WO2016174049A1 - Anti-parasitic combinations including halogen-substituted compounds - Google Patents

Anti-parasitic combinations including halogen-substituted compounds Download PDF

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WO2016174049A1
WO2016174049A1 PCT/EP2016/059332 EP2016059332W WO2016174049A1 WO 2016174049 A1 WO2016174049 A1 WO 2016174049A1 EP 2016059332 W EP2016059332 W EP 2016059332W WO 2016174049 A1 WO2016174049 A1 WO 2016174049A1
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alkyl
methyl
spp
ethyl
nitrogen
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PCT/EP2016/059332
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French (fr)
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Christina Mertens
Werner Hallenbach
Hans-Georg Schwarz
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Bayer Animal Health Gmbh
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    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • 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
    • C07D401/14—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 three or more hetero 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
    • C07D403/14—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 three or more hetero rings
    • 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
    • C07D405/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • Anti-parasitic combinations including halogen-substituted compounds
  • the present application relates to novel anti-parasitic combinations of halogen-substituted compounds, which are useful for controlling animal pests in the field of animal health.
  • the present invention provides: Combinations of compounds of the general formula (I) below with ectoparasiciticides, anthelmintics or anti-protozoal agents.
  • halogen-substituted compounds of the invention are defined by the general formula (I)
  • R ' represents hydrogen, optionally substituted C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 7 - cycloalkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )- alkyl, or alternatively
  • R ! represents hydrogen, optionally substituted C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 7 - cycloalkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )- alkyl, the chemical groupings Ai represents CR 2 or nitrogen, A2 represents CR 3 or nitrogen, A3 represents CR 4 or nitrogen and A4 represents CR 3 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
  • R 2 , R ⁇ R 4 and R 5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, N-C 1 -C 6 -alkoxy-imino-C 1 -C 3 -alkyl, C 1 - C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, N- C 1 -C 6 -alkylamino or 7V,N-di-C 1 - C 6 -alkylamino; if none of the groupings A2 and A3 represents nitrogen, R 3 and R 4 together with the carbon atom to which they are attached may form a 5- or 6-membered ring which contains 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and
  • Q represents hydrogen, formyl, hydroxy, amino or one of the optionally substituted groupings alkyl, alkyloxy, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl or represents a grouping N-alkylamino, N-alkylcarbonylamino, N,N- dialkylamino; or
  • Q represents an unsaturated 6-membered carbocycle which is optionally mono- or polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally mono- or polysubstituted by V, or alternatively
  • (,) represents an unsaturated 6-membered carbocycle which is optionally polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally polysubstituted by V, where in both last cases of Q
  • V represents halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, N-alkoxyiminoalkyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, N,N-dialkylamino,
  • T represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
  • R ' independently of one another represent halogen, cyano, nitro, amino or optionally substituted C 1 - C 6 -alkyl, C 1 -C 6 - alkyloxy, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 - C 6 -alkylsulphonyl, and n represents the values 0-2;
  • Z 1 represents optionally substituted alkyl and cycloalkyl
  • Z 2 represents hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, and
  • Z 3 represents hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or hetaryl .
  • R 1 represents hydrogen, optionally substituted C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C7- cycloalkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )- alkyl, or alternatively
  • R ! represents hydrogen, optionally substituted C 1 -C 6 -alkyl, C2-C 6 -alkenyl, C2-C 6 -alkynyl, C 3 -C7- cycloalkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )- alkyl, the chemical groupings Ai represents CR 2 or nitrogen, A2 represents CR 3 or nitrogen, A3 represents CR 4 or nitrogen and A4 represents CR 5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
  • R 2 , R ' . R 4 and R 5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, N-alkoxyiminoalkyl, C 1 -C 6 - alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, N-C 1 -C 6 -alkylamino, N,N-di- C 1 - C 6 alkylamino; if none of the groupings A2 and A3 represents nitrogen, R 3 and R 4 together with the carbon atom to which they are attached may form a 5- or 6-membered ring which contains 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulphur atom, or if none of
  • W represents oxygen or sulphur
  • Q represents hydrogen, formyl, hydroxy, amino or one of the optionally substituted groupings C 1 -C 6 - alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 2 -C 5 -heterocy c loa Iky 1, C 1 -C 4 -alkoxy, C 1 - C 6 -alkyl-C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )- alkyl or represents a grouping N-C 1 -C 4 -alkylamino, N-C 1 -C 4 -alkylcarbonylamino, N,N-di-C 1 -C 4 - alkyla
  • Q represents an unsaturated 6-membered carbocycle which is optionally mono- or polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally mono- or polysubstituted by V,
  • V independently of one another represent halogen, cyano, nitro, optionally substituted C 1 -C 6 -alkyl, C 1 -C 4 -alkenyl, C 1 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, N-C 1 -C 6 -alkoxy-imino-C 1 -C 3 - alkyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, N,N-di-(C 1 -C 6 - alkyl)amino;
  • T represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
  • R 1 represents hydrogen or represents C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 3 -alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 ) -alkyl which are optionally mono- or polysubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl, the chemical groupings
  • Ai represents CR 2 or nitrogen
  • A2 represents CR ' or nitrogen
  • A3 represents CR 4 or nitrogen and A4 represents CR 3 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
  • R 2 , R 3 , R 4 and R 5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, N-C 1 -C 6 -alkoxy-imino-C 1 -C 3 -alkyl, C 1 - C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, N-C 1 -C 6 -alkylamino or N,N-di-C 1 - C 6 -alkylamino;
  • W represents oxygen or sulphur;
  • Q represents hydrogen, hydroxy, formyl or one of the groupings C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 - alkynyl, C 3 -C 6 -cycloalkyl, C 2 -C 5 -heterocycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 6 -alkyl-C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )-alkyl, N-C 1 -C 4 -alkylamino, N-C 1 -C4-alkylcarbonylamino or N,N-di-C 1 -C 4 -alkylamino
  • Q represents aryl substituted by 0 - 4 substituents V or a 5- or 6-membered heteroaromatic substituted by 0 - 4 substituents V, where V independently of one another represent halogen, cyano, nitro, optionally substituted C 1 -C 6 -alkyl, C 1 -C 4 -alkenyl, C 1 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, N-C 1 -C 6 -alkoxy-imino-C 1 -C 3 - alkyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, N,N-di-(C 1 -C 6 - alkyl) amino;
  • T represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
  • R' independently of one another represent halogen, cyano, nitro, amino or optionally mono- or polyhalogen-substituted C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, and n represents the values 0-1 ;
  • Z 1 represents optionally substituted C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, and represents hydrogen, halogen, cyano, nitro, amino or optionally mono- or polysubstituted C 1 -C 6 - alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, and represents hydrogen or optionally substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkenyl, C 1 -C 4 - alkynyl, aryl or hetaryl.
  • R 1 represents hydrogen or represents C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 3 -alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 ) -alkyl which are optionally mono- to pentasubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl, the chemical groupings A 1 represents CR 2 or nitrogen,
  • a 2 represents CR 3 or nitrogen
  • a 3 represents CR 4 or nitrogen
  • a 4 represents CR 5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
  • R 4 and R 5 independently of one another represent hydrogen, halogen, cyano, nitro, or represent C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, N-C 1 -C 6 -alkoxy-imino-C 1 -C 3 -alkyl, C 1 -C 6 - alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, N-C 1 -C 6 -alkylamino or N,N-di-C 1 -C 6 - alkylamino which are optionally mono- to pentasubstituted independently of one another by hydroxy, nitro, amino, halogen, alk
  • W represents oxygen or sulphur
  • Q represents hydrogen, hydroxy, formyl or one of the groupings C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 - alkynyl, C 3 -C 6 -cycloalkyl, C 2 -Cs-heterocycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 6 -alkyl-C 3 -C 6 cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl, aryl-(C 1 -C 3 )-alkyl, heteroaryl-(C 1 -C 3 )-alkyl, 7V-C 1 -C 4 -alkylamino, N-C 1 -C 4 -alkylcarbonylamino or N,N-di-C 1 -C 4 -alkylamino
  • R 6 independently of one another represent halogen, cyano, nitro, amino or optionally mono- to pentahalogen-substituted C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, C 1 -C 6 -aikylcarbonyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, and n represents the values 0-1 ;
  • Z 1 represents C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl optionally mono- to pentasubstituted by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl, and
  • Z 2 represents hydrogen, halogen, cyano, nitro, amino or represents C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulphanyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl optionally independently of one another mono- to pentasubstituted by hydroxy, nitro, amino, halogen alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl, and
  • Z 3 represents hydrogen or represents C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl C 1 -C 4 -alkenyl, C 1 -C 4 -alkynyl, aryl or hetaryl optionally independently of one another mono- to pentasubstituted by hydroxy, nitro, amino, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl.
  • a 2 represents CR 3 or nitrogen
  • a 3 represents CR 4 or nitrogen
  • a 4 represents CR 5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
  • R and R 5 independently of one another represent hydrogen, methyl, fluorine or chlorine and
  • R ' and R 4 independently of one another represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, fluoromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 2,2,2- trifluoroethyl, methoxy, ethoxy, n-propoxy, 1 -methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichloro fluoromethoxy, trifluoromethoxy, 2,2,2 -trifluoroethoxy, 2-chloro-2,2- difluoroethoxy, pentafluoroethoxy, N-methoxyiminomethyl, 1 -(N-methoxyimino)ethyl, methylsulfanyl, trifluoromethylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl
  • W represents oxygen or sulphur
  • Q represents hydrogen, methyl, ethyl, n-propyl, 1 -methylethyl, 1 , 1 -dimethyl ethyl, 1 -methylpropyl, n-butyl, 2 -methylpropyl, 2-methylbutyl, hydroxyethyl, 2 -hydroxypropy 1, cyanomethyl, 2- cyanoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 -trifluoromethylethyl, 2,2- difluoropropyl, 3,3,3-trifluoropropyl, 2,2-dimethyl-3-fluoropropyl, cyclopropyl, 1 - cyanocyclopropyl, 1 -methoxycarbonylcyclopropyl, l -(N-methylcarbamoyl)cyclopropyl, 1- carbamoylcyclopropyl, 1 -car
  • R 6 independently of one another represent halogen, cyano, nitro, amino, methyl, ethyl, propyl, 1 - methylethyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, 2,2- difluoroethoxy, 2,2,2 -trifluoroethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methylsulphanyl, methylsulphinyl, methylsulphonyl, trifluoromethylsulphonyl, trifluoromethylsulphanyl, trifluoromethylsulphinyl, and n represents the values 0-1 ;
  • Z 1 represents methyl, ethyl, 1 , 1 -dimethylethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, 1 -fluoroethyl, 1 -fluoro- 1 -methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2- tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2 -trichloroethyl, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoroisopropyl
  • Z 3 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, ethenyl, 1 -propenyl, 1 -propynyl, 1 -butynyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 -fluoro- 1 -methylethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,5- dichlorophenyl, 3 ,4-dichlorophenyl, 2,6-dichlorophenyl, 2,6-dichloro-4-
  • Z 1 represents trifluoromethyl, 1 -chlorocyclopropyl, 1 -fluorocyclopropyl or pentafluoroethyl,
  • Z 2 represents trifluoromethyl, nitro, methylsulphanyl, methylsulphinyl, methylsulphonyl, fluorine, chlorine, bromine, cyano or iodine,
  • Z 3 represents methyl, ethyl, n-propyl or hydrogen
  • ⁇ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, methoxy c arbony 1, ethoxyc arbony 1, n- propoxy c arbony 1, isopropoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, cyanomethyl, 2- cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2-ylmethyl, pyrid-3 -ylmethyl, pyrid-4 -ylmethy 1, 4- chloropyrid-3 -ylmethyl,
  • a 1 , A 2 and A 4 each represent CH, where
  • a 2 may alternatively also represent CH or N,
  • A3 represents CR 4
  • R 4 represents fluorine, chlorine, bromine or iodine
  • R 4 may alternatively also represent methyl, ethyl, fluorine, chlorine, bromine or iodine,
  • T represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
  • R 6 represents hydrogen, methyl, ethyl, 2-methylethyl, 2,2-dimethylethyl, fluorine, chlorine, bromine, iodine, cyano, nitro, trifluoromethyl, amino, or alternatively
  • R 6 represents hydrogen, methyl, ethyl, 2-methylethyl, 2,2-dimethylethyl, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, amino,
  • W represents oxygen
  • Q represents hydrogen, methyl, ethyl, n-propyl, 1 -methylethyl, 1 , 1 -dimethylethyl, n-butyl, 1- methylpropyl, 2-methylpropyl, 2-methylbutyl, hydroxyniethyl, hydroxyethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1 - trifluoromethylethyl, 2,2-difluoropropyl, 3,3,3 -trifluoropropy 1, 2,2-dimethyl-3-fluoropropyl, cyclopropyl, 1 -cyanocyclopropyl, 1 -methoxycarbonylcyclopropyl, 1 -(N- methylcarbamoyl)cyclopropyl, 1 -carbamoylcyclo
  • Q represents phenyl, naphthyl, pyridazine, pyrazine, pyrimidine, triazine, pyridine, pyrazole, thiazole, isothiazole, oxazole, isoxazole, triazole, imidazole, furan, thiophene, pyrrole, oxadiazole, thiadiazole substituted by 0, 1, 2 or 3 substituents V, where
  • V independently of one another represents fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2- tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, heptafluoro -n-propy 1, heptafluoroisopropyl, nonafluoro-n- butyl, cyclo
  • Z 1 represents CF 2 CF 3
  • Z 2 represents CF3
  • Z 3 represents methyl, ethyl, phenyl, 4-N02-phenyl, 3 -chloropyridin-2-yl
  • the radicals R 1 , R 6a represent hydrogen or methyl
  • R 6b represents hydrogen, methyl or CF 3
  • a 1 , A 4 represent C-H
  • a 2 represents C-H or C-F
  • a 3 represents C-H or C-Cl
  • W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, benzyl, cyclopropyl, 2 -thienylmethyl, carbamoylthiocyclopropyl, pyrid-4-yl, 2,2,2-trifluoroethyl, methylsulphonyl, thietan-3-yl, 1 - c arbamoy Icy c lopropyl .
  • Z 1 represents CF 2 CF 3
  • Z 2 represents CF3
  • Z 3 represents methyl, ethyl, phenyl, 4-N02-phenyl, 3- chloropyridin-2 -y 1
  • the radicals R 1 , R 6a represent hydrogen or methyl
  • R 6b represents hydrogen, methyl or CF 3
  • a 1 , A 4 represent C-H
  • a 2 represents N
  • a 3 represents C-H or C-Cl
  • W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, benzyl, cyclopropyl, 2- thienylmethyl, carbamothioylcyclopropyl, pyrid-4-yl, 2,2,2-trifluoroethyl, methylsulphonyl, thietan-3-yl, 1 -carbamoylcyclopropyl.
  • alkyl on its own or as part of a chemical group - represents straight- chain or branched hydrocarbons preferably having 1 to 6 carbon atoms such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1 ,2-dimethylpropyl, 1 , 1 -dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,2-dimethylpropyl, 1 ,3 -dimethylbutyl, 1 ,4-dimethylbutyl, 2,3 -dimethylbutyl, 1
  • alkyl groups having 1 to 4 carbon atoms such as, inter alia, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl.
  • the alkyl groups according to the invention may be substituted by one or more identical or different radicals.
  • alkenyl on its own or as part of a chemical group - represents straight- chain or branched hydrocarbons preferably having 2 to 6 carbon atoms and at least one double bond such as, for example, vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1 -methyl-2 -propenyl, 2 -methyl-2 - propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-2 -butenyl, 2 -methyl -2 -buteny 1, 3 -methyl-2 - butenyl, 1 -methyl-3 -butenyl, 2-methyl-3-butenyl, 3 -methyl-3 -butenyl, 1 , 1 -dimethyl-2 -propenyl, 1,2- dimethyl-2 -propenyl, 1 -ethyl-2 -propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,
  • alkenyl groups having 2 to 4 carbon atoms such as, inter alia, 2-propenyl, 2-butenyl or 1- methyl -2 -propenyl .
  • the alkenyl groups according to the invention may be substituted by one or more identical or different radicals.
  • alkynyl on its own or as part of a chemical group - represents straight- chain or branched hydrocarbons preferably having 2 to 6 carbon atoms and at least one triple bond such as, for example, 2-propynyl, 2-butynyl, 3 -butynyl, 1 -methyl-2 -propynyl, 2-pentynyl, 3-pentynyl, 4- pentynyl, 1 -methyl-3 -butynyl, 2 -methyl-3 -butynyl, 1 -methyl -2 -butynyl, 1 , 1 -dimethyl -2 -propynyl, 1 - ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2 -pentynyl, 1 -methyl-3 - pentynyl,
  • alkynyl groups having 2 to 4 carbon atoms such as, inter alia, ethynyl, 2-propynyl or 2 -butynyl - 2-propenyl.
  • the alkynyl groups according to the invention may be substituted by one or more identical or different radicals.
  • cycloalkyl on its own or as part of a chemical group - represents mono-, bi- or tricyclic hydrocarbons preferably having 3 to 10 carbons such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl.
  • Preference is furthermore given to cycloalkyl groups having 3, 4, 5, 6 or 7 carbon atoms such as, inter alia, cyclopropyl or cyclobutyl.
  • alkylcycloalkyl represents mono-, bi- or tricyclic alkylcycloalkyl preferably having 4 to 10 or 4 to 7 carbon atoms such as, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is furthermore given to alkylcycloalkyl groups having 4, 5 or 7 carbon atoms such as, inter alia, ethylcyclopropyl or 4- methylcyclohexyl.
  • the alkylcycloalkyl groups according to the invention may be substituted by one or more identical or different radicals.
  • cycloalkylalkyl represents mono-, bi- or tricyclic cycloalkylalkyl preferably having 4 to 10 or 4 to 7 carbon atoms such as, for example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is furthermore given to cycloalkylalkyl groups having 4, 5 or 7 carbon atoms such as, inter alia, eye lopropylmethy 1 or cyclobutylmethyl.
  • the cycloalkylalkyl groups according to the invention may be substituted by one or more identical or different radicals.
  • halogen represents fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • halogen-substituted chemical groups according to the invention such as, for example, haloalkyl, halocycloalkyl, haloalkyloxy, haloalkylsulphanyl, haloalkylsulphinyl or haloalkylsulphonyl are mono- or polysubstituted by halogen up to the maximum possible number of substituents.
  • the halogen atoms can be identical or different, and can all be attached to one or to a plurality of carbon atoms.
  • halogen represents in particular fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferably fluorine.
  • halocycloalkyl represents mono-, bi- or tricyclic halocycloalkyl having preferably 3 to 10 carbon atoms such as, inter alia, 1 -fluorocyclopropyl, 2-fluorocyclopropyl or 1 - fluorocy c lobuty 1. Preference is furthermore given to halocycloalkyl having 3, 5 or 7 carbon atoms.
  • the halocycloalkyl groups according to the invention may be substituted by one or more identical or different radicals.
  • haloalkyl "hatoalkenyl” or “haloalkynyl” represents halogen-substituted alkyl, alkenyl or alkynyl groups having preferably 1 to 9 identical or different halogen atoms such as, for example, monohaloalkyl such as CH 2 CH 2 C1, CH 2 CH 2 F, CHC1CH 3 , CHFCH3, CH 2 C1, CH 2 F; perhaloalkyl such as CC1 3 or CF 3 or CF 2 CF 3 ; polyhaloalkyl such as CHF 2 , C H. F. CH 2 CHFC1, CHC1 2 , CF2CF2H, CH2CF3.
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , ( KTI. F. OCF 2 CF 3 , OCF 2 CF 3 and OCH 2 CH 2 Cl.
  • haloalkyl groups are trichloromethyl, chlorodifluoromethyl, di chlorofluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2- difluoroethyl, pentafluoroethyl and p entafluoro -t-buty 1.
  • haloalkyl groups having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine and chlorine such as, inter alia, difluoromethyl, trifluoromethyl or 2,2- difluoroethyl.
  • hydroxyalkyl represents a straight-chain or branched alcohol preferably having 1 to 6 carbon atoms such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol and t-butanol. Preference is furthermore given to hydroxyalkyl groups having 1 to 4 carbon atoms.
  • the hydroxyalkyl groups according to the invention may be substituted by one or more identical or different radicals.
  • alkoxy represents a straight-chain or branched O-alkyl preferably having 1 to 6 carbon atoms such as, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy and t-butoxy. Preference is furthermore given to alkoxy groups having 1 to 4 carbon atoms.
  • the alkoxy groups according to the invention may be substituted by one or more identical or different radicals.
  • haloalkoxy represents halogen-substituted straight- chain or branched O- alkyl preferably having 1 to 6 carbon atoms such as, inter alia, difluoromethoxy, trifluoromethoxy, 2,2- difluoroethoxy, 1 , 1 ,2,2-tetrafluoroethoxy, 2,2,2 -trifluoroethoxy and 2-chloro- 1 , 1 ,2 -trifluoroethoxy.
  • the haloalkoxy groups according to the invention may be substituted by one or more identical or different radicals.
  • alkylsulphanyl represents straight-chain or branched S-alkyl preferably having 1 to 6 carbon atoms such as, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n- butylthio, isobutylthio, s-butylthio and t-buty lthio. Preference is furthermore given to alkylsulphanyl groups having 1 to 4 carbon atoms.
  • the alkylsulphanyl groups according to the invention may be substituted by one or more identical or different radicals.
  • haloalkylsulphanylalkyl groups i.e. halogen-substituted alkylsulphanyl groups
  • di fluoromethy lthio trifluoromethylthio, trichloromethylthio, chlorodifluoromethylthio, 1 - fluoroethylthio, 2 -fluoroethy lthio, 2,2-difluoroethylthio, 1 , 1 ,2,2-tetrafluoroethylthio, 2,2,2- trifluoroethylthio or 2-chloro- 1 , 1 ,2-trifluoroethylthio.
  • alkylsulphinyl represents straight-chain or branched alkylsulphinyl preferably having 1 to 6 carbon atoms such as, for example, methylsulphinyl, ethylsulphinyl, n- propylsulphinyl, isopropylsulphinyl, n-butylsulphinyl, isobutylsulphinyl, s-butylsulphinyl and t- butylsulphinyl. Preference is furthermore given to alkylsulphinyl groups having 1 to 4 carbon atoms.
  • the alkylsulphinyl groups according to the invention may be substituted by one or more identical or different radicals.
  • haloalkylsulphinyl groups i.e. halogen-substituted alkylsulphinyl groups
  • difluoromethylsulphinyl trifluoromethylsulphinyl
  • trichloromethylsulphinyl chlorodifluoromethylsulphinyl, 1 -fluoroethylsulphinyl, 2-fluoroethylsulphinyl, 2,2- difluoroethylsulphinyl, 1 , 1 ,2,2-tetrafluoroethylsulphinyl, 2,2,2 -tri fluoroethylsulphinyl and 2-chloro- 1 , 1 ,2 -trifluoro ethylsulphinyl .
  • alkylsulphonyl represents straight-chain or branched alkylsulphonyl preferably having 1 to 6 carbon atoms such as, for example, methylsulphonyl, ethylsulphonyl, n- propylsulphonyl, isopropylsulphonyl, n-butylsulphonyl, isobutylsulphonyl, s-butylsulphonyl and t- butylsulphonyl. Preference is furthermore given to alkylsulphonyl groups having 1 to 4 carbon atoms.
  • the alkylsulphonyl groups according to the invention may be substituted by one or more identical or different radicals.
  • haloalkylsulphonyl groups i.e. halogen-substituted alkylsulphonyl groups
  • difluoromethylsulphonyl trifluoromethylsulphonyl
  • trichloromethylsulphonyl chlorodifluoromethylsulphonyl, 1 -fluoroethylsulphonyl, 2 - fluoro ethylsulphonyl, 2,2- difluoroethylsulphonyl, 1 , 1 ,2,2-tetrafluoroethylsulphonyl, 2,2,2 -trifluoroethylsulphonyl and 2-chloro- 1 , 1 ,2 -tri fluoroethylsulphonyl.
  • the alkylcarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
  • cycloalkylcarbonyl represents straight-chain or branched cycloalkylcarbonyl preferably having 3 to 10 carbon atoms in the cycloalkyl moiety such as, for example, eye lopropyle arbonyl, cyclobutylcarbonyl, eye lopenty lc arbonyl, eye lohexyle arbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, bicyclo[2.2. i]heptyl, bicyclo[2.2.2 ] octy lc arbonyl and adamantylcarbonyl.
  • alkoxycarbonyl alone or as a constituent of a chemical group - represents straight- chain or branched alkoxycarbonyl, preferably having 1 to 6 carbon atoms or having 1 to 4 carbon atoms in the alkoxy moiety such as, for example, methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl.
  • the alkoxycarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
  • alkylaminocarbonyl represents straight-chain or branched alkylaminocarbonyl having preferably 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as, for example, methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl.
  • the alkylaminocarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
  • N,N-dialkylaminocarbonyl represents straight-chain or branched N,N- dialkylaminocarbonyl having preferably 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as, for example, iV ⁇ V-dimethylaminocarbonyl, N,N-diethylaminocarbonyl, N,N-di(n- propylamino)carbonyl, N,N-di(isopropylamino)carbonyl and N,N-di-(s-butylamino)carbonyl.
  • the N,N- dialkylaminocarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
  • aryl represents a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring carbon atoms such as, for example, phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. Furthermore, aryl also represents polycyclic systems such as tetrahydronaphtyl, indenyl, indanyl, fluorenyl, biphenylyl, where the bonding site is on the aromatic system.
  • the aryl groups according to the invention may be substituted by one or more identical or different radicals.
  • substituted aryls are the arylalkyl groups which may likewise be substituted by one or more identical or different radicals in the alkyl and/or aryl moiety.
  • arylalkyl groups are inter alia benzyl and 1 -phenylethyl.
  • heterocycle represents a carbocyclic ring system having at least one ring in which at least one carbon atom is replaced by a heteroatom, preferably by a heteroatom from the group consisting of N, O, S, P, B, Si, Se, and which is saturated, unsaturated or heteroaromatic and may be unsubstituted or substituted by a substituent Z, where the point of attachment is located at a ring atom.
  • the heterocyclic ring contains preferably 3 to 9 ring atoms, especially 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group consisting of N, O, and S, although no two oxygen atoms should be directly adjacent.
  • the heterocyclic rings usually contain not more than 4 nitrogen atoms and/or not more than 2 oxygen atoms and/or not more than 2 sulphur atoms.
