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WO1994011352A1 - Benzimidazoles 2-cyano-substitues, leur fabrication et leur utilisation comme pesticides - Google Patents

Benzimidazoles 2-cyano-substitues, leur fabrication et leur utilisation comme pesticides Download PDF

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Publication number
WO1994011352A1
WO1994011352A1 PCT/EP1993/002945 EP9302945W WO9411352A1 WO 1994011352 A1 WO1994011352 A1 WO 1994011352A1 EP 9302945 W EP9302945 W EP 9302945W WO 9411352 A1 WO9411352 A1 WO 9411352A1
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Prior art keywords
optionally substituted
hetero
aryl
alkyl
formula
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PCT/EP1993/002945
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German (de)
English (en)
Inventor
Winfried Lunkenheimer
Christoph Erdelen
Ulrike Wachendorff-Neumann
Heinz-Wilhelm Dehne
Ulrich Görgens
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Bayer Aktiengesellschaft
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Priority to AU53707/94A priority Critical patent/AU5370794A/en
Publication of WO1994011352A1 publication Critical patent/WO1994011352A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • 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
    • C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • C07D403/06—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 only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • C07F9/65068—Five-membered rings having the nitrogen atoms in positions 1 and 3 condensed with carbocyclic rings or carbocyclic ring systems

