EP1135385A1 - Derives de thiochromanoylpyrazolone - Google Patents

Derives de thiochromanoylpyrazolone

Info

Publication number
EP1135385A1
EP1135385A1 EP99962201A EP99962201A EP1135385A1 EP 1135385 A1 EP1135385 A1 EP 1135385A1 EP 99962201 A EP99962201 A EP 99962201A EP 99962201 A EP99962201 A EP 99962201A EP 1135385 A1 EP1135385 A1 EP 1135385A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
formula
heterocyclyl
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99962201A
Other languages
German (de)
English (en)
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1135385A1 publication Critical patent/EP1135385A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to new thiochromanoylpyrazolone derivatives of the formula I,
  • R 1 Cyano, Rhodano, Nitro, OR 4 , SR 5 , SOR 6 , S0 2 R 6 , 0NR 6 R 7 , ON CR 6 R 8 , NR 9 R 10 , P (0) R 1: L 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 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or Ci-C 4 alkoxycarbonyl;
  • R 2 C ⁇ -C 6 -alkyl, C 6 haloalkyl, Ci-C ⁇ -alkoxy or Ci-C6 haloalkoxy;
  • R 3 is hydrogen, halogen or Ci -C 6 alkyl
  • R 4 , R 5 is a radical mentioned under R 6 ;
  • C 3 -C 6 -cycloalkyl where the radicals mentioned four may be partially or fully halogenated and / or may carry one to three of the following groups: cyano, C 4 alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -Alkylthio, -C-C 4 -Halogenalkylthio, C ⁇ -C 4 -Alkyl-sulfinyl, C ⁇ -C 4 -Halogenalkylsulfinyl, C ⁇ -C -Alkyl-sulfonyl, C ⁇ -C 4 -Halogenalkylsulfonyl, C 1 -C 4 - Alkylcarbonyl, -CC 4 alkoxycarbonyl and C 1 -C 4 haloalkoxycarbonyl;
  • R 7 is hydrogen or C ⁇ -C 6 alkyl
  • R 8 is hydrogen, C ⁇ -C 6 alkyl, Ci-C ⁇ alkoxycarbonyl, cyano or Ci -C 6 alkoxy;
  • R 9 is a radical mentioned under R 4 ; Ci-C ⁇ -alkoxy, C 3 -C 6 alkenyloxy, C 3 -C6 alkynyloxy, aminocarbonyl, N-C ⁇ -C 6 -alkylaminocarbonyl or N, N-di- (-CC 6 -alkyl) aminocarbonyl;
  • 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, Ci-C6 alkylthio, phenyl, phenyl -C ⁇ -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 ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 haloalkoxy or C ⁇ - C -alkoxycarbonyl;
  • R 13 , R 14 are hydrogen, nitro, halogen, cyano, C ⁇ -C 6 alkyl
  • 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 ⁇ -Ce-alkoxy or C -C 6 -haloalkoxy;
  • R 15 C ⁇ -C 6 alkyl, C ⁇ - C 6 haloalkyl, C ⁇ - C 6 alkoxy or
  • R 16 represents a radical Ha or Ilb
  • 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 alkoxy or C ⁇ -C 4 haloalkoxy;
  • R 18 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, hydroxy, C ⁇ -C 6 alkoxy or C ⁇ -C6 ⁇ haloalkoxy;
  • R 19 is hydrogen, halogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl, hydroxy, C ⁇ -C 6 -alkoxy, C ⁇ -C6-haloalkoxy, C ⁇ -C 6 -alkylthio or C ⁇ -C 6 -haloalkylthio ;
  • R 20 is C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C ⁇ -C 6 alkylcarbonyl, CC 6 -alkenylcarbonyl, C 2 -C 6 -alkynylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, C ⁇ -C 6 -alkoxycarbonyl, C 3 -C 6 -alkenyloxycarbonyl, C 3 -C 6 -alkynyloxycarbonyl , C ⁇ -C 6 -alkylthiocarbonyl, C ⁇ -C 6 -alkylaminocarbonyl, C 3 -C 6 -alkenylaminocarbonyl, C 3 -C 6 -alkynylaminocarbonyl,
  • R 21 C ⁇ -C 6 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 can carry the following groups: cyano, CC 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C ⁇ -C 4 -alkylthio, C ⁇ -C 4 -haloalkylthio, C ⁇ -C 4 -alkylcarbonyl, C -C -alkoxycarbonyl or
  • R 22 , R 23 are hydrogen, hydroxy, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -alkoxy, C6-C6-alkylthio, phenyl, phenyl -C ⁇ -C 4 -alkyl or phenoxy, the three latter substituents being partial or complete can be halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C haloalkyl, C ⁇ -C 4 alkoxy, C -C 4 haloalkoxy or C ⁇ -C 4 -Alkoxycarbonyl;
  • R 24 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl,
  • Di- (C ⁇ -C 6 -alkyl) -amino or C ⁇ -C 6 -alkylcarbonyl-amino where the alkyl, cycloalkyl and Alkoxy radicals can be partially or completely halogenated and / or can carry one to three radicals from the following group: cyano, C -C 4 -alkoxycarbonyl, C ⁇ -C 4 -alkylaminocarbonyl, di- (C ⁇ -C 4 - alkyl) -aminocarbonyl or C 3 -C 6 cycloalkyl;
  • R 25 is hydrogen, C ⁇ -C 6 alkyl or C 3 -C 6 alkenyl, C 3 -C 6 alkynyl;
  • 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.
  • WO 97/30993 and WO 97/09327 disclose dioxothiochroman derivatives which are linked to a substituted (5-hydroxypyrazol-4-yl) carbonyl radical.
  • 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.
