WO2015124606A1 - N-substituted imino heterocyclic compounds for combating invertebrate pests - Google Patents

N-substituted imino heterocyclic compounds for combating invertebrate pests Download PDF

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WO2015124606A1
WO2015124606A1 PCT/EP2015/053386 EP2015053386W WO2015124606A1 WO 2015124606 A1 WO2015124606 A1 WO 2015124606A1 EP 2015053386 W EP2015053386 W EP 2015053386W WO 2015124606 A1 WO2015124606 A1 WO 2015124606A1
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alkyl
cyc
haloalkyl
het
radicals
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PCT/EP2015/053386
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French (fr)
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Wolfgang Von Deyn
Martin John MCLAUGHLIN
Birgit GOCKEL
Karsten KÖRBER
Jochen Dietz
Matthias Pohlman
Kenichi Kojima
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—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
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-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
    • A01N43/48—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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-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
    • A01N43/48—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
    • A01N43/72—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
    • A01N43/74—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 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to N-substituted imino heterocyclic compounds, including their stereoisomers, tautomers and salts, and to compositions comprising such compounds.
  • the invention also relates to the use of the N-substituted imino heterocyclic compounds, their stereoisomers, their tautomers and their salts, for combating invertebrate pests. Furthermore the invention relates also to methods of combating invertebrate pests, which comprises applying such compounds.
  • Invertebrate pests such as insects, acaridae and nematode pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
  • EP 259738 discloses co ula A, which have insecticidal activity:
  • W is a substituted pyridyl radical or a 5-or 6-membered heterocyclic radical
  • R is hydrogen or alkyl
  • Y is inter alia a nitrogen atom
  • Z is an electron withdrawing group selected from nitro and cyano.
  • Pesticidal compounds which are similar to those of EP 259738, are known from
  • EP 639569 where the moiety electron withdrawing moiety Z is an electron withdrawing group such as alkoxcarbonyl, arylcarbonyl, heterocyclic carbonyl, Ci-C4-alkylsulfonyl, sulfamoyl or
  • Ar is an aryl or 5- or 6-membered heterocyclic group
  • R a is hydrogen or alkyi
  • Y' is hydrogen, halogen, a hydroxyl group, an alkyi group or an alkoxy group
  • Rb is an alkyi group substituted with halogen or an alkoxy group, optionally substituted with halogen.
  • Pesticidal compounds which are similar to those of US 2013/0150414, are known from WO 2013/129688.
  • EP 535227 describes N-substituted heterocyclic amidine compounds of the formula C
  • Ri represents optionally substituted nitrogen contain- ing hetaryl
  • R2 represents optionally substituted alkyi, alkenyl, alkynyl, cycloalkyi, cycloalkenyl, aryl etc.
  • R3 represents optionally substituted alkyi, alkenyl, alkynyl, cycloalkyi, cycloalkenyl or R2 and R3 may be combined together to form a ring
  • R 4 represents an optionally substituted nitrogenous heterocycle.
  • the pesticidal activity of the compounds is not satisfactory. It is therefore an object of the present invention to provide compounds having a good pesticidal activity, especially against difficult to control insects and acarid pests.
  • N-substituted imino compounds of the general formula (I) described below by their stereoisomers, their tautomers and their salts. Therefore, the present invention relates to N-substituted imino compounds of formula (I):
  • ( ⁇ ) a 8-, 9- or 10-membered, saturated, partially unsaturated or maximally unsaturated heterobicycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R 4 ;
  • Het is a 5- or 6-membered carbon-bound or nitrogen-bound heterocyclic or heteroaro- matic ring, comprising 2, 3, 4 or 5 carbon atoms and 1 , 2 or 3 heteroatoms as ring members, which are independently selected from sulfur, oxygen or nitrogen, wherein the sulfur and nitrogen ring members can independently be partly or fully oxidized, and wherein each ring is optionally substituted by k identical or different substituents R 6 , wherein k is an integer selected from 0, 1 , 2, 3 or 4;
  • each R v independently from each other, is hydrogen, halogen, cyano, azido, nitro,
  • each R w independently from each other, are selected from the group consisting of hydrogen, halogen, cyano, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl and C2-Cio-alkynyl, wherein the carbon atoms of the aforementioned four aliphatic and cycloaliphatic radicals may be unsubstituted or may be partly or fully halogenated or may optionally be further substituted with 1 , 2 or 3 identical or different radicals R 7 ; or
  • R 1 , R 2 are independently from each other selected from the group consisting of hydrogen, halogen, CN, SCN, nitro, Ci-C6-alkyl, C3-C6-cycloalkyl, wherein each of the two aforementioned radicals are unsubstituted, partly or completely hal- ogenated or may carry any combination of 1 , 2 or 3 radicals R 7 ,
  • heterocyclic ring comprising 1 , 2 or 3 identical or different het- eroatoms as ring members, which are selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identi- cal or different substituents R 10 , and wherein the nitrogen and/or the sulfur at- om(s) of the heterocyclic ring may optionally be oxidized, or
  • R 1 and R 2 form, together with the carbon atom, which they attached to, a 3-, 4-, 5- or 6-membered saturated or partly unsaturated carbocyclic or heterocyclic ring, wherein each of the carbon atoms of said cycle are unsubstituted or may carry any combination of 1 or 2 identical or different radicals R 7 , or