Definitions

  • the invention relates to the use of partially new substituted benzimidazoles as pesticides.
  • X 1 , X 2 , X 3 and X 4 independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl , Alkoxycarbonyl, cycloalkyloxycar bonyl represent each case optionally substituted amino or aminocarbonyl, or represents in each case optionally substituted aryl, aryloxy, Aryltl ⁇ o, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulphonyl, but where at least one of the substituents X 1, X 2, X 3 and
  • R 1 represents hydrogen, alkyl, cycloalkyl or optionally substituted aryl
  • R 2 represents hydroxy, cyano or optionally substituted in each case
  • the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or regioisomers or their isomer mixtures in different compositions. Both the use of the pure isomers and that of the isomer mixtures are claimed according to the invention.
  • the substituted benzimidazoles of the general formula (I) which can be used according to the invention have a considerably better insecticidal activity compared to the phosphoric acid esters or carbamates known from the prior art, such as, for example, the compound O, S-dimethyl-thiolophosphoric acid amide or the compound N- Methyl-O- (2-isopropoxyphenyl) carbamate, which are effective compounds.
  • Formula (I) provides a general definition of the substituted benzimidazoles which can be used according to the invention.
  • Compounds of formula (I) are preferred in which
  • X 1 , X 2 , X 3 and X 4 independently of one another each for hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, for straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms, for cycloalkyl with 3 to 8 carbon atoms, for each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl each with 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms or for optionally single or multiple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atom
  • Hydroxycarbonyl for each straight-chain or branched alkylcarbonyl or alkoxycarbonyl each having 1 to 6 carbon atoms in the alkyl part, for cycloalkyloxycarbonyl having 3 to 8 carbon atoms in the cycloalkyl part or for each optionally mono- or polysubstituted, identical or differently substituted amino or aminocarbonyl, with amino substituents in question in each case come: in each case straight-chain or branched alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 13 halogen atoms, alkoxyalkyl or alkylcarbonyl each having 1 to 6 carbon atoms in the individual alkyl parts or in the aryl part in each case, if appropriate, once or several times, identically or differently substituted arylcarbonyl, arylsulfonyl, arylaminocarbonyl or arylmethylsulfonyl each having 6 to 10 carbon
  • R 1 represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms or phenyl which may be mono- or polysubstituted by identical or different substituents, the following being suitable as substituents: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,
  • Alkoxycarbonyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts, optionally one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 6 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 up to 13 identical or different halogen atoms substituted, doubly linked dioxyalkylene with 1 to 5 carbon atoms or optionally single or multiple, identical or different by halogen and / or straight-chain or branched alkyl with 1 to 6 carbon atoms and / or straight-chain or branched halogenoalkyl with 1 to 6 Carbon atoms and 1 to 13 identical or different halogen atoms substituted phenyl,
  • R 2 for hydroxy, cyano or for each optionally mono- or polysubstituted, identical or differently substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 8 carbon atoms in the individual NEN is alkyl or alkenyl or alkynyl parts, the following being suitable as substituents:
  • R 2 furthermore represents amino or aminocarbonyl which may be mono- or disubstituted in the same way or differently, the substituents being suitable: straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 Carbon atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxythiocarbonyl or alkylthio-thiocarbonyl each with 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, doubly linked, ring-closed alkanediyloxycarbonyl with 2 to 6 carbon atoms in the
  • R 2 also represents aryl, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy or arylaminocarbonylaminocarbonyloxy, each of which is mono- or polysubstituted by identical or different substituents, each having 6 to 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R 1 ,
  • R 2 also for heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy, each of which is optionally mono- or polysubstituted by identical or different substituents, each having 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - im Hetero- aryl part, the heteroaryl substituents in each case being the aryl substituents mentioned for R 1 .
  • X 1 , X 2 , X 3 and X 4 independently of one another each for hydrogen, fluorine, chlorine, bromine, cyano, nitro, for each straight-chain or branched alkyl, alkoxy,
  • Alkoxyalkyl or alkylcarbonyl each having 1 to 4 carbon atoms in the individual alkyl parts or in the aryl part, in each case optionally up to five times, the same or differently substituted arylcarbonyl, arylsulfonyl, arylaminocarbonyl or arylmethylsulfonyl each having 6 or 10 carbon atoms in the aryl part, the aryl substituents in each case being those in R 1 mentioned in question; in addition, each aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylthiomethylsulfonyl or arylazo, each having 6 or 10 carbon atoms in the aryl part, in each case having 6 or 10 carbon atoms in the aryl part, in each case with aryl substituents 1 mentioned are
