EP0937046A2 - 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang - Google Patents

3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang

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Publication number
EP0937046A2
EP0937046A2 EP97948864A EP97948864A EP0937046A2 EP 0937046 A2 EP0937046 A2 EP 0937046A2 EP 97948864 A EP97948864 A EP 97948864A EP 97948864 A EP97948864 A EP 97948864A EP 0937046 A2 EP0937046 A2 EP 0937046A2
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European Patent Office
Prior art keywords
alkyl
iic
formula
iii
halogen
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German (de)
English (en)
Inventor
Cyrill Zagar
Gerhard Hamprecht
Markus Menges
Olaf Menke
Peter SHÄFER
Karl-Otto Westphalen
Ulf Misslitz
Helmut Walter
Robert Reinhard
Robert Brian Jones
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • A61P3/08—Drugs for disorders of the metabolism for glucose homeostasis
    • A61P3/10—Drugs for disorders of the metabolism for glucose homeostasis for hyperglycaemia, e.g. antidiabetics
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to new substituted 3-benzylpyrazoles of the formula I.
  • R 1 are hydrogen, C 4 -alkyl, C, 4 haloalkyl, C ⁇ -C4 -Alkylsul- fonyl or C ⁇ -C4 haloalkylsulfonyl;
  • R 2 C ⁇ -C -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, halo-C alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C4-haloalkylthio, C ⁇ -C4 ⁇ alkyl - Sulfinyl, -C-C 4 haloalkylsulfinyl, C ⁇ -C 4 alkylsulfonyl or C ⁇ -C 4 haloalkylsulfonyl;
  • R 3 is hydrogen, cyano, nitro, halogen, -CC 4 alkyl or C 1 -C 4 haloalkyl;
  • X 1 , X 2 , X 3 , X 4 , X 5 independently of one another are a chemical bond or a methylene, ethylene, ethene-1, 2-diyl or oxymethylene or thiamethylene chain bonded to the phenyl ring via the hetero atom, where all chains can be unsubstituted or carry one or two substituents, each selected from the group consisting of cyano, halogen, C ⁇ -C 4 ⁇ alkyl and (-C-C 4 alkoxy) carbonyl;
  • R, R 5 , R 6 , R 7 , R 8 independently of one another
  • Cyano nitro, amino, hydroxy, carboxy, halogen, C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C alkoxy, C -C 4 alkylthio, C ⁇ -C alkyl sulfonyl, (C ⁇ - C 4 -alkyl) carbonyl, (C ⁇ -C 4 -alkyl) carbonyloxy and (C ⁇ -C 4 -alkoxy) carbonyl, and
  • R 11 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, phenyl or phenyl-C ⁇ -C 4 -alkyl stand,
  • the invention relates to the use of the compounds I and their salts as herbicides and / or for the desiccation / defoliation of plants, herbicidal compositions and compositions for the desiccation and / or de-foliation of plants which the compounds I or their salts as active substances contain,
  • Ila, Ilb, IIc and III or their salts contain as active substances, and
  • EP-A 485 929 and WO 96/04273 for the production of angiotensin II receptor antagonists
  • EP-A 420 397 JP-A 63/166 879 and JP-A 01/085 974 for the production of photochromic data carriers
  • the object of the present invention was to provide new herbicidally active compounds which can be used to combat undesirable plants better than known ones.
  • the up g ä be extended desiccant to the provision of new / defoliant active compounds as well as new active substances in the pharmaceutical field.
  • 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 I are also suitable for the desiccation / defoliation of parts of plants, for which crop plants such as cotton, potatoes, rape, sunflower,
  • Soybeans or field beans, especially cotton, are suitable.
  • agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with the compounds I have been found.
  • compounds I In addition to their activity in the field of plant protection, compounds I, their precursors Ila, Ilb and IIc and by-products III have been found to have a pharmaceutical, in particular hypoglycemic, effect.
  • One aspect of the present invention is therefore also corresponding pharmaceutical preparations.