  • Het * is a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 6 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci- Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or complete- ly halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R 7 ,
  • heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • phenyl, phenoxy, phenyl-Ci-C4-alkyl where the phenyl ring in the last three groups is optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 10 , and and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 7 may form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partly unsaturated carbocyclic or heterocyclic ring together with the carbon atoms to which the two R 7 are bonded, where the heterocyclic ring comprises 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 ; independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halo
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
  • R 7b independently of its occurrence, is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 10 , and
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
  • R 7c is OR 8b or N R 17a R 17b ;
  • phenyl phenyl-Ci-C- 4 -alkyl, where the phenyl ring in the last two mentioned radicals is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 10 , and
  • heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 8a independently of its occurrence, is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C 6 -haloalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-Ci-C 4 -alkyl, C 3 -C 8 - halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, phenyl-Ci-C- 4 -alkyl, where the phenyl ring in the last two mentioned radicals is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents
  • a 5- or 6-membered aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 iden- tical or different substituents R 10 ;
  • R 8b independently of its occurrence is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C 6 -haloalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-Ci-C 4 -alkyl, C 3 -C 8 - halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6 haloal- kynyl;
  • R 9a , R 9b are each independently from one another selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C 3 -C 8 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 3 - C 8 -cycloalkyl-Ci-C 4 -alkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-
  • phenyl benzyl, 1 -phenethyl or 2-phenethyl, where the phenyl ring in the last four mentioned radicals is unsubstituted or may be substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 10 ; and
  • heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 10 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 9a and R 9b are together a C2-C7 alkylene chain and form a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partly unsaturated or maximally unsaturated ring together with the nitrogen atom they are bonded to, wherein the alkylene chain may contain one or two heteroatoms, which are, independently of each other, selected from oxygen, sulfur or nitrogen, and where the alkylene chain may optionally be substituted with 1 , 2, 3 or 4 radicals selected from halogen, C1-C6- alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C 6 -alkylthio, Ci-C 6 - haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkyn
  • R 10 independently of its occurrence, is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-C10- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may optionally be substituted with 1 , 2, 3, 4 or 5 identical or different radicals R 7 ,
  • phenyl optionally substituted with 1 , 2, 3, 4 or 5 identical or different radicals selected from OH, halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heter- ocyclic ring is unsubstituted or may be substituted with 1 , 2, 3, 4 or 5 substituents selected independently from one another from halogen, cyano, NO2, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
  • R 11 , R 12 independently of their occurrence, are selected from the group consisting of d-Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkoxy-Ci-C 4 -alkyl, C 2 -C 6 - alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8-halocycloalkyl, C3-C8-cycloalkyl-Ci-C 4 -alkyl, C3-C8-halocycloalkyl-Ci-C 4 - alkyl, Ci-C6-haloalkoxy-Ci-C 4 -alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals are unsubstituted or substituted with 1
  • R 13 , R 14 independently of their occurrence, are selected from the group consisting of hydrogen, halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C 4 -alkoxy-Ci-C 4 - alkyl, phenyl and benzyl;
  • R 15 independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;
  • phenyl, benzyl and pyridyl wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
  • R 16 independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-alkylcarbonyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3- C8-cycloalkyl-Ci-C4-alkyl, wherein the six last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,
  • phenyl, benzyl and pyridyl wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino and di-(Ci-C6-alkyl)amino;
  • R 16a independently of its occurrence, is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,
  • phenyl, benzyl and pyridyl wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
  • R 17 independently of its occurrence, is selected from the group consisting of hydrogen, trimethylsilyl, triethylsilyl, fer/butyldimethylsilyl,
  • Ci-C6-alkyl C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Cs-Cs-cycloalkoxy, C3-C8- cycloalkyl-Ci-C4-alkoxy, Ci-C6-alkylthio, wherein the 1 1 last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkoxy, phenyl, benzyl, pyridyl, phenoxy, benzyloxy and pyridyloxy, wherein the six last mentioned radicals may be unsubstituted
  • R 17a , R 17b are each independently from one another selected from the group consisting of hydrogen, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, ferfbutyldimethylsilyl,