  • heterocyclyl radical or the heterocyclic ring is optionally substituted, it can be fused to other carbocyclic or heterocyclic rings, in the case of optionally substituted heterocyclyl, the invention also embraces polycyclic systems such as, for example, 8-azabicyclo[3.2.1 Joctanyl or 1 - azabicyclo[2.2. ljheptyl. In the case of optionally substituted heterocyclyl, the invention also embraces spirocyclic systems such as, for example, l-oxa-5-azaspiro[2.3]hexyl.
  • Heterocyclyl groups according to the invention are, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanyl, dioxolyl, pyrazolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, oxiranyl, azetidinyl, aziridinyl, oxazetidinyl, oxaziridinyl, oxazepanyl, oxazinanyl, azepanyl, oxopyrrolidinyl, dioxopyrrolidinyl, oxomorph
  • heteroarylene i.e. heteroaromatic systems
  • heteroaryl represents heteroaromatic compounds, i.e. completely unsaturated aromatic heterocyclic compounds which fall under the above definition of heterocycles.
  • Heteroaryl groups according to the invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5- oxadiazolyl, azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3- triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl and 1 ,2.4- diazepinyl.
  • the heteroaryl groups according to the invention may also be substituted by one or more identical or different radicals.
  • Substituted groups such as a substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical are, for example, a substituted radical derived from the unsubstituted base structure, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group of halogen, alkoxy, alkylsulphanyl, hydroxyl, amino, nitro, carboxyl or a group equivalent to the carboxyl group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and N,N-dialkylaminocarbonyl, substituted amino such as acylamino, mono- and N,N-dialkylamino, trialkylsilyl and optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted hetero
  • substituted groups such as substituted alkyl etc.
  • substituents in addition to the saturated hydrocarbonaceous radicals mentioned, corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and N,N-dialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- and N,N-dialkenylamino, mono- and ⁇ , ⁇ -dialkynylamino, trialkenylsilyl, trialkynylsilyl, optionally substituted cycloalkenyl, optionally substituted cycloalkynyl, phenyl, phenoxy etc.
  • cyclic systems with those substituents bonded to the ring by a double bond are also included, for example those having an alkylidene group such as methylidene or ethylidene, or an oxo group, imino group and a substituted imino group.
  • radicals When two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partly saturated, unsaturated, for example also aromatic and further substituted.
  • first substituent level may, if they contain hydrocarbon-containing moieties, optionally be further substituted therein (“second substituent level”), for example by one of the substituents as defined for the first substituent level.
  • second substituent level may be further substituted therein, for example by one of the substituents as defined for the first substituent level.
  • substituent levels are possible.
  • substituted radical preferably embraces just one or two substituent levels.
  • Preferred substituents for the substituent levels are, for example, amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxyl, carboxamide, SF 5 , aminosulphonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, N-monoalkylamino, N,N- dialkylamino, N-alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkeny loxyc arbony 1, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylsulphanyl, cycloalkylsulphanyl, alkenylthio,
  • Substituents composed of a plurality of substituent levels are preferably alkoxyalkyl, alkylsulphanylalkyl, alkylsulphanylalkoxy, alkoxyalkoxy, phenethyl, benzyloxy, haloalkyl, halocycloalkyl, haloalkoxy, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, haloalkoxyalkylsulphanyl, haloalkoxyalkanoyl, haloalkoxyalkyl.
  • radicals having carbon atoms preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 or 2 carbon atoms.
  • substituents from the group of halogen, e.g. fluorine and chlorine, (C 1 -C4)-alkyl, preferably methyl or ethyl, (C 1 -C4) -haloalkyl, preferably trifluoromethyl, (C 1 -C4)-alkoxy, preferably methoxy or ethoxy, (C 1 - C4)-haloalkoxy, nitro and cyano.
  • substituents methyl, methoxy, fluorine and chlorine.
  • Substituted amino such as mono- or disubstituted amino means a radical from the group of the substituted amino radicals which are N- substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably N-mono- and TV,N-dialkylamino, (for example methylamino, ethylamino, ⁇ , ⁇ '-dimethylamino, N,N-diethylamino, A T ,7V-di-n-propylamino, N,N-diisopropylamino or N,N-dibutylamino), N-mono- or TV,N- dialkoxyalkylamino groups (for example N-methoxymethylamino, N-methoxyethylamino, N,N- di(methoxymethyl)amino or A r , A- di(methoxy e
  • cyclic amino groups embraces heteroaromatic or aliphatic ring systems having one or more nitrogen atoms.
  • the heterocycles are saturated or unsaturated, consist of one or more optionally fused ring systems and optionally contain further heteroatoms such as, for example, one or two nitrogen, oxygen and/or sulphur atoms.
  • the term also includes groups having a spiro ring or a bridged ring system.
  • the number of atoms which form the cyclic amino group is not limited, and in the case of a one-ring system, for example, can consist of 3 to 8 ring atoms, and in the case of a two-ring system of 7 to 11 atoms.
  • Examples of cyclic amino groups having saturated and unsaturated monocyclic groups having a nitrogen atom as heteroatom which may be mentioned are 1-azetidinyl, pyrrolidino, 2-pyrrolidin- 1 -yl, 1 -pyrrolyl, piperidino, 1 ,4-dihydropyrazin- 1 -yl, 1 ,2,5,6-tetrahydropyrazin- 1 -yl, 1 ,4-dihydropyridin- 1 -yl, 1,2,5,6- tetrahydropyridin- 1 -yl, homopiperidinyl; examples of cyclic amino groups having saturated and unsaturated monocyclic groups having two or more nitrogen atoms as heteroatoms which may be mentioned are 1 -imidazolidinyl, 1 -imidazolyl, 1 -pyrazolyl, 1 -triazolyl, 1 -tetrazolyl, 1 -piperazinyl, 1- homopiperazin
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, (C 1 -Gi)-alkyl, (C 1 -GO-alkoxy, (C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkoxy, (C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 1 - C 4 )-haloalkoxy, (C 1 -C 4 )-alkylsulphanyl, (C 1 -C 4 )-haloalkylsulphanyl, cyano, isocyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophen
  • Optionally substituted cycloalkyl is preferably cycloalkyl, which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, cyano, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkoxy, (C 1 -C 4 )-alkoxy-(C 1 -C 4 )- alkyl, (C 1 -C 4 )-haloalkyl and (C 1 -C 4 )-haloalkoxy, especially by one or two (C 1 -C 4 )-alkyl radicals.
  • Optionally substituted heterocyclyl is preferably heterocyclyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, cyano, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkoxy, (C 1 -C 4 )-alkoxy-(C 1 -C 4 )- alkyl, (C i -C 4 )-haloalkyl, (C i -C 4 ) -haloalkoxy , nitro and oxo, especially mono- or polysubstituted by radicals from the group of halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-haloalky
  • alky 1 - sub stituted heteroaryl groups are furylmethyl, thienylmethyl, pyrazolylmethyl, imidazolylmethyl, 1 ,2,3- and 1 ,2,4-triazolylmethyl, isoxazolylmethyl, thiazolylmethyl, isothiazolylmethyl, 1,2,3-, 1,3,4-, 1 ,2,4- and 1 ,2,5-oxadiazolylmethyl, azepinylmethyl, pyrrolylmethyl, pyridylmethyl, pyridazinylmethyl, pyrimidinylmethyl, pyrazinylmethyl, 1,3,5-, 1,2,4- and 1,2,3- triazinylmethyl, 1,2,4-, 1,3,2-, 1,3,6- and 1 ,2,6-oxazinylmethyl, oxepinylmethyl, thiepinylmethyl and 1 ,2,4-diazepinylmethyl.
  • the compounds of formula (I) described in detail above are combined with other active compounds, namely (1) ectoparasiciticides in particular having acaricidal and/or insecticidal activity; (2) anthelmintics in particular having nematicidal, trematicidal and/or cestodicial activity; (3) anti-protozoal agents, in order to widen the activity spectrum.
  • active compounds namely (1) ectoparasiciticides in particular having acaricidal and/or insecticidal activity; (2) anthelmintics in particular having nematicidal, trematicidal and/or cestodicial activity; (3) anti-protozoal agents, in order to widen the activity spectrum.
  • Potential mixing components for compounds of the formula (I) according to the invention for applications in animal health may be one or more compounds of the groups of active compounds listed below. The following active compounds can be used in the present combinations:
  • Exemplary active ingredients from the group of ectoparsiticides, as mixing partners, include, without limitation, the following insecticidal and/or acaricidal compounds
  • acetylcholinesterase (AChE) inhibitors for example carbamates, e.g. alanycarb, aldicarb,
  • aldoxycarb aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate, formparanate or organophosphates, e.g.
  • GABA-gated chloride channel antagonists for example organochlorines, e.g. camphechlor,
  • chlordane endosulfan, heptachlor, lindane or m-diamides, e.g. broflanilide or phenylpyrazoles, e.g. flufiprole, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole or arylisoxazo lines, not excluding related classes with pyrroline or pyrrolidine moiety replacing the isoxazoline ring , e.g.
  • sodium channel modulators / voltage-dependent sodium channel blockers for example pyrethroids, e.g. heptafluthrin, tetramethylfluthrin, acrinathrin, allethrin (d-cis-trans, d-trans-), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-s-cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin (lambda-), cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin
  • methoxychlor or oxadiazines e.g. indoxacarb or semicarbazones, e.g. metaflumizone;
  • acetylcholine receptor agonists/ antagonists for example neonicotinoids, e.g. imidacloprid, thiacloprid, imidaclothiz, nitenpyram, thiamethoxam, clothianidin, dinotefuran, acetamiprid, nithiazine, paichongding, cycloxaprid, guadipyr, N-[(2E)-l-[(6-chloropyridin-3-yl)methyl]pyridin- 2(lH)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012/029672), (3E)-3-[l-[(6-chloro-3- pyridyl)methyl] -2-pyridylidene]- 1 ,1,1 -trifluoro-propan-2-one (known from WO2013/144213) or sulfoximine insecticides, e.g.
  • sulfoxaflor or butenolides e.g. flupyradifurone or nereistoxin analogues, e.g. cartap, bensultap, thiocyclam, thiosultap sodium, thiocyclam hydrogen oxalate; acetylcholine receptor modulators, for example spinosynes, e.g. spinosad, spinetoram or zwitterionic insecticides, e.g.
  • ligand-gated chloride channel activators for example macrocyclic lactones, e.g. emamectin benzoate, abamectin, ivermectin, milbemectin, milbemycin oxime, latidectin, lepimectin, selamectin, doramectin, eprinomectin, moxidectin, nemadectin or indole diterpenes, e.g.
  • macrocyclic lactones e.g. emamectin benzoate, abamectin, ivermectin, milbemectin, milbemycin oxime, latidectin, lepimectin, selamectin, doramectin, eprinomectin, moxidectin, nemadectin or indole diterpenes, e.g.
  • juvenile hormone mimetics for example juvenile hormon analogues, e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxyfen, triprene;
  • juvenile hormon analogues e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxyfen, triprene;
  • selective homopteran feeding blockers for example triazinones, e.g. pymetrozine or pyridine carboxamides, e.g. flonicamid;
  • Bios, hormones or pheromones for example natural products, e.g. codlemone, thuringiensin or neem components, e.g. azadirachtin A or other classes, e.g. preparations based on bacillus firmus (i-1582; bioneem; votivo);
  • inhibitors of oxidative phosphorylation for example organotin compounds, e.g. azocyclotin, cyhexatin, fenbutatin-oxide or other classes, e.g.
  • decouplers of oxidative phosphorylation by interruption of H-proton gradients for example dinitrophenols, e.g. binapacryl, dinobuton, dinocap, DNOC or pyrroles, e.g. chlorfenapyr or other decouplers, e.g. sulfluramid; inhibitors of chitin biosynthesis or cuticle development, for example benzoylureas, e.g.
  • ecdysone agonists/ disrupters for example diacylhydrazines, e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide, fufenozide;
  • diacylhydrazines e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide, fufenozide;
  • octopaminergic agonists for example amidine derivatives, e.g. amitraz, cymiazole, demiditraz, chlormebuform;
  • mitochondrial complex I electron transport inhibitors for example METIs, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, dicofol or rotenones, e.g.
  • METIs e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, dicofol or rotenones, e.g.
  • mitochondrial complex 11 electron transport inhibitors for example beta-ketonitrile derivatives, e.g. cyenopyrafen, cyflumetofen or hydrazones, e.g. hydramethylnon or other classes, e.g. fluopyram, 4- (7-bromo- 1 ,3 -benzodioxol-5 -yl) - 1 -(3 -methoxypyrazin-2-yl) -3 -(trifluoromethyl) - 1 H-pyrazol-5 - amine (known from WO 2010136145, example 74, CAS No 1257061-92-9);
  • beta-ketonitrile derivatives e.g. cyenopyrafen, cyflumetofen or hydrazones, e.g. hydramethylnon or other classes, e.g. fluopyram, 4- (7-bromo- 1 ,3 -benzodioxol-5
  • mitochondrial complex I I I electron transport inhibitors for example quinones, e.g. acequinocyl or strobilurines, e.g. flufenoxystrobin, pyriminostrobin or other classes, e.g. fluacrypyrim;
  • quinones e.g. acequinocyl or strobilurines, e.g. flufenoxystrobin, pyriminostrobin or other classes, e.g. fluacrypyrim;
  • inhibitors of acetylCoA carboxylase for example tetronic and tetramic acids, e.g. spirodiclofen, spiromesifen, spirotetramat, 3 -(2 , 5 -dimethy lpheny 1) -4 -hydroxy- 8 -methoxy- 1 ,8- diazaspiro[4.5]dec-3-en-2-one (known from WO2009/049851), butyl [2-(2,4-dichlorophenyl)-3- oxo-4-oxaspiro[4.5]dec-l -en-l-yl] carbonate (known from CN 102060818) or other classes, e.g.
  • tetronic and tetramic acids e.g. spirodiclofen, spiromesifen, spirotetramat, 3 -(2 , 5 -dimethy lpheny 1) -4 -hydroxy- 8 -methoxy
  • ryanodine receptor modulators for example phthalic acid diamides, e.g. flubendiamide, cyhalodiamide or anthranilamides, e.g. chlorantraniliprole, cyantraniliprole, tetraniliprole, tetrachloroantraniliprole (SYP9080), cyclaniliprole, methyl 2-[2-( ⁇ [3-bromo- 1 -(3-chloropyridin-2- yl)-lh-pyrazol-5-yl]carbonyl ⁇ amino)-5-cyano-3-methylbenzoyl]-2-methylhydrazinecarboxylate (known from WO2005/085216), methyl 2-[3,5-dibromo-2-( ⁇ [3-bromo-l-(3-chloropyridin-2-yl)-lh- pyrazol-5 -yl] carbonyl ⁇ amino)benzoyl]
  • mite growth inhibitors e.g. clofentezine, etoxazole, hexythiazox, amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, quinomethionate, chlordimeform, chlorobenzilate, clothiazoben, cycloprene, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, f!ufenerim, flutenzin, gossyplure, japonilure, metoxadiazone, petroleum, potassium oleate, pyridalyl, tetrasul, triarathene or other classes, e.g.
  • diflovidazin, chinomethionat, pyrifluquinazon or feeding inhibitors e.g. cryolite; ⁇ compounds, from other classes, e.g. 4-(but-2-yn-l-yloxy)-6-(3-chlorophenyl)pyrimidine (known from WO2003/076415), fluazaindolizine, afidopyropen, flometoquin, fluensulfone, fluhexafon, iprodione, meperfluthrin, N-(methylsulfonyl)-6-[2-(pyridin-3-yl)-l,3-thiazol-5-yl]pyridine-2- carboxamide (known from WO2012/000896), N-[2-(5-amino-l ,3,4-thiadiazol-2-yl)-4-chloro-6- methylphenyl]-3-bromo-l -(3-chloropyridin-2-y
  • MGK264 N- octylbicycloheptenecarboxamide
  • PBO piperonyl butoxide
  • acetylcholine receptor agonists/ antagonists acetylcholine receptor modulators
  • GABA-gated chloride channel antagonists ligand-gated chloride channel activators
  • octopaminergic agonists sodium channel modulators / voltage- dependent sodium channel blockers.
  • active ingredients from the group of anthelmintics, as mixing partners include, without limitation, the following nematicidally, trematicidally and/or cestocidally active compounds:
  • milbemectin latidectin, lepimectin, selamectin, doramectin, eprinomectin, moxidectin, milbemycin, nemadectin;
  • amidantel deacylated amidantel (dAMD), tribendimidine ;
  • paraherquamides • from the class of paraherquamides, for example: derquantel, paraherquamide;
  • salicylanilides for example: bromoxanide, brotianide, clioxanide, closantel, niclosamide, oxyclozanide, rafoxanide, tribromsalan;
  • organophosphates for example: coumaphos, haloxon, crufomate,
  • piperazines for example: piperazine, hydroxyzine;
  • tetracyclines for example: chlorotetracycline, doxycyclin, oxytetracyclin,
  • amoscanate bephenium
  • bunamidine clonazepam
  • active ingredients from the group of antiprotozoal active compounds include, without limitation, the following active compounds:
  • monensin • from the class of macrocyclic lactones, for example: erythromycin, milbemycin;
  • sulfonamides for example: sulfaquinoxaline, trimethoprim, sulfaclozin;
  • Babesia canis canis • from the class of vaccines or antigenes from microorganisms, for example: Babesia canis canis, Babesia canis rossi, Babesia canis vogeli, Dictyocaulus viviparus, Eimeria acervulina, Eimeria brunetti, Eimeria maxima, Eimeria mitis, Eimeria necatrix, Eimeria praecox, Eimeria tenella, Leishmania infantum;
  • the active compounds identified here by their common names are known and are described, for example, in the pesticide handbook ("The Pesticide Manual” 14th Ed., British Crop Protection Council 2006) or can be found on the Internet (e.g. http://www.alanwood.net/pesticides).
  • the active compounds described herein may form salts and in this case may be used in salt form as well.
  • Salts which are suitable according to the invention for example salts with bases or acid addition salts, are all customary non-toxic salts, preferably agriculturally and/or physiologically acceptable salts.
  • salts with bases or acid addition salts Preference is given to salts with inorganic bases such as, for example, alkali metal salts (e.g.
  • alkaline earth metal salts e.g. calcium or magnesium salts
  • ammonium salts or salts with organic bases in particular with organic amines, such as, for example, triethylammonium, dicyclohexylammonium, N,A P - dibenzylethylenediammonium, pyridinium, picolinium or ethanolammonium salts
  • salts with inorganic acids e.g. hydrochlorides, hydrobromides, dihydrosulphates, trihydrosulphates or phosphates
  • salts with organic carboxylic acids or organic sulphoacids e.g.
  • t-amines such as some of the compounds contemplated herein are capable of forming N-oxides, which also represent salts according to the invention.
  • the compounds described herein may, depending on the nature of the substituents, be in the form of geometric and/or optically active isomers or corresponding isomer mixtures in different compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixture of these isomers. If appropriate, the compounds may be present in various polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are provided by the invention and can be used in accordance with the invention.
  • the present invention is directed to combinations of compounds of formula (I) with ectoparasiciticides, anthelmintics or anti-protozoal agents.
  • the compounds of the general formula (I) can be mixed or applied jointly with other ectoparasiticidal, anthelmintic or anti-protozoal agents.
  • the spectrum of activity of the agents is widened and/or improved as compared to the the individual active compounds in these applications.
  • the active compounds according to the present invention act against animal parasites, in particular ectoparasites and/or endoparasites.
  • animal parasites in particular ectoparasites and/or endoparasites.
  • endoparasites includes especially helminths such as cestodes, nematodes or trematodes, and protozoa such as coccidia.
  • Ectoparasites are typically and preferably arthropods, especially insects such as flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; or acarids such as ticks, for example hard ticks or soft ticks, or mites such as scab mites, harvest mites, bird mites and the like, and also aquatic ectoparasites such as copepods.
  • insects such as flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like
  • acarids such as ticks, for example hard ticks or soft ticks, or mites such as scab mites, harvest mites, bird mites and the like, and also aquatic ectoparasites such as copepods.
  • parasites include the following ectoparasites (in particular insects, acarids):
  • Anoplurida for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phthirus spp. and Solenopotes spp.; specific examples are: Linognathus setosus, Linognathus vituli, Linognathus ovillus, Linognathus oviformis, Linognathus pedalis, Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotes capillatus;
  • Nematocerina and Brachycerina for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora s
  • Pulex spp. Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.
  • specific examples are: Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis; From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
  • helminths include platyhelmintha (e.g. monogenea, cestodes and trematodes), nematodes, acanthocephala, and pentastoma. Additional exemplary helminths include , without any limitation:
  • Monogenea e.g.: Gyrodactylus spp., Dactylogyrus spp., Polystoma spp..
  • Cestodes From the order of the Pseudophyllidea for example: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp..
  • Cyclophyllida for example: Mesocestoides spp., Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosoma spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., Andyra spp., Bertiella spp., Taenia spp., Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp..
  • Trematodes From the class of the Digenea for example: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoeluin spp., Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoron spp., Gigantocoty
  • Trichinellida for example: Trichuris spp., Capillaria spp., Trichomosoides spp., Trichinella spp..
  • Parelaphostrongylus spp. Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp., Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp.
  • Acantocephala From the order of the Oligacanthorhynchida z.B: Macracanthorhynchus spp., Prosthenorchis spp.; from the order of the Polymorphida for example: Filicollis spp.; from the order of the Moniliformida for example: Moniliformis spp.,
  • Echinorhynchida for example Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp.
  • Pentastoma From the order of the Porocephalida for example Linguatula spp.
  • Exemplary parasitic protozoa include , without any limitation:
  • Mastigophora such as, for example, Trypanosomatidae, for example, Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, L. donovani, L. tropica, such as, for example, Trichomonadidae, for example, Giardia lamblia, G. canis.
  • Trichomonadidae for example, Giardia lamblia, G. canis.
  • S arcomastigophora such as Entamoebidae, for example, Entamoeba histolytica, Hartmanellidae, for example, Acanthamoeba sp., Harmanella sp. Apicomplexa (Sporozoa), such as Eimeridae, for example, Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bo vis, E. brunetti, E. canis,
  • Besnoitia besnoitii such as Sarcocystidae, for example, Sarcocystis bovicanis, S. bovihominis, S. ovicanis, S. ovifelis, S. neurona, S. spec, S. suihominis, such as Leucozoidae, for example,
  • Leucozytozoon simondi such as Plasmodiidae, for example, Plasmodium berghei, P. falciparum, P. malariae, P. ovale, P. vivax, P. spec, such as Piroplasmea, for example, Babesia argentina, B. bovis, B. canis, B. spec, Theileria parva, Theileria spec, such as Adeleina, for example, Hepatozoon canis, H. spec.
  • the combinations according to the invention are also suitable for controlling arthropods, helminths and protozoa which attack animals.
  • the animals include agricultural livestock, for example cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, cultured fish, honey bees.
  • the animals also include domestic animals - also referred to as companion animals - for example dogs, cats, caged birds, aquarium fish, and what are known as test animals, for example hamsters, guinea pigs, rats and mice.
  • control of these ectoparasites - or, in other embodiments, helminths and/or protozoa - should reduce cases of death and improve the performance (for meat, milk, wool, hides, eggs, honey etc.) and the health of the host animal, and so the use of the active compounds according to the invention enables more economically viable and easier animal husbandry.
  • control of the parasites can also contribute to preventing the transmission of infectious substances.
  • control as used herein with regard to the field of animal health means that the active compounds act by reducing the occurrence of the parasite in question in an animal infested with such parasites to a harmless level. More specifically, "control” as used herein means that the active compound kills the parasite in question, retards its growth or inhibits its proliferation.
  • the combinations according to the invention can be employed directly when they are used for the treatment of animals. They are preferably employed in the form of pharmaceutical compositions which may comprise the pharmaceutically acceptable excipients and/or auxiliaries known in the prior art. In general, such compositions comprise from 0.01 to 98% by weight of active compound, preferably from 0.5 to 90% by weight.
  • the combinations are employed (administered) in a known manner, by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, for example by injection (intramuscular, subcutaneous, intravenous, intraperitoneal inter alia), implants, by nasal administration, by dermal administration in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, earmarks, tailmarks, limb bands, halters, marking devices, etc.
  • enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories
  • parenteral administration for example by injection (intramuscular, subcutaneous
  • the active compounds can be formulated as a shampoo or as suitable formulations applicable in aerosols or unpressurized sprays, for example pump sprays and atomizer sprays, In the case of employment for livestock, poultry, domestic pets, etc., the active compounds can be employed as formulations (for example powders, wettable powders ["WP"], emulsions, emulsifiable concentrates ["EC”], free-flowing compositions, homogeneous solutions and suspension concentrates ["SC”]), which contain the active compounds in an amount of 1 to 80% by weight, directly or after dilution (e.g. 100- to 10 000-fold dilution ), or they can be used as a chemical bath.
  • the compounds according to general formula (I) can be prepared as described in WO2014/122083 .
  • the reaction mixture is concentrated to dryness and the residue is taken up in ethyl acetate.
  • the organic phase is washed twice with water, dried over sodium sulphate, filtered and concentrated to dryness.
  • the crude product is purified by column chromatography on silica gel.
  • the reaction mixture is concentrated to dryness and the residue is taken up in ethyl acetate.
  • the organic phase is washed twice with water, dried over sodium sulphate, filtered and concentrated to dryness.
  • the crude product is purified by column chromatography on silica gel.
  • reaction mixture is acidified with 1M hydrochloric acid and the product is extracted with ethyl acetate.
  • the organic phase is washed with saturated sodium chloride solution, dried over sodium sulphate, filtered and concentrated under reduced pressure. This gives 127 mg of 2-chloro-5- ⁇ 1 -[ 1 -methyl-3 -(pentafluoroethyl)-4-(trifluoromethyl)- 1 H-pyrazol-5 - yl] - 1 H-imidazol-4-yl ⁇ benzoic acid as a colourless solid.
  • the stated mass is the peak of the isotope pattern of the [M+H] + ion of the highest intensity; if the [M- H ]- ion was detected, the stated mass is marked with 2 .
  • the stated mass is the peak of the isotope pattern of the [M-H]- ion of the highest intensity. If the mass was determined by a GCMS (see below for methods) measurement, the stated mass is marked with 3 . *) Note regarding the determination of the logP values and mass detection: The determination of the given logP values was carried out in accordance with EEC Directive 79/831 Annex V.A8 by 1 1 PLC (High Performance Liquid Chromatography) on a reversed-phase column (CI 8).
