ou des agents les contenant pour lutter contre les mauvaises herbes.
PCT/EP2000/002565 1999-04-01 2000-03-23 Derives tricycliques de dione de cyclohexane Ceased WO2000059911A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU35578/00A AU3557800A (en) 1999-04-01 2000-03-23 Tricyclic cyclohexanedione derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914952 1999-04-01
DE19914952.6 1999-04-01

Publications (2)

Publication Number Publication Date
WO2000059911A2 true WO2000059911A2 (fr) 2000-10-12
WO2000059911A3 WO2000059911A3 (fr) 2001-04-19

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PCT/EP2000/002565 Ceased WO2000059911A2 (fr) 1999-04-01 2000-03-23 Derives tricycliques de dione de cyclohexane

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WO (1) WO2000059911A2 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0286346B1 (fr) * 1987-04-09 1994-04-06 E.I. Du Pont De Nemours And Company Indazoles substitués insecticides
EP0365201A1 (fr) * 1988-10-11 1990-04-25 E.I. Du Pont De Nemours And Company Indazoles substitués comme arthropodicides
US5985799A (en) * 1995-11-17 1999-11-16 E.I. Du Pont De Nemours And Company Tricyclic herbicidal heterocycles
AU2822697A (en) * 1996-05-07 1997-11-26 E.I. Du Pont De Nemours And Company 1,2-benzoxathiin and thiepin 2,2-dioxide herbicides
AU5612898A (en) * 1996-12-20 1998-07-17 E.I. Du Pont De Nemours And Company Substituted benzothiopyranes salts and their use as herbicides
US5885936A (en) * 1997-02-24 1999-03-23 E. I. Du Pont De Nemours And Company Heterotricyclic herbicides

Also Published As

Publication number Publication date
AU3557800A (en) 2000-10-23
WO2000059911A3 (fr) 2001-04-19

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