  • R 17a and R 17b may together be a C2-C6 alkylene chain forming a 3- to 7- membered saturated, partly unsaturated or unsaturated ring together with the nitrogen atom R 17a and R 17b are bonded to, wherein the alkylene chain may contain 1 or 2 heteroatoms selected, independently of each other, from oxygen, sulfur or nitrogen, and may optionally be substituted with halogen, C1-C4- haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized; or
  • R 17c independently of its occurrence, is selected from the group consisting of hydrogen, CN, d-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-Ci- C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy, phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-
  • the present invention relates to and includes the following embodiments:
  • compositions comprising an amount of at least one compound of the formula (I) or a stereoisomer, tautomer or salt thereof;
  • a method for protecting growing plants from attack or infestation by invertebrate pests comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound of the formula (I) or a stereoisomer, a tautomer or salt thereof, in particular a method protecting crop plants from attack or infestation by animal pests, which comprises contacting the crop plants with a pesticidally effective amount of at least one compound of the formula (I) or stereoisomer, a tautomer or salt thereof;
  • seeds comprising a compound of the formula (I) or an enantiomer, diastereomer or salt thereof;
  • a method for treating animals infested or infected by parasites or preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites which comprises administering or applying to the animals a parasiticidal- ly effective amount of a compound of formula (I) or the stereoisomers and/or salts, in par- ticular veterinary acceptable salts, thereof;
  • a process for the preparation of a veterinary composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises formulating a compound of formula (I) or a stereoisomer, tautomer and/or veterinary acceptable salt thereof with a carrier composition suitable for veterinary use;
  • the present invention also relates to plant propagation materials, in particular as mentioned above to seeds, containing at least one compound of formula (I), a stereoisomer, a tau- tomer and/or an agriculturally acceptable salt thereof.
  • plant propagation materials in particular as mentioned above to seeds, containing at least one compound of formula (I), a stereoisomer, a tau- tomer and/or an agriculturally acceptable salt thereof.
  • the present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers, diastereomers and E/Z-isomers as well as to mixtures thereof and also to the salts thereof.
  • the present invention relates to each isomer alone, or mixtures or combinations of the isomers in any proportion to each other.
  • Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (E/Z-isomers, cis/trans isomers) and mixtures thereof.
  • the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • One center of chirality is the carbon ring atom carrying radical R 1 .
  • the invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantiomers or diastereomers of the compound I or its mixtures.
  • the present invention also relates to potential tautomers of the compounds of formula (I) and also to the salts of such tautomers.
  • the present invention relates to the tautomer as such as well as to mixtures or combinations of the tautomers in any proportion to each other.
  • the term "tautomers” encompasses isomers, which are derived from the compounds of formula (I) by the shift of an H-atom involving at least one H-atom located at a nitrogen, oxygen or sulphur atom. Examples of tautomeric forms are keto-enol forms, imine-enamine forms, urea-isourea forms, thiourea-isothiourea forms, (thio)amide-(thio)imidate forms etc.
  • the compounds of the present invention i.e. the compounds of formula (I), their stereoisomers, their tautomers as well as their salts, in particular their agriculturally acceptable salts and their veterinarily acceptable salts, may be amorphous or may exist in one ore more different crystalline states (polymorphs) or modifications which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention includes both amorphous and crystalline compounds of the formula (I), mixtures of different crystalline states or modifications of the respective stereoisomers or tautomers, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula (I) are preferably agriculturally salts as well as veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.
  • Suitable agriculturally or veterinary useful salts are especially the salts of those cations or anions, in particular the acid addition salts of those acids, whose cations and anions, respec- tively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 + ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy- Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammo- nium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen car- bonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4- alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Cn-Cm indicates in each case the possible number of carbon atoms in the group.
  • Halogen will be taken to mean fluoro, chloro, bromo and iodo.
  • partially or fully halogenated will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in partic- ular by fluorine or chlorine.
  • partially or fully halogenated alkyl is also termed haloalkyl
  • partially or fully halogenated cycloalkyl is also termed halocycloalkyl
  • partially or fully halogenated alkylenyl is also termed haloalkenyl
  • partially or fully halogenated alkylynyl is also termed haloalkynyl
  • partially or fully halogenated alkoxy is also termed haloalkoxy
  • partially or fully halogenated alkylthio is also termed haloalkthio
  • partially or fully halogenated alkylsulfinyl is also termed haloalkylsulfinyl
  • partially or fully halogenated alkylsulfonyl is also termed haloalsulfonyl
  • partially or fully halogenated cycloalkylalkylalkyl is also termed halocycloalkylalkyl.
  • C n -C m -alkyl refers to a branched or unbranched saturated hydrocarbon group hav- ing n to m, e.g.