  • Agilent 1100 LC system 50*4.6 Zorbax Eclipse Plus C18 1.8 micron; mobile phase A: acetonitrile (0.1% formic acid); mobile phase B: water (0.09% formic acid); linear gradient from 10%i acetonitrile to 95%i acetonitrile in 4.25 min, then 95% acetonitrile for a further 1.25 min; oven temperature 55°C; flow rate: 2.0 ml/min.
  • Mass detection is carried out via an Agilend MSD system.
  • MS instrument Waters SQD; UPLC instrument: Waters U PLC: column: Zorbax SB-Aq (Agilent), 50 mm x 2.1 mm, 1.8 ⁇ m; mobile phase A: water + 0.025%o formic acid, mobile phase B: acetonitrile (ULC) + 0.025% formic acid; gradient: 0.0 min 98%A - 0.9 min 25%A - 1.0 min 5%A - 1.4 min 5%A 1.41 min 98%A - 1 .5 min 98%A; oven: 40°C; flow rate: 0.600 ml/min; UV detection: DAD; 210 nm.
  • Solvent dimethyl sulphoxide To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.
  • Tick nymphs (Amblyomma hehraeum) are placed into perforated plastic beakers and immersed in the desired concentration for one minute. The ticks are transferred on filter paper into a Petri dish and stored in a climate-controlled cabinet. After 42 days, the kill in % is determined. 100% means that all of the ticks have been killed; 0% means that none of the ticks have been killed.
  • Test animals cattle ticks (Boophilus microplus) Parkhurst strain, SP-resistant
  • the active compound solution is diluted with water to the concentration desired in each case.
  • This active compound preparation is pipetted into tubes. 8-10 adult engorged female cattle ticks (Boophilus microplus) are transferred into a further tube with holes. The tube is immersed into the active compound formulation, and all ticks are completely wetted. After the liquid has run out, the ticks are transferred on filter discs into plastic dishes and stored in a climate-controlled room. The activity is assessed after 7 days by laying of fertile eggs. Eggs whose fertility is not visible from the outside are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all eggs are fertile.
  • Boophilus microplus - injection test (BOOPMI Inj)
  • Solvent dimethyl sulphoxide To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of solvent, and the concentrate is diluted with solvent to the desired concentration.
  • the activity is assessed after 7 days by laying of fertile eggs. Eggs whose fertility is not visible from the outside are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all eggs are fertile.
  • the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 20 ⁇ g/animal: Ia-1, I a -2. Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic-10, Ic-11, Ic-12, Ic-13, Ic- 14, Ic-16, Ic-17, Ic-18, Ic-19, Ic-20, lc-2 1.
  • active compound 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide. Dilution with titrated cattle blood gives the desired concentration. About 20 unfed adult cat fleas ( Ctenocephalides felis) are placed into a chamber which is closed at the top and bottom with gauze. A metal cylinder whose bottom end is closed with a parafilm is placed onto the chamber. The cylinder contains the blood/active ingredient preparation, which can be imbibed by the fleas through the parafilm membrane.
  • the kill in % is determined. 100% means that all of the fleas have been killed; 0% means that none of the fleas have been killed.
  • the following compounds of the Preparation Examples show an efficacy of 100 at an application rate of 100 ppm: Ia-1 , Ia-2, Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic- 11, Ic-12, Ic-13, Ic-16, Ic-18, Ic-19, Ic-20, Ic-21, Ic-22, Ic-23, Ic-24, Ic-27, Ic-28, Ic-29, lc-3 1.
  • Solvent dimethyl sulphoxide To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide, and the concentrate is diluted with water to the desired concentration.
  • the following compounds of the Preparation Examples show an efficacy of 100%o at an application rate of 100 ppm: Ia-1 , Ia-2, Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic- 10, Ic-11, Ic-12, Ic-13, Ic-14, Ic-16, Ic-17, Ic-18, Ic- 19, Ic-20, Ic-2 ! .
  • Ic-22, Ic-23, lc-24 show an efficacy of 100%o at an application rate of 100 ppm: Ia-1 , Ia-2, Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic- 10, Ic-11, Ic-12, Ic-13, Ic-14, Ic-16, Ic-17, Ic-18, Ic- 19, Ic-20, Ic-2 ! .
  • Vessels containing a sponge treated with sugar solution and the active compound preparation of the desired concentration are populated with 10 adult houseflies ⁇ Musca domestica).
  • the kill in % is determined. 100% means that all of the flies have been killed; 0% means that none of the flies have been killed.
  • the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of lOO ppm: Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-7, Ic-11, Ic- 12, Ic-16, Ic-18, Ic-19, Ic-21, Ic-23, Ic-24.
  • the tubes After evaporation of the solvent, the tubes are populated with 5-10 adult cat fleas ( Ctenocephalides felis), sealed with a perforated plastic lid and incubated in a horizontal position at room temperature and ambient humidity. After 48 h, the efficacy is determined. To this end, the test tubes are stood upright and the fleas are knocked to the floor of the tube. Fleas which remain motionless on the floor or move in an uncoordinated manner are considered to be dead or moribund. A substance shows good activity against Ctenocephalides felis if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 ⁇ g/cm 2 . An efficacy of 100% means that all fleas were dead or moribund. 0% efficacy means that none of the fleas had been damaged.
  • the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 5 ⁇ g/cm 2 : Ia-1, Ia-2, Ib-2, lb-3.
  • the tubes After evaporation of the solvent, the tubes are populated with 5-10 adult dog ticks ⁇ Rhipicephalus sanguineus), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at room temperature and ambient humidity. After 48 h, the efficacy is determined. To this end, the ticks are knocked to the floor of the tube and incubated on a hotplate at 45-50°C for at most 5 min. Ticks which remain motionless on the floor or move in an uncoordinated manner such that they are not able to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.
  • a substance shows good activity against Rhipicephalus sanguineus if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 ⁇ g/cm 2 .
  • An efficacy of 100% means that all ticks were dead or moribund. 0% efficacy means that none of the ticks had been damaged.
  • the following compounds of the Preparation Examples show an efficacy of 100%o at an application rate of 1 ⁇ g/cm 2 : Ia-1, Ia-2, Ib-3. Ic-1, Ic-2, Ic-11 , Ic-16, Ic-18, Ic-19, Ic-21, Ic- 23, Ic-24, Ic-25, Ic-27, Ic-36, Ic-37, Ic-43, Ic-46, Ic-47, Ic-48, Ic-49, Ic-54, Ic-59, Ic-66, Ic-68, Ic-70, Ic- 77, Ic-78, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-94, Ic-95, Ic-96, Ic- 103, Ic-109, Ic- 111, Ic- 112, Ic-143, Ic-151, Ic-152.
  • the tubes are populated with 5-10 adult castor bean ticks ⁇ Ixodes ricinus), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at 22°C and 90%) humidity in a climate-controlled cabinet. After 48 h, the efficacy is determined. To this end, the ticks are knocked to the floor of the tube and incubated on a hotplate at 45-50°C for at most 5 min. Ticks which remain motionless on the floor or move in an uncoordinated manner such that they are not able to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.
  • a substance shows good activity against Ixodes ricinus if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 ⁇ g/cm 2 .
  • An efficacy of 100%> means that all ticks were dead or moribund. 0%> efficacy means that none of the ticks had been damaged.
  • the following compounds of the Preparation Examples show an efficacy of 100 at an application rate of 5 ⁇ g/cm 2 : Ia-1, la-2. Ic- 1, Ic-2, Ic-11, Ic-16, Ic-21, Ic-23, Ic-37, Ic-47, Ic- 48, Ic-81, Ic-83, Ic-84, Ic-86, Ic-87, Ic-90, Ic-94
  • the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 5 ⁇ g/cm 2 : ib-3.
  • Ic-18 In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 1 ⁇ g/cm 2 : Ia-1, Ia-2. Ic- 1, Ic-2, Ic-16, Ic-23, Ic-37, Ic-81, Ic-84, Ic-90, Ic- 94
  • the tubes are populated with 5-10 bont tick nymphs (Amblyomma hebraeum), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at 27°C and 85%) humidity in a climate-controlled cabinet. After 48 h, the efficacy is determined. To this end, the ticks are knocked to the floor of the tube and incubated on a hotplate at 45-50°C for at most 5 min. Ticks which remain motionless on the floor or move in an uncoordinated manner such that they are not able to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.
  • a substance shows good activity against Amblyomma hebraeum nymphs if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 ⁇ g/cm 2 .
  • An efficacy of 100%> means that all ticks were dead or moribund. 0%> efficacy means that none of the ticks had been damaged.
  • mice 5 rats per group are used, the results are reported as arithmetic means.
  • all rats Prior to the tick infestations, all rats are provided with collars.
  • the rats are sedated with 30-50 ⁇ of medetomidine hydrochloride (e.g. Domitor®) s.c/rat.
  • All rats are infested on day 0 (at least 1 h after the treatemt), day 7, day 14 etc. with 30 un engorged Dermacentor variabilis nymphs.
  • day 2 day 9, day 16 etc. the collar is removed and the entire body of the sedated rats is examined systematically for ticks. Ticks are removed with tweezers and, by being squashed on blotting paper, examined for blood sucked.
  • the efficacy of the treatment is determined by comparison with a placebo-treated control group.
  • a compound is considered to be highly effective if, at a dosage of 10 mg/kg, it shows an efficacy of 90% against nymphs of the American dog tick (Dermacentor variabilis) on day 2 after intraperitoneal treatment. The effect is considered to be longer-lasting if the efficacy on day 9 is still higher than 80%.
  • the rats are sedated with 30-50 ⁇ of medetomidine hydrochloride (e.g. Domitor®) s.c/rat. All rats are infested on day 0 (at least 1 h after the treatemt), day 7, day 14 etc. with 30 unfed Ctenocephalides felis adults. On day 2, day 9, day 16 etc. the collar is removed and the entire body of the sedated rats is examined systematically for fleas using a flea comb. The fleas are counted and removed.
  • medetomidine hydrochloride e.g. Domitor®
  • the efficacy of the treatment is determined by comparison with a placebo-treated control group.
  • a compound is considered to be highly effective if, at a dosage of 10 mg/kg, it shows an efficacy of 95% against adult fleas ( Ctenocephalides felis) on day 2 after intraperitoneal treatment. The effect is considered to be longer-lasting if the efficacy on day 9 is still higher than 90%.
  • the following compounds of the Preparation Examples show an efficacy of >95% against fleas on day 2 at an application rate of 10 mg/kg: Ic-1, Ic-2
  • the kill in % is determined. 100% means that all of the larvae have been killed; 0% means that none of the larvae have been killed. in this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 20 ppm: Ic-1, Ic-16

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Abstract

The present application relates to novel anti-parasitic combinations of halogen-substituted compounds, which are useful for controlling animal pests in the field of animal health.

Description

Anti-parasitic combinations including halogen-substituted compounds
The present application relates to novel anti-parasitic combinations of halogen-substituted compounds, which are useful for controlling animal pests in the field of animal health.
It is known that certain halogen-substituted compounds have herbicidal action (cf. J. Org. Chem. 1997, 62(17), 5908-5919, J. Heterocycl. Chem. 1998, 35(6), 1493-1499, WO 2004/035545, WO 2004/106324, US 2006/069132, WO 2008/029084).
Furthermore, it is known that certain halogen-substituted compounds have insecticidal action (EP 1 911 751, WO2012/069366, WO2012/080376 & WO2012/107434).
In addition, it is known that certain halogen-substituted compounds have cytokine-inhibitory activities (WO 2000/07980).
Modern anti-parasitic compositions have to meet many demands, for example in relation to efficacy, persistence and spectrum of their action and possible use. Questions of toxicity, the combinability with other active compounds or formulation auxiliaries play a role, as well as the question of the expense that the synthesis of an active compound requires. Furthermore, resistances may occur. For all these reasons, the search for novel anti-parasitic agents can never be considered as having been concluded, and there is a constant need for novel compounds and compound combinations having properties which, compared to the known compounds, are improved at least in respect of individual aspects.
It was an object of the present invention to provide compound combinations which widen the spectrum of the pesticides under various aspects and/or improve their activity. In WO2014/122083 certain halogen-substituted compounds and their N-oxides and salts have been disclosed which have biological properties and are particularly suitable for controlling animal pests, and can therefore be employed particularly well in the agrochemical field and in the animal health sector.
Similar compounds are already known from WO 2010/051926.
The present invention provides: Combinations of compounds of the general formula (I) below with ectoparasiciticides, anthelmintics or anti-protozoal agents.
Compounds of formula (I) are known from WO2014/122083 and they are defined as follows:
The halogen-substituted compounds of the invention are defined by the general formula (I)
Figure imgf000003_0001
in which
R ' represents hydrogen, optionally substituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7- cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)- alkyl, or alternatively
R ! represents hydrogen, optionally substituted C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, C3-C7- cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)- alkyl, the chemical groupings Ai represents CR2 or nitrogen, A2 represents CR3 or nitrogen, A3 represents CR4 or nitrogen and A4 represents CR3 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
R2, R\ R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1-C3-alkyl, C1- C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N- C1-C6-alkylamino or 7V,N-di-C1- C6-alkylamino; if none of the groupings A2 and A3 represents nitrogen, R3 and R4 together with the carbon atom to which they are attached may form a 5- or 6-membered ring which contains 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulphur atom, or if none of the groupings Ai and A2 represents nitrogen, R and R3 together with the carbon atom to which they are attached may form a 6-membered ring which contains 0, 1 or 2 nitrogen atoms; W represents oxygen or sulphur;
Q represents hydrogen, formyl, hydroxy, amino or one of the optionally substituted groupings alkyl, alkyloxy, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl or represents a grouping N-alkylamino, N-alkylcarbonylamino, N,N- dialkylamino; or
Q represents an unsaturated 6-membered carbocycle which is optionally mono- or polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally mono- or polysubstituted by V, or alternatively
(,) represents an unsaturated 6-membered carbocycle which is optionally polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally polysubstituted by V, where in both last cases of Q
V represents halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, N-alkoxyiminoalkyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, N,N-dialkylamino,
T represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000004_0001
where
R' independently of one another represent halogen, cyano, nitro, amino or optionally substituted C1- C6-alkyl, C1-C6- alkyloxy, C1-C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1- C6-alkylsulphonyl, and n represents the values 0-2;
Z1 represents optionally substituted alkyl and cycloalkyl, and Z2 represents hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, and
Z3 represents hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or hetaryl .
Preference is given to compounds of the formula (I)
Figure imgf000005_0001
in which R1 represents hydrogen, optionally substituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7- cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)- alkyl, or alternatively
R ! represents hydrogen, optionally substituted C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C7- cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)- alkyl, the chemical groupings Ai represents CR2 or nitrogen, A2 represents CR3 or nitrogen, A3 represents CR4 or nitrogen and A4 represents CR5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
R2, R '. R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-alkoxyiminoalkyl, C1-C6- alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N-C1-C6-alkylamino, N,N-di- C1- C6alkylamino; if none of the groupings A2 and A3 represents nitrogen, R3 and R4 together with the carbon atom to which they are attached may form a 5- or 6-membered ring which contains 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulphur atom, or if none of the groupings Ai and A2 represents nitrogen, R and \V together with the carbon atom to which they are attached may form a 6-membered ring which contains 0, 1 or 2 nitrogen atoms;
W represents oxygen or sulphur;
Q represents hydrogen, formyl, hydroxy, amino or one of the optionally substituted groupings C1-C6- alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, C2 -C5 -heterocy c loa Iky 1, C1-C4-alkoxy, C1- C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)- alkyl or represents a grouping N-C1-C4-alkylamino, N-C1-C4-alkylcarbonylamino, N,N-di-C1-C4- alkylamino; or alternatively
Q represents an unsaturated 6-membered carbocycle which is optionally mono- or polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally mono- or polysubstituted by V,
V independently of one another represent halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1-C3- alkyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N,N-di-(C1-C6- alkyl)amino;
T represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000006_0001
independently of one another represent halogen, cyano, nitro, amino or optionally halogen- substituted C1-C6-alkyl, C1-C6-alkyloxy, C1-C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6- alkylsulphinyl, C1-C6-alkylsulphonyl, and represents the values 0-1 ; represents optionally substituted C1-C6-haloalkyl or C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and represents hydrogen, halogen, cyano, nitro, amino or optionally substituted C1-C6-alkyl, C1-C6- alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, and represents hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or hetaryl.
Preference is furthermore given to compounds of the formula (I)
Figure imgf000007_0001
in which
R 1 represents hydrogen or represents C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3 -C7-cycloalkyl, C3 -C7-cycloalkyl-C1-C3 -alkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3) -alkyl which are optionally mono- or polysubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl, the chemical groupings
Ai represents CR2 or nitrogen,
A2 represents CR ' or nitrogen,
A3 represents CR4 or nitrogen and A4 represents CR3 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen; R2, R 3, R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1-C3-alkyl, C1- C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N-C1-C6-alkylamino or N,N-di-C1- C6-alkylamino; W represents oxygen or sulphur;
Q represents hydrogen, hydroxy, formyl or one of the groupings C1-C6-alkyl, C3-C6-alkenyl, C3-C6- alkynyl, C3-C6-cycloalkyl, C2-C5-heterocycloalkyl, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1-C6-hydroxyalkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)-alkyl, N-C1-C4-alkylamino, N-C1-C4-alkylcarbonylamino or N,N-di-C1-C4-alkylamino which are optionally mono- or polysubstituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbanioyl, phenyl; or
Q represents aryl substituted by 0 - 4 substituents V or a 5- or 6-membered heteroaromatic substituted by 0 - 4 substituents V, where V independently of one another represent halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1-C3- alkyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N,N-di-(C1-C6- alkyl) amino;
T represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000008_0001
where
R' independently of one another represent halogen, cyano, nitro, amino or optionally mono- or polyhalogen-substituted C1-C6-alkyl, C1-C6-alkyloxy, C1-C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, and n represents the values 0-1 ;
Z1 represents optionally substituted C1-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and represents hydrogen, halogen, cyano, nitro, amino or optionally mono- or polysubstituted C1-C6- alkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, and represents hydrogen or optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkenyl, C1-C4- alkynyl, aryl or hetaryl.
Particular preference is given to compounds of the formula (I)
Figure imgf000009_0001
in which R 1 represents hydrogen or represents C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C3 -C7-cycloalkyl-C1-C3 -alkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3) -alkyl which are optionally mono- to pentasubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl, the chemical groupings A1 represents CR2 or nitrogen,
A2 represents CR3 or nitrogen,
A3 represents CR4 or nitrogen and
A4 represents CR5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen; R2, R 3. R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, or represent C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1-C3-alkyl, C1-C6- alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N-C1-C6-alkylamino or N,N-di-C1-C6- alkylamino which are optionally mono- to pentasubstituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl;
W represents oxygen or sulphur;
Q represents hydrogen, hydroxy, formyl or one of the groupings C1-C6-alkyl, C3-C6-alkenyl, C3-C6- alkynyl, C3-C6-cycloalkyl, C2-Cs-heterocycloalkyl, C1-C4-alkoxy, C1-C6-alkyl-C3-C6 cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1-C6-hydroxyalkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)-alkyl, 7V-C1-C4-alkylamino, N-C1-C4-alkylcarbonylamino or N,N-di-C1-C4-alkylamino which are optionally mono- to pentasubstituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl; or represents aryl substituted by 0 - 4 substituents V or a 5- or 6-membered heteroaromatic substituted by 0 - 4 substituents V, where v independently of one another represents halogen, cyano, nitro, or represents C1-C6-alkyl, C1-C4- alkenyl, C1-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1-C3-alkyl, C1- C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N,N-di-(C1-C6-alkyl) amino optionally independently of one another mono- to pentasubstituted by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxy c arbony 1, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl; represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000010_0001
where R6 independently of one another represent halogen, cyano, nitro, amino or optionally mono- to pentahalogen-substituted C1-C6-alkyl, C1-C6-alkyloxy, C1-C6-aikylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, and n represents the values 0-1 ;
Z1 represents C1-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl optionally mono- to pentasubstituted by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl, and
Z2 represents hydrogen, halogen, cyano, nitro, amino or represents C1-C6-alkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl optionally independently of one another mono- to pentasubstituted by hydroxy, nitro, amino, halogen alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl, and
Z3 represents hydrogen or represents C1-C6-alkyl, C3-C6-cycloalkyl C1-C4-alkenyl, C1-C4-alkynyl, aryl or hetaryl optionally independently of one another mono- to pentasubstituted by hydroxy, nitro, amino, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl.
Especially preferred are compounds of the formula (I)
Figure imgf000011_0001
in which represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- propoxy c arbony 1, isopropoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, cyanomethyl, 2- cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2 -ylmethyl, pyrid-3 -ylmethyl, pyrid-4 -ylmethyl, 4- chloropyrid- 3 -ylmethyl ; chemical groupings A1 represents CR2 or nitrogen,
A2 represents CR3 or nitrogen, A3 represents CR4 or nitrogen and A4 represents CR5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
R and R5 independently of one another represent hydrogen, methyl, fluorine or chlorine and
R ' and R4 independently of one another represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, fluoromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 2,2,2- trifluoroethyl, methoxy, ethoxy, n-propoxy, 1 -methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichloro fluoromethoxy, trifluoromethoxy, 2,2,2 -trifluoroethoxy, 2-chloro-2,2- difluoroethoxy, pentafluoroethoxy, N-methoxyiminomethyl, 1 -(N-methoxyimino)ethyl, methylsulfanyl, trifluoromethylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl ;
W represents oxygen or sulphur;
Q represents hydrogen, methyl, ethyl, n-propyl, 1 -methylethyl, 1 , 1 -dimethyl ethyl, 1 -methylpropyl, n-butyl, 2 -methylpropyl, 2-methylbutyl, hydroxyethyl, 2 -hydroxypropy 1, cyanomethyl, 2- cyanoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 -trifluoromethylethyl, 2,2- difluoropropyl, 3,3,3-trifluoropropyl, 2,2-dimethyl-3-fluoropropyl, cyclopropyl, 1 - cyanocyclopropyl, 1 -methoxycarbonylcyclopropyl, l -(N-methylcarbamoyl)cyclopropyl, 1- carbamoylcyclopropyl, 1 -carbamothioylcyclopropyl, 1 -(N- eye lopropyle arbamoy 1) eye lopropy 1, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1 -cyclopropylethyl, bis(cyclopropyl)methyl, 2 ,2 -dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2,2- dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2,2-difluorocyclopropyl, trans -2 - fluorocyc lopropyl, cis-2-fluorocyclopropyl, trans -4-hydroxycyclohexyl, 4- trifluoromethylcyclohexyl, prop-2-enyl, 2 -methylprop-2 -enyl, prop-2-ynyl, 1 , 1 -dimethylbut-2- ynyl, 3-chloroprop-2-enyl, 3 -fluoroprop-2 -enyl, 3 ,3 -dichloroprop-2 -enyl, 3,3-dichloro-l,l- dimethylprop-2-enyl, oxetan-3-yl, thietan-3-yl, 1 -oxidothietan-3-yl, 1 , 1 -dioxidothietan-3-yl, isoxazol-3-ylmethyl, l,2,4-triazol-3-ylmethyl, 3 -methyloxetan- 3 -y lmethy 1, benzyl, 2,6- difluorophenylmethyl, 3-fluorophenylmethyl, 2 -fluorophenylmethyl, 2,5 -difluorophenylmethyl, 1 - phenylethyl, 4-chlorophenylethyl, 2 -trifluoromethylphenyl ethyl, 1 -pyridin-2 -ylethyl, pyridin-2- ylmethyl, 5 -fluoropyridin-2 -ylmethyl, (6-chloropyridin-3-yl)methyl, pyrimidin-2 -y lmethy 1, methoxy, 2 -ethoxy ethyl, 2 -methoxy ethyl, 2-(methylsulphanyl)ethyl, 1 -methyl -2- (ethylsulphanyl)ethyl, 2 -methyl- 1 -(methylsulphanyl)propan-2-yl, methoxycarbonyl, methoxyc arbony lmethy 1, NH2, N-ethylamino, N-allylamino, N,N-dimethylamino, N,N- diethylamino; or represents phenyl, naphthyl, pyridazine, pyrazine, pyrimidine, triazine, pyridine, pyrazole, thiazole, isothiazole, oxazole, isoxazole, triazole, imidazole, furan, thiophene, pyrrole, oxadiazole, thiadiazole substituted by 0, 1, 2, 3 or 4 substituents V, where independently of one another represents fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2- tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2 ,2 ,2 -trichloroethy 1, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n- butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodi fluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2,2-difluoroethoxy, pentafluoroethoxy, N-methoxyiminomethyl, l -(N- methoxyimino) ethyl, methylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl, trifluoromethylsulphanyl, N,N- dimethylamino; represents one of the 5-membered heteroaromatics T1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000013_0001
where
R6 independently of one another represent halogen, cyano, nitro, amino, methyl, ethyl, propyl, 1 - methylethyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, 2,2- difluoroethoxy, 2,2,2 -trifluoroethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methylsulphanyl, methylsulphinyl, methylsulphonyl, trifluoromethylsulphonyl, trifluoromethylsulphanyl, trifluoromethylsulphinyl, and n represents the values 0-1 ;
Z1 represents methyl, ethyl, 1 , 1 -dimethylethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, 1 -fluoroethyl, 1 -fluoro- 1 -methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2- tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2 -trichloroethyl, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n- butyl, cyclopropyl, 1 -chlorocyclopropyl, 1 -fluorocyclopropyl, 1 -bromocyclopropyl, 1- cyanocyclopropyl, 1 -trifluoromethylcyclopropyl, cyclobutyl and 2,2-difluoro-l - methylcyclopropyl, and
7: represents hydrogen, halogen, cyano, nitro, amino, methyl, ethyl, 1 , 1 -dimethylethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, 1-fluoroethyl, 1 -fluoro- 1 -methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,2,2,2-tetrafluorethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2 -trichloroethyl, 2-chloro-2,2 -difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, methylsulphanyl, methylsulphinyl, methylsulphonyl, ethylthio, ethylsulphinyl, ethylsulphonyl, trifluoromethylsulphanyl, trifluoromethylsulphinyl, trifluoromethylsulphonyl, chlorodifluoromethylsulphanyl, chlorodifluoromethylsulphinyl, chlorodifluoromethylsulphonyl, dichlorofluoromethylsulphanyl, dichlorofluoromethylsulphinyl, dichlorofluoromethylsulphonyl and
Z3 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, ethenyl, 1 -propenyl, 1 -propynyl, 1 -butynyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 -fluoro- 1 -methylethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,5- dichlorophenyl, 3 ,4-dichlorophenyl, 2,6-dichlorophenyl, 2,6-dichloro-4-trifluoromethylphenyl, 3- chloro-5 -trifluoromethylpyridin-2 -yl.