  • R 2 also for aryl, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy which are each mono- to pentasubstituted or substituted in the same way or differently or arylaminocarbonylaminocarbonyloxy, each having 6 or 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R 1 ,
  • R 2 also for heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl which are each mono- to pentasubstituted by identical or different substituents,
  • Heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy each having 2 to 9 carbon atoms and 1 to 4 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - is in the heteroaryl part, the heteroaryl substituents mentioned in R 1 being suitable in each case.
  • Phenyl or naphthyl may be mentioned as aryl radicals, and pyridyl may be mentioned as heteroaryl radicals.
  • X 1 , X 2 , X 3 and X 4 independently of one another each for hydrogen, chlorine, bromine, cyano, nitro, for straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, for cycloalkyl having 3 , 5 or 6 carbon atoms, each for straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl each having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms or for optionally up to four times, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7
  • Alkoxycarbonyl or alkoximinoalkyl each having 1 to 3 carbon atoms in the individual alkyl parts, optionally one to four times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 up to 7 identical or different halo Genetically atom-substituted, double-linked dioxyalkylene with 1 to 3 carbon atoms or optionally single to triple, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 phenyl substituted by the same or different halogen atoms,
  • R 2 for hydroxy, cyano or for each optionally mono- to trisubstituted, identically or differently, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 4 carbon atoms in represents the individual alkyl or alkenyl or alkynyl parts, or represents in each case optionally mono- or disubstituted, identically or differently substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 4 carbon atoms in is the individual alkyl or alkenyl or alkynyl parts, the substituents in each case being suitable: straight-chain or
  • R 2 furthermore represents phenyl, phenylcarbonyl, phenyloxycarbonyl, phenylcarbonyloxy or phenylaminocarbonylaminocarbonyloxy which may be monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents in each case being those mentioned in R 1 ,
  • R 2 also represents in each case monosubstituted to trisubstituted, identically or differently, heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy, each having 2 to 9 carbon atoms and 1 to 3 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - in the hetero atom , the heteroaryl substituents in each case being the phenyl substituents mentioned for R 1 ,
  • heteroaryl is pyridyl.
  • substituted benzimidazoles of the general formula (I) may be mentioned individually:
  • substituted benzimidazoles of the formula (I) are known (cf., for example, DE 20 47 369; DE 20 14 293; EP 448 206; J. Chem. Soc. C, 1967, 2536-2540).
  • X 1 -1 , X 2-2 , X 3-1 and X 4-1 independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted , condensed dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for optionally substituted amino or aminocarbonyl or for optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonylthyl, aryl, at least one, are aryl, aryloxycarbonylthyl, aryl, at least one, the substituents
  • R 1 represents hydrogen, alkyl or optionally substituted aryl
  • R 2 for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryloxycarbonyl, (Hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy.
  • R 1 and R 2 have the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.
  • reaction sequence of the production process can be represented by the following formula:
  • Formula (II) provides a general definition of the 1H-benzimidazoles required as starting materials for carrying out the production process.
  • this formula (II) ste hen X 1 , X 2 , X 3 and X 4 preferably for those radicals which have already been mentioned as preferred for this substituent in connection with the description of the compounds of the formula (I) which can be used according to the invention.
  • Formula (III) provides a general definition of the alkylating agents which are furthermore required as starting products for carrying out the production process.
  • R 1 and R 2 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) which can be used according to the invention.
  • E stands for a leaving radical customary in alkylating agents, preferably for halogen, in particular for chlorine, bromine or iodine or for optionally substituted alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy, such as in particular methanesulfonyloxy, trifluoromethanesulfonyloxy, methoxysulfonyloxy, ethoxysulfonyloxy or p-toluenesulfonyl.
  • E also stands for an alcohol, alkanoyloxy or alkoxy group, such as a hydroxy, acetoxy or methoxy group, in particular if compounds of the formula (I) in which R 1 is different from hydrogen are prepared using the process according to the invention should.