  • 1 to 10 carbon atoms preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 - methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 - dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl,
  • Ci-C4-alkyl means for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl.
  • C n -C m -alkanediyl as used herein is synonym to "C n -C m -alkylene” and refers to a linear or branched saturated bivalent hydrocarbon group having n to m, e.g.
  • 1 to 6 carbon atoms preferably 1 to 4 carbon atoms, for example methylene, ethane-1 ,1 -diyl, ethane-1 ,2-diyl, propane-1 ,1 -diyl, propane-1 ,2-diyl, propane-1 ,3-diyl, propane-2,2-diyl, butane-1 ,1 -diyl, butane- 1 ,2-diyl, butane-2,3-diyl, butane-2,2-diyl, butane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,1 -diyl, pen- tane-2,2-diyl, pentane-3,3-diyl, pentane-1 ,2-diyl, pentane-1 ,3-diyl, pentane-1 ,4-diyl, pent
  • linear Ci-C6-alkanediyl refers to a linear saturated bivalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, for example methylen, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl and hexane-1 ,6-diyl.
  • C n -C m -haloalkyl refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g.
  • Ci-C4-haloalkyl such as chloro- methyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluorome- thyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pent
  • Ci-C4-haloalkyl such as chloro- methyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl
  • Ci-Cio-haloalkyl in particular comprises Ci-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoro- methyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.
  • Halomethyl is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluo- romethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like.
  • C n -C m -haloalkoxy refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g.
  • Ci-C2-Alkoxy is methoxy or ethoxy.
  • Ci-C4-Alkoxy is, for example, methoxy, ethoxy, n- propoxy, 1 -methylethoxy (isopropoxy), butoxy, 1 -methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy).
  • Ci-C6-Alkoxy includes the meanings given for Ci-C4-alkoxy and also includes, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3- methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 - dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethyl butoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2- trimethylpropoxy, 1 -ethyl-1 -methylpropoxy or 1 -ethyl-2-methylpropoxy.
  • Ci-Cs-Alkoxy includes the meanings given for Ci-C6-alkoxy and also includes, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof.
  • Ci-Cio-Alkoxy includes the meanings given for Ci- Ce-alkoxy and also includes, for example, nonyloxy, decyloxy and positional isomers thereof.
  • C n -C m -alkylthio is a C n -C m -alkyl group, as defined above, attached via a sulfur atom.
  • Ci-C2-Alkylthio is methylthio or ethylthio.
  • Ci-C4-Alkylthio is, for example, methylthio, ethylthio, n-propylthio, 1 -methylethylthio (isopropylthio), butylthio, 1 -methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1 -dimethylethylthio (tert-butylthio).
  • Ci-C6-Alkylthio includes the meanings given for Ci-C4-alkylthio and also includes, for example, pentylthio, 1 - methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1 ,1 -dimethylpropylthio, 1 ,2- dimethylpropylthio, 2,2-dimethylpropylthio, 1 -ethylpropylthio, hexylthio, 1 -methylpentylthio, 2- methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2- dimethylbutylthio, 1 ,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 -ethylbutylthio
  • Ci-Cs-Alkylthio includes the meanings given for Ci-C6-alkylthio and also includes, for example, heptylthio, oc- tylthio, 2-ethylhexylthio and positional isomers thereof.
  • Ci-Cio-Alkylthio includes the meanings given for Ci-Cs-alkylthio and also includes, for example, nonylthio, decylthio and positional isomers thereof.
  • C n -C m -haloalkyloxy is a C n -C m -haloalkyl group, as defined above, attached via an oxygen atom.
  • Examples include Ci-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluo- romethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1 -bromoethoxy, 1 - fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pen
  • C n -C m -haloalkylthio is a C n -C m -haloalkyl group, as defined above, attached via a sulfur atom.
  • Examples include Ci-C2-haloalkylthio, such as chloromethylthio, bromomethyl- thio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethyl- thio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1 -chloroethylthio, 1 -bromoethylthio, 1 -fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2- trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2, 2-
  • Ci-C2-fluoroalkoxy and Ci-C2-fluoroalkylthio refer to Ci-C2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
  • 1 - pentenyl 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-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, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-
  • C2-C m -haloalkenyl refers to C2-C m -alkenyl, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example 1 -fluoroethenyl, 2-fluoroethenyl, 2,2-difluoroethenyl, 1 ,2,2-trifluoroethenyl, 1 -fluoro-2-propenyl, 2-fluoro-2-propenyl, 3-fluoro-2-propenyl, 1 -fluoro-1 - propenyl, 1 ,2-difluoro-1 -propenyl, 3,3-difluoropropen-2-yl, 1 -chloroethenyl, 2-chloroethenyl
  • C2-C m -alkynyl refers to linear or branched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one C- C-triple bond, such as ethynyl, propynyl, 1 -butynyl, 2-butynyl, and the like.