  • the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Haloalkyl preferably carry one to five identical or different halogen atoms.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • C ⁇ -C 4 alkyl for: CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2 , n-butyl, CH (CH 3 ) -C 2 H 5 , CH 2 -CH (CH 3 ) 2 or C (CH 3 ) 3 ;
  • C ⁇ -C 4 -haloalkyl for: a C ⁇ -C 4 ⁇ alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CH 2 F, CHF, CF 3 , CH 2 C1 , CH (C1) 2 , C (C1) 3 , 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, C 2 F 5 , 2-fluoropropyl, 3-fluoroprop
  • C ⁇ -C 6 alkyl for: C ⁇ -C 4 alkyl as mentioned above, and for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1- methylpropyl or l-ethyl-2-methylpropyl, preferably for CH 3 , C 2 H 5
  • C ⁇ -C 6 -haloalkyl for: a C ⁇ -C 6 -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example one of the radicals mentioned under C ⁇ -C 4 -haloalkyl or for 5 - fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-penyl, undecafluoropentyl, 6 - Fluorine-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6 - iodine-1-hexyl, 6, 6, 6-trichloro-1-hexyl or dodecafluorohexyl;
  • Phenyl-C ⁇ -C 4 -alkyl for: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-l-yl, 1- phenylbut-1- yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2- yl, 4-phenylbut-2-yl, 1- (benzyl) eth-1-yl. 1- (benzyl) -1- (methyl) -eth-l-yl or 1- (benzyl) prop-1-yl, preferably for benzyl or 2-phenylethyl;
  • C ⁇ -C 4 ⁇ haloalkoxy for: a C ⁇ -C 4 alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 0CHF, OCHF 2 , 0CF 3 , 0CH 2 C1, OCH (Cl) 2 , 0C (C1) 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2,2, 2- Trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy,
  • C ⁇ -C-Alkylthio for: SCH 3 , SC 2 H 5 , SCH 2 -C 2 H 5 , SCH (CH 3 ) 2 , n-butylthio, 1-methylpropylthio, 2-methylpropylthio or SC (CH 3 ) 3 , preferably for SCH 3 or SCHs;
  • C ⁇ -C 4 ⁇ haloalkylthio for: a C ⁇ -C 4 alkylthio radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example SCHF, SCHF 2 , SCF 3 , SCH 2 C1, SCH (C1) 2 , SC (C1) 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2, 2-difluoroethylthio, 2,2, 2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2, 2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, 2,
  • C 1 -C 4 -alkoxy-C ⁇ -C 4 -alkyl for: C ⁇ -C 4 -alkoxy - as mentioned above - substituted C ⁇ -C 4 -alkyl, for example for CH 2 -0CH 3 , CH 2 -0C 2 H 5 , n-propoxymethyl, CH 2 -0CH (CH 3 ) 2 , n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -0C (CH 3 ) 3 , 2- (0CH 3 ) ethyl, 2- (OC 2 H 5 ) ethyl, 2- (n-propoxy) ethyl, 2- [OCH (CH 3 ) 2 ] ethyl, 2- (n-butoxy) ethyl, 2- (l-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- [OC (CH 3 ) 3 ] ethyl, 2- (0CH
  • C ⁇ -C 4 -haloalkoxy-C ⁇ -C 4 -alkyl for: C ⁇ -C 4 -haloalkoxy substituted as mentioned above C ⁇ -C 4 -alkyl, for example for 2- (OCHF 2 ) ethyl, 2- (OCF 3 ) ethyl or 2- (OC 2 F 5 ) ethyl;
  • C ⁇ -C 4 -alkylthio-C ⁇ -C 4 -alkyl for: C ⁇ -C 4 ⁇ alkylthio - as mentioned above - substituted C ⁇ -C 4 -alkyl, for example for CH 2 -SCH 3 , CH 2 -SC 2 H 5 , n-propylthiomethyl, CH 2 -SCH (CH 3 ) 2 , n-butylthiomethyl, (1-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH 2 -SC (CH 3 ) 3 , 2- (SCH 3 ) ethyl, 2- (SCH 5 ) ethyl, 2- (n-propylthio) ethyl, 2- (1-methylethylthio) ethyl, 2- (n-butylthio) ethyl, 2- (1-methylpropylthio) ethyl , 2- (2-methylpropylthio) ethyl,
  • C ⁇ -C 4 -haloalkylthio-C ⁇ -C 4 -alkyl for: C ⁇ -C 4 ⁇ haloalkylthio substituted as above-mentioned C ⁇ -C 4 alkyl, for example for 2- (SCHF 2 ) ethyl, 2- ( SCF 3 ) ethyl or 2- (SC 2 F 5 ) ethyl;
  • CO-CH (CH 3 ) 2 n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , C0-CH 2 -CH (CH 3 ) 2 or CO-C (CH 3 ) 3 , preferably for C0 -CH 3 or C0-C 2 Hs;
  • (C ⁇ -C-Alkyl) carbonyloxy for: O-CO-CH 3 , 0-CO-C 2 H 5 , 0-CO-CH 2 -C 2 H 5 , 0-CO-CH (CH 3 ) 2 , 0 -CO-CH 2 -CH 2 -C 2 H 5 , 0-CO-CH (CH 3 ) -C 2 H 5 , 0-CO-CH 2 -CH (CH 3 ) 2 or O-CO-C (CH 3 ) 3 , preferably for 0-CO-CH 3 or 0-CO-C 2 H 5 ;
  • (-C-C 4 -alkoxy) carbonyl for: CO-OCH 3 , CO-OC 2 H 5 , CO-OCH 2 -C 2 H 5 , CO-OCH (CH 3 ) 2 , n-butoxycarbonyl, CO-OCH ( CH 3 ) -CH 5 , CO-OCH-CH (CH 3 ) 2 or CO-OC (CH 3 ) 3 , preferably for CO-OCH 3 or CO-OC 2 H 5 ;