Especially preferred are compounds of the general formula (I) in which
Z1 represents trifluoromethyl, 1 -chlorocyclopropyl, 1 -fluorocyclopropyl or pentafluoroethyl,
Z2 represents trifluoromethyl, nitro, methylsulphanyl, methylsulphinyl, methylsulphonyl, fluorine, chlorine, bromine, cyano or iodine,
Z3 represents methyl, ethyl, n-propyl or hydrogen,
\\ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, methoxy c arbony 1, ethoxyc arbony 1, n- propoxy c arbony 1, isopropoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, cyanomethyl, 2- cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2-ylmethyl, pyrid-3 -ylmethyl, pyrid-4 -ylmethy 1, 4- chloropyrid-3 -ylmethyl,
A1, A2 and A4 each represent CH, where
A2 may alternatively also represent CH or N,
A3 represents CR4 and
R4 represents fluorine, chlorine, bromine or iodine, where
R4 may alternatively also represent methyl, ethyl, fluorine, chlorine, bromine or iodine,
T represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000015_0001
Figure imgf000015_0002
where
R6 represents hydrogen, methyl, ethyl, 2-methylethyl, 2,2-dimethylethyl, fluorine, chlorine, bromine, iodine, cyano, nitro, trifluoromethyl, amino, or alternatively
R6 represents hydrogen, methyl, ethyl, 2-methylethyl, 2,2-dimethylethyl, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, amino,
W represents oxygen and
Q represents hydrogen, methyl, ethyl, n-propyl, 1 -methylethyl, 1 , 1 -dimethylethyl, n-butyl, 1- methylpropyl, 2-methylpropyl, 2-methylbutyl, hydroxyniethyl, hydroxyethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1 - trifluoromethylethyl, 2,2-difluoropropyl, 3,3,3 -trifluoropropy 1, 2,2-dimethyl-3-fluoropropyl, cyclopropyl, 1 -cyanocyclopropyl, 1 -methoxycarbonylcyclopropyl, 1 -(N- methylcarbamoyl)cyclopropyl, 1 -carbamoylcyclopropyl, 1 -carbamoylthiocyclopropyl, 1 -(N- cyclopropylcarbamoyl)cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1 - cyclopropylethyl, bis(cyclopropyl)methyl, 2,2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2,2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2,2- difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-f!uorocyclopropyl, trans -4- hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2 -methy lprop -2 - enyl, prop-2-ynyl, 1 , 1 -dimethylbut-2-ynyl, 3 -chloroprop-2-enyl, 3-fluoroprop-2-enyl, 3 ,3 -dichloroprop-2 -enyl, 3,3- dichloro- 1 , 1 -dimethylprop-2-enyl, oxetan-3-yl, thietan-3-yl, 1 -oxidothietan-3 -yl, 1,1- dioxidothietan-3 -yl, isoxazol-3 -ylmethyl, 1 ,2,4-triazol-3 -ylmethyl, 3 -methy loxetan- 3 -y lmethyl, benzyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-difluorophenylmethyl, 3- fluorophenylmethyl, 2 - fluoropheny lmethyl, 2,5 -difluorophenylmethyl, 1 -phenylethyl, 4- chlorophenylethyl, 2-trifluormethylphenylethyl, 1 -pyridin-2-ylethyl, pyridin-2-ylmethyl, (6- chloropyridin-3 -yl)methyl, 5 - fluoropyridin-2 -ylmethyl, pyrimidin-2 -ylmethyl, methoxy, 2- ethoxyethyl, 2 -methoxy ethyl, 2 - (methy lsulphanyl) ethyl, 1 -methyl -2-(ethylsulphanyl)ethyl, 2- methyl- 1 -(methylsulphanyl)propan-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH;, N- ethylamino, N-allylamino, N,N-dimethylamino, N,N-diethylamino; or alternatively
Q represents phenyl, naphthyl, pyridazine, pyrazine, pyrimidine, triazine, pyridine, pyrazole, thiazole, isothiazole, oxazole, isoxazole, triazole, imidazole, furan, thiophene, pyrrole, oxadiazole, thiadiazole substituted by 0, 1, 2 or 3 substituents V, where
V independently of one another represents fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2- tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, heptafluoro -n-propy 1, heptafluoroisopropyl, nonafluoro-n- butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodi fluoromethoxy, dichlorofluoromethoxy, tri fluoromethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2,2-difluoroethoxy, pentafluoroethoxy, N-methoxyiminomethyl, 1 -(N- methoxyimino) ethyl, methylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl, trifluoromethylsulphanyl, N,N- dimethylamino.
Very especially preferred are furthermore the compounds in each case defined by one of the general formulae 1(a), 1(b), 1(c), 1(d), 1(e), 1(f), 1(g) in which the radicals A1-A4, n, W, Q, R1 and Z1-Z3 have the general, preferred or particularly preferred meanings described above. 
Figure imgf000017_0001
Especially preferred are all compounds of the general formula (Ic), where the preferred ranges for the radicals A1, A2, A3, A4, Q, R \ R6, W, Z1, Z2 and Z3 apply correspondingly to the above preferred ranges for the compounds of the general formula (I).
Very particular preference is given to compounds of the general formula (la) in which 7 ' represents CF2CF3, Z2 represents CF3, Z3 represents CH3, the radicals R1, R6a, R6b and R6c represent hydrogen, A1, A2, A4 represent C-H, A3 represents C-Cl, W represents oxygen and Q represents 1- cyanocyclopropyl or cyclopropyl.
Very particular preference is alternatively given to compounds of the general formula (la) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents CH3, the radicals R1. R6a, R6b and R6c represent hydrogen, A1, A4 represent C-H, A2 represents N, A3 represents C-Cl, W represents oxygen and Q represents 1 -cyanocyclopropyl or cyclopropyl.
Very particular preference is furthermore given to compounds of the general formula (lb) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents CH3, the radicals R1, R6a and R6b represent hydrogen, A1, A2, A4 represent C-H, A3 represents C-Cl, W represents oxygen and Q represents 1 - cyanocyclopropyl or cyclopropyl.
Very particular preference is alternatively given to compounds of the general formula (lb) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents CH3, the radicals R1, R6a, R6b and R6c represent hydrogen, A1, A4 represent C-H, A2 represents N, A3 represents C-Cl, W represents oxygen and Q represents 1 -cyanocyclopropyl or cyclopropyl. Very particular preference is furthermore given to compounds of the general formula (Ic) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents methyl, ethyl, phenyl, 4-NO2 -phenyl, 3- chloropyridin-2 -y 1 , the radicals R1, R6a represent hydrogen or methyl, R6b represents hydrogen, methyl or CF3, A1, A4 represent C-H, A2 represents C-H or C-F, A3 represents C-H or C-Cl , W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, benzyl, cyclopropyl, 2-thienylmethyl, carbamothioylcyclopropyl, pyrid-4-yl, 2,2,2-trifluoroethyl, niethylsulphonyl, thietan-3-yl, 1 -carbamoylcyclopropyl.
Very particular preference is alternatively given to compounds of the general formula (Ic) in which 7. represents CF2CF3, Z2 represents CF3, Z3 represents methyl, ethyl, phenyl, 4-N02-phenyl, 3- chloropyridin-2 -y 1 , the radicals R1, R6a represent hydrogen or methyl, R6b represents hydrogen, methyl or CF3, A1, A4 represent C-H, A2 represents N, A3 represents C-H or C-Cl, W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, benzyl, cyclopropyl, 2- thienylmethyl, carbamoylthiocyclopropyl, pyrid-4-yl, 2,2,2-trifluoroethyl, niethylsulphonyl, thietan-3-yl, 1 -carbamoylcyclopropyl. Very particular preference is furthermore given to compounds of the general formula (Id) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents C'H the radicals R1, R6a and R6b represent hydrogen, A1, A2, A4 represent C-H, A3 represents C-Cl, W represents oxygen and Q represents 1 - cyanocyclopropyl or cyclopropyl. Very particular preference is alternatively given to compounds of the general formula (Id) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents C'H;, the radicals R1, R6a, R6b and R6c represent hydrogen, A1, A4 represent C-H, A2 represents N, A3 represents C-Cl, W represents oxygen and Q represents 1 -cyanocyclopropyl or cyclopropyl.
Very particular preference is furthermore given to compounds of the general formula (Ie) in which Ί) represents CF2CF3, Z2 represents CF3, Z3 represents CH3, the radicals R1, R6a and R6b represent hydrogen, A1, A2, A4 represent C-H, A3 represents C-Cl, W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, 2-thienylmethyl, 6-chloropyridin-3-yl, 1- carbamoylthiocyclopropyl or cyclopropyl.
Very particular preference is alternatively given to compounds of the general formula (Ie) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents C'H.-., the radicals R1, R6a and R6b represent hydrogen, A1, A4 represent C-H, A2 represents N, A3 represents C-Cl, W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, 2-thienylmethyl, 6-chloropyridin-3-yl, 1 - carbamoylthiocyclopropyl or cyclopropyl.
Most preference is given to the compounds of the general formula (Ic) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents methyl, ethyl, phenyl, 4-N02-phenyl, 3 -chloropyridin-2-yl , the radicals R1, R6a represent hydrogen or methyl, R6b represents hydrogen, methyl or CF3, A1, A4 represent C-H, A2 represents C-H or C-F, A3 represents C-H or C-Cl, W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, benzyl, cyclopropyl, 2 -thienylmethyl, carbamoylthiocyclopropyl, pyrid-4-yl, 2,2,2-trifluoroethyl, methylsulphonyl, thietan-3-yl, 1 - c arbamoy Icy c lopropyl .
Most preference is alternatively given to the compounds of the general formula (Ic) in which Z1 represents CF2CF3, Z2 represents CF3, Z3 represents methyl, ethyl, phenyl, 4-N02-phenyl, 3- chloropyridin-2 -y 1 , the radicals R1, R6a represent hydrogen or methyl, R6b represents hydrogen, methyl or CF3, A1, A4 represent C-H, A2 represents N, A3 represents C-H or C-Cl, W represents oxygen and Q represents one of the radicals 1 -cyanocyclopropyl, benzyl, cyclopropyl, 2- thienylmethyl, carbamothioylcyclopropyl, pyrid-4-yl, 2,2,2-trifluoroethyl, methylsulphonyl, thietan-3-yl, 1 -carbamoylcyclopropyl.
According to the invention, "alkyl" - on its own or as part of a chemical group - represents straight- chain or branched hydrocarbons preferably having 1 to 6 carbon atoms such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1 ,2-dimethylpropyl, 1 , 1 -dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,2-dimethylpropyl, 1 ,3 -dimethylbutyl, 1 ,4-dimethylbutyl, 2,3 -dimethylbutyl, 1 , 1 -dimethylbutyl, 2 ,2 -dimethylbutyl, 3 , 3 -dimethylbutyl, 1,1,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethylbutyl and 2-ethylbutyl. Preference is furthermore given to alkyl groups having 1 to 4 carbon atoms such as, inter alia, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl. The alkyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "alkenyl" - on its own or as part of a chemical group - represents straight- chain or branched hydrocarbons preferably having 2 to 6 carbon atoms and at least one double bond such as, for example, vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1 -methyl-2 -propenyl, 2 -methyl-2 - propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-2 -butenyl, 2 -methyl -2 -buteny 1, 3 -methyl-2 - butenyl, 1 -methyl-3 -butenyl, 2-methyl-3-butenyl, 3 -methyl-3 -butenyl, 1 , 1 -dimethyl-2 -propenyl, 1,2- dimethyl-2 -propenyl, 1 -ethyl-2 -propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-2 - pentenyl, 2 -methyl -2-pentenyl, 3 -methyl-2 -pentenyl, 4-methyl-2-pentenyl, 3 -methyl-3 -pentenyl, 4- methyl-3 -pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl -4-pentenyl, 4-methyl-4- pentenyl, 1 , 1 -dimethyl -2 -butenyl, l,l -dimethyl-3-butenyl, 1 ,2-dimethyl -2 -butenyl, l,2-dimethyl-3- butenyl, 1 ,3-dimethyl -2 -butenyl, 2,2-dimethyl-3 -butenyl, 2, 3-dimethyl-2 -butenyl, 2,3-dimethyl-3- butenyl, 1 -ethyl-2-butenyl, 1 -ethyl-3 -butenyl, 2-ethyl-2 -butenyl, 2-ethyl-3 -butenyl, 1 , 1 ,2-trimethyl-2- propenyl, 1 -ethyl- 1 -methyl-2-propenyl and 1 -ethyl-2-methyl-2-propenyl. Preference is furthermore given to alkenyl groups having 2 to 4 carbon atoms such as, inter alia, 2-propenyl, 2-butenyl or 1- methyl -2 -propenyl . The alkenyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "alkynyl" - on its own or as part of a chemical group - represents straight- chain or branched hydrocarbons preferably having 2 to 6 carbon atoms and at least one triple bond such as, for example, 2-propynyl, 2-butynyl, 3 -butynyl, 1 -methyl-2 -propynyl, 2-pentynyl, 3-pentynyl, 4- pentynyl, 1 -methyl-3 -butynyl, 2 -methyl-3 -butynyl, 1 -methyl -2 -butynyl, 1 , 1 -dimethyl -2 -propynyl, 1 - ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2 -pentynyl, 1 -methyl-3 - pentynyl, 1 -methyl -4-pentynyl, 2 -methyl-3 -pentynyl, 2-methyl-4-pentynyl, 3-methyl -4-pentynyl, 4- methyl -2 -pentynyl, 1 , 1 -dimethyl-3 -butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3 -butynyl, l -ethyl-3- butynyl, 2-ethyl-3 -butynyl, 1 -ethyl-1 -methyl-2 -propynyl and 2,5-hexadiynyl. Preference is furthermore given to alkynyl groups having 2 to 4 carbon atoms such as, inter alia, ethynyl, 2-propynyl or 2 -butynyl - 2-propenyl. The alkynyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "cycloalkyl" - on its own or as part of a chemical group - represents mono-, bi- or tricyclic hydrocarbons preferably having 3 to 10 carbons such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl. Preference is furthermore given to cycloalkyl groups having 3, 4, 5, 6 or 7 carbon atoms such as, inter alia, cyclopropyl or cyclobutyl. The cycloalkyl groups according to the invention may be substituted by one or more identical or different radicals. According to the invention, "alkylcycloalkyl" represents mono-, bi- or tricyclic alkylcycloalkyl preferably having 4 to 10 or 4 to 7 carbon atoms such as, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is furthermore given to alkylcycloalkyl groups having 4, 5 or 7 carbon atoms such as, inter alia, ethylcyclopropyl or 4- methylcyclohexyl. The alkylcycloalkyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "cycloalkylalkyl" represents mono-, bi- or tricyclic cycloalkylalkyl preferably having 4 to 10 or 4 to 7 carbon atoms such as, for example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is furthermore given to cycloalkylalkyl groups having 4, 5 or 7 carbon atoms such as, inter alia, eye lopropylmethy 1 or cyclobutylmethyl. The cycloalkylalkyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "halogen" represents fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
The halogen-substituted chemical groups according to the invention such as, for example, haloalkyl, halocycloalkyl, haloalkyloxy, haloalkylsulphanyl, haloalkylsulphinyl or haloalkylsulphonyl are mono- or polysubstituted by halogen up to the maximum possible number of substituents. In the case of polysubstitution by halogen, the halogen atoms can be identical or different, and can all be attached to one or to a plurality of carbon atoms. Here, halogen represents in particular fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferably fluorine. According to the invention, "halocycloalkyl" represents mono-, bi- or tricyclic halocycloalkyl having preferably 3 to 10 carbon atoms such as, inter alia, 1 -fluorocyclopropyl, 2-fluorocyclopropyl or 1 - fluorocy c lobuty 1. Preference is furthermore given to halocycloalkyl having 3, 5 or 7 carbon atoms. The halocycloalkyl groups according to the invention may be substituted by one or more identical or different radicals. According to the invention, "haloalkyl" "hatoalkenyl" or "haloalkynyl" represents halogen-substituted alkyl, alkenyl or alkynyl groups having preferably 1 to 9 identical or different halogen atoms such as, for example, monohaloalkyl such as CH2CH2C1, CH2CH2F, CHC1CH3, CHFCH3, CH2C1, CH2F; perhaloalkyl such as CC13 or CF3 or CF2CF3; polyhaloalkyl such as CHF2, C H. F. CH2CHFC1, CHC12, CF2CF2H, CH2CF3. This applies correspondingly to haloalkenyl and other halogen-substituted radicals. Haloalkoxy is, for example, OCF3, OCHF2, ( KTI. F. OCF2CF3, OCF2CF3 and OCH2CH2Cl.
Further examples for haloalkyl groups are trichloromethyl, chlorodifluoromethyl, di chlorofluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2- difluoroethyl, pentafluoroethyl and p entafluoro -t-buty 1. Preference is given to haloalkyl groups having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5, identical or different halogen atoms selected from the group consisting of fluorine, chlorine and bromine. Particular preference is given to haloalkyl groups having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine and chlorine such as, inter alia, difluoromethyl, trifluoromethyl or 2,2- difluoroethyl.
According to the invention, "hydroxyalkyl" represents a straight-chain or branched alcohol preferably having 1 to 6 carbon atoms such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol and t-butanol. Preference is furthermore given to hydroxyalkyl groups having 1 to 4 carbon atoms. The hydroxyalkyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "alkoxy" represents a straight-chain or branched O-alkyl preferably having 1 to 6 carbon atoms such as, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy and t-butoxy. Preference is furthermore given to alkoxy groups having 1 to 4 carbon atoms. The alkoxy groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "haloalkoxy" represents halogen-substituted straight- chain or branched O- alkyl preferably having 1 to 6 carbon atoms such as, inter alia, difluoromethoxy, trifluoromethoxy, 2,2- difluoroethoxy, 1 , 1 ,2,2-tetrafluoroethoxy, 2,2,2 -trifluoroethoxy and 2-chloro- 1 , 1 ,2 -trifluoroethoxy. Preference is furthermore given to haloalkoxy groups having 1 to 4 carbon atoms. The haloalkoxy groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "alkylsulphanyl" represents straight-chain or branched S-alkyl preferably having 1 to 6 carbon atoms such as, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n- butylthio, isobutylthio, s-butylthio and t-buty lthio. Preference is furthermore given to alkylsulphanyl groups having 1 to 4 carbon atoms. The alkylsulphanyl groups according to the invention may be substituted by one or more identical or different radicals.
Examples of haloalkylsulphanylalkyl groups, i.e. halogen-substituted alkylsulphanyl groups, are inter alia di fluoromethy lthio, trifluoromethylthio, trichloromethylthio, chlorodifluoromethylthio, 1 - fluoroethylthio, 2 -fluoroethy lthio, 2,2-difluoroethylthio, 1 , 1 ,2,2-tetrafluoroethylthio, 2,2,2- trifluoroethylthio or 2-chloro- 1 , 1 ,2-trifluoroethylthio. According to the invention, "alkylsulphinyl" represents straight-chain or branched alkylsulphinyl preferably having 1 to 6 carbon atoms such as, for example, methylsulphinyl, ethylsulphinyl, n- propylsulphinyl, isopropylsulphinyl, n-butylsulphinyl, isobutylsulphinyl, s-butylsulphinyl and t- butylsulphinyl. Preference is furthermore given to alkylsulphinyl groups having 1 to 4 carbon atoms. The alkylsulphinyl groups according to the invention may be substituted by one or more identical or different radicals.
Examples of haloalkylsulphinyl groups, i.e. halogen-substituted alkylsulphinyl groups, are inter alia difluoromethylsulphinyl, trifluoromethylsulphinyl, trichloromethylsulphinyl, chlorodifluoromethylsulphinyl, 1 -fluoroethylsulphinyl, 2-fluoroethylsulphinyl, 2,2- difluoroethylsulphinyl, 1 , 1 ,2,2-tetrafluoroethylsulphinyl, 2,2,2 -tri fluoroethylsulphinyl and 2-chloro- 1 , 1 ,2 -trifluoro ethylsulphinyl .
According to the invention, "alkylsulphonyl" represents straight-chain or branched alkylsulphonyl preferably having 1 to 6 carbon atoms such as, for example, methylsulphonyl, ethylsulphonyl, n- propylsulphonyl, isopropylsulphonyl, n-butylsulphonyl, isobutylsulphonyl, s-butylsulphonyl and t- butylsulphonyl. Preference is furthermore given to alkylsulphonyl groups having 1 to 4 carbon atoms. The alkylsulphonyl groups according to the invention may be substituted by one or more identical or different radicals.
Examples of haloalkylsulphonyl groups, i.e. halogen-substituted alkylsulphonyl groups, are inter alia difluoromethylsulphonyl, trifluoromethylsulphonyl, trichloromethylsulphonyl, chlorodifluoromethylsulphonyl, 1 -fluoroethylsulphonyl, 2 - fluoro ethylsulphonyl, 2,2- difluoroethylsulphonyl, 1 , 1 ,2,2-tetrafluoroethylsulphonyl, 2,2,2 -trifluoroethylsulphonyl and 2-chloro- 1 , 1 ,2 -tri fluoroethylsulphonyl.
According to the invention, "alkylcarbonyl" represents straight-chain or branched alkyl-C(=0) preferably having 2 to 7 carbon atoms such as methy lc arbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl and t-butylcarbonyl. Preference is furthermore given to alkylcarbonyl groups having 1 to 4 carbon atoms. The alkylcarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "cycloalkylcarbonyl" represents straight-chain or branched cycloalkylcarbonyl preferably having 3 to 10 carbon atoms in the cycloalkyl moiety such as, for example, eye lopropyle arbonyl, cyclobutylcarbonyl, eye lopenty lc arbonyl, eye lohexyle arbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, bicyclo[2.2. i]heptyl, bicyclo[2.2.2 ] octy lc arbonyl and adamantylcarbonyl. Preference is furthermore given to eye loalky lc arbonyl having 3, 5 or 7 carbon atoms in the cycloalkyl moiety. The cycloalkylcarbonyl groups according to the invention may be substituted by one or more identical or different radicals. According to the invention, "alkoxycarbonyl" - alone or as a constituent of a chemical group - represents straight- chain or branched alkoxycarbonyl, preferably having 1 to 6 carbon atoms or having 1 to 4 carbon atoms in the alkoxy moiety such as, for example, methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl. The alkoxycarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "alkylaminocarbonyl" represents straight-chain or branched alkylaminocarbonyl having preferably 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as, for example, methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl. The alkylaminocarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "N,N-dialkylaminocarbonyl" represents straight-chain or branched N,N- dialkylaminocarbonyl having preferably 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as, for example, iV^V-dimethylaminocarbonyl, N,N-diethylaminocarbonyl, N,N-di(n- propylamino)carbonyl, N,N-di(isopropylamino)carbonyl and N,N-di-(s-butylamino)carbonyl. The N,N- dialkylaminocarbonyl groups according to the invention may be substituted by one or more identical or different radicals.
According to the invention, "aryl" represents a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring carbon atoms such as, for example, phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. Furthermore, aryl also represents polycyclic systems such as tetrahydronaphtyl, indenyl, indanyl, fluorenyl, biphenylyl, where the bonding site is on the aromatic system. The aryl groups according to the invention may be substituted by one or more identical or different radicals.
Examples for substituted aryls are the arylalkyl groups which may likewise be substituted by one or more identical or different radicals in the alkyl and/or aryl moiety. Examples for such arylalkyl groups are inter alia benzyl and 1 -phenylethyl.
According to the invention, "heterocycle", "heterocyclic ring" or "heterocyclic ring system" represents a carbocyclic ring system having at least one ring in which at least one carbon atom is replaced by a heteroatom, preferably by a heteroatom from the group consisting of N, O, S, P, B, Si, Se, and which is saturated, unsaturated or heteroaromatic and may be unsubstituted or substituted by a substituent Z, where the point of attachment is located at a ring atom. Unless defined differently, the heterocyclic ring contains preferably 3 to 9 ring atoms, especially 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group consisting of N, O, and S, although no two oxygen atoms should be directly adjacent. The heterocyclic rings usually contain not more than 4 nitrogen atoms and/or not more than 2 oxygen atoms and/or not more than 2 sulphur atoms. If the heterocyclyl radical or the heterocyclic ring is optionally substituted, it can be fused to other carbocyclic or heterocyclic rings, in the case of optionally substituted heterocyclyl, the invention also embraces polycyclic systems such as, for example, 8-azabicyclo[3.2.1 Joctanyl or 1 - azabicyclo[2.2. ljheptyl. In the case of optionally substituted heterocyclyl, the invention also embraces spirocyclic systems such as, for example, l-oxa-5-azaspiro[2.3]hexyl.
Heterocyclyl groups according to the invention are, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanyl, dioxolyl, pyrazolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, oxiranyl, azetidinyl, aziridinyl, oxazetidinyl, oxaziridinyl, oxazepanyl, oxazinanyl, azepanyl, oxopyrrolidinyl, dioxopyrrolidinyl, oxomorpholinyl, oxopiperazinyl and oxepanyl.
Heteroarylene, i.e. heteroaromatic systems, has a particular meaning. According to the invention, the term heteroaryl represents heteroaromatic compounds, i.e. completely unsaturated aromatic heterocyclic compounds which fall under the above definition of heterocycles. Preference is given to 5- to 7- membered rings having 1 to 3, preferably 1 or 2, identical or different heteroatoms from the group above. Heteroaryl groups according to the invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5- oxadiazolyl, azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3- triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl and 1 ,2.4- diazepinyl. The heteroaryl groups according to the invention may also be substituted by one or more identical or different radicals.
Substituted groups such as a substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical are, for example, a substituted radical derived from the unsubstituted base structure, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group of halogen, alkoxy, alkylsulphanyl, hydroxyl, amino, nitro, carboxyl or a group equivalent to the carboxyl group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and N,N-dialkylaminocarbonyl, substituted amino such as acylamino, mono- and N,N-dialkylamino, trialkylsilyl and optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclyl, where each of the latter cyclic groups may also be bonded via heteroatoms or divalent functional groups such as in the alkyl radicals mentioned, and alkylsulphinyl, including both enantiomers of the alkylsulphonyl group, alkylsulphonyl, alkylphosphinyl, alkylpho sphony 1 and, in the case of cyclic radicals (= "cyclic skeleton"), also alkyl, haloalkyl, alkylsulphanylalkyl, alkoxyalkyl, optionally substituted mono- and N,N-dialkylaminoalkyl and hydroxyalkyl.