  • C2-C m -haloalkynyl as used herein, which is also expressed as “C2-C m -alkynyl which is partially or fully halogenated”, refers to C2-C m -alkynyl, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • Examples of C2-C m -haloalkynyl include 1 -fluoro-2-propenyl, 2- fluoro-2-propenyl, 3-fluoro-2-propenyl, 1 -fluoro-2-propynyl and 1 ,1 -difluoro-2-propenyl, and the like.
  • C3-C m -cycloalkyl refers to monocyclic and polycyclic 3- to m- membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohex- yl, cycloheptyl, cyclooctyl, cyclodecyl, bicyclo[2.2.1 ]heptyl, bicyclo[3.1 .1]heptyl, bicy- clo[2.2.2]octyl and bicyclo[3.2.1 ]octyl.
  • cycloalkyl denotes a monocyclic saturated hydrocarbon radical.
  • C3-C m -cycloalkenyl refers to monocyclic and polycyclic 3- to m- membered monounsaturated cycloaliphatic radicals, e.g. 1 -cyclopropenyl, 3-cyclopropenyl, 1 - cyclobutenyl, 3-cyclobutenyl, cyclopentenyl, 3-cyclopentenyl, 1 -cyclohexenyl, 3-cyclohexenyl, or 4-cyclohexenyl.
  • cycloalkenyl denotes a monocyclic mono-unsaturated hy- drocarbon radical.
  • C3-C m -halocycloalkyl as used herein, which is also expressed as “cycloalkyl which is partially or fully halogenated”, refers C3-C m -cycloalkyl as mentioned above, in which some or all of the hydrogen atoms are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • C3-C m -halocycloalkyl examples include 1 - fluorocycloprpyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 1 -chlorocyclcopropyl, 2- chlorocyclopropyl, 2,2-dichlorocyclopropyl, 2,3-difluorocyclopropyl, 1 -fluorocycobutyl etc.
  • C3-C m -cycloalkyl-Ci-C4-alkyl refers to a C3-C m -cycloalkyl group as defined above, which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above.
  • C3-C m -cycloalkyl-Ci-C4-alkyl examples include cyclopropyl methyl, cyclopropylethyl, cy- clopropyl propyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclo- pentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl.
  • C3-C m -halocycloalkyl-Ci-C4-alkyl refers to a C3-C m -halocycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above.
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an Ci-C4-alkoxy group.
  • Examples are methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, isobutoxymethyl, tert- butoxymethyl, 1 -methoxyethyl, 1 -ethoxyethyl, 1 -propoxyethyl, 1 -isopropoxyethyl, 1 -n- butoxyethyl, 1 -sec-butoxyethyl, 1 -isobutoxyethyl, 1 -tert-butoxyethyl, 2-methoxyethyl, 2- ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 2-sec-butoxyethyl, 2- isobutoxyethyl, 2-tert-butoxyethyl, 1 -methoxypropyl, 1 -ethoxypropyl, 1 -propoxypropyl, 1 - is
  • Ci-C4-haloalkoxy-Ci-C4-alkyl is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms, wherein one of the hydrogen atoms is replaced by a Ci-C4-alkoxy group and wherein at least one, e.g. 1 , 2, 3, 4 or all of the remaining hydrogen atoms, either in the alkoxy moiety or in the alkyl moiety or in both, are replaced by halogen atoms.
  • Examples are difluoromethoxymethyl (CHF2OCH2), trifluoromethoxymethyl, 1 -difluoromethoxyethyl, 1 - trifluoromethoxyethyl, 2-difluoromethoxyethyl, 2-trifluoromethoxyethyl, difluoro-methoxy-methyl (CH3OCF2), 1 ,1 -difluoro-2-methoxyethyl, 2,2-difluoro-2-methoxyethyl and the like.
  • Ci-C m -alkoxycarbonyl is a Ci-C m -alkoxy group, as defined above, attached via a carbonyl group atom.
  • Ci-C2-Alkoxycarbonyl is methoxycarbonyl or ethoxycarbonyl.
  • C1-C4- Alkoxy is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1 - methylethoxycarbonyl, butoxycarbonyl, 1 -methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1 ,1 -dimethylethoxycarbonyl.
  • Ci-C6-Alkoxycarbonyl includes the meanings given for C1-C4- alkoxycarbonyl and also includes, for example, pentoxycarbonyl, 1 -methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 1 ,1 -dimethylpropoxycarbonyl, 1 ,2- dimethylpropoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1 -ethylpropoxycarbonyl, hexoxycar- bonyl, 1 -methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4- methylpentoxycarbonyl, 1 ,1 -dimethylbutoxycarbonyl, 1 ,2-dimethylbutoxycarbonyl,
  • aryl refers to an aromatic hydrocarbon radical such as naphthyl or in particular phenyl.