  • (C ⁇ -C 4 ⁇ alkoxy) carbonyl-C ⁇ -C 4 alkyl for: by (C ⁇ -C 4 ⁇ alkoxy) carbonyl - as mentioned above - substituted C -C 4 alkyl, so for example for CH 2 -CO -OCH 3 , CH 2 -CO-OC 2 H 5 , n-prop-oxycarbonyl-methyl, CH 2 -CO-OCH (CH 3 ) 2 , n-butoxycarbonylmethyl, CH 2 -CO-OCH (CH 3 ) -C 2 H 5 , CH 2 -CO-OCH 2 -CH (CH 3 ) 2 , CH 2 -CO-OC (CH 3 ) 3 , 1- (methoxycarbonyl) ethyl, 1- (ethoxycarbonyl) ethyl, l- (n- Propoxycarbonyl) ethyl, 1- (1-methylethoxycarbonyl) ethyl, 1- (n-butoxycarbon
  • C ⁇ -C-alkylsulfinyl for: SO-CH 3 , SO-C 2 H 5 , SO-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , n-butylsulfinyl, SO-CH (CH 3 ) - C 2 H 5 , SO-CH 2 -CH (CH 3 ) 2 or SO-C (CH 3 ) 3 , preferably for SO-CH 3 or SO-CH 5 ;
  • C ⁇ -C 4 -haloalkylsulfinyl for: a C ⁇ -C 4 -alkylsulfinyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example SO-CH 2 F, S0-CHF 2 , SO-CF 3 , S0-CH 2 C1, S0-CH (C1) 2 ,
  • S0-C (C1) 3 chlorofluoromethylsulfinyl, dichlorofluoromethylsulfinyl, chlorodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2, 2, 2-trifluoroethylsulfinyl Chloro-2-fluoroethylsulfinyl, 2-chloro-2, 2-difluoroethylsulfinyl, 2, 2-dichloro-2-fluoroethylsulfinyl, 2, 2, 2-trichloroethylsulfinyl, S0-CF 5 , 2-fluoropropylsulfinyl, 3-fluoropropyl
  • C -C -alkylsulfonyl for: S0 2 -CH 3 , S0 2 -C 2 H 5 , S0-CH 2 -C 2 H 5 , S0 2 -CH (CH 3 ) 2 , n-butylsulfonyl, S0 2 -CH ( CH 3 ) -C 2 H 5 , S0 2 -CH 2 -CH (CH 3 ) 2 or S0 2 -C (CH 3 ) 3 , preferably for S0 2 -CH 3 or S0-CH 5 # -
  • C ⁇ -C 4 haloalkylsulfonyl for: a C ⁇ -C 4 alkylsulfonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example S0 -CH 2 F, S0 2 -CHF 2 , S0 2 -CF 3 , S0 2 -CH 2 C1, S0 2 -CH (C1) 2 , S0 -C (C1) 3 , chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl , 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2, 2,
  • C ⁇ -C 4 ⁇ alkylsulfonyl-C ⁇ -C4-alkyl for: C ⁇ -C 4 alkylsulfonyl as mentioned above substituted C ⁇ -C 4 alkyl, for example for CH 2 S0 2 -CH 3 , CH 2 S0 2 -C 2 H 5 , CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 S0 2 -CH 2 CH 2 -C 2 H 5 , (1-methylpropylsulfonyl) methyl, (2-methyl-propylsulfonyl) methyl, CH 2 S0 2 -C (CH 3 ) 3 , CH (CH 3 ) S0 2 -CH 3 , CH (CH 3 ) S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 3 , CH 2 CH 2 S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH
  • C ⁇ -C4-alkyl e.g. for 2- (2, 2, 2-trifluoroethylsulfonyl) ethyl;
  • CO- (C 2 H 5 ) -CH (CH 3 ) 2 CO- (C 2 H 5 ) -CH 2 -C 2 H 5 , CO-N (C 2 H 5 ) -CH (CH 3 ) -C 2 H 5 , CO-N (C 2 H 5 ) -CH 2 -CH (CH 3 ) 2 , CO-N (C 2 H 5 ) -C (CH 3 ) 3 , CO-N [CH (CH 3 ) 2 ] -CH 2 -C 2 H 5 , CO-N (CH 2 -C 2 H 5 ) -CH 2 CH 2 -C 2 H 5 , CO-N (CH 2 -C 2 H 5 ) -CH (CH 3 ) -C 2 H 5 , CO-N (CH 2 -C 2 H 5 ) -CH 2 -CH (CH 3 ) 2 H 5 , CO-N (CH 2 -C 2 H 5 ) -CH 2 -CH (CH 3 ) 2 ,
  • C 2 -C 6 alkenyl for: vinyl, prop-1-en-l-yl, allyl, 1-methylethenyl, 1-buten-l-yl, l-buten-2-yl, l-buten-3 -yl, 2-butene-1-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1 -yl, 2-methyl-prop-2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1 -Methyl-but-l-en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl-but-1-en-l-yl, 1-methyl-but-2-ene -l-yl, 2-methyl-but-2-en- 1-yl, 3-methyl-but-2-en-l-yl, l-
  • C 2 -Cg alkynyl for: ethynyl and C 3 -Cg alkynyl such as prop-1-in-1-yl, prop-2-in-1-yl, n-but-1-in-1-yl, n -But-1-in-3-yl, n-but-1-in-4-yl, n-but-2-in-1-yl, n-pent-1-in-1-yl, n-pent -l-in-3-yl, n-pent-l-in-4-yl, n-pent-l-in-5-yl, n-pent-2-in-l-yl, n-pent-2 -in-4-yl, n-pent-2-yn-5-yl, 3-methyl-but-l-yn-3-yl, 3-methylbut-l-yn-4-yl, n-hex -1-in-1-yl, n-hex-1-in-3-yl,
  • C 3 -C 8 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
  • C 3 -C 8 cycloalkyl which contains a carbonyl or thiocarbonyl ring member, for example for cyclobutanone-2-yl, cyclobutanone-3-yl, cyclopentanone-2-yl, cyclopentanone-3-yl, cyclohexanone-2 - yl, Cyclohexanon-4-yl, Cycloheptanon-2 -yl, Cyclooctanon-2 -yl, Cyclobutanthion-2 -yl, Cyclobutanthion-3 -yl, Cyclopentanthion-2-yl, Cyclopentanthion-3 -yl, Cyclohexanthion-2 -yl, Cyclohexanthion-4-yl, cycloheptanthion-2-yl or cyclooctanethion-2-yl, preferably for cyclopentanone-2-yl or cyclohexanone-2-yl
  • 3- to 7-membered heterocyclyl is understood to mean both saturated, partially or completely unsaturated and aromatic heterocycles having one to three heteroatoms, selected from a group consisting of one to three nitrogen atoms, one or two oxygen atoms and one or two sulfur atoms.
  • saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are: oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan 2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3- yl, tetra-hydrothiophene-2-yl, tetrahydrothiophene-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-di
  • unsaturated heterocycles which may contain a carbonyl or thiocarbonyl ring member are: dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazoline-5-yl, 1,3-oxazoline 2-yl;
  • heteroaromatics the 5- and 6-membered ones are preferred, e.g.
  • Furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-0xazolyl, 4-0xazolyl and 5-0xazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, Imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as 1, 2, 4-0xadiazol-3-yl,
  • 1,2,4-0xadiazol-5-yl and 1,3,4-oxadiazol-2-yl 1,2,4-0xadiazol-5-yl and 1,3,4-oxadiazol-2-yl
  • thiadiazolyl such as 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and l, 3,4-thiadiazol-2-yl
  • triazolyl such as 1,2,4-triazol-l-yl, 1,2,4-triazol-3-yl and 1,2,4-triazol-4-yl
  • Pyridinyl such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl like
  • R 1 C -C 4 alkyl or C ⁇ -C 4 ⁇ haloalkyl, especially methyl, ethyl or C ⁇ -C 2 haloalkyl, particularly preferably methyl;
  • Haloalkoxy in particular, C ⁇ -C4-haloalkyl or C ⁇ -C ⁇ 4 haloalkoxy, particularly preferably trifluoromethyl, or di- fluoromethoxy; difluoromethoxy is very particularly preferred;
  • R 3 cyano, nitro, halogen, C -C 4 alkyl or C ⁇ -C haloalkyl, especially halogen, particularly preferably chlorine;
  • X 1 and X 2 each represent a chemical bond;
  • R 4 and R 5 independently of one another halogen, in particular chlorine or bromine;
  • X 5 stands for a chemical bond and R 8 for hydrogen and one of the two groups -X 3 R 6 or -X 4 R 7 denotes hydrogen which is linked to the phenyl ring via a chemical bond;
  • R 9 and R 10 independently of one another are hydrogen, C ⁇ -C 6 -alkyl, C--C 6 -haloalkyl, C 2 -C 6 -alkenyl, C -C 6 -alkynyl, C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -haloalkoxy- C ⁇ -C 4 ⁇ alkyl, C ⁇ -C 4 -alkylthio-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -haloalkylthio- C ⁇ -C 4 -alkyl, C ⁇ -C 4 ⁇ Alkylsulfonyl-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -haloalkyl-sulfonyl-C ⁇ -C 4 -alkyl, (C ⁇ -C 4 -alkyl) carbonyl-C ⁇ -C 4 -alkyl, (C ⁇ -C 4 ⁇ alk
  • C 3 -C 8 cycloalkyl which may contain a carbonyl or thiocarbonyl ring member, phenyl or 3- to 7-membered heterocyclyl, which may contain a carbonyl or thiocarbonyl ring member, each cycloalkyl, the phenyl and each heterocyclyl Ring can be unsubstituted or carry one or two substituents, each selected from the group consisting of cyano, nitro, amino, hydroxy, carboxy, halogen, C ⁇ -C 4 ⁇ alkyl, C ⁇ -C 4 ⁇ haloalkyl, C ⁇ -C 4 - Alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 ⁇ alkyl sulfonyl, (C ⁇ -C 4 alkyl) carbonyl, (C ⁇ -C 4 alkyl) carbonyloxy and (C ⁇ -C 4 ⁇ alkoxy) carbonyl.
  • the compounds Ib.2 to Ib.767 which differ from the corresponding compounds Ia.2 to Ia.767 only in that the corresponding
  • the variables preferably have the following meanings, each individually or in combination:
  • R 1 is hydrogen, C ⁇ -C 4 alkyl or C 1 -C 4 haloalkyl, in particular hydrogen or methyl;
  • R 2 C ⁇ -C 4 haloalkyl or C ⁇ -C 4 haloalkoxy, in particular dif1uormethoxy;
  • R 3 is hydrogen or halogen, especially hydrogen
  • R 4 and R 5 independently of one another halogen, in particular chlorine or bromine;
  • X 5 represents a chemical bond and R 8 represents hydrogen and one of the two groups -X 3 R 6 or -X 4 R 7 represents hydrogen which is linked to the phenyl ring via a chemical bond;
  • Ci-Cg-alkyl Ci-Cg-alkyl, C ⁇ -C 6 -haloalkyl, C -C 6 -alkenyl, C -C 6 -alkynyl, C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, C ⁇ -C 4 ⁇ haloalkoxy-
  • R 12 C -C 4 haloalkyl, especially difluoromethyl.
  • the compounds of the formulas Ia to Id are particularly preferred, in particular
  • the compounds of the formulas Ilaa to Ilah, Ilba to Ilbh and Ilca to lie are particularly preferred, in particular
  • the compounds of the formulas purple to IIIn are particularly preferred, in particular
  • the substituted 3-benzylpyrazoles of the formula I can be obtained in various ways, in particular by one of the following processes:
  • Suitable halogenating agents are, for example, fluorine, chlorine, bromine, diethylaminosulfur trifluoride (DAST), N-chlorosuccinimide, N-bromosuccimide, sulfuryl chloride, thionyl chloride, phosgene, phosphorus trichloride, phosphorus oxychloride, phosphorus tribromide and phosphorus oxybromide.