  • Subject of invention are both the pure enantiomers or diastereomers and 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. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I
  • 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-alkyl, hydroxy-C ⁇ -C 4 -alkyl, C -C 4 -alkoxy-C ⁇ -C 4 -alkyl, hydroxy-C ⁇ -C -alkoxy-C ⁇ -C -alkyl, phenyl or benzyl can be replaced, preferably ammonium , Dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2 - (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) ammonium, trimethylbenzylammonium, furthermore 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.
  • Ha also represents the tautomeric forms Ha 'and Ha''
  • Ilb also represent the tautomeric forms Ilb 'and Ilb''.
  • C ⁇ -C 4 alkyl and the alkyl parts of phenyl -C ⁇ -C 4 -alkyl, heterocyclyl -C ⁇ -C 4 -alkyl, phenyl -C ⁇ -C 4 -alkylcarbonyl or heterocyclyl -C ⁇ -C 4 - alkylcarbonyl: for example methyl, Ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl; C ⁇ -C 6 alkyl, as well as the alkyl parts of C ⁇ -C 6 alkoxyimino
  • 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,
  • C ⁇ -C 4 haloalkyl a C ⁇ -C 4 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, bromomethyl, iodomethyl, 1-fluoroethyl, 1-bromomethyl, 1-chloroethyl, 1-iodoethyl, 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-chloro
  • 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-alkoxy for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy; C ⁇ -C 6 ⁇ alkoxy, and the alkoxy parts of N-C ⁇ -C 6 -alkoxyamino, N-C ⁇ -C 6 -alkoxy-NC -C 6 - alkylamino, C ⁇ -C6-alkoxyimino-C--C6-al - kyl, N- (CC 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 6 -alkoxy) -aminocarbonyl:
  • C ⁇ -C 4 ⁇ haloalkoxy a C ⁇ -C 4 alkoxy radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodi-fluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 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-ch
  • C ⁇ -C 6 -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 -alkylthio and the alkylthio parts of C ⁇ -C 6 -alkylthio-carbonyl: C -C 4 -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-ethylbutyl
  • 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-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2, 2-di-fluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, pentafluoroethyl
  • C ⁇ -C 6 -haloalkylthio C ⁇ -C -haloalkylthio, as mentioned above, and 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluoro-hexylthio, 6-chlorohexylthio, 6- Bromhexylthio, 6-iodohexylthio or dodecafluorohexylthio;
  • C ⁇ -C 6 -alkylsulfinyl Cx -C 4 -alkylsulfinyl, as mentioned above, and pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfinyl, 1, 1 -Dimethylpropylsulfinyl, 1, 2-Dimethylpropylsulfinyl, Hexylsulfinyl, 1-Methylpentylsulfinyl, 2-Methylpentylsulfinyl, 3-Methylpentylsulfinyl, 4-Methylpentylsulfinyl, 1, 1-Dimethylbutylsulfinyl, 1, 2-Dimethyl - butylsulfinyl
  • 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 , 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2,2, 2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulf
  • C ⁇ -C 6 haloalkylsulfinyl C ⁇ -C 4 haloalkylsulfinyl, as mentioned above, and 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, udecafluoropentylsulfinyl, 6-fluorohexylhexylsulfinyl, 6-chloro , 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl;
  • Cx -C 6 alkylsulfonyl C ⁇ -C 4 alkylsulfonyl, as mentioned above, and pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl , 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl , as mentioned
  • C ⁇ -C 4 -haloalkylsulfonyl is 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, chlorodifluoromethylsulfonyl, bromodifluoromethyl -Fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2,2, 2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,
  • C ⁇ -C 6 -Halogenalkysulfonyl C ⁇ -C 4 -Halogenalkylsulfonyl, as mentioned above, and 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorhexylsulfonyl, 6-bromhexyl-sulfonyl-hexylsulfonyl or hexylsulfonylyl-hexylsulfonyl or 6-bromohexylsulfonyl ;
  • 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 and the alkylcarbonyl radicals of C ⁇ -C 6 -alkylcarbonylamino: C ⁇ -C 4 -alkylcarbonyl, as mentioned above, and for example pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2 , 2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropy1 - carbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1, 1-dimethylbutylcarbonyl , 1, 2-Dimethylbutylcarbonyl, 1, 3-Dimethylbutyl - carbonyl, 2, 2, -Dirnethylbutylcarbonyl
  • C ⁇ -C 6 -haloalkylcarbonyl a C ⁇ -C 4 -haloalkylcarbonyl radical as mentioned above, and 5-fluoropentylcarbonyl, 5-chloropentylcarbonyl, 5-bromopentylcarbonyl, perfluoropentylcarbonyl, 6 -fluorohexylcarbonyl, 6-chlorohexylcarbonyl, 6-bromo-hexylcarbonyl or perfluorohexylcarbonyl;