  • the compounds of the formula (III) are generally known or can be obtained analogously to known processes (cf., for example, DE 20 40 175; DE 21 19 518; Synthesis 1973, 703).
  • Inert organic solvents are suitable as diluents for carrying out the production process.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformaniiide
  • the production process is preferably carried out in the presence of a suitable reaction auxiliary.
  • All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, lithium diethylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide , Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, lithium-organic compounds such as n-butyllithium and tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine, tetramethylguanidine , N-dimethylaniline,
  • organic or inorganic acids such as, for example, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, perfluorobutanesulfonic acid or strongly acidic ion exchangers, are also suitable as reaction auxiliaries, especially if the alkylating agents of the formula (III) E used are hydroxyl, acyloxy or alkoxy.
  • the production process can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst.
  • Such catalysts may be mentioned / C 14 alkyl benzyl ammonium chloride, dimethyl C 12 / C 14 alkyl benzyl ammonium bromide, tetrabutyl ammonium hydroxide, triethylbenzylammonium chloride, methyltrio
  • reaction temperatures can be varied within a substantial range when carrying out the production process. In general, temperatures between -70 ° C and + 200 ° C, preferably at temperatures between 0 ° C and 130 ° C.
  • the manufacturing process is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol, of alkylating agent of the formula (III) and, if appropriate, 0.01 to 0.1 mol are generally employed per mol of 1H-benzimidazole of the formula (II) 5.0 moles, preferably 1.0 to 3.0 moles of reaction auxiliary.
  • the end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization.
  • the characterization takes place with the help of the melting point or with non-crystallizing compounds - in particular with regioisomer mixtures - with the help of proton nuclear magnetic resonance spectroscopy ( 1 H-NMR).
  • the active substances are suitable for combating animal damage, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include: From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber;
  • Diplopoda e.g. Blaniulus guttulatus
  • Chilopoda e.g. Geophilus carpophagus, Scutigera spec
  • Symphyla e.g. Scutigerella immaculata
  • Thysanura e.g. Lepisma saccharina
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria;
  • Dermaptera e.g. Auricular forficula
  • anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .;
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci;
  • Hymenoptera From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp .; from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • the active compounds according to the invention are notable for high insecticidal activity. They can be used with particularly good success for controlling plant-damaging insects, for example against the tobacco bud caterpillar (Heliothis virescens), and for combating plant-damaging mites, for example for the common spider mite (Tetranychus urticae).
  • the active compounds according to the invention have a strong fungicidal action and can be used practically to combat unwanted microorganisms.
  • the active ingredients are also suitable for use as fungicides.
  • Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubense;
  • Plasmopara species such as, for example, Plasmopara viticola
  • Peronospora species such as, for example, Peronospora pisi or Peronospora brassicae
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca Faniginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or Pyrenophora graminea
  • Drechslera (Conidial form: Drechslera, synonym: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum;
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment above ground
  • the active compounds according to the invention can be used with particularly good results to combat diseases in fruit and vegetable cultivation, such as, for example, against the pathogen causing tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or for combating cereal diseases, such as against Pathogen of the powdery mildew (Erysiphe graminis) or against the pathogen of brown-furred wheat (Septoria nodorum) or against the pathogen of barley mesh spot disease (Pyrenophora teres).
  • diseases in fruit and vegetable cultivation such as, for example, against the pathogen causing tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or for combating cereal diseases, such as against Pathogen of the powdery mildew (Erysiphe graminis) or against the pathogen of brown-furred wheat (Septoria nodorum) or against
  • the active compounds can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, fine encapsulation in polymeric substances and in coating compositions for seeds, furthermore in formulations with fuel sets, such as smoking cartridges, cans, spirals etc. , as well as ULV cold and warm fog formulations.
  • customary formulations such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, fine encapsulation in polymeric substances and in coating compositions for seeds, furthermore in formulations with fuel sets, such as smoking cartridges, cans, spirals etc. , as well as ULV cold and warm fog formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and the like Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide;