  • DAST diethylaminosulfur trifluoride
  • an inert solvent / diluent for example in a hydrocarbon such as n-hexane and toluene, a halogenated hydrocarbon such as dichloromethane, an ether such as diethyl ether, tetrahydrofuran and dioxane, an alcohol such as methanol and ethanol, one lower carboxylic acid such as acetic acid, or in an aprotic solvent such as acetonitrile.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 100 ° C.
  • R 12 represents C -C 4 alkyl or C ⁇ -C 4 haloalkyl;
  • L 1 stands for a common leaving group such as halide, methanesulfonate, toluenesulfonate (tosylate), trifluoromethanesulfonate (triflate) or 0-S0 2 -R 12 .
  • the procedure is normally carried out in an inert solvent / diluent, for example in a hydrocarbon such as n-hexane and toluene, a halogenated hydrocarbon such as dichloromethane, an ether such as diethyl ether, tetrahydrofuran and dioxane, or in an aprotic solvent such as acetonitrile, dimethylformamide and dimethyl sulfoxide .
  • a hydrocarbon such as n-hexane and toluene
  • a halogenated hydrocarbon such as dichloromethane
  • an ether such as diethyl ether, tetrahydrofuran and dioxane
  • an aprotic solvent such as acetonitrile, dimethylformamide and dimethyl sulfoxide .
  • the bases include both inorganic bases, for example alkali or alkaline earth metal carbonates such as sodium carbonate, alkali or alkaline earth metal hydroxides such as sodium hydroxide, alkali metal hydrides such as sodium hydride, and also organic bases, for example tertiary amines such as triethylamine and 1,8-diazabicyclo [5.4.0] undec-7 -en (DBU).
  • inorganic bases for example alkali or alkaline earth metal carbonates such as sodium carbonate, alkali or alkaline earth metal hydroxides such as sodium hydroxide, alkali metal hydrides such as sodium hydride, and also organic bases, for example tertiary amines such as triethylamine and 1,8-diazabicyclo [5.4.0] undec-7 -en (DBU).
  • inorganic bases for example alkali or alkaline earth metal carbonates such as sodium carbonate, alkali or alkaline earth metal hydroxides such as sodium hydro
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 100 ° C.
  • base and alkylating agent are used in approximately equimolar amounts, based on the amount of II.
  • base and / or alkylating agent in excess, up to about five times the molar amount on the amount of II.
  • Process products I and III can be separated in a conventional manner, e.g. by means of distillation, extraction, crystallization or chromatography.
  • the 3-benzyl-5-hydroxy-pyrazoles / pyrazolones II required as starting materials can preferably be synthesized in three stages from phenylacetic acid chlorides V, which are either known or can be prepared by processes known per se:
  • V is reacted with Meldrum's acid or a Meldrum's acid derivative (VI) in the presence of a base.
  • solvents / diluents and reaction temperature the information given above for reaction II + L 1 -R 12 applies.
  • the base can be both inorganic, e.g. an alkali or alkaline earth metal hydroxide such as sodium hydroxide, an alkali or alkaline earth metal carbonate such as sodium carbonate, an alkali or alkaline earth metal hydrogen carbonate such as sodium hydrogen carbonate, as well as organic, e.g. a tertiary amine such as triethylamine and pyridine.
  • inorganic e.g. an alkali or alkaline earth metal hydroxide such as sodium hydroxide, an alkali or alkaline earth metal carbonate such as sodium carbonate, an alkali or alkaline earth metal hydrogen carbonate such as sodium hydrogen carbonate, as well as organic, e.g. a tertiary amine such as triethylamine and pyridine.
  • the Meldrum's acid or its derivative (VI) is used in an approximately equimolar amount or in excess, up to about five times the molar amount, based on the amount of V.
  • phenylacetylmeldrum's acid is then reacted with an alcohol of the formula HR 13 , where R 13 is C ⁇ -C 4 -alkoxy, to give a phenylacetoacetic acid derivative IV, the alcohol preferably being used as a solvent.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 100 ° C.
  • Solvents / diluents for example in a hydrocarbon such as n-hexane and toluene, a halogenated hydrocarbon such as dichloromethane, an ether such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether and dioxane, an alcohol such as methanol and ethanol, a lower car- bonic acid such as acetic acid, or in an aprotic solvent such as acetonitrile, dimethylformamide and dimethyl sulfoxide.
  • a hydrocarbon such as n-hexane and toluene
  • a halogenated hydrocarbon such as dichloromethane
  • an ether such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether and dioxane
  • an alcohol such as methanol and ethanol
  • a lower car- bonic acid such as acetic acid
  • an aprotic solvent such
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 100 ° C.
  • an approximately equimolar amount of hydrazine (derivative) or an excess, up to about five times the molar amount, based on the amount of IV or VII, is used.
  • the base can be both inorganic, e.g. an alkali or alkaline earth metal hydroxide such as sodium hydroxide, an alkali or
  • Alkaline earth metal carbonate such as sodium carbonate, an alkali or alkaline earth metal hydrogen carbonate such as sodium hydrogen carbonate, as well as organic, e.g. a tertiary amine such as triethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and pyridine.
  • a tertiary amine such as triethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and pyridine.
  • alkyne and base are used, based on the amount of VIII.
  • An excess of alkyne and / or base up to about five times the molar amount, based on the amount of VIII, is used.