  • C ⁇ -C 4 alkoxycarbonyl for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1, 1-dimethylethoxycarbonyl;
  • C ⁇ -C 6 ⁇ alkoxycarbonyl C ⁇ -C 4 alkoxycarbonyl, as mentioned above, and for example pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethyibutoxycarbonyl, 1, 2-dimethylbutoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1,2-trimethylpropoxycarbonyl,
  • C ⁇ -C 6 -haloalkoxycarbonyl a C ⁇ -C -haloalkoxycarbonyl radical as mentioned above, as well as 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6 -fluoro-hexoxycarbonyl, 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-alkylamino) carbonyl e.g. Methylaminocarbonyl, ethyl - aminocarbonyl, 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-ethylpropyl minocarbonyl, hexylaminocarbonyl, 1, l-dimethylpropylaminocarbonyl, 1, 2-dimethylpropylaminocarbonyl, 1-methylpentylaminocarbonyl, 2-methylpentylaminocarbonyl, 3-methylpentylaminocarbonyl, 4-methylpentylaminocarbonyl, 1,1-di- methylbutylaminocarbonyl, 1, 2-Dimethylbutylaminocarbonyl, 1, 3-Dimethylbutylaminocarbonyl, 2, 2-Dimethylbuty
  • 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-propylaminocarbonyl, N-methyl-N- (1-methylethyl) aminocarbonyl, N-butyl- N-methylaminocarbonyl, N-methyl-N- (1-methyle
  • 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 ) amino carbonyl, N-methyl-N- (2-methylbutyl) aminocarbonyl,
  • N-methyl-N- (3-methylbutyl) aminocarbonyl N-methyl-N- (2,2-dimethylpropyl) aminocarbonyl, N-methyl-N- (1-ethylpropyl) aminocarbonyl, N-methyl- N-hexylaminocarbonyl, N-methyl-N- (1,1-dimethylpropyl) aminocarbonyl, N-methyl-N- (1,2-dimethylpropyl) aminocarbonyl, N-methyl-N- (1-methyl-pentyl) - aminocarbonyl, N-methyl-N- (2-methylpentyl) aminocarbonyl, N-methyl-N- (3-methylpentyl) aminocarbonyl, N-methyl-N- (4-methylpentyl) aminocarbonyl, N-methyl-N- (1, 1-dimethylbutyl) aminocarbonyl, N-methyl-N- (1, 2-dimethylbutyl) aminocarbonyl, N- Methyl-N- (1, 3-dimethyl
  • N-ethyl-N- (2-ethylbutyl) aminocarbonyl N-ethyl-N- (1, 1, 2-trimethylpropyl) aminocarbonyl, N-ethyl-N- (1,2, 2-trimethyl-propyl ) -aminocarbonyl, N-ethyl-N- (1-ethyl-l-methyl-propyl) -aminocarbonyl, N-ethyl-N- (l-ethyl-2-methyl-propyl) -aminocarbonyl, N-propyl-N- pentylaminocarbonyl,
  • N-butyl-N-pentylaminocarbonyl N, N-dipentylaminocarbonyl, N-propyl-N-hexylaminocarbonyl, N-butyl-N-hexylaminocarbonyl, N-pentyl-N-hexylaminocarbonyl or N, N-dihexylaminocarbonyl;
  • 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-methylpropy1) -aminothiocarbonyl, N, N-Di- (2-methylpropyl) -aminothiocarbonyl, N, N-Di- (1, 1-dimethylethyl) -aminothiocarbonyl, N-ethyl - N-methylaminothiocarbonyl, N-methyl-N-propylaminothiocarbonyl, N-methyl-N- (1-methylethyl) aminothiocarbonyl
  • C ⁇ -C4-alkoxy-C ⁇ -C 4 -alkyl C ⁇ -C 4 -alkoxy, as mentioned above, substituted C ⁇ -C-alkyl, for example for methoxy-methyl, ethoxymethyl, propoxymethyl, (1-methylethoxy) methyl, Butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- ( 1-methylethoxy) ethyl, 2- (butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- (2-methylprooxy) ethyl, 2- (1, 1-dimethylethoxy) ethyl, 2- (methoxy) - propyl, 2- (ethoxy) propyl, 2- (propoxy) propyl, 2- (l-methylethoxy) prop
  • C ⁇ -C-alkoxy-C ⁇ -C 4 -alkoxy C ⁇ -C 4 alkoxy, as mentioned above, substituted C ⁇ -C 4 alkoxy, so e.g.
  • C 3 -Cg 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 ⁇ - alkenyl) -N- (C ⁇ -C 6 ) alkyl-aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C ⁇ -C 6 -alkoxy) aminocarbonyl: e.g.
  • C -C 6 alkenyl and the alkenyl parts of C -C 6 alkenyl carbonyl, phenyl C 2 -C 6 alkenylcarbonyl and heterocyclyl-C -C 6 alkenylcarbonyl: C 3 -C 6 alkenyl, as mentioned above , as well as ethenyl;
  • C 3 -C 6 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 -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 ⁇ -C 6 -alkoxyamino-carbonyl: for example 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, pent
  • 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 ⁇ -C 6 -alkanediyl methanediyl, ethane-1, 1-diyl, ethane-1, 2-diyl, propane-1, 1-diyl, propane-1, 2-diyl, propane-1, 3 -diyl, propane -2,2-diyl, butane-1,1-diyl, butane-1,2-diyl,
  • Pentane-1,3-diyl pentane-1,5-diyl, pentane-2,3-diyl,
  • C 2 -C 6 alkadiene diyl 1,3-butadiene-1,1-diyl, 1,3-butadiene-1,2-diyl, 1,3-butadiene-1,3-diyl, 1,3-butadiene- 1,4-diyl, 1,3-pentadiene-1,1-diyl, 1,3-pentadiene-1,2-diyl, 1,3-pentadiene-1,3-diyl, 1,3-pentadiene 1,4-diyl, 1,3-pentadiene-1,5-diyl, 2,4-pentadiene-1,1-diyl, 2,4-pentadiene-1,2-diyl, 2,4-pentadiene- 1, 3-diyl, 2, 4 -pentadiene-1, -diyl, 2, 4 -pentadiene-1, 5-diyl, 1-methyl-1, 3-butadiene-1, 4