The term "substituted groups", such as substituted alkyl etc., includes, as substituents, in addition to the saturated hydrocarbonaceous radicals mentioned, corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and N,N-dialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- and N,N-dialkenylamino, mono- and Ν,Ν-dialkynylamino, trialkenylsilyl, trialkynylsilyl, optionally substituted cycloalkenyl, optionally substituted cycloalkynyl, phenyl, phenoxy etc. In the case of substituted cylic radicals with aliphatic components in the ring, cyclic systems with those substituents bonded to the ring by a double bond are also included, for example those having an alkylidene group such as methylidene or ethylidene, or an oxo group, imino group and a substituted imino group.
When two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partly saturated, unsaturated, for example also aromatic and further substituted.
The substituents mentioned by way of example ("first substituent level") may, if they contain hydrocarbon-containing moieties, optionally be further substituted therein ("second substituent level"), for example by one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. The term "substituted radical" preferably embraces just one or two substituent levels.
Preferred substituents for the substituent levels are, for example, amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxyl, carboxamide, SF5, aminosulphonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, N-monoalkylamino, N,N- dialkylamino, N-alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkeny loxyc arbony 1, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylsulphanyl, cycloalkylsulphanyl, alkenylthio, cycloalkenylthio, alkynylthio, alkylsulphenyl and alkylsulphinyl, where both enantiomers of the alkylsulphinyl group are included, alkylsulphonyl, N-monoalkylaminosulphonyl, N,N-dialkylaminosulphonyl, alkylphosphinyl, alkylphosphonyl, where in the case of alkylphosphinyl and alkylphosphonyl both enantiomers are included, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, N-alkanoylaminocarbonyl, N-alkanoyl-N- alkylaminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclyl and trialkylsilyl.
Substituents composed of a plurality of substituent levels are preferably alkoxyalkyl, alkylsulphanylalkyl, alkylsulphanylalkoxy, alkoxyalkoxy, phenethyl, benzyloxy, haloalkyl, halocycloalkyl, haloalkoxy, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, haloalkoxyalkylsulphanyl, haloalkoxyalkanoyl, haloalkoxyalkyl.
In the case of radicals having carbon atoms, preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 or 2 carbon atoms. Preference is generally given to substituents from the group of halogen, e.g. fluorine and chlorine, (C1-C4)-alkyl, preferably methyl or ethyl, (C1-C4) -haloalkyl, preferably trifluoromethyl, (C1-C4)-alkoxy, preferably methoxy or ethoxy, (C1- C4)-haloalkoxy, nitro and cyano. Particular preference is given here to the substituents methyl, methoxy, fluorine and chlorine. Substituted amino such as mono- or disubstituted amino means a radical from the group of the substituted amino radicals which are N- substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably N-mono- and TV,N-dialkylamino, (for example methylamino, ethylamino, Τν,Λ'-dimethylamino, N,N-diethylamino, AT,7V-di-n-propylamino, N,N-diisopropylamino or N,N-dibutylamino), N-mono- or TV,N- dialkoxyalkylamino groups (for example N-methoxymethylamino, N-methoxyethylamino, N,N- di(methoxymethyl)amino or Ar, A- di(methoxy ethy l)amino) , N-mono- and TV,N-diarylamino, such as optionally substituted anilines, acylamino, Ar,N-diacylamino, A-alkyl-N-arylamino, N-alkyl-A-acylamino and also saturated Af-heterocycles; preference is given here to alkyl radicals having 1 to 4 carbon atoms; here, aryl is preferably phenyl or substituted phenyl; for acyl, the definition given further below applies, preferably (C 1 -C4) - alkanoyl . The same applies to substituted hydroxylamino or hydrazine
According to the invention, the term "cyclic amino groups" embraces heteroaromatic or aliphatic ring systems having one or more nitrogen atoms. The heterocycles are saturated or unsaturated, consist of one or more optionally fused ring systems and optionally contain further heteroatoms such as, for example, one or two nitrogen, oxygen and/or sulphur atoms. Furthermore, the term also includes groups having a spiro ring or a bridged ring system. The number of atoms which form the cyclic amino group is not limited, and in the case of a one-ring system, for example, can consist of 3 to 8 ring atoms, and in the case of a two-ring system of 7 to 11 atoms.
Examples of cyclic amino groups having saturated and unsaturated monocyclic groups having a nitrogen atom as heteroatom which may be mentioned are 1-azetidinyl, pyrrolidino, 2-pyrrolidin- 1 -yl, 1 -pyrrolyl, piperidino, 1 ,4-dihydropyrazin- 1 -yl, 1 ,2,5,6-tetrahydropyrazin- 1 -yl, 1 ,4-dihydropyridin- 1 -yl, 1,2,5,6- tetrahydropyridin- 1 -yl, homopiperidinyl; examples of cyclic amino groups having saturated and unsaturated monocyclic groups having two or more nitrogen atoms as heteroatoms which may be mentioned are 1 -imidazolidinyl, 1 -imidazolyl, 1 -pyrazolyl, 1 -triazolyl, 1 -tetrazolyl, 1 -piperazinyl, 1- homopiperazinyl, 1 ,2-dihydropiperazin- 1 -yl, 1 ,2-dihydropyrimidin- 1 -yl, perhydropyrimidin- 1 -yl, 1,4- diazacycloheptan- 1 -yl; examples of cyclic amino groups having saturated and unsaturated monocyclic groups having one or two oxygen atoms and one to three nitrogen atoms as heteroatoms, such as, for example, oxazolidin-3-yl, 2,3-dihydroisoxazol-2-yl, isoxazol-2-yl, l,2,3-oxadiazin-2-yl, morpholino, examples of cyclic amino groups having saturated and unsaturated monocyclic groups having one to three nitrogen atoms and one to two sulphur atoms as heteroatoms which may be mentioned are thiazolidin-3-yl, isothiazolin-2-yl, thiomorpholino, or dioxothiomorpholino; examples of cyclic amino groups having saturated and unsaturated fused cyclic groups which may be mentioned are indol-l-yl, 1 ,2-dihydrobenzimidazol- 1 -yl, perhydropyrrolo[l ,2-a]pyrazin-2-yl; examples of cyclic amino groups having spirocyclic groups which may be mentioned are 2-azaspiro[4,5]decan-2-yl; examples of cyclic amino groups having bridged heterocyclic groups which may be mentioned are 2- azabicyclo[2.2. l]heptan-7-yl. Substituted amino also includes quaternary ammonium compounds (salts) with four organic substituents on the nitrogen atom.
Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, (C1-Gi)-alkyl, (C1-GO-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1- C4)-haloalkoxy, (C1-C4)-alkylsulphanyl, (C1-C4)-haloalkylsulphanyl, cyano, isocyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and -trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3 -dichlorophenyl, o-, m- and p- methoxyphenyl.
Optionally substituted cycloalkyl is preferably cycloalkyl, which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)- alkyl, (C1-C4)-haloalkyl and (C1-C4)-haloalkoxy, especially by one or two (C1-C4)-alkyl radicals.
Optionally substituted heterocyclyl is preferably heterocyclyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)- alkyl, (C i -C4)-haloalkyl, (C i -C4) -haloalkoxy , nitro and oxo, especially mono- or polysubstituted by radicals from the group of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl and oxo, most preferably substituted by one or two (C1-C4)-alkyl radicals.
Examples of alky 1 - sub stituted heteroaryl groups are furylmethyl, thienylmethyl, pyrazolylmethyl, imidazolylmethyl, 1 ,2,3- and 1 ,2,4-triazolylmethyl, isoxazolylmethyl, thiazolylmethyl, isothiazolylmethyl, 1,2,3-, 1,3,4-, 1 ,2,4- and 1 ,2,5-oxadiazolylmethyl, azepinylmethyl, pyrrolylmethyl, pyridylmethyl, pyridazinylmethyl, pyrimidinylmethyl, pyrazinylmethyl, 1,3,5-, 1,2,4- and 1,2,3- triazinylmethyl, 1,2,4-, 1,3,2-, 1,3,6- and 1 ,2,6-oxazinylmethyl, oxepinylmethyl, thiepinylmethyl and 1 ,2,4-diazepinylmethyl.
In the present combinations the compounds of formula (I) described in detail above are combined with other active compounds, namely (1) ectoparasiciticides in particular having acaricidal and/or insecticidal activity; (2) anthelmintics in particular having nematicidal, trematicidal and/or cestodicial activity; (3) anti-protozoal agents, in order to widen the activity spectrum. Potential mixing components for compounds of the formula (I) according to the invention for applications in animal health may be one or more compounds of the groups of active compounds listed below. The following active compounds can be used in the present combinations:
Exemplary active ingredients from the group of ectoparsiticides, as mixing partners, include, without limitation, the following insecticidal and/or acaricidal compounds
• acetylcholinesterase (AChE) inhibitors, for example carbamates, e.g. alanycarb, aldicarb,
aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate, formparanate or organophosphates, e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), aromophos-ethyl, aromfenvinfos (-methyl), autathiofos, cadusafos, c arbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/- ethyl), cyanofenphos, cyanophos, demeton-s-methyl, demeton-s-methylsulphone, dialifos, diazinon, dichlofenthion, dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, epn, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl o-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion (- methyl/-ethyl), phenthoate, phorate, phosalone, phosmet, phosphamidone, phosphocarb, phoxim, pirimiphos ( -methyl/'- ethyl) , profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, vamidothion, trichlorfon, imicyafos;
• GABA-gated chloride channel antagonists, for example organochlorines, e.g. camphechlor,
chlordane, endosulfan, heptachlor, lindane or m-diamides, e.g. broflanilide or phenylpyrazoles, e.g. flufiprole, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole or arylisoxazo lines, not excluding related classes with pyrroline or pyrrolidine moiety replacing the isoxazoline ring , e.g. fluralaner, afoxolaner, sarolaner, lotilaner, fluxametamide, 4 - [ 5 -(3 , 5 -dichlorophenyl) - 5 - (trifluoromethyl)-4,5-dihydro-l,2-oxazol-3-yl]-2-methyl-n-(l -oxidothietan-3-yl)benzamide (known from WO2009/080250);
• sodium channel modulators / voltage-dependent sodium channel blockers, for example pyrethroids, e.g. heptafluthrin, tetramethylfluthrin, acrinathrin, allethrin (d-cis-trans, d-trans-), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-s-cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin (lambda-), cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, deltamethrin, empenthrin (lr-isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, garnrna-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (lr-trans isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU15525, silafluofen, tau-f!uvalinate, tefluthrin, terallethrin, tetramethrin (-lr- isomer), tralomethrin, trans fluthrin, pyrethrins (pyrethrum), halfenprox, momfiuorothrin or halogenated carbonhydrogen compounds (HCHs), e.g.
methoxychlor or oxadiazines, e.g. indoxacarb or semicarbazones, e.g. metaflumizone;
acetylcholine receptor agonists/ antagonists, for example neonicotinoids, e.g. imidacloprid, thiacloprid, imidaclothiz, nitenpyram, thiamethoxam, clothianidin, dinotefuran, acetamiprid, nithiazine, paichongding, cycloxaprid, guadipyr, N-[(2E)-l-[(6-chloropyridin-3-yl)methyl]pyridin- 2(lH)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012/029672), (3E)-3-[l-[(6-chloro-3- pyridyl)methyl] -2-pyridylidene]- 1 ,1,1 -trifluoro-propan-2-one (known from WO2013/144213) or sulfoximine insecticides, e.g. sulfoxaflor or butenolides, e.g. flupyradifurone or nereistoxin analogues, e.g. cartap, bensultap, thiocyclam, thiosultap sodium, thiocyclam hydrogen oxalate; acetylcholine receptor modulators, for example spinosynes, e.g. spinosad, spinetoram or zwitterionic insecticides, e.g. triflumezopyrim, dicloromezotiaz, l-[(2-chloro-l,3-thiazol-5- yl)methyl] -4-oxo-3 -phenyl-4H-pyrido[ 1 ,2-a]pyrimidin- 1 -ium-2-olate (known from
WO2009/099929), l-[(6-chloropyridin-3-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[l,2-a]pyrimidin-l - ium-2-olate (known from WO2009/099929);
ligand-gated chloride channel activators, for example macrocyclic lactones, e.g. emamectin benzoate, abamectin, ivermectin, milbemectin, milbemycin oxime, latidectin, lepimectin, selamectin, doramectin, eprinomectin, moxidectin, nemadectin or indole diterpenes, e.g.
nodulisporic acid A;
juvenile hormone mimetics, for example juvenile hormon analogues, e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxyfen, triprene;
selective homopteran feeding blockers, for example triazinones, e.g. pymetrozine or pyridine carboxamides, e.g. flonicamid;
Biologicals, hormones or pheromones, for example natural products, e.g. codlemone, thuringiensin or neem components, e.g. azadirachtin A or other classes, e.g. preparations based on bacillus firmus (i-1582; bioneem; votivo);
inhibitors of oxidative phosphorylation, mitochondrial ATP synthase disruptors, for example organotin compounds, e.g. azocyclotin, cyhexatin, fenbutatin-oxide or other classes, e.g.
diafenthiuron, tetradifon, propargite;
decouplers of oxidative phosphorylation by interruption of H-proton gradients, for example dinitrophenols, e.g. binapacryl, dinobuton, dinocap, DNOC or pyrroles, e.g. chlorfenapyr or other decouplers, e.g. sulfluramid; inhibitors of chitin biosynthesis or cuticle development, for example benzoylureas, e.g. bistrifluron, chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron or other inhibitors of cuticle development, e.g. buprofezin, cyromazine;
ecdysone agonists/ disrupters, for example diacylhydrazines, e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide, fufenozide;
octopaminergic agonists, for example amidine derivatives, e.g. amitraz, cymiazole, demiditraz, chlormebuform;
mitochondrial complex I electron transport inhibitors, for example METIs, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, dicofol or rotenones, e.g.
rotenone (Derris);
mitochondrial complex 11 electron transport inhibitors, for example beta-ketonitrile derivatives, e.g. cyenopyrafen, cyflumetofen or hydrazones, e.g. hydramethylnon or other classes, e.g. fluopyram, 4- (7-bromo- 1 ,3 -benzodioxol-5 -yl) - 1 -(3 -methoxypyrazin-2-yl) -3 -(trifluoromethyl) - 1 H-pyrazol-5 - amine (known from WO 2010136145, example 74, CAS No 1257061-92-9);
mitochondrial complex I I I electron transport inhibitors, for example quinones, e.g. acequinocyl or strobilurines, e.g. flufenoxystrobin, pyriminostrobin or other classes, e.g. fluacrypyrim;
inhibitors of acetylCoA carboxylase (fatty acid synthesis), for example tetronic and tetramic acids, e.g. spirodiclofen, spiromesifen, spirotetramat, 3 -(2 , 5 -dimethy lpheny 1) -4 -hydroxy- 8 -methoxy- 1 ,8- diazaspiro[4.5]dec-3-en-2-one (known from WO2009/049851), butyl [2-(2,4-dichlorophenyl)-3- oxo-4-oxaspiro[4.5]dec-l -en-l-yl] carbonate (known from CN 102060818) or other classes, e.g. 3- (2,5-dimethylphenyl)-8-methoxy-2-oxo-l,8-diazaspiro[4.5]dec-3-en-4-yl-ethylcarbonate (known from WO2009/04985 i);
ryanodine receptor modulators, for example phthalic acid diamides, e.g. flubendiamide, cyhalodiamide or anthranilamides, e.g. chlorantraniliprole, cyantraniliprole, tetraniliprole, tetrachloroantraniliprole (SYP9080), cyclaniliprole, methyl 2-[2-( { [3-bromo- 1 -(3-chloropyridin-2- yl)-lh-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-methylhydrazinecarboxylate (known from WO2005/085216), methyl 2-[3,5-dibromo-2-({[3-bromo-l-(3-chloropyridin-2-yl)-lh- pyrazol-5 -yl] carbonyl } amino)benzoyl] -2 -ethylhydrazinecarboxylate (known from
WO2005/085216), N-[2-(tert-butylcarbamoyl)-4-chloro-6-methylphenyl]-l -(3-chloropyridin-2-yl)- 3-(fluoromethoxy)-lh-pyrazole-5-carboxamide (known from WO2008/134969, methyl N-[[2-[[5- bromo-2-(3-chloro-2-pyridyl)pyrazole-3-carbonyl]amino]-5-cyano-3-methyl-benzoyl]-ethyl- amino] carbamate (known from WO2005/085216), methyl 2-[2-( {[3-bromo- 1 -(3-chloropyridin-2 - yl)-lH-pyrazol-5-yl]carbonyl}amino)-5-chloro-3-methylbenzoyl]-2-methylhydrazinecarboxylate (known from WO2005/085216);
active compounds with unknown or non-specific mode of action, for example mite growth inhibitors, e.g. clofentezine, etoxazole, hexythiazox, amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, quinomethionate, chlordimeform, chlorobenzilate, clothiazoben, cycloprene, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, f!ufenerim, flutenzin, gossyplure, japonilure, metoxadiazone, petroleum, potassium oleate, pyridalyl, tetrasul, triarathene or other classes, e.g. diflovidazin, chinomethionat, pyrifluquinazon or feeding inhibitors, e.g. cryolite; · compounds, from other classes, e.g. 4-(but-2-yn-l-yloxy)-6-(3-chlorophenyl)pyrimidine (known from WO2003/076415), fluazaindolizine, afidopyropen, flometoquin, fluensulfone, fluhexafon, iprodione, meperfluthrin, N-(methylsulfonyl)-6-[2-(pyridin-3-yl)-l,3-thiazol-5-yl]pyridine-2- carboxamide (known from WO2012/000896), N-[2-(5-amino-l ,3,4-thiadiazol-2-yl)-4-chloro-6- methylphenyl]-3-bromo-l -(3-chloropyridin-2-yl)-lh-pyrazole-5-carboxamide (known from CN 102057925), N-[3-(benzylcarbamoyl)-4-chlorophenyl] - 1 -methyl-3-(pentafluoroethyl)-4-
(trifluoromethyl)-lh-pyrazole-5-carboxamide (known from WO2010/051926)., PF1364 (CAS Reg. No. 1204776-60-2), pyflubumide, tioxazafen, { 1 '- [(2E) -3 -(4-chlorophenyl)prop-2 -en- 1 -yl] -5 - fluorospiro[indol-3,4'-piperidin]-l(2H)-yl}(2-chloropyridin-4-yl)methanone (known from
WO2003/106457), l-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl} -3- (trifluoromethyl)- 1 H- 1 ,2,4-triazole-5 -amine (known from WO2006/043635), 2-chloro-N-[2-{ l -
[(2E)-3-(4-chlorophenyl)prop-2-en-l -yl]piperidin-4-yl} -4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006/003494), 4-(3-{2,6-dichloro-4-[(3,3-dichloroprop-2-en-l- yl)oxy]phenoxy}propoxy)-2-methoxy-6-(trifluoromethyl)pyrimidine (known from CN101337940), 4-(but-2-yn-l-yloxy)-6-(3,5-dimethylpiperidin-l-yl)-5-fluoropyrimidine (known from
WO2004/099160);
• bee hive varroa acaricides, for example organic acids, e.g. formic acid, oxalic acid;
• synergists that can be used to further enhance the activity, MGK264 (N- octylbicycloheptenecarboxamide), piperonyl butoxide (PBO) and verbutin.
In addition to these groups, it is also possible to use short-term repellents in mixtures or a combined application. Examples are DEET (N,N-diethyl-3 -methylbenzamide), icaridin (sec-butyl 2-(2- hydroxyethyl)piperidine- 1 -carboxylate), indalone (butyl 3,4-dihydro-2, 2-dimethyl-4-oxo-2H-pyran-6- carboxylate), dihydronepetalactones, nootkatone, IR3535 (3 -[N-butyl-N-acetyl] -aminopropionic acid ethyl ester), 2-ethylhexane- 1 ,3 -diol, (lR,2R,5R)-2-(2-hydroxypropan-2-yl)-5-methyl-cyclohexan-i-ol, dimethyl benzene- 1 ,2 -dicarboxylate , dodecanoic acid, undecan-2-one, N,N-diethyl-2-phenylacetamide and essential oils or other plant ingredients of known repellent action such as, for example, borneol, callicarpenal, 1,8- cineol (eucalyptol), carvacrol, b-citronellol, a-copaene, coumarin (or its synthetic derivatives known from US20120329832).
The following groups of the aforementioned groups are prefer ed mixing partners: acetylcholine receptor agonists/ antagonists, acetylcholine receptor modulators, GABA-gated chloride channel antagonists, ligand-gated chloride channel activators, octopaminergic agonists, sodium channel modulators / voltage- dependent sodium channel blockers. Exemplary active ingredients from the group of anthelmintics, as mixing partners, include, without limitation, the following nematicidally, trematicidally and/or cestocidally active compounds:
• from the class of macrocyclic lactones, for example: abamectin, emamectin, ivermectin,
milbemectin, latidectin, lepimectin, selamectin, doramectin, eprinomectin, moxidectin, milbemycin, nemadectin;
• from the class of benzimidazoles and probenzimidazoles, for example: albendazole, albendazole- sulphoxide, cambendazole, cyclobendazole, febantel, fenbendazole, flubendazole, mebendazole, netobimin, oxfendazole, oxibendazole, parbendazole, thiabendazole, thiophanate, triclabendazole; · from the class of depsipeptides, preferably cyclic depsipetides, in particular 24-membered cyclic depsipeptides, for example: emodepside, PF1022A (known from EP 382173, compound I);
• from the class of tetrahydropyrimidines, for example: morantel, pyrantel, oxantel;
• from the class of imidazothiazoles, for example: butamisole, levamisole, tetramisole;
• from the class of aminophenylamidines, for example: amidantel, deacylated amidantel (dAMD), tribendimidine ;
• from the class of aminoacetonitriles, for example: monepantel;
• from the class of paraherquamides, for example: derquantel, paraherquamide;
• from the class of salicylanilides, for example: bromoxanide, brotianide, clioxanide, closantel, niclosamide, oxyclozanide, rafoxanide, tribromsalan;
· from the class of substituted phenols, for example: bithionol, disophenol, hexachlorophene,
niclofolan, meniclopholan, nitroxynil;
• from the class of organophosphates, for example: coumaphos, haloxon, crufomate,
dichlorvos/ ddvp, naphthalofos, trichlorfon;
• from the class of piper azinones / quinolines, for example: praziquantel, epsiprantel;
· from the class of piperazines, for example: piperazine, hydroxyzine;
• from the class of tetracyclines, for example: chlorotetracycline, doxycyclin, oxytetracyclin,
rolitetracyclin, tetracyclin;
• from diverse other classes, for example: amoscanate, bephenium, bunamidine, clonazepam,
clorsulon, diamfenetide, dichlorophen, diethylcarbamazine, emetine, hetolin, hycanthone, lucanthone, miracil, mirasan, niridazole, nitroxynile, nitroscanate, oltipraz, omphalotin, resorantel, oxamniquine;
Exemplary active ingredients from the group of antiprotozoal active compounds (including anticoccidial compounds), include, without limitation, the following active compounds:
• from the class of triazines, for example: toltrazuril, diclazuril, ponazuril, letrazuril;
· from the class of polylether ionophores, for example: salinomycin, maduramicin, narasin,
monensin; • from the class of macrocyclic lactones, for example: erythromycin, milbemycin;
• from the class of quinolones, for example: enrofloxacin, pradofloxacin;
• from the class of quinines, for example: chloroquine;
• from the class of pyrimidines, for example: pyrimethamine ;
· from the class of sulfonamides, for example: sulfaquinoxaline, trimethoprim, sulfaclozin;
• from the class of thiamines, for example: amprolium;
• from the class of lincosamides, for example: clindamycin;
• from the class of carbanilides, for example: imidocarb;
• from the class of nitrofuranes, for example: nifurtimox;
· from the class of quinazolinone alkaloids, for example: halofuginon;
• from the class of diverse other classes, for example: oxamniquine, paromomycin;
• from the class of vaccines or antigenes from microorganisms, for example: Babesia canis canis, Babesia canis rossi, Babesia canis vogeli, Dictyocaulus viviparus, Eimeria acervulina, Eimeria brunetti, Eimeria maxima, Eimeria mitis, Eimeria necatrix, Eimeria praecox, Eimeria tenella, Leishmania infantum;
The active compounds identified here by their common names are known and are described, for example, in the pesticide handbook ("The Pesticide Manual" 14th Ed., British Crop Protection Council 2006) or can be found on the Internet (e.g. http://www.alanwood.net/pesticides). The active compounds described herein may form salts and in this case may be used in salt form as well. Salts which are suitable according to the invention, for example salts with bases or acid addition salts, are all customary non-toxic salts, preferably agriculturally and/or physiologically acceptable salts. For example salts with bases or acid addition salts. Preference is given to salts with inorganic bases such as, for example, alkali metal salts (e.g. sodium, potassium or caesium salts), alkaline earth metal salts (e.g. calcium or magnesium salts), ammonium salts or salts with organic bases, in particular with organic amines, such as, for example, triethylammonium, dicyclohexylammonium, N,AP- dibenzylethylenediammonium, pyridinium, picolinium or ethanolammonium salts, salts with inorganic acids (e.g. hydrochlorides, hydrobromides, dihydrosulphates, trihydrosulphates or phosphates), salts with organic carboxylic acids or organic sulphoacids (e.g. formates, acetates, trifluoroacetates, maleates, tartrates, methanesulphonates, benzenesulphonates or 4-toluenesulphonates). It is known that t-amines such as some of the compounds contemplated herein are capable of forming N-oxides, which also represent salts according to the invention.
The compounds described herein may, depending on the nature of the substituents, be in the form of geometric and/or optically active isomers or corresponding isomer mixtures in different compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixture of these isomers. If appropriate, the compounds may be present in various polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are provided by the invention and can be used in accordance with the invention.
The present invention is directed to combinations of compounds of formula (I) with ectoparasiciticides, anthelmintics or anti-protozoal agents. I.e..the compounds of the general formula (I) can be mixed or applied jointly with other ectoparasiticidal, anthelmintic or anti-protozoal agents. In these mixtures or joint applications the spectrum of activity of the agents is widened and/or improved as compared to the the individual active compounds in these applications.