  • nitration reagents used are, for example, nitric acid in different concentrations, also concentrated and fuming nitric acid, mixtures of
  • the reaction can either be carried out solvent-free in an excess of the nitrating reagent or in an inert solvent or diluent, e.g. Water, mineral acids, organic acids, halogenated hydrocarbons such as methylene chloride, anhydrides such as acetic anhydride and mixtures of these solvents are suitable.
  • an inert solvent or diluent e.g. Water, mineral acids, organic acids, halogenated hydrocarbons such as methylene chloride, anhydrides such as acetic anhydride and mixtures of these solvents are suitable.
  • nitrating reagent are expediently used in approximately equimolar amounts; However, in order to optimize the conversion of the starting compound, it may be advantageous to use the nitrating reagent in excess, up to about ten times the molar amount. When carrying out the reaction without a solvent in the nitrating reagent, this is present in an even greater excess.
  • the reaction temperature is normally from (- 100) to 200 ° C, preferably at (- 30) to 50 ° C.
  • Process products I, Ha, Ilb, IIc or III with at least one nitro group on the phenyl ring can then be reduced to corresponding compounds I, Ha, Ilb, IIc or III with at least one amino group:
  • the reduction can be carried out with a metal such as iron, zinc or tin under acidic reaction conditions or with a complex hydride such as lithium aluminum hydride and sodium borohydride, the solvents being - depending on the chosen reducing agent - for example water, alcohols such as methanol, ethanol and isopropanol or ether such as diethyl ether, methyl tert. butyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether.
  • a metal such as iron, zinc or tin under acidic reaction conditions or with a complex hydride such as lithium aluminum hydride and sodium borohydride
  • the solvents being - depending on the chosen reducing agent - for example water, alcohols such as methanol, ethanol and isopropanol or ether such as diethyl ether, methyl tert. butyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl
  • the process is preferably carried out in a solvent-free manner in an inorganic acid, in particular in concentrated or dilute hydrochloric acid, or in an organic acid such as acetic acid.
  • an inert solvent to the acid, e.g. to mix one of the above.
  • the starting compound I, Ha, Ilb, IIc or III ⁇ -X 1 R 4 , -X 2 R 5 , -X 3 R 6 , -XR 7 or -X 5 R 8 N0 2 ⁇ and the reducing agent are expediently approximately equimolar amounts used; To optimize the course of the reaction, however, it may also be advantageous to use the reducing agent in excess, up to about ten times the molar amount.
  • the amount of acid is not critical.
  • the reaction temperature is generally from (-30) to 200 ° C., preferably from 0 to 80 ° C.
  • the reaction mixture is usually diluted with water and the product by filtration, crystallization or extraction with a solvent which is largely immiscible with water, e.g. isolated with ethyl acetate, diethyl ether or methylene chloride. If desired, the product can then be cleaned as usual.
  • Suitable catalysts for this are, for example, Raney nickel, palladium on carbon, palladium oxide, platinum and platinum oxide, mean a catalyst amount of 0.05 to 10.0 mol%, based on the compound to be reduced, is sufficient.
  • reaction solution can be worked up to the product in the customary manner.
  • the hydrogenation can be carried out at normal pressure or under elevated pressure.
  • the conversion of the diazonium salt thus obtained into the corresponding compound I, Ha, Ilb, IIc or III, each with -X i R 4 , -XR 5 , -X 3 R 6 , -X 4 R 7 or -X 5 R 8 cyano Chlorine, bromine or iodine is particularly preferably carried out by treatment with a solution or suspension of a copper (I) salt such as copper (I) cyanide, chloride, bromide and iodide, or with an alkali metal salt solution.
  • a copper (I) salt such as copper (I) cyanide, chloride, bromide and iodide
  • Meerwein arylation is usually the reaction of the diazonium salts with alkenes or alkynes.
  • the alkene or alkyne is preferably used in excess, up to about 3000 mol%, based on the amount of the diazonium salt.
  • the reactions of the diazonium salt described above can e.g. in water, in aqueous hydrochloric acid or hydrobromic acid, in a ketone such as acetone, diethyl ketone and methyl ethyl ketone, in a nitrile such as acetonitrile, in an ether such as dioxane and tetrahydrofuran or in an alcohol such as methanol and ethanol.
  • reaction temperatures are normally from (- 30) to + 50 ° C. All reactants are preferably used in approximately stoichiometric amounts, but an excess of one or the other component, up to approximately 3000 mol%, can also be advantageous.
  • Useful reducing agents are e.g. Transition metals such as iron, zinc and tin (see, for example, "The Chemistry of the Thiol Group", John Wiley, 1974, p. 216).
  • Halosulfonation can be carried out in one solvent
  • Excess sulfonating reagent or in an inert solvent / diluent e.g. in a halogenated hydrocarbon, an ether, an alkyl nitrile or a mineral acid.
  • Chlorosulfonic acid is both the preferred reagent and solvent.
  • the reaction temperature is usually between 0 ° C and the boiling point of the reaction mixture.
  • the reaction mixture is mixed with water, for example, after which the product can be isolated as usual.
  • Suitable solvents are organic acids, inorganic acids, aliphatic or aromatic hydrocarbons, which can be halogenated, and ethers, sulfides, sulfoxides and sulfones.
  • halogenating agents are chlorine, bromine, N-bromosuccinimide, N-chlorosuccinimide or sulfuryl chloride.
  • a radical initiator for example an organic peroxide such as dibenzoyl peroxide or an azo compound such as azobisisobutyronitrile, or irradiation with light can have an advantageous effect on the course of the reaction.