  • C 2 -C 6 alkynediyl ethyne-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-propin-1,3-diyl, l-pentyne-1,3-diyl, 1-pentyne-1,4-diyl, 1-pentyne-1,5-diyl, 2-pentyne-1, 1-diyl, 2-pentyne-1,4-diyl, 2-pentyne-1,5-diyl, 3-pentyn
  • C 3 -C 6 cycloalkyl and the cycloalkyl parts of C 3 -C 6 cycloalkylcarbonyl: for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • 5-membered rings with three heteroatoms such as 1,2,3- ⁇ 2 -oxadiazolin-4-yl, 1, 2, 3- ⁇ 2 -oxadiazolin-5-yl, 1, 2, 4- ⁇ 4 -oxadiazolin -3-yl, 1, 2, 4- ⁇ -oxadiazolin-5-yl, 1,2, 4- ⁇ 2 -oxadiazolin-3-yl, 1, 2, 4- ⁇ 2 -oxadiazolin-5-yl, 1 , 2, 4- ⁇ 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- ⁇ -thiadiazolin-3-yl, 1, 2, 4- ⁇ -thiadiazolin-5-yl, 1, 2, - ⁇ 3
  • 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,
  • 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 or
  • 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 one heteroatom 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-1-yl, 2,5-di
  • N-linked 5-membered rings with three heteroatoms such as 1, 2, 4- ⁇ 4 -oxadiazolin-2-yl, 1, 2, 4- ⁇ 2 -oxadiazolin-4-yl, 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, 1, 2,3- ⁇ 2 -Triazolin-l-yl, 1, 2, 4- ⁇ 2 -triazolin-l-yl, 1, 2, 4- ⁇ 2 -triazolin-4-yl, 1, 2, 4- ⁇ 3 -triazolin-l-yl, l, 2,4- ⁇ 1- triazolin-4-yl, 1, 2, 3-triazol-l-yl or 1,2,4-triazol
  • N-linked 5-membered rings with four heteroatoms e.g. Tetrazol-1-yl
  • N-linked 6-membered rings with a hetero atom such as: 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 e.g. 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-l, 2-oxazin- 2-yl, 2H-5, 6-dihydro-l, 2-thiazin-2-yl,
  • N-linked cyclic imides such as:
  • the variables preferably have the following meanings, in each case individually or in combination:
  • C ⁇ -C 4 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 -alkenediyl, such as ethene-1, 1-diyl, Ethene-1,2-diyl, 1-methyl-ethene-1,2-diyl or 1,2-propen- 1,2-diyl; particularly preferably methane-1, 1-diyl or ethene-1, 2-diyl;
  • R 2 C ⁇ -C 4 alkyl, such as methyl, ethyl, propyl or 1-methyl-ethyl;
  • 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 ;
  • 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 can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy, C ⁇ -C 4 haloalkoxy, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C 4 haloalkylsulfonyl, C ⁇ -C alkylcarbonyl, CAl-C 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 C ⁇ -C 4 alkoxycarbonyl;
  • R 7 is hydrogen or C ⁇ -C 4 alkyl, such as methyl or ethyl
  • R 8 is hydrogen, C ⁇ -C ⁇ alkyl, C ⁇ -C 6 alkoxycarbonyl or Cx -C 6 alkoxy; preferably hydrogen, C ⁇ -C 4 alkyl or C ⁇ -C 4 alkoxy; R 9 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C ⁇ -C 4 alkylcarbonyl, C ⁇ -C 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 - C 6 alkynyloxy;
  • R 10 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
  • 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 Cx -C 6 haloalkyl; preferably hydrogen or C ⁇ -C 6 alkyl, such as methyl, ethyl or propyl;
  • R1 3 / 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 13 , R 14 preferably (R 13 , R 14 ) hydrogen, C ⁇ -C 4 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;
  • C ⁇ -C 4 haloalkyl C ⁇ -C alkoxy or C ⁇ -C 4 haloalkoxy; preferably hydroxy, mercapto, halogen, OR 20 , SR 20 , S0 2 R 21 , OS0R 21 , NR 2 R 25 , 0NR 1 R 21 or N-linked heterocyclyl, which can be partially or completely halogenated and / or one to three of the can carry the following leftovers:
  • R 18 is hydrogen or C ⁇ -C alkyl, such as methyl, ethyl or propyl or 1-methylethyl; preferably methyl, ethyl, propyl or 1-methylethyl; particularly preferably methyl or ethyl;
  • R 19 is hydrogen or C ⁇ -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl; particularly preferably hydrogen;
  • R 2 ° 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 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 - Alkylthio or C ⁇ -C alkoxycarbonyl; Phenyl, phenyl -C ⁇ -C 6 alkyl, phenylcarbonyl -C -C6 alkyl, phenylcarbonyl, phenoxycarbonyl, heterocyclyl, heterocyclyl -C -C 6 alkyl, heterocyclyl
  • R 21 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 22 , R 23 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 one to can carry three of the following radicals: nitro, cyano, C ⁇ -C 4 -alkyl, C ⁇ -C 4 -halogenoalkyl, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy or Cx-C 4 -alkoxycarbonyl;
  • R 24 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl,