In the animal health sector, i.e. in the field of veterinary medicine, the active compounds according to the present invention act against animal parasites, in particular ectoparasites and/or endoparasites. The term "endoparasites" includes especially helminths such as cestodes, nematodes or trematodes, and protozoa such as coccidia. Ectoparasites are typically and preferably arthropods, especially insects such as flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; or acarids such as ticks, for example hard ticks or soft ticks, or mites such as scab mites, harvest mites, bird mites and the like, and also aquatic ectoparasites such as copepods.
These parasites include the following ectoparasites (in particular insects, acarids):
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phthirus spp. and Solenopotes spp.; specific examples are: Linognathus setosus, Linognathus vituli, Linognathus ovillus, Linognathus oviformis, Linognathus pedalis, Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotes capillatus;
From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.; specific examples are: Bovicola bo vis, Bovicola ovis, Bovicola limbata, Damalina bo vis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis, Werneckiella equi;
From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp., Tipula spp.; specific examples are: Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus , Anopheles gambiae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Fannia canicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludosa, Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomus papatasi, Phlebotomus longipalpis, Odagmia ornata, Wilhelmia equina, Boophthora erythrocephala, Tabanus bromius, Tabanus spodopterus, Tabanus atratus, Tabanus sudeticus, Hybomitra ciurea, Chrysops caecutiens, Chrysops relictus, Haematopota pluvialis, Haematopota italica, Musca autumnalis, Musca domestica, Haematobia irritans irritans, Haematobia irritans exigua, Haematobia stimulans, Hydrotaea irritans, Hydrotaea albipuncta, Chrysomya chloropyga, Chrysomya bezziana, Oestrus ovis, Hypoderma bovis, Hypoderma lineatum, Przhevalskiana silenus, Dermatobia hominis, Melophagus ovinus, Lipoptena capreoli, Lipoptena cervi, Hippobosca variegata, Hippobosca equina, Gasterophilus intestinalis, Gasterophilus haemorroidalis, Gasterophilus inermis, Gasterophilus nasalis, Gasterophilus nigricornis, Gasterophilus pecorum, Braula coeca;
From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.; specific examples are: Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis; From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp. (e.g. Suppella longipalpa);
From the subclass of the Acari (Acarina) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Qrnithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalus spp. (the original genus of multihost ticks), Qrnithonyssus spp., Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp., Acarapis spp.; specific examples are: Argas persicus, Argas reflexus, Qrnithodorus moubata, Otobius megnini, Rhipicephalus (Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus, Rhipicephalus (Boophilus) annulatus, Rhipicephalus (Boophilus) calceratus, Hyalomma anatolicum, Hyalomma aegypticum, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes canisuga, Ixodes pilosus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Haemaphysalis concinna, Haemaphysalis punctata, Haemaphysalis cinnabarina, Haemaphysalis otophila, Haemaphysalis leachi, Haemaphysalis longicorni, Dermacentor marginatus, Dermacentor reticulatus, Dermacentor pictus, Dermacentor albipictus, Dermacentor andersoni, Dermacentor variabilis, Hyalomma mauritanicum, Rhipicephalus sanguineus, Rhipicephalus bursa, Rhipicephalus appendiculatus, Rhipicephalus capensis, Rhipicephalus turanicus, Rhipicephalus zambeziensis, Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum, Amblyomma hebraeum, Amblyomma cajennense, Dermanyssus gallinae, Ornithonyssus bursa, Ornithonyssus sylviarum, Varroa j acobsoni; From the order of the Actinedida (Prostigmata) und Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.; specific examples are: Cheyletiella yasguri, Cheyletiella blakei, Demodex canis, Demodex bo vis, Demodex ovis, Demodex caprae, Demodex equi, Demodex caballi, Demodex suis, Neotrombicula autumnalis, Neotrombicula desaleri, Neoschongastia xerothermobia, Trombicula akamushi, Otodectes cynotis, Notoedres cati, Sarcoptis canis, Sarcoptes bo vis, Sarcoptes ovis, Sarcoptes rupicaprae (=S. caprae), Sarcoptes equi, Sarcoptes suis, Psoroptes ovis, Psoroptes cuniculi, Psoroptes equi, Chorioptes bo vis, Psoergates ovis, Pneumonys soidic mange, Pneumonyssoides caninum, Acarapis woodi.
From the subclass of the copepods with the order of the Siphonostomatoida in particular the genera Lepeophtheirus and Caligus; the species Lepeophtheirus salmonis, Caligus elongatus and Caligus clemensi may be mentioned by way of example and with particular preference. Exemplary pathogenic endoparasites, which are helminths, include platyhelmintha (e.g. monogenea, cestodes and trematodes), nematodes, acanthocephala, and pentastoma. Additional exemplary helminths include , without any limitation:
Monogenea: e.g.: Gyrodactylus spp., Dactylogyrus spp., Polystoma spp..
Cestodes: From the order of the Pseudophyllidea for example: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp..
From the order of the Cyclophyllida for example: Mesocestoides spp., Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosoma spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., Andyra spp., Bertiella spp., Taenia spp., Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp..
Trematodes: From the class of the Digenea for example: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoeluin spp., Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoron spp., Gigantocotyle spp., Fischoederius spp., Gastrothylacus spp., Notocotylus spp., Catatropis spp., Plagiorchis spp., Prosthogonimus spp., Dicrocoelium spp., Eurytrema spp., Troglotrema spp., Paragonimus spp., Collyriclum spp., Nanophyetus spp., Opisthorchis spp., Clonorchis spp. Metorchis spp., Heterophyes spp., Metagonimus spp.. Nematodes: Trichinellida for example: Trichuris spp., Capillaria spp., Trichomosoides spp., Trichinella spp..
From the order of the Tylenchida for example: Micronema spp., Strongyloides spp..
From the order of the Rhabditina for example: Strongylus spp., Triodontophorus spp., Oesophagodontus spp., Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., Cyclococercus spp., Cylicostephanus spp., Oesophagostomum spp., Chabertia spp., Stephanurus spp., Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., Elaphostrongylus spp. Parelaphostrongylus spp., Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp., Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp.
From the order of the Spirurida for example: Oxyuris spp., Enterobius spp., Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp.; Ascaris spp., Toxascaris spp., Toxocara spp., Baylisascaris spp., Parascaris spp., Anisakis spp., Ascaridia spp.; Gnathostoma spp., Physaloptera spp., Thelazia spp., Gongylonema spp., Habronema spp., Parabronema spp., Draschia spp., Dracunculus spp.; Stephanofilaria spp., Parafilaria spp., Setaria spp., Loa spp., Dirofilaria spp., Litomosoides spp., Brugia spp., Wuchereria spp., Onchocerca spp. Acantocephala: From the order of the Oligacanthorhynchida z.B: Macracanthorhynchus spp., Prosthenorchis spp.; from the order of the Polymorphida for example: Filicollis spp.; from the order of the Moniliformida for example: Moniliformis spp.,
From the order of the Echinorhynchida for example Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp. Pentastoma: From the order of the Porocephalida for example Linguatula spp.
Exemplary parasitic protozoa include , without any limitation:
Mastigophora (Flagellata), such as, for example, Trypanosomatidae, for example, Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, L. donovani, L. tropica, such as, for example, Trichomonadidae, for example, Giardia lamblia, G. canis.
S arcomastigophora (Rhizopoda), such as Entamoebidae, for example, Entamoeba histolytica, Hartmanellidae, for example, Acanthamoeba sp., Harmanella sp. Apicomplexa (Sporozoa), such as Eimeridae, for example, Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bo vis, E. brunetti, E. canis,
E. chinchillae, E. clupearum, E. columbae, E. contorta, E. crandalis, E. debliecki, E. dispersa, E. ellipsoidales, E. falciformis, E. faurei, E. flavescens, E. gallopavonis, E. hagani, E. intestinalis, E. iroquoina, E. irresidua, E. labbeana, E. leucarti, E. magna, E. maxima, E. media, E. meleagridis, E. meleagrimitis, E. mitis, E. necatrix, E. ninakohlyakimovae, E. ovis, E. parva, E. pavonis, E. perforans,
E. phasani, E. piriformis, E. praecox, E. residua, E. scabra, E. spec, E. stiedai, E. suis, E. tenella, E. truncata, E. truttae, E. zuernii, Globidium spec, Isospora belli, I. canis, I. felis, I. ohioensis, I. rivolta, I. spec, I. suis, Cystisospora spec, Cryptosporidium spec, in particular C. parvum; such as Toxoplasmadidae, for example, Toxoplasma gondii, Hammondia heydornii, Neospora caninum,
Besnoitia besnoitii; such as Sarcocystidae, for example, Sarcocystis bovicanis, S. bovihominis, S. ovicanis, S. ovifelis, S. neurona, S. spec, S. suihominis, such as Leucozoidae, for example,
Leucozytozoon simondi, such as Plasmodiidae, for example, Plasmodium berghei, P. falciparum, P. malariae, P. ovale, P. vivax, P. spec, such as Piroplasmea, for example, Babesia argentina, B. bovis, B. canis, B. spec, Theileria parva, Theileria spec, such as Adeleina, for example, Hepatozoon canis, H. spec.
The combinations according to the invention are also suitable for controlling arthropods, helminths and protozoa which attack animals. The animals include agricultural livestock, for example cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, cultured fish, honey bees. The animals also include domestic animals - also referred to as companion animals - for example dogs, cats, caged birds, aquarium fish, and what are known as test animals, for example hamsters, guinea pigs, rats and mice.
The control of these ectoparasites - or, in other embodiments, helminths and/or protozoa - should reduce cases of death and improve the performance (for meat, milk, wool, hides, eggs, honey etc.) and the health of the host animal, and so the use of the active compounds according to the invention enables more economically viable and easier animal husbandry.
For example, it is desirable to prevent or to interrupt the uptake of blood from the host by the parasites (if relevant). Control of the parasites can also contribute to preventing the transmission of infectious substances. The term "control" as used herein with regard to the field of animal health means that the active compounds act by reducing the occurrence of the parasite in question in an animal infested with such parasites to a harmless level. More specifically, "control" as used herein means that the active compound kills the parasite in question, retards its growth or inhibits its proliferation. In general, the combinations according to the invention can be employed directly when they are used for the treatment of animals. They are preferably employed in the form of pharmaceutical compositions which may comprise the pharmaceutically acceptable excipients and/or auxiliaries known in the prior art. In general, such compositions comprise from 0.01 to 98% by weight of active compound, preferably from 0.5 to 90% by weight.
The combinations are employed (administered) in a known manner, by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, for example by injection (intramuscular, subcutaneous, intravenous, intraperitoneal inter alia), implants, by nasal administration, by dermal administration in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, earmarks, tailmarks, limb bands, halters, marking devices, etc. The active compounds can be formulated as a shampoo or as suitable formulations applicable in aerosols or unpressurized sprays, for example pump sprays and atomizer sprays, In the case of employment for livestock, poultry, domestic pets, etc., the active compounds can be employed as formulations (for example powders, wettable powders ["WP"], emulsions, emulsifiable concentrates ["EC"], free-flowing compositions, homogeneous solutions and suspension concentrates ["SC"]), which contain the active compounds in an amount of 1 to 80% by weight, directly or after dilution (e.g. 100- to 10 000-fold dilution ), or they can be used as a chemical bath. The compounds according to general formula (I) can be prepared as described in WO2014/122083 .
Experimental part
Preparation Process A (known from WO2014/122083)
Example (Ic-1) 2 -Chloro-N-cyclopropyl-5 -[2 '-methyl-5 '-(pentafluoroethyl) -4'-(trifluoromethyl) -2 Ή- 1 ,3 '- bipyrazol-4-yl]benzamide
Figure imgf000040_0001
2.00 g (6.99 mmol) of 5-fluoro-l-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole, 1.03 g (6.99 mmol) of 4-bromo- 1 H-pyrazole and 1.93 g of potassium carbonate are suspended in 50 ml of tetrahydrofuran p. a. The reaction mixture is heated under reflux for 16 h. The cooled reaction mixture is filtered and the solvent is removed under reduced pressure. The residue is purified by column chromatography on silica gel.
This gives 0.69 g of 4-bromo-2'-methyl-5'-(pentafluoroethyl)-4'-(trifluoromethyl)-2'H-l ,3'-bipyrazole as a colourless solid. 1H-NMR (400 MHz, d3-acetonitrile): δ = 8.00 (s, 1H), 7.91 (s, 1H), 3.71 (s, 3H). HPLC -MS a : logP = 4.14, mass (m/z) = 413 [M+H]+. 10.5 ml of isopropyl alcohol are added to 150 mg (0.36 mmol) of 4 -bromo-2 '-methyl-5 '- (pentafluoroethyl)-4'-(trifluoromethyl)-2'H-l,3'-bipyrazole, 87 mg (0.36 mmol) of [4-chloro-3- (cyclopropylcarbamoyl)phenyljboronic acid, 21 mg (0.01 mmol) of tetrakis(triphenylphosphine)palladium and 1.1 ml of a 1M aqueous sodium bicarbonate solution, and the mixture is heated under reflux for 3 h. The reaction mixture is concentrated to dryness and the residue is taken up in ethyl acetate. The organic phase is washed twice with water, dried over sodium sulphate, filtered and concentrated to dryness. The crude product is purified by column chromatography on silica gel.
This gives 71 mg of 2-chloro-N-cyclopropyl-5-[2'-methyl-5'-(pentafluoroethyl)-4'-(trifluoromethyl)-2'H- 1 ,3'-bipyrazol-4-yl]benzamide as a colourless solid. 1H-NMR (400 MHz, d3-acetonitrile): δ = 8.26 (s, 1H), 8.24 (s, 1H), 7.67 (d, 1H), 7.65 (dd, 1H), 7.48 (d, 1H), 6.95 (s, lH), 3.75 (s, 3H), 2.82-2.87 (m, 1H), 0.75-0.80 (m, 2H). 0.57-0.62 (m, 2H).
HPLC-MSa): logP = 3.79, mass (m/z) = 528 [M+H]+.
Preparation Process B (known from WO2014/ 122083)
Example (Ibl) N-Benzyl-2-ehloro-5- { 1 -[1 -methvl-3-(pentafluoroethvl)-4-(trifluoromethvl)-l_ff-pyrazol- 5-yl]-1H-imidazol-4-yl}benzamide
Figure imgf000042_0001
500 mg (1.74 mmol) of 5-fluoro- 1 -methyl-3 -(pentafluoroethyl)-4-(trifluoromethyl)- 1 H-pyrazole, 339 mg (1.74 mmol) of 4-iodo- 1 H-imidazole and 483 mg (3.49 mmol) of potassium carbonate are suspended in 20 ml of tetrahydrofuran p. a. The reaction mixture is heated under reflux until the reaction has gone to completion. The cooled reaction mixture is filtered and the solvent is removed under reduced pressure. The residue is purified by column chromatography on silica gel.
This gives 370 mg of 5-(4-iodo- 1 H-imidazol- 1 -yl)-l -methyl-3 -(pentafluoroethyl)-4-(trifluoromethyl)- 1 H-pyrazole as a colourless solid.
1H-NMR (400 MHz, ds-acetonitrile): δ = 7.68 (d, 1H), 7.43 (d, 1H), 3.68 (s, 3H) ppm. HPLC-MSa): logP = 3.47, mass (m/z) = 461 [M+H]+ .
20 ml of isopropyl alcohol are added to 250 mg (0.54 mmol) of 5 -(4-iodo- 1 H-imidazol- 1 -yl) - 1 -methyl - 3-(pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole, 161 mg (0.54 mmol) of methyl 2-chloro-5- (4,4,5, 5-tetramethyl-l,3,2-dioxaborolan-2-yl)benzoate, 31 mg (0.02 mmol) of tetrakis(triphenylphosphine)palladium and 1.66 mL of a 1M aqueous sodium bicarbonate solution, and the mixture is heated under reflux for 3 h. The reaction mixture is concentrated to dryness and the residue is taken up in ethyl acetate. The organic phase is washed twice with water, dried over sodium sulphate, filtered and concentrated to dryness. The crude product is purified by column chromatography on silica gel.
This gives 160 mg of methyl 2-chloro-5- { l-[l -methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-lH- pyrazol-5 -yl] - 1 H-imidazol-4-yl } benzoate as a colourless solid. 1H-NMR (400 MHz, ds-acetonitrile): δ = 8.28 (d, 1H), 7.95 (dd, 1H), 7.83 (d, 1H), 7.71 (d, 1H), 7.55 (d, 1H), 3.91 (s, 311), 3.73 (s, 3H) ppm.
HPLC-MSa): logP = 4.26, mass (m/z) = 503 [M+H]+.
150 mg (0.29 mmol) of methyl 2-chloro-5- { 1 -[ 1 -methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)- 1H- pyrazol-5 -yl] - 1 H-imidazol-4-yl } benzoate are dissolved in 6.3 ml of tetrahydrofuran p. a., and the mixture is cooled with ice. 8.54 mg of lithium hydroxide, dissolved in 0.7 ml of water, are added drop wise to the reaction solution. After 10 minutes, the ice cooling is removed and the reaction mixture is stirred at room temperature for another 18 h. The reaction mixture is acidified with 1M hydrochloric acid and the product is extracted with ethyl acetate. The organic phase is washed with saturated sodium chloride solution, dried over sodium sulphate, filtered and concentrated under reduced pressure. This gives 127 mg of 2-chloro-5- { 1 -[ 1 -methyl-3 -(pentafluoroethyl)-4-(trifluoromethyl)- 1 H-pyrazol-5 - yl] - 1 H-imidazol-4-yl } benzoic acid as a colourless solid. 1H-NMR (400 MHz, d3-acetonitrile): δ = 8.31 (d, 1H), 7.96 (dd, 1H), 7.83 (d, 1H), 7.72 (d, 1H), 7.55 (d, 1H), 3.73 (s, 3H) ppm.
HPLC-MSa): logP = 3.30, mass (m/z) = 489 [M+H]+. 127 mg (0.26 mmol) of 2-chloro-5- { 1 -[ 1 -methyl-3 -(pentafluoroethyl)-4-(trifluoromethyl)- 1 H-pyrazol-5 - yl] - 1 H-imidazol-4-yl } benzoic acid, 42 mg (0.39 mmol) of benzylamine and 67 mg (0.52 mmol) of N,N- diethylisopropylamine are dissolved in a mixture of 4.6 ml of dichloromethane and 0.4 ml of N,N- dimethylformamide. 53 mg (0.39 mmol) of N-hydroxybenzotriazole and 60 mg (0.31 mmol) of N-ethyl- N'-(3-dimethylaminopropyl)carbodiimide hydrochloride are added. The reaction mixture is stirred at room temperature for 16 h. The reaction solution is diluted with ethyl acetate and then washed successively with 1M hydrochloric acid, 1M aqueous sodium hydroxide solution and saturated sodium chloride solution. The crude product is purified by column chromatography on silica gel.
This gives 77 mg of /V-benzyl-2-chloro-5- { 1 -[ 1 -methyl-3 -(pentafluoroethyl)-4-(trifluoromethyl)- 1 H- pyrazol-5 -yl] - 1 H-imidazol-4-yl } benzamide as a colourless solid.
1H-NMR (400 MHz, ds-acetonitrile): δ = 7.94 (d, 1H), 7.88 (dd, 1H), 7.82 (d, 1H), 7.71 (d, 1H), 7.49 (d,
1H), 7.25-7.43 (m, 5H), 4.56 (d, 2H), 3.73 (s, 3H) ppm.
HPLC-MSa): logP = 4.00, mass (m/z) = 578 [M+H]+. a) Note regarding the determination of the logP values and mass detection: The determination of the given logP values was carried out in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C18). Agilent 1100 LC system; 50*4.6 Zorbax Eclipse Plus CI 8 1.8 micron; mobile phase A: acetonitrile (0.1% formic acid); mobile phase B: water (0.09% formic acid); linear gradient from 10% acetonitrile to 95% acetonitrile in 4.25 min, then 95% acetonitrile for a further 1 .25 min; oven temperature 55°C; flow rate: 2.0 ml/min. Mass detection is carried out via an Agilend MSD system. The compounds listed in Tables 1 & 2 were prepared using the Preparation Processes A to C described above.
Figure imgf000044_0001
Figure imgf000044_0002
Table 2
Figure imgf000045_0001
Figure imgf000045_0002
Table 3
Figure imgf000046_0001
Figure imgf000046_0002
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000068_0002
Figure imgf000069_0001
Figure imgf000070_0001
The stated mass is the peak of the isotope pattern of the [M+H]+ ion of the highest intensity; if the [M- H ]- ion was detected, the stated mass is marked with 2.
2 The stated mass is the peak of the isotope pattern of the [M-H]- ion of the highest intensity. If the mass was determined by a GCMS (see below for methods) measurement, the stated mass is marked with 3. *) Note regarding the determination of the logP values and mass detection: The determination of the given logP values was carried out in accordance with EEC Directive 79/831 Annex V.A8 by 1 1 PLC (High Performance Liquid Chromatography) on a reversed-phase column (CI 8). Agilent 1100 LC system; 50*4.6 Zorbax Eclipse Plus C18 1.8 micron; mobile phase A: acetonitrile (0.1% formic acid); mobile phase B: water (0.09% formic acid); linear gradient from 10%i acetonitrile to 95%i acetonitrile in 4.25 min, then 95% acetonitrile for a further 1.25 min; oven temperature 55°C; flow rate: 2.0 ml/min. Mass detection is carried out via an Agilend MSD system.
**' Note regarding the determination of the retention times. Measurement of retention times and associated mass spectroscopy was carried out using the following methods: a) Instrument: Micromass Quattro Premier with Waters UPLC Acquity; column: Thermo Hypersil GOLD 1.9 μ 50 x I mm; mobile phase A: 1 1 of water + 0.5 ml of 50%o strength formic acid, mobile phase B: 1 1 of acetonitrile + 0.5 ml of 50% strength formic acid; gradient: 0.0 min 97% A → 0.5 min 97% A→ 3.2 min 5% A→ 4.0 min 5% A; oven: 50°C; flow rate: 0.3 ml/min; UV detection: 210 nm. b) Instrument: Waters ACQU ITY SQD UPLC System; column: Waters Acquity U PLC HSS T3 1.8 μ 50 x 1 mm; mobile phase A: 1 1 of water + 0.25 ml of 99% strength formic acid, mobile phase B: 1 1 of acetonitrile + 0.25 ml of 99% strength formic acid; gradient: 0.0 min 90% A→ 1.2 min 5% A→ 2.0 min 5% A; oven: 50°C; flow rate: 0.40 ml/min; UV detection: 208 - 400 nm. c) MS instrument: Waters SQD; UPLC instrument: Waters U PLC: column: Zorbax SB-Aq (Agilent), 50 mm x 2.1 mm, 1.8 μm; mobile phase A: water + 0.025%o formic acid, mobile phase B: acetonitrile (ULC) + 0.025% formic acid; gradient: 0.0 min 98%A - 0.9 min 25%A - 1.0 min 5%A - 1.4 min 5%A 1.41 min 98%A - 1 .5 min 98%A; oven: 40°C; flow rate: 0.600 ml/min; UV detection: DAD; 210 nm. d) Instrument: Waters ACQUITY SQD UPLC System; column: Waters Acquity UPLC HSS T3 1.8 μ 50 x 1 mm; mobile phase A: 1 1 of water + 0.25 ml of 99%> strength formic acid, mobile phase B: 1 1 of acetonitrile + 0.25 ml of 99% strength formic acid; gradient: 0.0 min 95%o A → 6.0 min 5% A→ 7.5 min 5% A; oven: 50°C; flow rate: 0.35 ml/min; UV detection: 210 - 400 nm. Biological working examples for applications in the animal health sector I.
A. Amblvomma hebaraetim test (AMBYHE)
Solvent: dimethyl sulphoxide To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.
Tick nymphs (Amblyomma hehraeum) are placed into perforated plastic beakers and immersed in the desired concentration for one minute. The ticks are transferred on filter paper into a Petri dish and stored in a climate-controlled cabinet. After 42 days, the kill in % is determined. 100% means that all of the ticks have been killed; 0% means that none of the ticks have been killed.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 100 ppm: Ia-1 , Ia-2, Ib-3, Ic-1, Ic-2, Ic-11 , Ic-16, lc-2 ! . Ic-23, lc-24. Ic- 27, Ic-34, Ic-36, Ic-37, Ic-47, Ic-49, Ic-83, Ic-84, Ic-85, Ic-87, Ic-91, Ic-94, ic-95 B. Boophilus microplus - dip test (BOOPMI Dip)
Test animals: cattle ticks (Boophilus microplus) Parkhurst strain, SP-resistant
Solvent: dimethyl sulphoxide
10 mg of active compound are dissolved in 0.5 ml of dimethyl sulphoxide. For the purpose of preparing a suitable formulation, the active compound solution is diluted with water to the concentration desired in each case.
This active compound preparation is pipetted into tubes. 8-10 adult engorged female cattle ticks (Boophilus microplus) are transferred into a further tube with holes. The tube is immersed into the active compound formulation, and all ticks are completely wetted. After the liquid has run out, the ticks are transferred on filter discs into plastic dishes and stored in a climate-controlled room. The activity is assessed after 7 days by laying of fertile eggs. Eggs whose fertility is not visible from the outside are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all eggs are fertile.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 100 ppm: Ia-1, la-2. Ib-2, Ib-3, Ic-1 , Ic-2, Ic-11, Ic- 16, lc-2 1 , Ic-23, lc-24. Ic-27, Ic-34, Ic-36, Ic-37, Ic-47, Ic-49, Ic-65, Ic-66, Ic-77, Ic-78, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-91, Ic-94, Ic-95, Ic-96, Ic-109, Ic-1 11, Ic-112, Ic-113, Ic-130, Ic-139, Ic-147, Ic-151, Ic-152, Ic-153, Ic-158, Ic-160, Ic-164, Ic-166
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 90% at an application rate of 100 ppm: Ic-97, Ic-103, Ic-175
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 100 ppm: Ic-29, Ic-48, Ic-80, Ic-159
C. Boophilus microplus - injection test (BOOPMI Inj)
Solvent: dimethyl sulphoxide To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of solvent, and the concentrate is diluted with solvent to the desired concentration.
1 μΐ of the active compound solution is injected into the abdomen of 5 engorged adult female cattle ticks (Boophilus microplus). The animals are transferred into dishes and kept in a climate-controlled room.