  • Solid carrier materials are suitable: for example natural rock powders such as
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and tin can be used.
  • inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and tin can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active ingredient concentration of the use forms can be from 0.0000001 to 95 percent by weight of active ingredient, preferably between 0.0001 and 1 percent by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active compounds according to the invention can also be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and growth regulators.
  • the active compounds When used as fungicides, the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated. In the treatment of parts of plants, when used as fungicides, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • active compound when used as fungicides, amounts of active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
  • X represents fluorine or chlorine, at -20 to + 20 ° C with formaldehyde and hydrogen chloride.
  • X 1 , X 2 , X 3 and X 4 independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl , Alkoxycarbonyl, cycloalkyl oxycarbonyl, for in each case optionally substituted amino or aminocarbonyl or for in each case optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl, where X is at least one, but at least one of the substituents 2
  • chloromethyl radical haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted condensed dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each optionally substituted amino or aminocarbonyl or for each optionally substituted aryl,
  • X represents hydrogen, fluorine, chlorine or bromine and R 1 and R 4 can be the same or different from one another and each hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen-C 1 -C 6 alkyl, C 6 -C 10 aryl, COOH, CN, NCO, COO-C 1 -C 6 - alkyl, NH-C 1 -C 6 alkyl, N (C 1 -C 6 alkyl) 2, mean,
  • R 2 and R 3 represent NO 2 or NH 2 , can be obtained by reacting 1,2-dihydroxybenzenes or 2,3-dihydroxypyridines
  • R 1 to R 4 have the meaning given above, in the presence of a base and a diluent at -20 to + 200 ° C with a hexafluorobutene of the formula
  • X 2 represents halogen
  • R 1 to R 4 have the meaning given above and
  • R 5 for a protective group
  • R 5 together with R 1 represent a -C (CH 3 ) 2 -O radical
  • 1,3-Benzo-dioxoles which contain two adjacent amino groups, can in a known manner by reaction with trichloroacetimidomethyl ester and then with ammonia in the corresponding benzimidazole e.g. the following formula
  • 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole 110 g of pyrocatechol were dissolved in 1,500 ml of acetonitrile and 200 g of triethylamine were added. 235 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise to the mixture at 75 ° C. The mixture was stirred at 75 ° C for 2 hours. 1,200 ml of the solvent were then distilled off in vacuo and the residue was taken up in 1,500 ml of water.
  • 1,2-Dihydroxy-3- (1,1,1,4,4,4-hexafluoro-2-butenoxy) -benzene 65 g of the product from Example 9a were boiled with 200 ml of concentrated aqueous hydrochloric acid for 4 hours with stirring heated at reflux. The mixture was then diluted with 300 ml of water and extracted with methylene chloride. After drying with magnesium sulfate, the organic Phase the solvent is stripped off and 54 g of a 90% pure product are obtained. Recrystallization from cyclohexane gave colorless crystals with a melting point of 105 ° C. The characteristic absorptions in the NMR spectra were as follows: 19 F-NMR -57.7 and -67.7 ppm. 1 H NMR: 6.77, 6.50, 6.21 and 5.42 ppm.
  • Example 12a 18 g of the product from Example 12a were reacted with 50 ml of concentrated hydrochloric acid analogously to Example 10a. 15.7 g of a 97% pure product were obtained. The product was a 1: 1 molar mixture of the cis / trans isomers.
  • the characteristic absorptions in the NMR spectra were as follows: 19 F-NMR: -60.2, -61.3, -62.2 and -63.3 ppm. 1 H NMR: 6.80, 6.45 and 6.25 ppm.
  • R 1 for CF 3 , OCF 3 , SCF 3 , SO 2 -C 1 -C 6 alkyl which can be straight-chain or branched and can be completely or partially substituted by fluorine, N (CF 3 ) 2 , a phenyl or phenoxy radical CF 3 or CN in the 4-position and optionally further substituents, 1,1,2,3,3,3-hexafluoropropoxy, 1,1,2-trifluoro-2-chloroethoxy, 1,1,2,2-tetra1luoroethoxy , 1,1,2-trifluoro-2-chloroethylthio or 1,1,2,3,3,3-hexafluoropropylthio, regardless of which R 2 is F, Cl, Br, CN, CH 3 , OCF 3 , SO 2 -C 1 -C 6 alkyl, which can be straight-chain or branched and can be completely or partially substituted by fluorine, COO-C 1 - C 6 alkyl, CO
  • R 3 represents hydrogen, COCH 3 or COCF 3 , where R 1 and R 2 together can represent an -O-CFCl-CFCl-O radical, with the exception of those in EP-A 251 013 and EP-A 487
  • Compounds described 286 can be obtained by using a benzene derivative of the formula in D 1 for CF 3 O, CF 3 S, CHF 2 CF 2 O, CHFCl-CF 2 O, CF 3 CHFCF 2 O, CF 3 CF 2 O, CF 3 CF 2 CF 2 O, CF 3 CF 2 S or CF 3 CHFCF 2 O and D 2 for CF 3 O, CF 3 S, CHF 2 CF 2 O, CHFCl-CF 2 O, CF 3 CHF-CF 2 O, CF 3 CF 2 O, CF 3 CF 2 O, CF 3 CF 2 S , CF 3 CHFCF 2 O, fluorine, chlorine, bromine, C 1 -C 6 alkyl or C 1 -C 6