  • C 3 -C 6 cycloalkyl C ⁇ -Cg alkoxy, C 3 -C 6 alkenyloxy or di- (C ⁇ -C 6 alkyl) amino
  • 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 -C ⁇ - cycloalkyl;
  • R 25 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-haloalkoxy, C ⁇ -C 4 alkylsulfonyl, C x -C 4 haloalkylsulfonyl, C ⁇ -C4-alkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl or C ⁇ -C 4 -Halo- genalkoxycarbonyl;
  • the compounds of the formula I are also extremely preferred Rl7 halogen, OR 20 , SR 20 , S0 2 R 21 , 0S0 2 R 21 , NR 24 R 25 , 0NR 21 R 21 or N-linked heterocyclyl, which can be partially or completely halogenated and / or one to three of the following radicals can wear: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy;
  • R 18 C -C 4 alkyl
  • Ri 9 is hydrogen or C ⁇ -C 4 alkyl.
  • a C ⁇ -C 6 alkanediyl particularly preferably methanediyl
  • R 3 is hydrogen
  • X CR 13 R 14 , C 0 or S0 2 ; particularly preferably CR 13 R 14 ;
  • R 4 C ⁇ -C ⁇ alkyl, which can be partially or completely halogenated
  • R 5 is C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or heterocyclyl; particularly preferably C ⁇ -C 6 alkyl or heterocyclyl; particularly preferably Cx -C 6 alkyl; R 6 C ⁇ -C 6 alkyl, which can be partially or completely halogenated; particularly preferably C ⁇ -C 6 alkyl;
  • R 9 is C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C ⁇ -C 4 haloalkylcarbonyl;
  • R 19 is hydrogen or C -C 6 alkyl; particularly preferably hydrogen
  • 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 18 is ethyl.
  • the compounds of the formula Ia4 in particular the compounds Ia4.1 to Ia4.285, which differ from the compounds Ial.l to Ial.285 in that R 19 is methyl.
  • the compounds of the formula Ia5 in particular the compounds Ia5.1 to Ia5.285, which differ from the compounds Ial.l to Ial.285 in that R 18 is ethyl and R 19 is methyl.
  • the compounds of the formula Ia6 in particular the compounds Ia6.1 to Ia6.285, which differ from the compounds Ial.l to Ial.285, differ in that R 18 is propyl and R 19 is methyl.
  • 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 17 is methylsulfonyloxy.
  • the compounds of formula IalO especially the compounds IalO.l to IalO.285, which differ from the compounds Ial.l to Ial.285, characterized in that R 17 is methylsulfonyloxy and R 19 is methyl.
  • the compounds of the formula Ial4 in particular the compounds Ial4.1 to Ial4.285, which differ from the compounds Ial.l to Ial.285, in that R 17 is 4-methylphenylsulfonyloxy and R 18 is ethyl.
  • the compounds of the formula Ial5 in particular the compounds Ial5.1 to Ial5.285, which differ from the compounds Ial.l to Ial.285, in that R 17 is 4-methylphenylsulfonyloxy and R 18 is propyl.
  • the compounds of the formula Ial ⁇ in particular the compounds Ial ⁇ .l to Ial6.285, which differ from the compounds Ial.l to Ial.285, in that R 17 is 4-methylphenylsulfonyloxy and R 19 is methyl.
  • the compounds of the formula Ial9 in particular the compounds Ial9.1 to Ial9.285, which differ from the compounds Ial.l to Ial.285, in that R 17 is phenylcarbonylmethoxy.
  • the compounds of formula Ia20 in particular the compounds Ia20.1 to Ia20.285, which differ from the compounds Ial.l to Ial.285, characterized in that R 17 is phenylcarbonylmethoxy and R 18 is ethyl.
  • the compounds of the formula Ia22 in particular the compounds Ia22.1 to Ia22.285, which differ from the compounds Ial.l to Ial.285, in that R 17 is phenylcarbonylmethoxy and R 19 is methyl.
  • the compounds of the formula Ia23 in particular the compounds Ia23.1 to Ia23.285, which differ from the compounds Ial.l to Ial.285, in that R 17 is phenylcarbonylmethoxy, R 18 is ethyl and R 19 is methyl.
  • the compounds of formula Ia30 in particular the compounds Ia30.1 to Ia30.285, which differ from the compounds Ial.l to Ial.285, characterized in that R 17 4 -methylphenylmethoxy, R 18 propyl and R 19 are methyl.
  • Carboxylic acid IVb which is preferably activated in situ, with a pyrazolone of the formula III to the acylation product and subsequent rearrangement.
  • L 1 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 IVa can be used directly, as in the case of the benzoyl halides or generated in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid. ester, 2-pyridine disulfide id / 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 IVa or IVb, 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 dichloromethyl 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, t
  • 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 in
  • 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.
  • 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 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.).