  • a catalytic amount is usually sufficient.
  • the reaction temperature is normally from (- 100) to 200 ° C, especially at 10 to 100 ° C or the boiling point of the reaction mixture.
  • Alcohols, thiols, carboxylic acids or amines in which case it is preferably carried out in the presence of a base (for example an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate), or the reaction is carried out by reacting the alcohols, thiols, carboxylic acids or amines with one Base (eg an alkali metal hydride) obtained alkali metal salts of these compounds.
  • a base for example an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate
  • Base eg an alkali metal hydride
  • Aprotic organic solvents e.g. Tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, or hydrocarbons such as toluene and n-hexane.
  • the reaction is carried out at a temperature between the melting point and the boiling point of the reaction mixture, preferably at 0 to 100 ° C.
  • the reaction temperature is usually 0 to 120 ° C.
  • Dimethyl sulfoxide for example, is suitable as a solvent.
  • Ethene-1,2-diyl ⁇ The olefination is preferably carried out using the Wittig method or one of its modifications, phosphorylides, phosphonium salts and phosphates being used as reactants, or by aldol condensation.
  • alkali metal alkyls such as n-butyllithium
  • alkali metal hydrides and alcoholates such as sodium hydride, sodium ethanolate and potassium tert. -butanolate
  • alkali metal and alkaline earth metal hydroxides such as calcium hydroxide
  • reaction temperature is (-40) to 150 ° C.
  • phosphonium salts, phosphonates or phosphorylides required as reactants are known or can be prepared in a manner known per se ⁇ cf. see, for example, Houben-Weyl, Methods of Organic Chemistry, Vol. El, pp. 636ff. and Vol. E2, pp. 345ff., Georg Thieme Verlag Stuttgart 1982; Chem. Ber. __ . , 3993 (1962) ⁇ .
  • reaction mixtures are generally worked up in a manner known per se. Unless stated otherwise in the processes described above, the valuable products are obtained e.g. after dilution of the reaction solution with water by filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase onto the product.
  • Both the substituted 3-benzylpyrazoles I and the 3-benzyl -5-hydroxypyrazoles Ha and the pyrazolones Ilb, IIc and III can be obtained in the preparation as isomer mixtures, which, however, if desired according to the usual methods such as crystallization or chromatography, also on one optically active adsorbate into which largely pure isomers can be separated. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
  • Agricultural salts of the compounds I or physiologically acceptable salts of the compounds I, Ha, Ilb, IIc and III can be obtained by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride, or by reaction with an acid of the corresponding anion, preferably that Hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid are formed.
  • a base of the corresponding cation preferably an alkali metal hydroxide or hydride
  • an acid of the corresponding anion preferably that Hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid are formed.
  • Salts of I, Ha, Ilb, Hc or III can also be prepared in a conventional manner by salting over the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, Sulfonium or sulfoxonium hydroxides.
  • 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 herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly 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 I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the substituted 3-benzylpyrazoles I are also suitable for the desiccation and / or defoliation of plants.
  • desiccants are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables a fully mechanical harvesting of these important crops.
  • 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, oil 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 and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and 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.
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives,
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substrates as such or dissolved in an oil or solvent, by means of wetting agents, adhesives, dispersants or emulsifiers in water be homogenized.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols 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 silica, silica gels, silicates, talc, kaolin, limestone, lime,
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations contain about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient I.
  • the active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the active ingredients 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 active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.
  • the substituted 3-benzylpyrazoles I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • substituted 3-benzylpyrazoles I their precursors Ha, Ilb and IIc, the by-products III and the physiologically tolerable salts of all these compounds are suitable - both as isomer mixtures and in the form of the pure isomers - as active pharmaceutical ingredients, in particular for lowering the blood sugar Salary.
  • the compounds, I, Ha, Ilb, IIc and III can be in free form or in the form of a salt with a physiologically compatible acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, malonic acid, succinic acid, fumaric acid, maleic acid, citric acid, tartaric acid, lactic acid and oxalic acid can be administered orally, parenterally or intravenously.
  • a physiologically compatible acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, malonic acid, succinic acid, fumaric acid, maleic acid, citric acid, tartaric acid, lactic acid and oxalic acid can be administered orally, parenterally or intravenously.
  • the daily dose of active substance is between 0.01 and 25, preferably between 0.1 and 20, in particular between 1 and 10 mg / kg of body weight in the case of oral, and between 0.5 and 5, preferably between 1 and 3 mg / kg body weight with intravenous use.
  • the compounds, I, Ha, Ilb, IIc and III can be used in the customary pharmaceutical application forms in solid or liquid form, for example as tablets, film-coated tablets, coated tablets, capsules. be pills, powders, solutions or suspensions, infusion or injection solutions as well as pastes, ointments, gels, creams, lotions, powders, emulsions and sprays.
  • the active ingredients can be processed with the usual pharmaceutical auxiliaries such as tablet binders, fillers, plasticizers, wetting agents, dispersants, emulsifiers, solvents, retardants and / or antioxidants (cf. H. Sucker et al., Pharmaceutical Technology, Thieme Verlag Stuttgart 1978 ).
  • the preparations thus obtained normally contain the active ingredient in an amount of 0.1 to 99% by weight.
  • Precursor 1 4- (2, 3-dichlorophenyl) -3-oxobutyric acid methyl ester
  • 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 covers 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 transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 0.125 kg / ha aS (active substance).