  • R 1 has the meaning given in the formula and Hal represents fluorine, chlorine or bromine, react with ammonia, so replace the Hal group with an amino group and reduce the nitraniline thus obtained.
  • nitraniline can be used, for example of the formula
  • R 1 has the meaning given above. react with a chlorinating or brominating agent, so insert a chlorine or bromine atom in the meta position to the nitro group and then reduce the nitro group.
  • R 1 is a donor group in the 4-position to the two amino groups
  • R 2 is an acceptor group, for example COO-C 1 -C 6 -alkyl, CN, CF 3 or SO 2 -C 1 -C 6 represents alkyl and R3 is not hydrogen, for example, a benzene derivative of the formula
  • the fluoroalkyl (en) group-containing o-phenylenediamines in which R 3 is hydrogen can first with trichloroacetimidomethyl ester and subsequent reaction with ammonia to 2-cyanobenzimidazoles of the following formula
  • R 1 and R 2 assume the above scope
  • R 4 represents hydrogen, alkyl, alkoxy or optionally substituted aryl
  • R 5 for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, aminocarbonyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphonyl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) Aryloxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy and
  • A means a suitable leaving group
  • Leaving groups are known to the person skilled in the art and are, for example, halogen, alkyl (alkoxy, aryl) sulfonyloxy, hydroxy or alkoxy.
  • 1,2-dichloroethane was 350 g of 96% by weight of pure 1,2-dinitro-4,5-bis- (2-chloro-1,1,2- n .
  • Example 2 b Analogous to Example 1, the ent was obtained from 1,2-bis (1,1,2,3,3,3-hexafluoropropoxy) benzene
  • Example 4 b (1,1,2-trifluoro-2-chloroethoxy) -2-chlorobenzene was converted into the corresponding 4,5-dinitro compound (melting point 56 to 57 ° C) and the corresponding 4,5-diamino compound ( Melting point 67 to 68 ° C) prepared.
  • Example 4 b (1,1,2-trifluoro-2-chloroethoxy) -2-chlorobenzene was converted into the corresponding 4,5-dinitro compound (melting point 56 to 57 ° C) and the corresponding 4,5-diamino compound ( Melting point 67 to 68 ° C) prepared.
  • Example 4 b 1- (1,1,2-trifluoro-2-chloroethoxy) -2-chlorobenzene was converted into the corresponding 4,5-dinitro compound (melting point 56 to 57 ° C) and the corresponding 4,5-diamino compound ( Melting point 67 to 68 ° C) prepared.
  • Diamino compound (oil, 98 wt .-% pure, D 1.5485) prepared.
  • Example 5 b Diamino compound (oil, 98 wt .-% pure, D 1.5485) prepared.
  • Example 2 Analogously to Example 1, the corresponding 4,5-dinitro compound (melting point 55 to 56 ° C.) and the corresponding 4,5-diamino compound (melting point 56-57 ° C.) were prepared from 1-trifluoromethoxy-2-chlorobenzene.
  • Example 6 b The corresponding 4,5-dinitro compound (oil) and the corresponding 4,5-diamino compound (oil) were prepared from 1- (1,1,2,3,3,3-hexafluoropropoxy) -2-chlorobenzene .
  • 3-bromo-5-nitro-6-chlorobenzotrifluoride was first used to make 3-bromo-5-nitro-6-amino-benzotrifluoride (melting point 80 to 82 ° C.) and 3-bromo-5,6-diamino- benzotrifluoride (melting point 52 to 54 ° C).
  • Example 12b 2-Bromo-4-fluoro-5-nitro- (1,1,2-trifluoro-2-chloro) ethoxybenzene was first used to give 2-bromo-4-amino-5-nitro- (1,1, 2-trifluoro-2-chloro-ethoxy) -benzene (melting point 90 ° C) and from it 2-bromo-4,5-diamino- (1,1,2-, rifluoro-2-chloro) -ethoxybenzene.
  • 155 g of the nitraniline thus prepared were refluxed in 700 ml of ethanol with 15 ml of water, 10 ml of concentrated aqueous hydrochloric acid and 70 g of iron shavings for 15 hours, then the mixture was filtered off, the filtrate was freed from the solvent under reduced pressure and the solid Crude product recrystallized from cyclohexane. 112 g of 6-bromo-4-trifluoromethyl-mercapto-1,2-diaminobenzene with a melting point of 60 to 61 ° C. were obtained.
  • Example 14b Analogously to Example 13, 27 g of 2-nitro-4-trifluoromethylsulfonylaniline in 100 ml of acetic acid were brominated with 18 g of bromine.
  • 3-trifluoromethyl-4-methoxy-acetanilide was initially 3-trifluoromethyl-4-methoxy-6-nitro-acetanilide (melting point 143-144 ° C.) and from it 3-trifluoromethyl-4-methoxy-6-amino -acetanilide (melting point 164-165 ° C).
  • 3-trifluoromethyl-4-bromo-trifluoromethylacetanilide was first converted into 3-trifluoromethyl-4-bromo-6-nitro-trifluoromethylacetanilide (melting point 110-112 ° C.) and from it 3-trifluoromethyl-4-bromo-6-amino- trifluoromethylacetanilide (melting point 63 - 65 ° C).
  • 3-trifluoromethylthio-4-chloro-trifluoromethylacetanilide was first converted to 3-trifluoromethylthio-4-chloro-6-nitro-trifluoromethylacetanilide (melting point 99-100 ° C.) and from it 3-trifluoromethylthio-4-chloro-6-amino- trifluoromethylacetanilide (melting point 88 - 90 ° C).
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the tobacco bud caterpillar (Heliothis virescens) while the leaves are still moist.
  • the kill is determined in percent. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted to the desired concentrations with water containing emulsifier.
  • Bean plants Phaseolus vulgaris
  • which are heavily infested with all stages of development of the common spider mite (Tetranychus urticae) are immersed in an active ingredient preparation of the desired concentration.
  • the kill is determined in percent. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%. Evaluation is carried out 12 days after the inoculation.