  • R 17 SR 21 with an oxidizing agent.
  • 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.
  • the 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.
  • M stands for a metal, in particular for an alkali metal such as lithium or sodium, an alkaline earth metal such as magnesium or a transition metal such as palladium, nickel etc. and L 1 for a nucleophilically displaceable leaving group such as halogen, for example
  • alkyl sulfonate such as mesylate
  • haloalkyl sulfonate such as triflate or cyanide
  • the reaction is usually carried out at temperatures from -100 ° C. to the reflux temperature of the reaction mixture.
  • Inert aprotic solvents such as ethers, e.g. Diethyl ether, tetrahydrofuran.
  • ethers e.g. Diethyl ether
  • tetrahydrofuran e.g. Tetrahydrofuran.
  • the compounds of the formula IVa are generally used in excess, but it may also be advantageous to use them in equimolar amounts or in a deficit.
  • the processing takes place towards the product.
  • the metalated pyrazole derivatives of the formula VII can be formed in a manner known per se by reacting pyrazoles halogenated in the 4-position with metals such as lithium, sodium, magnesium etc. or with organometallic compounds such as butyl-lithium .
  • metals such as lithium, sodium, magnesium etc. or with organometallic compounds such as butyl-lithium .
  • organometallic compounds such as butyl-lithium .
  • the reactions are generally carried out in an inert aprotic solvent, preferably in ethers such as diethyl ether, tetrahydrofuran etc.
  • the reaction temperature is in the range from -100 ° C. to the boiling point. tes of the reaction mixture.
  • the compounds of the formula VII are generally reacted further directly or produced in situ.
  • pyrazolones of the formula III used as starting materials are known or can be prepared by processes known per se (e.g. EP-A 240 001, J. Chem. Soc. 315, 383 (1997)).
  • alkylating agents V ⁇ sulfonylating agents Vß, phosphonylating agents V ⁇ and v ⁇
  • compounds Vl ⁇ , Vlß, 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 13 ⁇ 12 , P ( S) R 11 R 12 , COR 6 , C0 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 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 haloalkoxy or C ⁇ -C 4 alkoxycarbonyl;
  • R 2 is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -C 6 alkoxy or Cx-C ⁇ haloalkoxy;
  • R 3 is hydrogen, halogen or Ci -C ⁇ -alkyl
  • n 0, 1, 2, 3 or 4;
  • R 4 , R 5 is a radical mentioned under R 6 ;
  • R 6 C ⁇ -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 can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy, C ⁇ -C 4 haloalkoxy, C ⁇ -C 4 alkylthio, Cx-C4 haloalkylthio, C -C 4 alkylsulfinyl, C ⁇ -C 4 -Halogenalkylsul ynyl, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C4-haloalkylsulfonyl, C ⁇ -C 4 alkylcarbonyl,
  • R 7 is hydrogen or C x -C 6 alkyl
  • R 8 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C6 alkoxycarbonyl, cyano or Cx -C ⁇ alkoxy;
  • R 9 is a radical mentioned under R 4 ; C ⁇ -C 6 alkoxy, C 3 - C ⁇ alkenyloxy, C 3 -C 6 alkynyloxy, aminocarbonyl, N-C ⁇ -C 6 alkylaminocarbonyl or N, N-di- (Cx -C 6 alkyl) aminocarbonyl;
  • 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, C ⁇ -C 6 -alkoxy,
  • R 13 , R 14 are hydrogen, nitro, halogen, cyano, C ⁇ -C 6 alkyl
  • C-C6 haloalkyl C ⁇ -C ⁇ alkoxy, C ⁇ -Ce haloalkoxy, C ⁇ -C 6 alkylthio, C ⁇ -C 6 haloalkylthio, C ⁇ -C 6 alkyl sulfinyl, C ⁇ -C6 haloalkylsulfinyl, C ⁇ - C 6 -alkylsulfonyl, C ⁇ -C 6 -haloalkylsulfonyl, N-C ⁇ -C 6 -alkylamino,
  • N-C ⁇ -C6-haloalkylamino N, N- (di-C ⁇ -C 6 -alkyl) amino, N-C ⁇ -C 6 -alkoxyamino, N- (C ⁇ -C 6 -alkoxy) -N- (C ⁇ -C 6 -alkyl) amino, 1-tetrahydropyrrolyl, 1 -piperidinyl, 4 -morpholinyl or 1-hexahydropyrazinyl;
  • 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 Cx -C 6 haloalkoxy;
  • hydrolyzable residues are alkoxy, phenoxy, alkylthio, phenylthio residues, which can optionally be substituted, halides, hetaryl residues, which are bonded via nitrogen, amino, imino residues, which can optionally be substituted, etc.
  • Carboxylic acids of the formula IVb are also preferred.
  • Carboxylic acid esters of the formula IVc are also preferred.
  • M is C ⁇ -C 6 alkoxy.
  • IVb with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.
  • the carboxylic acid esters of the formula IVc can be obtained in various ways, for example by the following processes:
  • suitable oxidizing agents are m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen peroxide, 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, Dinitriles, ketonitriles, cyanocarboxylic acid derivatives or bissulfones can be considered.