  • 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:
  • the young cotton plants were treated to runoff with aqueous preparations of the active compounds (with the addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac LF 700 X based on the spray mixture).
  • the amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.
  • Homozygous diabetes mice (40-60 g, from Harlan UK) were used as experimental animals, which were initially not fed for one night and then divided into different groups.
  • the active substances were administered by gavage as a solution or suspension in 0.25% aqueous hydroxyethyl cellulose (CELLOSIZE from UCC), namely 5 ml / kg live weight.
  • CELLOSIZE aqueous hydroxyethyl cellulose
  • the compounds Icl, IHcl and Ia.l reduced the plasma glucose content by approx. 20-60%, whereby the plasma insulin level remained largely unchanged.
  • mice received 0.25% aqueous Cellosize without active ingredient.
  • the urine was then collected for 24 hours and its total volume measured. Each 10 ⁇ l urine was examined for its glucose content. In the 10 mice to which Cellosize had been administered without active ingredient, the total amount of urine after 24 hours was 9.0 ml, with a glucose concentration of 5.15 mmol / l. This corresponds to a total excretion of glucose of 46.35 ⁇ mol.
  • Compound No. IHcl thus increased the excretion of glucose (via the urine) in CD1 mice by 52%.

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Abstract

L'invention concerne des 3-benzylpyrazoles substitués de formule (I), leurs précurseurs de formules (IIa), (IIb), (IIc) et leurs sous-produits de formule (III), ainsi que les sels de ces composés, formules dans lesquelles R<1> = H, alkyle en C1-C4, halogénoalkyle en C1-C4, alkylsulfonyle en C1-C4, halogénoalkylsulfonyle en C1-C4; R<2> = alkyle en C1-C4, halogénoalkyle en C1-C4, alcoxy en C1-C4, halogénoalcoxy en C1-C4, alkylthio en C1-C4, halogénoalkylthio en C1-C4, alkylsulfinyle en C1-C4, halogénoalkylthio en C1-C4, alkylsulfonyle en C1-C4, halogénoalkylsulfonyle en C1-C4; R<3> = H, CN, NO2, halogène, alkyle en C1-C4, halogénoalkyle en C1-C4; X<1> - X<5> = liaison chimique, chaîne méthylène-, éthylène-, éthène-1,2-diyle ou chaîne oxyméthylène ou thiaméthylène liée au noyau phényle par l'intermédiaire de l'hétéroatome; R<4> - R<8> = H, CN, NO2, halogène, -O-Y<1>-R<9>, -O-CO-Y<1>-R<9>, -N(Y<1>-R<9>) (Y<2>-R<10>), -N(Y<1>-R<9>)-SO2-Y<2>-R<10>, -N(SO2-Y<1>-R<9>) (SO2-Y<2>-R<10>), -N(Y<1>-R<9>),-CO-Y<2>-R<10>, -N(Y<1>-R<9>) (O-Y<2>-R<10>), -S-Y<1>-R<9>, -SO-Y<1>-R<9>, -SO2-Y<1>-R<9>, -SO2-O-Y<1>-R<9>, -SO2-N(Y<1>-R<9>) (Y<2>-R<10>), -CO-Y<1>-R<9>, -C(=NOR<11>)-Y<1>-R<9>, -C(=NOR<11>)-O-Y<1>-R<9>, C-(=NOR<11>)-CO-O-Y<1>-R<9>, -CO-O-Y<1>-R<9>, -CO-S-Y<1>-R<9>, -CO-N(Y<1>-R<9>) (Y<2>-R<10>), -CO-N(Y<1>-R<9>) (O-Y<2>-R<10>); R<12> = alkyle en C1-C4, halogénoalkyle en C1-C4. L'invention concerne en outre l'utilisation des produits (I) comme herbicides, ainsi que pour la dessication et la défoliation des plantes, et des produits (I), (IIa), (IIb), (IIc), et (III) pour l'abaissement de la teneur en sucre du sang.
EP97948864A 1996-11-04 1997-11-03 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang Withdrawn EP0937046A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19645313A DE19645313A1 (de) 1996-11-04 1996-11-04 Substituierte 3-Benzylpyrazole
DE19645313 1996-11-04
PCT/EP1997/006057 WO1998020000A2 (fr) 1996-11-04 1997-11-03 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang

Publications (1)

Publication Number Publication Date
EP0937046A2 true EP0937046A2 (fr) 1999-08-25

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EP97948864A Withdrawn EP0937046A2 (fr) 1996-11-04 1997-11-03 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang

Country Status (7)

Country Link
US (1) US6451734B1 (fr)
EP (1) EP0937046A2 (fr)
JP (1) JP2001503421A (fr)
AU (1) AU7001798A (fr)
CA (1) CA2270545A1 (fr)
DE (1) DE19645313A1 (fr)
WO (1) WO1998020000A2 (fr)

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SG171307A1 (en) * 2008-11-21 2011-07-28 Glaxosmithkline Llc Chemical process
EP2424543A4 (fr) * 2009-04-30 2012-10-17 Glaxosmithkline Llc Processus chimique

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Publication number Publication date
WO1998020000A3 (fr) 1998-10-29
WO1998020000A2 (fr) 1998-05-14
DE19645313A1 (de) 1998-05-07
AU7001798A (en) 1998-05-29
JP2001503421A (ja) 2001-03-13
US6451734B1 (en) 2002-09-17
CA2270545A1 (fr) 1998-05-14

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