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Abstract

L'invention concerne l'utilisation, comme pesticides, de benzimidazoles substitués, partiellement nouveaux, de formule générale (I), où X?1, X2, X3 et X4¿ désignent respectivement, indépendamment l'un de l'autre, un hydrogène, halogène, cyano, nitro, un alkyle, alcoxy, alkylthio, alkylsulfinyle, alkylsulfonyle ou cycloalkyle, chacun éventuellement substitué, un dioxyalkylène condensé éventuellement substitué, un hydroxycarbonyle, alkylcarbonyle, alcoxycarbonyle, cycloalkyloxycarbonyle; un amino ou un aminocarbonyle, chacun éventuellement substitué, ou un aryle, aryloxy, arylthio, arylsulfinyle, arylsulfonyle, arylsulfonyloxy, arylcarbonyle, aryloxycarbonyle, arylazo ou arylthiométhylsulfonyle, chacun éventuellement substitué, où toutefois, au moins l'un des substituants X?1, X2, X3 et X4¿ est différent de l'hydrogène et d'un halogène, et où R1 désigne un hydrogène, un alkyle ou un aryle éventuellement substitué; R2 désigne un hydroxy, un cyano ou un alkyle, alcényle, alcinyle, alcoxy, alcényloxy, alcinyloxy, alkylthio, amino, alkylcarbonyle, alcoxycarbonyle, alkylcarbonyloxy, dialcoxyphosphoryle, (hétéro)aryle, (hétéro)arylcarbonyle, (hétéro)aryloxycarbonyle, (hétéro) arylcarbonyloxy ou (hétéro)arylaminocarbonylaminocarbonyloxy, chacun éventuellement substitué. L'invention concerne en outre de nouveaux benzimidazoles substitués et leur fabrication.
PCT/EP1993/002945 1992-11-06 1993-10-25 Benzimidazoles 2-cyano-substitues, leur fabrication et leur utilisation comme pesticides WO1994011352A1 (fr)

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AU53707/94A AU5370794A (en) 1992-11-06 1993-10-25 2-cyano-substituted benzimidazoles, their production and their use as pesticides

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DEP4237567.3 1992-11-06
DE19924237567 DE4237567A1 (de) 1992-11-06 1992-11-06 Schädlingsbekämpfungsmittel

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP0596359A3 (fr) * 1992-11-06 1995-01-25 Bayer Ag 1,3-benzo- et 1,3-pyrido-dioxoles fluorées, procédé pour leur préparation et leur utilisation pour la préparation des produits protecteurs pour plantes.
WO1996032395A1 (fr) * 1995-04-13 1996-10-17 Bayer Aktiengesellschaft Derives benzimidazole

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4415435A1 (de) * 1994-05-03 1995-11-09 Bayer Ag Benzimidazol-Derivate

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DE2014293A1 (de) * 1969-03-29 1970-10-08 Fisons Ltd., Felixstowe, Suffolk (Grossbritannien) Substituierte Benzimidazole und Verfahren zu ihrer Herstellung und Verwendung
DE2047369A1 (de) * 1969-09-26 1971-04-01 Merck & Co Inc , Rahway, N J (VStA) Polyhalobenzimidazole
EP0448206A2 (fr) * 1990-02-16 1991-09-25 Zeneca Limited Dérivés de benzimidazole et indazole substitués, procédés pour leur préparation et leur utilisation comme herbicides

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JOURNAL OF THE CHEMICAL SOCIETY (C) 1967, Seiten 2536 - 2540 GARNER R. & SUSCHITZKY H. 'Syntheses of heterocyclic compounds. Part XX. Synthesis and reactions of 1,2-disubstituted benzimidazoles' in der Anmeldung erwähnt Seite 2537, Formel (VI); Seite 2539, Tabelle 1 *

Cited By (6)

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Publication number Priority date Publication date Assignee Title
EP0596359A3 (fr) * 1992-11-06 1995-01-25 Bayer Ag 1,3-benzo- et 1,3-pyrido-dioxoles fluorées, procédé pour leur préparation et leur utilisation pour la préparation des produits protecteurs pour plantes.
US5420309A (en) * 1992-11-06 1995-05-30 Bayer Aktiengesellschaft Fluorinated 1,3-benzo- and 1,3-pyrido-dioxoles, their preparation and their use
WO1996032395A1 (fr) * 1995-04-13 1996-10-17 Bayer Aktiengesellschaft Derives benzimidazole
US5925663A (en) * 1995-04-13 1999-07-20 Bayer Aktiengesellschaft Benzimidazole derivatives
US6080776A (en) * 1995-04-13 2000-06-27 Bayer Aktiengesellschaft Benzimidazole derivatives
US6235765B1 (en) 1995-04-13 2001-05-22 Bayer Aktiengesellschaft Benzimidazole derivatives

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