  • 3- to 6-membered carbocyclic ring refers to cyclopropane, cy- clobutane, cyclopentane and cyclohexane rings.
  • 3- to 7-membered carbocyclic ring refers to cyclopropane, cyclobutane, cyclopentane, cyclohexane and cyclohep- tane rings.
  • heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or “containing heteroatom groups", wherein those heteroatom(s) (group(s)) are selected from N, O, S, NO, SO and SO2 and are ring members, as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • Examples of 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic rings include: oxiranyl, aziridinyl, azetidinyl, 2 tetrahydrofuranyl, 3-tetrahydrofuranyl, 2 tetrahydrothienyl, 3 tetrahy- drothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3 pyrazolidinyl, 4 pyrazolidinyl, 5-pyrazolidinyl, 2 imidaz- olidinyl, 4 imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5 oxazolidinyl, 3-isoxazolidinyl, 4 isoxa- zolidinyl, 5 isoxazolidinyl, 2 thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3 isothiazolidinyl, 4- is
  • Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3- dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2-pyrrolin-2- yl, 2-pyrrolin-3-yl, 3 pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4 isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2 isoxazolin-5-yl,
  • Examples of 5- or 6-membered maximally unsaturated heterocyclic rings also termed heteroaromatic rings or hetaryl, include: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1 -pyrrolyl, 2-pyrrolyl, 3- pyrrolyl, 1 -pyrazolyl, 3-pyrazolyl, 4-pyrazo-"lyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4 thiazolyl, 5-thiazo-"lyl, 3-isoxazolyl, 3-isothiazolyl, 4-isoxazolyl, 4-isothiazolyl, 5- isoxazolyl, 5-isothiazolyl, 1 -imidazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4- thiadiazol-2-yl, 1 ,2,4-
  • Examples of 8-, 9- or 10-membered, saturated, partially unsaturated heterobicycles having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members include 2- azabicyclo[2.2.1]heptyl, 5-azabicyclo[2.2.1 ]heptyl, 2,5-diazabicyclo[2.2.1 ]heptyl, 3- azabicyclo[3.2.1]octyl, 8-azabicyclo[3.2.1 ]octyl, 3,8-diazabicyclo[3.2.1]octyl, indolin-1 -yl, indolin- 2-yl, indolin-3-yl, 2,3-dihydroindazol-2-yl, 2,3-dihydroindazol-3-yl, 2,3-dihydroindazol-1 -yl, 3,4- dihydroquinolinyl, 1 ,2,3,4-tetrahydroquinolinyl, 3,4-di
  • Examples of 8-, 9- or 10-membered maximally unsaturated heterobicycles also termed bicyclic hetaryl, having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members include quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizynyl, isoindolyl, indazolyl, benzofuryl, ben- zothienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, pyrrolo[1 ,2- a]imidazolyl, imidazo[1 ,2-b]pyrazolyl, imidazo[1 ,2-a]pyridinyl, imidazo[1 ,2-a]pyrimidinyl, imidazo[1 ,2-a]pyridine-2-yl, thieno[3,2-b]pyridine-5-yl, imidazo
  • Embodiments of the present invention as well preferred compounds of the present inven- tion are outlined in the following paragraphs.
  • the remarks made below concerning preferred embodiments of the variables of the compounds of formula (I), especially with respect to their substituents W, W 2 , W 3 , W 4 , Het, R 1 ,R 2 and Cyc and the variable k and m are valid both on their own and, in particular, in every possible combination with each other.
  • R 3 , R 4 are independently from each other selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-C10- alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R 7 ,
  • Het * is a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 16 independently of its occurrence, is selected from the group consisting of hydrogen, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci- C 4 alkoxy,
  • phenyl, benzyl and pyridyl wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino; where n, R 5 , R 7 , R 7a , R 7 , R 7c , R 8a , R 8 , R 9a , R 9 , R 11 , R 12 , R 13 , R 14 , R 16 , R 7 , R 7a , R 7 , R 7c and R 17d have one of the meanings given above.
  • Cyc is 5- or 6-membered, partially unsaturated or maximally unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring mem- bers, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R 3 .
  • Cyc is 5-membered maximally unsaturated heteromonocycle, i.e. 5-membered monocyclic hetaryl, having 1 heteroatom as ring member, which is selected from O and S, and 1 or 2 nitrogen atoms as ring members, where the heter- omonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R 3 .