The activity is assessed after 7 days by laying of fertile eggs. Eggs whose fertility is not visible from the outside are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all eggs are fertile.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 20 μg/animal: Ia-1, I a -2. Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic-10, Ic-11, Ic-12, Ic-13, Ic- 14, Ic-16, Ic-17, Ic-18, Ic-19, Ic-20, lc-2 1. Ic-22, Ic-23, Ic-24, Ic-25, Ic-27, Ic-28, Ic-29, Ic-32, Ic-33, Ic-34, Ic-36, Ic-37, Ic-38, Ic-39, Ic-40, Ic-41, Ic-42, Ic-43, Ic-44. Ic-46, Ic-47, Ic-48, Ic-49, Ic-53, Ic-54, Ic-55, Ic-56, Ic-58, Ic-59, Ic-60, Ic-61, Ic-62, Ic-63, Ic-64, Ic-65, Ic-66, Ic-67, Ic-68, Ic-70, Ic-71, Ic-72, Ic-73, Ic-74. Ic-75, Ic-76, Ic-77, Ic-78, Ic-80, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-88, Ic-89, Ic-90, Ic-91, Ic-92, Ic-94, Ic-95, Ic-96, Ic-97, Ic-99, Ic-103, Ic-106, Ic-136, Ic-137, Ic-139, Ic-140, Ic-147, Ic-149, Ic-150, Ic-151, k- 152. Ic- 153, Ic-154. Ic-157. Ic-158, Ic-159, Ic-160, Ic- 161, Ic-163, Ic-164, Ic-165, Ic- 166, Ic-174, Ic-175, Id-1, Id-2, Ie-1
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 90% at an application rate of 20 μg/animal: Ic-1 56
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 20 μg/animal: Ic-15, Ic-35 D. Ctenocephalides felis - oral test (CTECFE)
Solvent: dimethyl sulphoxide
To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide. Dilution with titrated cattle blood gives the desired concentration. About 20 unfed adult cat fleas ( Ctenocephalides felis) are placed into a chamber which is closed at the top and bottom with gauze. A metal cylinder whose bottom end is closed with a parafilm is placed onto the chamber. The cylinder contains the blood/active ingredient preparation, which can be imbibed by the fleas through the parafilm membrane.
After 2 days, the kill in % is determined. 100% means that all of the fleas have been killed; 0% means that none of the fleas have been killed.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100 at an application rate of 100 ppm: Ia-1 , Ia-2, Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic- 11, Ic-12, Ic-13, Ic-16, Ic-18, Ic-19, Ic-20, Ic-21, Ic-22, Ic-23, Ic-24, Ic-27, Ic-28, Ic-29, lc-3 1. Ic-32, Ic- 33, Ic-34, Ic-35, Ic-36, Ic-37, Ic-38, Ic-39, Ic-40, Ic-41, Ic-42, Ic-43, lc-44. Ic-45, Ic-46, Ic-47. Ic-48, Ic- 49, Ic-53, Ic-54, Ic-55, Ic-56, Ic-57, Ic-58, Ic-59, Ic-60, Ic-61, Ic-64, Ic-65, Ic-66, Ic-67, Ic-68, Ic-70, Ic- 71, Ic-73, Ic-74, Ic-75, Ic-76, Ic-77, Ic-78, Ic-80, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-91, Ic- 94, Ic-95, Ic-96, Ic-97, Ic-99, Ic-103, Ic-106, Ic-136, Ic-137, Ic-139, Ic-140, Ic-147, Ic-149, Ic-150, Ic- 151, Ic-1 52, Ic-153. ic- 154. Ic-156, Ic-158, Ic-159, Ic-160, Ic-161, Ic-163, Ic-164, Ic-165. Ic-166, Ic- 174, Ic-175, Id-l, Id-2, Ie-I In this test, for example, the following compounds of the Preparation Examples show an efficacy of 98% at an application rate of 100 ppm: Ic-10
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 95% at an application rate of 100 ppm: Ic-25, lc-62. lc-63
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 90% at an application rate of 100 ppm: Ic- 17, Ic-89, Ic-157
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 100 ppm: lc-92
E. Lucilia cuprina test (LUCICU)
Solvent: dimethyl sulphoxide To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide, and the concentrate is diluted with water to the desired concentration.
About 20 LI larvae of the Australian sheep blowfly (Lucilia cuprina) are transferred into a test vessel containing minced horsemeat and the active compound preparation of the desired concentration. After 2 days, the kill in % is determined. 100% means that all of the larvae have been killed; 0% means that none of the larvae have been killed.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100%o at an application rate of 100 ppm: Ia-1 , Ia-2, Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-4, Ic-6, Ic-7, Ic-8, Ic- 10, Ic-11, Ic-12, Ic-13, Ic-14, Ic-16, Ic-17, Ic-18, Ic- 19, Ic-20, Ic-2 ! . Ic-22, Ic-23, lc-24. Ic-25, Ic-27, Ic- 28, Ic-29, Ic-32, Ic-33, Ic-34, Ic-35, Ic-36, Ic-37, Ic-38, Ic-39, Ic-40, Ic-41, Ic-42, Ic-43, Ic-44. Ic-45, Ic- 46. Ic-47. Ic-48, Ic-49, Ic-53, Ic-54, Ic-55, Ic-56, Ic-57, Ic-58, Ic-59, Ic-60, Ic-61, Ic-62, Ic-63, Ic-64. Ic- 65, Ic-66, Ic-67, Ic-68, Ic-70, Ic-71, Ic-73, Ic-74, Ic-75, Ic-76, Ic-77, Ic-78, Ic-80, Ic-81, Ic-83, Ic-84, Ic- 85, Ic-86, Ic-87, Ic-88, Ic-89, Ic-90, Ic-91, lc-94. Ic-95, lc-96. Ic-97, Ic-103, Ic-106, Ic-136, Ic-137, lc- 140, Ic-147, Ic-149, Ic-150, Ic-151, Ic-152, Ic-153. Ic-1 54. Ic-1 57. Ic-158, Ic-1 59. Ic-160, Ic-161, Ic- 163, Ic-164, Ic- 1 65. Ic- 166. Ic- 174, Ic-175, Id-I
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 95% at an application rate of 100 ppm: Ic-92, Id-2
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 90% at an application rate of 100 ppm: Ic-31 In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 100 ppm: Ic-72, Ic-99
F. Musca domestica test (MUSCDO)
Solvent: dimethyl sulphoxide
To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide, and the concentrate is diluted with water to the desired concentration.
Vessels containing a sponge treated with sugar solution and the active compound preparation of the desired concentration are populated with 10 adult houseflies {Musca domestica).
After 2 days, the kill in % is determined. 100% means that all of the flies have been killed; 0% means that none of the flies have been killed. In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of lOO ppm: Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-7, Ic-11, Ic- 12, Ic-16, Ic-18, Ic-19, Ic-21, Ic-23, Ic-24. Ic-27, Ic-28, Ic-29, Ic-32, ic-33, Ic-34, Ic-36, Ic-37, Ic-38, Ic-39, Ic-40, Ic-41, ic-43, Ic-45, Ic-46, ic-47, Ic-48, Ic-49, Ic-55, Ic-57, Ic-59, Ic-60, Ic-62, Ic-65, lc-66. Ic-70, Ic-77, Ic-78, Ic-80, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-91, Ic-94, Ic-95, Ic-96, Ic-97, Ic-106, Ic-147, Ic-151, Ic- 152, Ic-153, Ic-159, Ic-160, Ic- 166, Ic-174, Ic-175, Id-1
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 95% at an application rate of 100 ppm: Ic-67
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 90% at an application rate of 100 ppm: Ia-2, Ic-6, Ic-25, Ic-73, Ic-136, Ic-140, Ic-1 54, Ic-158, Ic-163, Ic-164
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 100 ppm: Ia-1, ic-44, Ic-58, Ic-61, Ic-64, Ic-68, Ic-71, Ic-76, Ic-103, Ic-161
Biological working examples for applications in the animal health sector ΙΪ:
Tl. Ctenocephalides felis - in vitro contact tests with adult cat fleas For the coating of the test tubes, initially 9 mg of active compound are dissolved in 1 ml of acetone p. a. and then diluted with acetone p. a. to the desired concentration. By turning and rocking on an orbital shaker (2 h of rocking rotation at 30 rpm), 250 μΐ of the solution are distributed homogeneously on the internal walls and the floor of a 25 ml test tube. At 900 ppm active compound solution and 44.7 cm2 internal surface, an area dose of 5 μg/cm2 is achieved for homogeneous distribution. After evaporation of the solvent, the tubes are populated with 5-10 adult cat fleas ( Ctenocephalides felis), sealed with a perforated plastic lid and incubated in a horizontal position at room temperature and ambient humidity. After 48 h, the efficacy is determined. To this end, the test tubes are stood upright and the fleas are knocked to the floor of the tube. Fleas which remain motionless on the floor or move in an uncoordinated manner are considered to be dead or moribund. A substance shows good activity against Ctenocephalides felis if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 μg/cm2. An efficacy of 100% means that all fleas were dead or moribund. 0% efficacy means that none of the fleas had been damaged.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 5 μg/cm2: Ia-1, Ia-2, Ib-2, lb-3. Ic-1, Ic-2, Ic-11, Ic-12, Ic-16, Ic-18, Ic-19, Ic-21, Ic-23, Ic-24, Ic-27, Ic-28, Ic-29, Ic-34. Ic-36, Ic-37, Ic-41, Ic-47, Ic-48, Ic-49, Ic-65, lc-66. Ic-68, Ic-70, Ic-71, Ic-77, Ic-78, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-91, Ic-94, Ic-95, Ic-96, Ic-97, Ic-107, Ic-108, Ic-109, Ic-110, Ic-111, Ic-112, Ic-113, Ic- 118, Ic-139, Ic-140, Ic-141, Ic-142. Ic-143, Ic- 144, Ic-145, Ic-147, Ic-148, Ic-149, Ic-151, Ic-152, Ic-153, Ic-155, Ic-158, Ic-159, Ic-160, Ic-163, Ic- 164, Ic-165, Ic-166, Ic-167, Ic- 175, Ic-199, Ic-211 in this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 5 μg/cm2: ic-32, Ic-138, Ic-146, Ic-154 In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 1 μg/cm2: Ia-1, la-2. Ib-2. lb-3. Ic-1, Ic-2, Ic-11, Ic-12, Ic-16, Ic-18, Ic-19, Ic-2 1 . Ic-23, Ic-24, Ic-27, Ic-28, lc-29. Ic-34, Ic-36, Ic-37, Ic-41, ic-47, Ic-48, lc-49. Ic-65, Ic-66, Ic-70, Ic-71, Ic-77, Ic-78, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-91, Ic-94, Ic-95, Ic-96, Ic-97, Ic- 107, Ic-108, Ic-109, Ic-111, Ic-1 12, Ic-113, Ic-118, Ic-139, Ic-140, Ic-141, Ic-1 42. Ic-143, Ic-144, Ic- 145, Ic-147, Ic-151 , Ic-152, Ic-153, Ic-154, Ic-155, Ic-158, Ic-159, Ic-160, Ic-163, Ic-163, Ic-164, Ic- 165, Ic-166, Ic-167, Ic-175, Ic- 199, Ic-211
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 1 μg/cm2: Ic-146, Ic-149
T2. Rhipicephalus sanguineus - in vitro contact tests with adult brown dog ticks For the coating of the test tubes, initially 9 mg of active compound are dissolved in 1 ml of acetone p. a. and then diluted with acetone p. a. to the desired concentration. By turning and rocking on an orbital shaker (2 h of rocking rotation at 30 rpm), 250 μΐ of the solution are distributed homogeneously on the internal walls and the floor of a 25 ml test tube. At 900 ppm active compound solution and 44.7 cm2 internal surface, an area dose of 5 μg/cm2 is achieved for homogeneous distribution. After evaporation of the solvent, the tubes are populated with 5-10 adult dog ticks {Rhipicephalus sanguineus), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at room temperature and ambient humidity. After 48 h, the efficacy is determined. To this end, the ticks are knocked to the floor of the tube and incubated on a hotplate at 45-50°C for at most 5 min. Ticks which remain motionless on the floor or move in an uncoordinated manner such that they are not able to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.
A substance shows good activity against Rhipicephalus sanguineus if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 μg/cm2. An efficacy of 100% means that all ticks were dead or moribund. 0% efficacy means that none of the ticks had been damaged.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100%) at an application rate of 5 μg/cm2: Ia-1, la-2. Ic- 1, Ic-2, Ic-11, Ic-16, Ic-18, Ic-21, Ic-23, Ic-24, Ic- 25, Ic-27, Ic-28, Ic-34, Ic-36, Ic-37, Ic-47, Ic-48, lc-49, Ic-54, Ic-66, Ic-70, Ic-71, Ic-77, Ic-78, Ic-81, Ic- 83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-94, Ic-95, Ic-96, Ic-103, Ic-106, Ic-109, Ic-111, Ic-112, Ic-113, Ic-141, Ic-142. Ic-143, Ic-151, Ic-152, Ic-155, Ic-160, Ic-161, Ic-164, Ic-166, Ic-167, Ic-174, Ic-201 In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 5 μg/cm2: Ib-3, Ic-19, Ic-61, Ic-73, Ic-91, Ic-108, Ic-153
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100%o at an application rate of 1 μg/cm2: Ia-1, Ia-2, Ib-3. Ic-1, Ic-2, Ic-11 , Ic-16, Ic-18, Ic-19, Ic-21, Ic- 23, Ic-24, Ic-25, Ic-27, Ic-36, Ic-37, Ic-43, Ic-46, Ic-47, Ic-48, Ic-49, Ic-54, Ic-59, Ic-66, Ic-68, Ic-70, Ic- 77, Ic-78, Ic-81, Ic-83, Ic-84, Ic-85, Ic-86, Ic-87, Ic-90, Ic-94, Ic-95, Ic-96, Ic- 103, Ic-109, Ic- 111, Ic- 112, Ic-143, Ic-151, Ic-152. Ic- 155, Ic-160, Ic-163, Ic-164, Ic-166, Ic-167, Ic-174, Ic-201
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80 at an application rate of 1 μg/cm2: Ic-32, Ic-34, Ic-67, Ic-71, Ic-73, Ic-113, Ic-141, Ic-142. Ic- 147, Ic- 148, Ic-153, Ic-161
T3. Ixodes ricinus - in vitro contact tests with adult castor bean ticks
For the coating of the test tubes, initially 9 mg of active compound are dissolved in 1 ml of acetone p. a. and then diluted with acetone p. a. to the desired concentration. By turning and rocking on an orbital shaker (2 h of rocking rotation at 30 rpm), 250 μΐ of the solution are distributed homogeneously on the internal walls and the floor of a 25 ml test tube. At 900 ppm active compound solution and 44.7 cm2 internal surface, an area dose of 5 μg/cm2 is achieved for homogeneous distribution.
After evaporation of the solvent, the tubes are populated with 5-10 adult castor bean ticks {Ixodes ricinus), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at 22°C and 90%) humidity in a climate-controlled cabinet. After 48 h, the efficacy is determined. To this end, the ticks are knocked to the floor of the tube and incubated on a hotplate at 45-50°C for at most 5 min. Ticks which remain motionless on the floor or move in an uncoordinated manner such that they are not able to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.
A substance shows good activity against Ixodes ricinus if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 μg/cm2. An efficacy of 100%> means that all ticks were dead or moribund. 0%> efficacy means that none of the ticks had been damaged.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100 at an application rate of 5 μg/cm2: Ia-1, la-2. Ic- 1, Ic-2, Ic-11, Ic-16, Ic-21, Ic-23, Ic-37, Ic-47, Ic- 48, Ic-81, Ic-83, Ic-84, Ic-86, Ic-87, Ic-90, Ic-94
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 5 μg/cm2: ib-3. Ic-18 In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 1 μg/cm2: Ia-1, Ia-2. Ic- 1, Ic-2, Ic-16, Ic-23, Ic-37, Ic-81, Ic-84, Ic-90, Ic- 94
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 1 μg/cm2: Ib-3, Ic-11, Ic-21, Ic-48, Ic-86, Ic-87
T4. Amblyomma hebraeum - in vitro contact tests with nymphs of the boat tick
For the coating of the test tubes, initially 9 mg of active compound are dissolved in 1 ml of acetone p. a. and then diluted with acetone p. a. to the desired concentration. By turning and rocking on an orbital shaker (2 h of rocking rotation at 30 rpm), 250 μΐ of the solution are distributed homogeneously on the internal walls and the floor of a 25 ml test tube. At 900 ppm active compound solution and 44.7 cm2 internal surface, an area dose of 5 μg/cm2 is achieved for homogeneous distribution.
After evaporation of the solvent, the tubes are populated with 5-10 bont tick nymphs (Amblyomma hebraeum), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at 27°C and 85%) humidity in a climate-controlled cabinet. After 48 h, the efficacy is determined. To this end, the ticks are knocked to the floor of the tube and incubated on a hotplate at 45-50°C for at most 5 min. Ticks which remain motionless on the floor or move in an uncoordinated manner such that they are not able to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.
A substance shows good activity against Amblyomma hebraeum nymphs if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 μg/cm2. An efficacy of 100%> means that all ticks were dead or moribund. 0%> efficacy means that none of the ticks had been damaged.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100%) at an application rate of 5 μg/cm2: Ia-1, Ia-2, Ib-2, Ib-3, Ic-1, Ic-2, Ic-3, Ic-11, Ic-16, Ic- 18, Ic-19, Ic-2 1. Ic-23, Ic-32, Ic-37, Ic-47, Ic-48, Ic-49, Ic-81, Ic-83, Ic-84, Ic-86, Ic-87, Ic-90, Ic-94, Ic-95
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of I μg/cm2: Ia-1, Ia-2, lb-2. Ic-1, Ic-2, Ic-11, Ic-16, Ic-18, Ic-19, Ic-21, Ic- 23, Ic-32, Ic-37, Ic-47, Ic-48, Ic-81 , Ic-83, Ic-84, Ic-86, Ic-87, Ic-90, Ic-94, Ic-95
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of I μg/cm2: Ib-3. Ic-3
T6. Dermacentor variabilis - systemic in vivo activity against American dog tick nymphs on rats In a randomized open placebo-controlled study, the efficacy of preparation examples of the halogen- substituted compounds of the formula (I) according to the invention against nymphs of the American dog tick (Dermacentor variabilis) on rats (Rattus norvegicus; strain: Whistar Unilever, HsdCpb:WU) is examined following intraperitoneal treatment. To this end, a suitable amount of the active compound is dissolved in glycerol formal and injected intraperitoneally. The volume administered is, depending on the active compound concentration, between 30 and 90 μl/100 g of body weight. 5 rats per group are used, the results are reported as arithmetic means. Prior to the tick infestations, all rats are provided with collars. For the infestation with ticks and counting, the rats are sedated with 30-50 μΐ of medetomidine hydrochloride (e.g. Domitor®) s.c/rat. All rats are infested on day 0 (at least 1 h after the treatemt), day 7, day 14 etc. with 30 un engorged Dermacentor variabilis nymphs. On day 2, day 9, day 16 etc. the collar is removed and the entire body of the sedated rats is examined systematically for ticks. Ticks are removed with tweezers and, by being squashed on blotting paper, examined for blood sucked. The efficacy of the treatment is determined by comparison with a placebo-treated control group. A compound is considered to be highly effective if, at a dosage of 10 mg/kg, it shows an efficacy of 90% against nymphs of the American dog tick (Dermacentor variabilis) on day 2 after intraperitoneal treatment. The effect is considered to be longer-lasting if the efficacy on day 9 is still higher than 80%.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of >90% against tick nymphs on day 2 at an application rate of 10 mg/kg: Ic-1, Ic-2
In this test, for example, the following compounds of the Preparation Examples show an efficacy of >80% against tick nymphs on day 9 at an application rate of 10 mg/kg: Ic-1, Ic-2
T7. Ctenoceohalides felis - systemic in vivo activity against fleas on rats
In a randomized open placebo-controlled study, the efficacy of preparation examples of the halogen- substituted compounds of the formula (I) according to the invention against adult cat fleas (Ctenocephalides felis) on rats (Rattus norvegicus; strain: Whistar Unilever, HsdCpb:WU) is examined following intraperitoneal treatment. To this end, a suitable amount of the active compound is dissolved in glycerol formal and injected intraperitoneally. The volume administered is, depending on the active compound concentration, between 30 and 90 μ 1/100 g of body weight. 5 rats per group are used, the results are reported as arithmetic means. Prior to the flea infestations, all rats are provided with collars. For the infestation with fleas and counting, the rats are sedated with 30-50 μΐ of medetomidine hydrochloride (e.g. Domitor®) s.c/rat. All rats are infested on day 0 (at least 1 h after the treatemt), day 7, day 14 etc. with 30 unfed Ctenocephalides felis adults. On day 2, day 9, day 16 etc. the collar is removed and the entire body of the sedated rats is examined systematically for fleas using a flea comb. The fleas are counted and removed.
The efficacy of the treatment is determined by comparison with a placebo-treated control group. A compound is considered to be highly effective if, at a dosage of 10 mg/kg, it shows an efficacy of 95% against adult fleas ( Ctenocephalides felis) on day 2 after intraperitoneal treatment. The effect is considered to be longer-lasting if the efficacy on day 9 is still higher than 90%. In this test, for example, the following compounds of the Preparation Examples show an efficacy of >95% against fleas on day 2 at an application rate of 10 mg/kg: Ic-1, Ic-2
In this test, for example, the following compounds of the Preparation Examples show an efficacy of >90% against fleas on day 9 at an application rate of 10 mg/kg: Ic-1, Ic-2 T8. Haemonchus contortus-test (HAEMCO)
Solvent: dimethyl sulphoxide
To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide, and the concentrate is diluted with "Ringer solution" to the desired concentration. Vessels containing the active compound preparation of the desired concentration are populated with about 40 larvae of the red stomach worm {Haemonchus contortus).
After 5 days, the kill in % is determined. 100% means that all of the larvae have been killed; 0% means that none of the larvae have been killed. in this test, for example, the following compounds of the Preparation Examples show an efficacy of 80% at an application rate of 20 ppm: Ic-1, Ic-16
Biological working _. examples for applications in the crop protection sector
Further working examples with data relating to pests that have relevance in the crop protection sector can be found in WO2014/122083.

Claims

Claims
Combination of Compounds of the general formula (I),
Figure imgf000082_0001
in which represents hydrogen, optionally substituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3- C6-cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl- (C1-C3)-alkyl, or alternatively represents hydrogen, optionally substituted C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, C3- C6-cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-
the chemical groupings
Ai represents CR2 or nitrogen, A2 represents CR3 or nitrogen, A3 represents CR4 or nitrogen and Ai represents CR3 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
R~. R R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino- C1-C3-alkyl, C1-C6-alkylsulphanyl, C1-C6-alkj'lsulphinyl, C1-C6-alkylsulphonyl, N-C1-C6- alkylamino or N,N-di-C1-C6-alkylamino; if none of the groupings A2 and A3 represents nitrogen, R3 and R4 together with the carbon atom to which they are attached may form a 5- or 6-membered ring which contains 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulphur atom, or if none of the groupings Ai and A2 represents nitrogen, R2 and R3 together with the carbon atom to which they are attached may form a 6-membered ring which contains 0, 1 or 2 nitrogen atoms;
W represents oxygen or sulphur;
Q represents hydrogen, formyl, hydroxy, amino or one of the optionally substituted groupings alkyl, alkyloxy, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl or represents a grouping N-alkylamino, N-alkylcarbonylamino, N,N-dialkylamino; or
Q represents an unsaturated 6-membered carbo cycle which is optionally mono- or polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally mono- or polysubstituted by V, or alternatively
Q represents an unsaturated 6-membered carbocycle which is optionally polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally polysubstituted by V, where in both last cases of Q
V represents halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, N-alkoxyiminoalkyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, N,N- dialkylamino,
T represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000083_0001
where
R6 independently of one another represent halogen, cyano, nitro, amino or optionally substituted C1-C6-alkyl, C1-C6-alkyloxy, C1-C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6- alkylsulphinyl, C1-C6-alkylsulphonyl, and n represents the values 0-2;
Z1 represents optionally substituted alkyl and cycloalkyl, and
Z2 represents hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, and
Z3 represents hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or hetaryl. with ectoparasiciticides, anthelmintics or anti-protozoal agents.
2. Combinations according to claim 1 with Compounds of general formula (I) in which R1 represents hydrogen, optionally substituted C1-C6-alkyl, C3-C6-alkenyl, C1-C6-alkynyl, C3- C7-cycloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3)- alkyl, the chemical groupings Ai represents CR2 or nitrogen, A2 represents CR3 or nitrogen, A3 represents CR4 or nitrogen and A4 represents CR5 or nitrogen, but where not more than three of the chemical groupings A1 to A4 simultaneously represent nitrogen;
R2 , R3 R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-alkoxyiminoalkyl, C1-C6- alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N- C1-C6-alkylamino, N,N-di-C1- C6alkylamino; if none of the groupings A2 and A3 represents nitrogen, R ' and R4 together with the carbon atom to which they are attached may form a 5- or 6-membered ring which contains 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulphur atom, or if none of the groupings Ai and A2 represents nitrogen, R2 and R ' together with the carbon atom to which they are attached may form a 6-membered ring which contains 0, 1 or 2 nitrogen atoms;
W represents oxygen or sulphur;
Q represents hydrogen, formyl, hydroxy, amino or one of the optionally substituted groupings C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, C1-C3-heterocycloalkyl, C1 -C4- alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-C3) -alkyl or represents a grouping 7Y-C1-C4-alkylamino, N-C1-C4- alkylcarbonylamino, N,N-di-C1-C4-alkylamino; or
Q represents an unsaturated 6-membered carbocycle which is optionally polysubstituted by V or an unsaturated 5- or 6-membered heterocyclic ring which is optionally polysubstituted by V, where
V independently of one another represent halogen, cyano, nitro, optionally substituted C1-C6- alkyl, C1-C4-alkenyl, C1-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1- C3 -alkyl, (C1-C6a- lkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N,N-di-(C1-C6- alkyl) amino;
T represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000085_0001
where
R6 independently of one another represent halogen, cyano, nitro, amino or optionally halogen- substituted C1-C6-alkyl, C1-C6-alkyloxy, C1-C6-alkylcarbonyl, C1 -C6-alkylsulphanyl, C1-C6- alkylsulphinyl, C1-C6-alkylsulphonyl, and n represents the values 0-1 ;
Z1 represents optionally substituted C1-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and
Z2 represents halogen, cyano, nitro, amino or optionally substituted C1-C6-alkyl, C1-C6- alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, and
Z3 represents hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or hetaryl.