  • CH-acidic bases such as alkali or alkaline earth 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 methanolate or potassium tert-butoxide, alkali or alkaline earth metal hydrides, e.g. Sodium hydride, or organometallic bases such as butyllithium.
  • alkali or alkaline earth 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 VIII can be obtained by halogenating the corresponding alkyl compounds XI 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 into consideration.
  • suitable radiation sources such as UV-Hg low-pressure or Hg high-pressure lamps.
  • Phosphorus pentachloride are suitable as halogenating agents
  • Phosphorus oxychloride Phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide, phosgene, carbonic acid bromide, oxalyl chloride, oxalyl bromide, as well as binary systems such as carbon tetrachloride / triphenylphosphine or tetrabromomethane / triphenylphosphine etc.
  • alkyl sulfonates or haloalkyl sulfonates of the formula VIII can be obtained by reacting alcohols of the formula XII with activated alkyl or haloalkylsulfonic acids, such as alkyl or haloalkylsulfonic anhydrides or halides.
  • aldehydes or ketones of the formula IX can be obtained by oxidation of corresponding compounds of the formula XII in a manner known per se.
  • 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 XII 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) 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 Cr0 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 .
  • 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.
  • Suitable halogenating agents include N-bromosuccinimide, N-chlorosuccinimide, 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, for example dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, chlorobenzene etc. or aromatics such as are suitable Benzene, toluene or xylene. It can also be advantageous to use solvent mixtures.
  • the reaction temperatures of the first stage are generally between -80 ° C and the reflux temperature of the reaction mixture. It is preferred to work 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, diisobutylaluminium hydride, boranates such as sodium boranate, diborane, metal hydrides such as trialkylzinc hydride, metals such as zinc, tin etc.
  • the reducing agent is generally used in an equimolar amount. However, it can also be advantageous to use an excess or deficit.
  • inert solvents such as ethers, e.g. Diethyl ether, methyl tert. -butyl ether or 1,4-dioxane, or dipolar solvents such as dirnethylformamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone.
  • 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
  • the compounds of the formula XIV are prepared from the corresponding cycl ⁇ hexanone 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, iley, New York, 1991).
  • Step c) 4, 4, 8 -trimethyl-1, 1-dioxothiochroman-7-carboxylic acid methyl ester
  • N-bromosuccinimide 20.5 g (0.12 mol) of N-bromosuccinimide was added in portions under UV radiation to a solution of 31 g (0.11 mol) of 4,4,8-trimethyl-1, 1-dioxothiochroman-7-carboxylic acid methyl ester added to 300 ml acetonitrile at reflux temperature. The mixture was stirred for a further 1.5
  • 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:
  • Prunus avium Prunus persica, Pyrus communis, Ribes sylvestre,
  • Ricinus communis Saccharu officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
  • 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 formula I or the herbicidal compositions containing them can be sprayed, 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 , 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 thiochromanoylpyrazolone derivatives of the formula I as such or in dissolved in an oil or solvent, using wetting, adhesive,
  • Dispersants or emulsifiers are homogenized in water.
  • Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared 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 and 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, tributylphenyl poly
  • 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 thiochromanoylpyrazolone 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 2.3 showed a very good effect against the harmful plants Echinocloa crus-gali, Ipomoea ssp., Solanum nigrum and Veronica ssp. with simultaneous tolerance in the crop Triticum aestivum. Furthermore, compound 2.17 showed very good activity against the undesirable plants Avena fatua, Setaria viridis, Polygonum persicaria and Sinapis alba.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)