  • Cyc is selected from the group consisting of thiazol-2-yl, oxazol-2-yl, isoxazol-5-yl, isothiazol-5-yl, 1 ,3,4- thiadiazol-2-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-oxadiazol- 5-yl and 1 ,2,4-thiadiazol-5-yl, where the aforementioned 5-membered heterocycles are unsub- stituted or carry 1 , 2 or 3, in particular 1 or 2 radicals R 3 .
  • Cyc is also selected from oxazol-5-yl.
  • Cyc is 6-membered maximally unsaturated heteromonocycle, i.e. 6-membered monocyclic hetaryl, having 1 , 2 or 3 nitrogen atoms as heteroatom ring member, where the heteromonocycle is unsubstituted or carries 1 , 2, 3 or 4 subsitutents R 3 .
  • Cyc is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4- pyridyl, 2-pyrimidinyl, 3-pyridazinyl and 4-pyridazinyl, where the aforementioned 6-membered heterocycles are unsubstituted or carry 1 , 2, 3 or 4, in particular 1 , 2 or 3 radicals R 3 .
  • Cyc is 5-membered partially unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O and S, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R 3 .
  • Cyc is selected from 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,3- dihydrothiophen-2-yl, 2,3-dihydrothiophen-5-yl and 2,5-dihydrothiophen-2-yl, where the aforementioned 5-membered partially unsaturated heterocycles are unsubstituted or carry 1 , 2 or 3, in particular 1 or 2 radicals R 3 .
  • Cyc is 5-membered partially unsaturated heteromonocycle, having 1 heteroatom as ring member, which is selected from O and S, and 1 or 2 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R 3 .
  • Cyc is selected from thiazolin-2-yl (4,5-dihydrothiazol-2-yl), and oxazolin-2-yl, where the aforementioned 5-membered heterocycles are unsubstituted or carry 1 , 2 or 3, in particular 1 or 2 radicals R 3 .
  • Cyc is 5-membered maximally unsaturated heteromonocycle, i.e. 5-membered monocyclic hetaryl, having 1 heteroatom as ring member, which is selected from O and S, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R 3 .
  • Cyc is selected from furan-2-yl, furan-3-yl, thiophen- 2-yl and thiophen-3-yl, where the aforementioned 5-membered heterocycles are unsubstituted or carry 1 or 2 radicals R 3 .
  • Cyc is thiazol-2-yl, which is unsubstituted or which carries in particular 1 or 2 radicals R 3 .
  • Cyc is oxazol-2-yl, which is unsubstitut- ed or which carries in particular 1 or 2 radicals R 3 .
  • Cyc is isothiazol-5-yl, which is un- substituted or which carries in particular 1 or 2 radicals R 3 .
  • Cyc is isoxazol-5-yl, which is unsub- stituted or which carries in particular 1 radical R 3 .
  • Cyc is 1 ,3,4-thiadiazol-2-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is 1 ,3,4-oxadiazol-2-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is 1 ,2,4-thiadiazol-3-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is 1 ,2,4-oxadiazol-3-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is 1 ,2,4-thiadiazol-5-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is 1 ,2,4-oxadiazol-5-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is oxazol-5-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is 2-pyridyl, which is unsubsti- tuted and which carries in particular 1 , 2, 3 or 4 radical R 3 .
  • Cyc is 3-pyridyl, which is unsubstituted and which carries in particular 1 , 2, 3 or 4 radical R 3 .
  • Cyc is 4-pyridyl, which is unsubstituted or which carries in particular 1 , 2, 3 or 4 radical R 3 .
  • Cyc is 2-pyrimidinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R 3 .
  • Cyc is 4-pyrimidinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R 3 .
  • Cyc is 5-pyrimidinyl, which is unsub- stituted or which carries in particular 1 , 2 or 3 radical R 3 .
  • Cyc is 3-pyridazinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R 3 .
  • Cyc is 4-pyridazinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R 3 .
  • Cyc is 2,3-dihydrothiophen-5-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is thiazolin-2-yl which is unsubstituted or which carries 1 radical R 3 .
  • Cyc is oxazolin-2-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • Cyc is thiophen-2-yl, which is unsubstituted or which carries in particular 1 radical R 3 .