Combinations according to claim 1 with compounds of general formula (I) in which R1 represents hydrogen or represents C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, C3-C7- cycloalkyl, C3-C7-cycloalkyl-C1-C3-alkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, aryl-(C1- C3)-alkyl, heteroaryl-(C1-C3)-alkyl which are optionally mono- or polysubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl, the chemical groupings
Ai represents CR2 or nitrogen,
A2 represents CR3 or nitrogen,
A3 represents CR4 or nitrogen and
A4 represents CR3 or nitrogen, but where not more than three of the chemical groupings A1 to A4 simultaneously represent nitrogen;
R- , R3, R4 and R5 independently of one another represent hydrogen, halogen, cyano, nitro, optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, iV-C1-C6-alkoxy-imino-C1-C3- alkyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N- C1 -C6-alkylamino or N,N-di-C1-C1-alkylamino;
W represents oxygen or sulphur;
Q represents hydrogen, hydroxy, formyl or one of the groupings C1-C6-alkyl, C1-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, C1-C5-heterocyc loalkyl, C1-C4-alkoxy, C1-C6-alkyl-C3-C6- cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1-C6-hydroxyalkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1- C3)-alkyl, N-C1-C4-alkylamino, N- C1-C4-alkylcarbonylamino or N,N-di-C1-C4-alkylamino which are optionally mono- or polysubstituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl; or
Q represents aryl substituted by 0 - 4 substituents V or a 5- or 6-membered heteroaromatic substituted by 0 - 4 substituents V, where
V independently of one another represent halogen, cyano, nitro, optionally substituted C1-C6- alkyl, C1-C4-alkenyl, C1-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, N-C1-C6-alkoxy-imino-C1- C3-alkyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, N,N-di-(C1-C6- alkyl) amino; T represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000087_0001
where
R6 independently of one another represent halogen, cyano, nitro, amino or optionally halogen- substituted C1-C6-alkyl, C1-C6-alkyloxy, C1-C6-alkylcarbonyl, C 1 -C6-alkylsulphanyl, C1-C6- alkylsulphinyl, C1-C6-alkylsulphonyl, and n represents the values 0-1 ; Z1 represents optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, and
Z2 represents hydrogen, halogen, cyano, nitro, amino or optionally substituted C1-C6-alkyl, C1- C6-alkylcarbonyl, C1-C6-alkylsulphanyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, and
Z3 represents hydrogen or optionally substituted C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkenyl, Cl-C4-alkynyl, aryl and hetaryl.
4. Combinations according to claim 1 with compounds of general formula (I) in which R1 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n- propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl, t- butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2 -y lmethy 1, pyrid-3 -ylmethyl, pyrid-4-ylmethyl, 4-chloropyrid-3-ylmethyl; the chemical groupings
A1 represents CR2 or nitrogen,
A2 represents CR3 or nitrogen,
A3 represents CR4 or nitrogen and
A4 represents CR5 or nitrogen, but where not more than three of the chemical groupings Ai to A4 simultaneously represent nitrogen;
R2 and R5 independently of one another represent hydrogen, methyl, fluorine or chlorine and
R3 and R4 independently of one another represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, fluoromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 2,2,2 -trifluoroethyl, methoxy, ethoxy, n-propoxy, 1 -methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2,2-difluoroethoxy, pentafluoroethoxy, N- methoxyiminomethyl, 1 -(N-methoxyimino)ethyl, methylsulphanyl, trifluoromethylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl;
W represents oxygen or sulphur;
Q represents hydrogen, methyl, ethyl, n-propyl, 1 -methylethyl, 1 , 1 -dimethyl ethyl, 1 - methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxyethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1- trifluoromethylethyl, 2,2-difluoropropyl, 3,3,3 -trifluoropropy 1, 2,2- dimethyl-3 -fluoropropyl, cyclopropyl, 1 -cyanocyclopropyl, 1 -methoxycarbonylcyclopropyl, 1-(N- methylcarbamoyl)cyclopropyl, l -(N-cyclopropylcarbamoyl)cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1 -cyclopropylethyl,
bis(cyclopropyl)methyl, 2,2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2,2- dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2,2- difluorocyclopropyl, trans-2-fluorocyclopropyl, cis -2 - fluorocy c lopropy 1, trans-4- hydroxycyclohexyl,
4-trifluoromethylcyclohexyl, prop-2-enyl, 2 -methy lprop -2 - eny 1, prop-2-ynyl,
1 , 1 -dimethylbut-2 -ynyl, 3-chloroprop-2-enyl, 3 ,3 -dichloroprop-2-enyl,
3,3-dichloro-i,l-dimethylprop-2-enyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4- chlorophenyl, oxetan-3-yl, thietan-3-yl, 1 -oxidothietan-3-yl, 1 , 1 -dioxidothietan-3 -yl, isoxazol-3-ylmethyl, 1 ,2,4-triazol-3 -ylmethyl, 3 -methy loxetan-3 -ylmethyl, benzyl, 2,6- difluorophenylmethyl, 3-fluorophenylmethyl, 2 - fluoropheny lmethy 1, 2,5- difluorophenylmethyl, 1 -phenylethyl, 4-chlorophenylethyl, 2-trifluoromethylphenylethyl, 1 -pyridin-2 -yl ethyl, pyridin-2-ylmethyl, 5 -fluoropyridin-2 -ylmethyl, (6-chloropyridin-3 - yl)methyl, pyrimidin-2 -ylmethyl, methoxy, 2-ethoxyethyl, 2 - (methy lsulphanyl) ethyl, 1- m ethyl -2 - (ethy lsulphany 1) ethyl, 2-methyl-l-(methylsulphanyl)propan-2-yl, methoxy c arbony 1, methoxycarbonylmethyl, NH2, N-ethylamino, N-allylamino, N,N- dimethylamino, N,N-diethylamino; or
Q represents phenyl, naphthyl, pyridazine, pyrazine, pyrimidine, triazine, pyridine, pyrazole, thiazole, isothiazole, oxazole, isoxazole, triazole, imidazole, furan, thiophene, pyrrole, oxadiazole, thiadiazole substituted by 0 - 4 substituents V, where
V independently of one another represent fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl,
dichlorofluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1 ,2,2,2-tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2- trichloroethyl, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, pentafluoro- tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1 -methylethoxy, fluoromethoxy,
difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2,2-difluoroethoxy, pentafluoroethoxy, N-methoxyiminomethyl, l-(N-methoxyimino)ethyl, methylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl, trifluoromethylsulphanyl, N,N- dimethylamino; T represents one of the 5-membered heteroaromatics T 1 -T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000090_0001
where
R6 independently of one another represent halogen, cyano, nitro, amino, methyl, ethyl, 1 - methylethyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, 2,2- difluoroethoxy, 2,2,2 -tnfluoroethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methylsulphanyl, methylsulphinyl, methylsulphonyl, trifluoromethylsulphonyl, trifluoromethylsulphanyl, trifluoromethylsulphinyl, and n represents the values 0-1 ;
Z1 represents methyl, ethyl, 1 , 1 -dimethylethyl, difluoromethyl, trichloromethyl,
chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, 1 - fluoroethyl, 1 -fluoro- 1 -methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1 ,2,2,2-tetrafluoroethyl, 1 -chloro- 1 ,2,2,2-tetrafluoroethyl, 2,2,2 -trichloroethyl, 2-chloro- 2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n- propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, 1 -chlorocyclopropyl, 1 - fluorocyclopropyl, 1 -bromocyclopropyl, 1 -cyanocyclopropyl, 1- trifluoromethylcyclopropyl, cyclobutyl and 2,2-difluoro-l -methylcyclopropyl, and
Z2 represents hydrogen, halogen, cyano, nitro, amino, methyl, ethyl, 1 , 1 -dimethylethyl,
difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl,
trifluoromethyl, bromodichloromethyl, 1 -fluoroethyl, 1 -fluoro- 1 -methylethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1 ,2,2,2-tetrafluorethyl, 1 -chloro- 1,2,2,2- tetrafluoroethyl, 2,2,2 -trichloroethyl, 2-chloro-2,2 -difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, methylsulphanyl, methylsulphinyl, methylsulphonyl, ethylthio, ethylsulphinyl, ethylsulphonyl, tri fluoromethylsulphanyl, trifluoromethylsulphinyl, trifluoromethylsulphonyl, chlorodifluoromethylsulphanyl, chlorodifluoromethylsulphinyl, chlorodifluoromethylsulphonyl, dichlorofluoromethylsulphanyl,
dichlorofluoromethylsulphinyl, dichlorof!uoromethylsulphonyl and
Z3 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, ethenyl, 1-propenyl, 2-propenyl, 1 -propynyl, 1 -butynyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1-fluoro-l- methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2 ,2,2-tri fluoroethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2 ,5 -dichlorophenyl, 3,4-dichlorophenyl, 2,6- dichlorophenyl 2,6-dichloro-4-trifluoromethylphenyl, 3 -chloro-5 -trifluoromethylpyridin-2 - yl.
5. Combinations according to claim 1 with compounds of general formula (I) in which
Z1 represents trifluoromethyl, 1 -chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl,
Z2 represents trifluoromethyl, nitro, methylsulphanyl, methylsulphinyl, methylsulphonyl, fluorine, chlorine, bromine, cyano or iodine,
Z3 represents methyl, ethyl, n-propyl or hydrogen, R1 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- propoxy c arbony 1, isopropoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, cyanomethyl, 2- cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2 -ylmethyl, pyrid-3 -ylmethyl, pyrid-4 -ylmethyl, 4- chloropyrid-3 -ylmethyl,
A1 and A4 each represent CH,
A2 represents CH or N,
A3 represents C'R" and
R4 represents methyl, ethyl, fluorine, chlorine, bromine or iodine,
T represents one of the 5-membered heteroaromatics T1-T7 listed below, where the bond to the pyrazole head group is marked with an asterisk,
Figure imgf000092_0001
Figure imgf000092_0002
where
R' represents hydrogen, methyl, ethyl, 2-methylethyl, 2,2-dimethylethyl, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, amino
W represents oxygen and
Q represents hydrogen, methyl, ethyl, n-propyl, 1 -methylethyl, 1 , 1 -dimethylethyl, n-butyl, 1 - methylpropyl, 2-methylpropyl, 2-methylbutyl, hydroxyethyl, 2 -hydroxypropy 1, cyanomethyl, 2- cyanoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 -trifluoromethylethyl, 2,2- difluoropropyl, 3,3,3 -trifluoropropyl, 2,2-dimethyl-3-fluoropropyl, cyclopropyl, 1- cyanocyclopropyl, 1 -methoxycarbonylcyclopropyl, l -( N-methylcarbamoyl)cyclopropyl, 1 -(N- cyclopropylcarbamoyl)cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1 - cyclopropylethyl, bis(cyclopropyl)methyl, 2,2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2,2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2,2- difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans -4- hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2 -methylprop-2 - eny 1, prop-2-ynyl, 1 , 1 -dimethylbut-2-ynyl, 3 -chloroprop-2-enyl, 3,3-dichloroprop-2-enyl, 3,3-dichloro-l,l - dimethylprop-2 -enyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, oxetan-3-yl, thietan-3-yl, 1 -oxidothietan-3 -yl, 1 , 1 -dioxidothietan-3 -yl, isoxazol-3 -ylmethyl, l,2,4-triazol-3- ylmethyl, 3 -methyloxetan-3 -ylmethyl, benzyl, 2 , 6 -di fluoropheny Imethy 1 , 3 -fluorophenylmethyl, 2-fluorophenylmethyl, 2,5 -difluorophenylmethyl, 1 -phenylethyl, 4-chlorophenylethyl, 2- trifluormethylphenylethyl, 1 -pyridin-2-ylethyl, pyridin-2 -ylmethyl, (6-chloropyridin-3-yl)methyl, 5-fluoropyridin-2-ylmethyl, pyrimidin-2 -ylmethyl, methoxy, 2-ethoxyethyl, 2- (methylsulphanyl)ethyl, 1 -methyl-2-(ethylsulphanyl)ethyl, 2 -methyl -1 -(methylsulphanyl)propan- 2-yl, methoxyc arbony 1, methoxyc arbony Imethy 1, NH2 N- ethylamino, N-allylamino, N,N- dimethylamino, N,N-diethylamino; or Q represents phenyl, naphthyl, pyridazine, pyrazine, pyrimidine, triazine, pyridine, pyrazole, thiazole, isothiazole, oxazole, isoxazole, triazole, imidazole, furan, thiophene, pyrrole, oxadiazole, thiadiazole substituted by 0 - 4 substituents V, where
V independently of one another represent fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl,
dichlorofluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 -trifluoroethyl, 1 ,2,2,2-tetrafluoroethyl, 1 -chloro- 1 ,2,2,2 -tetrafluoroethyl, 2,2,2- trichloroethyl, 2-chloro-2,2-difluoroethyl, 1 , 1 -difluoroethyl, pentafluoroethyl, pentafluoro- tert-butyl, heptafluoro-n-propyl, heptafiuoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1 -methylethoxy, fluoromethoxy,
difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, tri fluoromethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2,2-difluoroethoxy, pentafluoroethoxy, N-methoxyiminomethyl, 1 -(N-methoxyimino)ethyl, methylsulphanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl, trifluoromethylsulphanyl, N,N- dimethylamino.
6. Combinations according to claim 1 wherein the compounds of general formula (I) are those of the general formula (Ic)
Figure imgf000093_0001
(Ic) in which the radicals A1, A2, A3, A4, Q. R1, R6, W, Z1, Z2 and Z3 are defined according to any of Claims 1 to 5.
7. Combinations according to any of claims 1 to 6 of compounds of general formula (I) with anthelmintics.
8. Use of combinations according to any of Claims 1 to 7 for controlling insects, acarids, helminths or protozoa.
Pharmaceutical compositions comprising a combination according to any of Claims 1 to 7.
10. Use of combinations according to any of Claims 1 to 7 for preparing pharmaceutical compositions for controlling parasites on or in animals.
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EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3771711A1 (en) * 2019-07-29 2021-02-03 Bayer Animal Health GmbH Pyrazole derivatives for controlling arthropods
CN112424170A (en) * 2018-07-05 2021-02-26 拜耳动物保健有限责任公司 Novel compounds for controlling arthropods
WO2022167488A1 (en) 2021-02-02 2022-08-11 Basf Se Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors
CN115003159A (en) * 2019-12-13 2022-09-02 伟途制药公司 Mite infestation treatment
WO2022243521A1 (en) 2021-05-21 2022-11-24 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
WO2022243523A1 (en) 2021-05-21 2022-11-24 Basf Se Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor
WO2022268810A1 (en) 2021-06-21 2022-12-29 Basf Se Metal-organic frameworks with pyrazole-based building blocks
EP4151631A1 (en) 2021-09-20 2023-03-22 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP4198023A1 (en) 2021-12-16 2023-06-21 Basf Se Pesticidally active thiosemicarbazone compounds
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2023208447A1 (en) 2022-04-25 2023-11-02 Basf Se An emulsifiable concentrate having a (substituted) benzaldehyde-based solvent system
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds
EP4342885A1 (en) 2022-09-20 2024-03-27 Basf Se N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides

Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0382173A2 (en) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. PF 1022 substance, method of producing same and anthelmintic composition containing same
WO2000007980A1 (en) 1998-08-04 2000-02-17 Astrazeneca Ab Amide derivatives which are useful as cytokine inhibitors
WO2003076415A1 (en) 2002-03-12 2003-09-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and their use as pesticides
WO2003106457A1 (en) 2002-06-14 2003-12-24 Syngenta Limited Spiroindolinepiperidine derivatives
WO2004035545A2 (en) 2002-10-18 2004-04-29 E.I. Du Pont De Nemours And Company Azolecarboxamide herbicides
WO2004099160A1 (en) 2003-05-12 2004-11-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and pests controlling composition containing the same
WO2004106324A1 (en) 2003-05-27 2004-12-09 E.I. Dupont De Nemours And Company Azolecarboxamide herbicides
WO2005085216A1 (en) 2004-03-05 2005-09-15 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and noxious organism control agent
WO2006003494A2 (en) 2004-06-28 2006-01-12 Syngenta Participations Ag Piperidine derivatives and their use as insecticides, acaricides, molluscicides or nematicides
US20060069132A1 (en) 2004-04-07 2006-03-30 Armel Gregory R Azolecarboxamide herbicides
WO2006043635A1 (en) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient
WO2008029084A1 (en) 2006-09-06 2008-03-13 Syngenta Limited Herbicidal compounds and compositions
EP1911751A1 (en) 2005-06-21 2008-04-16 Mitsui Chemicals, Inc. Amide derivative and pesticide containing such compound
WO2008134969A1 (en) 2007-04-30 2008-11-13 Sinochem Corporation Benzamide compounds and applications thereof
CN101337940A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity
WO2009049851A1 (en) 2007-10-15 2009-04-23 Syngenta Participations Ag Spiroheterocyclic pyrrolidine dione derivatives useful as pesticides
WO2009080250A2 (en) 2007-12-24 2009-07-02 Syngenta Participations Ag Insecticidal compounds
WO2009099929A1 (en) 2008-02-06 2009-08-13 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2010051926A2 (en) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft New halogen-substituted bonds
WO2010136145A1 (en) 2009-05-29 2010-12-02 Bayer Cropscience Ag Pyrazinylpyrazoles
CN102060818A (en) 2011-01-07 2011-05-18 青岛科技大学 Novel spirodiclofen compound and preparation method and application thereof
CN102057925A (en) 2011-01-21 2011-05-18 陕西上格之路生物科学有限公司 Insecticidal composition containing thiacloprid amide and biogenic insecticide
WO2012000896A2 (en) 2010-06-28 2012-01-05 Bayer Cropscience Ag Heterocyclic compounds as agents for pest control
WO2012029672A1 (en) 2010-08-31 2012-03-08 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Noxious organism control agent
WO2012069366A1 (en) 2010-11-23 2012-05-31 Syngenta Participations Ag Insecticidal compounds
WO2012080376A1 (en) 2010-12-17 2012-06-21 Syngenta Participations Ag Insecticidal compounds
WO2012107434A1 (en) 2011-02-09 2012-08-16 Syngenta Participations Ag Insecticidal compounds
US20120329832A1 (en) 2011-06-27 2012-12-27 Jean Delaveau Novel Insect-Repellent Coumarin Derivatives, Syntheses, and Methods of Use
WO2013144213A1 (en) 2012-03-30 2013-10-03 Basf Se N-substituted pyridinylidene compounds and derivatives for combating animal pests
WO2014122083A1 (en) 2013-02-06 2014-08-14 Bayer Cropscience Ag Halogen-substituted pyrazol derivatives as pest-control agents
WO2015193216A1 (en) * 2014-06-18 2015-12-23 Bayer Cropscience Aktiengesellschaft Pyrazolyl-triazolyl-pyridines as pest-control agents
WO2016020436A1 (en) * 2014-08-08 2016-02-11 Bayer Cropscience Aktiengesellschaft Novel halogen-substituted compounds
WO2016020441A1 (en) * 2014-08-08 2016-02-11 Bayer Cropscience Aktiengesellschaft Novel halogen-substituted compounds
WO2016026789A1 (en) * 2014-08-19 2016-02-25 Bayer Cropscience Aktiengesellschaft Process for the preparation of 5-fluoro-1h-pyrazoles starting from hexafluoropropene

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0382173A2 (en) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. PF 1022 substance, method of producing same and anthelmintic composition containing same
WO2000007980A1 (en) 1998-08-04 2000-02-17 Astrazeneca Ab Amide derivatives which are useful as cytokine inhibitors
WO2003076415A1 (en) 2002-03-12 2003-09-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and their use as pesticides
WO2003106457A1 (en) 2002-06-14 2003-12-24 Syngenta Limited Spiroindolinepiperidine derivatives
WO2004035545A2 (en) 2002-10-18 2004-04-29 E.I. Du Pont De Nemours And Company Azolecarboxamide herbicides
WO2004099160A1 (en) 2003-05-12 2004-11-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and pests controlling composition containing the same
WO2004106324A1 (en) 2003-05-27 2004-12-09 E.I. Dupont De Nemours And Company Azolecarboxamide herbicides
WO2005085216A1 (en) 2004-03-05 2005-09-15 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and noxious organism control agent
US20060069132A1 (en) 2004-04-07 2006-03-30 Armel Gregory R Azolecarboxamide herbicides
WO2006003494A2 (en) 2004-06-28 2006-01-12 Syngenta Participations Ag Piperidine derivatives and their use as insecticides, acaricides, molluscicides or nematicides
WO2006043635A1 (en) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient
EP1911751A1 (en) 2005-06-21 2008-04-16 Mitsui Chemicals, Inc. Amide derivative and pesticide containing such compound
WO2008029084A1 (en) 2006-09-06 2008-03-13 Syngenta Limited Herbicidal compounds and compositions
WO2008134969A1 (en) 2007-04-30 2008-11-13 Sinochem Corporation Benzamide compounds and applications thereof
WO2009049851A1 (en) 2007-10-15 2009-04-23 Syngenta Participations Ag Spiroheterocyclic pyrrolidine dione derivatives useful as pesticides
WO2009080250A2 (en) 2007-12-24 2009-07-02 Syngenta Participations Ag Insecticidal compounds
WO2009099929A1 (en) 2008-02-06 2009-08-13 E. I. Du Pont De Nemours And Company Mesoionic pesticides
CN101337940A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity
WO2010051926A2 (en) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft New halogen-substituted bonds
WO2010136145A1 (en) 2009-05-29 2010-12-02 Bayer Cropscience Ag Pyrazinylpyrazoles
US20120190687A1 (en) * 2009-05-29 2012-07-26 Bayer Cropscience Ag Pyrazinylpyrazoles
WO2012000896A2 (en) 2010-06-28 2012-01-05 Bayer Cropscience Ag Heterocyclic compounds as agents for pest control
WO2012029672A1 (en) 2010-08-31 2012-03-08 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Noxious organism control agent
WO2012069366A1 (en) 2010-11-23 2012-05-31 Syngenta Participations Ag Insecticidal compounds
WO2012080376A1 (en) 2010-12-17 2012-06-21 Syngenta Participations Ag Insecticidal compounds
CN102060818A (en) 2011-01-07 2011-05-18 青岛科技大学 Novel spirodiclofen compound and preparation method and application thereof
CN102057925A (en) 2011-01-21 2011-05-18 陕西上格之路生物科学有限公司 Insecticidal composition containing thiacloprid amide and biogenic insecticide
WO2012107434A1 (en) 2011-02-09 2012-08-16 Syngenta Participations Ag Insecticidal compounds
US20120329832A1 (en) 2011-06-27 2012-12-27 Jean Delaveau Novel Insect-Repellent Coumarin Derivatives, Syntheses, and Methods of Use
WO2013144213A1 (en) 2012-03-30 2013-10-03 Basf Se N-substituted pyridinylidene compounds and derivatives for combating animal pests
WO2014122083A1 (en) 2013-02-06 2014-08-14 Bayer Cropscience Ag Halogen-substituted pyrazol derivatives as pest-control agents
WO2015193216A1 (en) * 2014-06-18 2015-12-23 Bayer Cropscience Aktiengesellschaft Pyrazolyl-triazolyl-pyridines as pest-control agents
WO2016020436A1 (en) * 2014-08-08 2016-02-11 Bayer Cropscience Aktiengesellschaft Novel halogen-substituted compounds
WO2016020441A1 (en) * 2014-08-08 2016-02-11 Bayer Cropscience Aktiengesellschaft Novel halogen-substituted compounds
WO2016026789A1 (en) * 2014-08-19 2016-02-25 Bayer Cropscience Aktiengesellschaft Process for the preparation of 5-fluoro-1h-pyrazoles starting from hexafluoropropene

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"The Pesticide Manual, 14th ed.,", 2006, BRITISH CROP PROTECTION COUNCIL
J. HETEROCYCL. CHEM., vol. 35, no. 6, 1998, pages 1493 - 1499
J. ORG. CHEM., vol. 62, no. 17, 1997, pages 5908 - 5919

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018011056A1 (en) 2016-07-12 2018-01-18 Basf Agrochemical Products B.V. Pesticidally active mixtures
US11330820B2 (en) 2016-07-12 2022-05-17 Basf Se Pesticidally active mixtures
WO2018162312A1 (en) 2017-03-10 2018-09-13 Basf Se Spirocyclic derivatives
WO2018177970A1 (en) 2017-03-31 2018-10-04 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
EP3978504A1 (en) 2017-03-31 2022-04-06 Basf Se Chiral 2,3-dihydrothiazolo[3,2-a]pyrimidine derivatives for combating animal pests
WO2018197466A1 (en) 2017-04-26 2018-11-01 Basf Se Substituted succinimide derivatives as pesticides
WO2019030358A1 (en) * 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
JP2020530476A (en) * 2017-08-11 2020-10-22 シンジェンタ パーティシペーションズ アーゲー Pest control active pyrazole derivative
US11252963B2 (en) 2017-08-11 2022-02-22 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030359A1 (en) * 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
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US11365187B2 (en) 2017-08-11 2022-06-21 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030355A1 (en) * 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019043183A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
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US11459318B2 (en) 2017-10-06 2022-10-04 Syngenta Participations Ag Pesticidally active pyrrole derivatives
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WO2019072906A1 (en) 2017-10-13 2019-04-18 Basf Se Imidazolidine pyrimidinium compounds for combating animal pests
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
WO2019145140A1 (en) 2018-01-09 2019-08-01 Basf Se Silylethynyl hetaryl compounds as nitrification inhibitors
WO2019137995A1 (en) 2018-01-11 2019-07-18 Basf Se Novel pyridazine compounds for controlling invertebrate pests
WO2019166560A1 (en) 2018-02-28 2019-09-06 Basf Se Use of n-functionalized alkoxy pyrazole compounds as nitrification inhibitors
WO2019166561A1 (en) 2018-02-28 2019-09-06 Basf Se Use of alkoxypyrazoles as nitrification inhibitors
WO2019166558A1 (en) 2018-02-28 2019-09-06 Basf Se Use of pyrazole propargyl ethers as nitrification inhibitors
WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019175712A1 (en) 2018-03-14 2019-09-19 Basf Corporation New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways
WO2019219529A1 (en) 2018-05-15 2019-11-21 Basf Se Mixtures comprising benzpyrimoxan and oxazosulfyl and uses and methods of applying them
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