Abstract

L'invention concerne des dérivés de thiochromanoylpyrazolone de formule (I) dans laquelle les variable ont les significations ci-après: A désigne une chaîne alkyle saturée ou insaturée, éventuellement substituée; R<1> désigne un 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>, COR<6>, CO2R<6>, phényle ou hétérocyclyle éventuellement substitué; R<2> désigne un alkyle, halogénonalkyle, alcoxy ou halogénoalcoxy; R<3> désigne un hydrogène, un alkyle ou un halogène; X désigne un oxygène, un soufre, S=O, S(=O)2, CR<13>R<14>, C=O ou C=NR<15>, m est égal à 0, 1 ou 2; n est égal à 0, 1, 2, 3 ou 4; R<16> désigne un pyrazol-4-yl-carbonyle substitué ou un (4,5-dihydro-5-oxo-pyrazol-4-yl)-méthylidène. L'invention concerne également les sels des dérivés précités, utilisables en agriculture. Elle concerne en outre un procédé de fabrication des dérivés de thiochromanoylpyrazolone, des produits renfermant ces dérivés, ainsi que l'utilisation de ces dérivés ou desdits produits les renfermant pour lutter contre les plantes indésirables.
EP99962201A 1998-12-04 1999-12-02 Derives de thiochromanoylpyrazolone Withdrawn EP1135385A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19856048 1998-12-04
DE19856048 1998-12-04
DE19857666 1998-12-15
DE19857666 1998-12-15
PCT/EP1999/009396 WO2000034270A1 (fr) 1998-12-04 1999-12-02 Derives de thiochromanoylpyrazolone

Publications (1)

Publication Number Publication Date
EP1135385A1 true EP1135385A1 (fr) 2001-09-26

Family

ID=26050574

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99962201A Withdrawn EP1135385A1 (fr) 1998-12-04 1999-12-02 Derives de thiochromanoylpyrazolone

Country Status (6)

Country Link
US (1) US6352959B1 (fr)
EP (1) EP1135385A1 (fr)
JP (1) JP2002531559A (fr)
AU (1) AU1861600A (fr)
CA (1) CA2353542A1 (fr)
WO (1) WO2000034270A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2127521A1 (fr) * 2008-05-29 2009-12-02 Bayer CropScience Aktiengesellschaft 4-(3-Alkylsulfinylbenzoyl)pyrazole actifs en tant qu'herbicide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19532312A1 (de) * 1995-09-01 1997-03-06 Basf Ag Pyrazol-4-yl-benzoylderivate
CZ230398A3 (cs) 1996-02-24 1999-01-13 Basf Aktiengesellschaft Derivát pyrazol-4-ylhetaroylu, způsob jeho přípravy a herbicidní prostředek, který ho obsahuje
EP1080089B1 (fr) * 1998-05-18 2003-11-05 Basf Aktiengesellschaft Derives du type pyrazolyldioxothiochromanoyle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0034270A1 *

Also Published As

Publication number Publication date
AU1861600A (en) 2000-06-26
US6352959B1 (en) 2002-03-05
JP2002531559A (ja) 2002-09-24
CA2353542A1 (fr) 2000-06-15
WO2000034270A1 (fr) 2000-06-15

Similar Documents

Publication Publication Date Title
WO1998031682A1 (fr) 4-(3-heterocyclyle-1-benzoyle)pyrazoles et leur utilisation comme herbicides
EP1177194B1 (fr) 4-(3&#39;,4&#39;-heterocyclyl benzoyl) pyrazoles en tant qu&#39;herbicides
US20070197393A1 (en) Tricyclic benzoylpyrazole derivatives
US6613717B1 (en) Phosphoric benzoyl derivatives and their use as herbicides
EP1080089B1 (fr) Derives du type pyrazolyldioxothiochromanoyle
EP1112256B1 (fr) Utilisation de derives de cyclohexenonchinolinoyl comme herbicides
EP1347969B1 (fr) 5- (pyrazol-4-yl)carbonyl]benzazolones en tant qu&#39;herbicides
AU764645B2 (en) Cyclohexenondioxothio chromanoyl derivatives
US6583089B1 (en) Tricyclic benzoylcyclohexanedione derivatives
US6352959B1 (en) Thiochromanoylpyrazolone derivatives
EP1237881B1 (fr) 3-(4,5-dihydroisoxazol-3-yl)-benzoyl-cyclohexenones substituees par un halogenalkyle et a action herbicide
EP1144401A2 (fr) Derives de cyclohexenone de thiochromanoyl
WO2000059911A2 (fr) Derives tricycliques de dione de cyclohexane
WO2000059910A2 (fr) Derives tricycliques de pyrazolone
DE19929259A1 (de) Cyclohexanon-Derivate von bicyclischen Benzoesäuren
MXPA00010574A (en) Cyclohexenondioxothio chromanoyl derivatives

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010519

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20011217

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20030131