  • R 3 and R 4 are preferably independently from each other selected from the group consisting of
  • Ci-C6-haloalkyl C3-C6-cycloalkyl, Ci-C6-alkyl, C3- C6-halocycloalkyl,
  • R 7 is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl;
  • R 8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl;
  • R 15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;
  • R 16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
  • R 17a and R 17b are independently from each other selected from hydrogen, Ci-C6-alkyl and d-Ce-haloalkyl; a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 5 , and
  • Het * is a 5- or 6- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring mem- bers, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substitu- ents R 5 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci- Ce-haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl, C 3 -C 6 -halocycloalkyl, OR 8b and S(0) n R 8b , where R 8b is Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl, and
  • Q irrespectively of its occurrence is selected from a single bond, Chb, O, S, S(O) and
  • the radical R 3 is prefer- ably selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , C1-C6- haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl,
  • a moiety Q-phenyl wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 5 , and a moiety Q-Het * , wherein Het * is a 3-, 4-, 5- or 6- mem- bered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 3 if present, is in particular selected from the group consisting of halogen, cyano, C1-C6- haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl, C 3 -C 6 -halocycloalkyl, OR 8b , S(0) n R 8b ,
  • R 3 is especially selected from the group consisting of halogen, cyano, C1-C2- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoroethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy,
  • R 3 is also especially selected from the group consisting of formyl, COOH , Ci-
  • C6-alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl, Ci-C4-alkylaminocarbonyl, such as methylaminocarbonyl or ethylaminocarbonyl and di-(Ci-C4-alkyl)aminocarbonyl, such as dimethylaminocarbonyl, diethylaminocarbonyl, N- methyl-N-ethylaminocarbonyl and Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R 7 .
  • NNR 9a R 9b are, but are not limited to, methylcarbamoylhydrazono, ethylcar- bamoylhydrazono, 2,2,2-trifluoroethylcarbamoylhydrazono, acetylhydrazono, propanoylhydra- zono and benzoylhydrazono.
  • Het * a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 het- eroatoms as ring members, which are identical or different and selected from oxygen, ni- trogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 ;
  • R 8b is Ci-C6-haloalkyl, in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, C3-C6-cycloalkyl, such as cyclobutyl, cyclopropyl, or cyclopentyl, Ci- C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, or C3-C6- halocycloalkyl, such as 1 -fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocycloprop
  • R 5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , C1-C6- haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl, C 3 -C 6 -halocycloalkyl, OR 8b and S(0) n R 8b , where R 8b is as defined herein and in particular Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or, C3-C6-halocycloalkyl, and especially Ci-C2-haloalkyl, such as difluoromethyl, trifluorome- thyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoro
  • Q irrespectively of its occurrence is selected from a single bond, CH2, O, S, S(O) and S(0)2.
  • Cyc is a 8-, 9- or 10-membered, saturated, partially unsaturated or maximally unsaturated heterobicycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R 4 , in particular an 8-, 9- or 10 membered maximally unsaturated fused heterobicycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring members, where the heterobicycle is unsubstituted or carries 1 , 2 or 3 subsitutents R 4 .
  • Cyc in the groups of embodiments (2) include: quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizynyl, isoindolyl, indazolyl, benzofuryl, ben- zothienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, pyrrolo[1 ,2- a]imidazolyl, imidazo[1 ,2-b]pyrazolyl, imidazo[1 ,2-a]pyridinyl, imidazo[1 ,2-a]pyrimidinyl, imid- azo[1 ,2-a]pyridine-2-yl, thieno[3,2-b]pyridine-5-yl, imidazo-[2,1 -b]-thiazol-6-yl and 1 ,2,4- triazolo[1 ,5-a]pyridine-2-
  • the radicals R 4 are preferably selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl, OR 8b and S(0) n R 8b .
  • R 4 is in particular selected from the group consisting of halogen, cyano, C1-C6- haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl, C 3 -C 6 -halocycloalkyl, OR 8b and S(0) n R 8b .
  • R 4 is especially selected from the group consisting of halogen, cyano, C1-C2- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoroethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy,
  • R w is preferably selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, C1-C4- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as meth- oxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-flu
  • R w3 , R w4 and R w6 are hydrogen while R w5 has one of the meanings given for R w , and where R w5 is in particular selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2- trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and C1-C4- haloalkoxy, in particular Ci-C2-haloalkoxy, in particular Ci-C
  • R w3 , R w4 and R w5 are hydrogen while R w6 has one of the meanings given for R w , and where R w6 is in particular selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluo- romethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci- C4-haloalkoxy, in particular Ci-C2-haloalkoxy, in particular Ci-
  • R w3 , R w4 , R w5 and R w6 are hydrogen.
  • RTM is preferably selected from the group consisting of halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluo- romethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci- C4-haloalkoxy, in particular Ci-C2-halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4
  • RTM is preferably located in para-position with respect to the carbon atom that carries the imino-nitrogen.
  • Cyc is preferably as defined for group (1 ) of embodiments, in particular as defined for groups (1 a) and (1 b) of embodiments and especially as defined for groups (1 a), (1 b), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7) and (1 b.8) of embodiments. Also preferred are compounds of formula (l-A), wherein Cyc is as defined for groups (1c) and (1d) of embodiments and especially as defined for groups (1c.1), (1d.1), (1 d.2) and (1e.1) of embodiments.
  • Het-21 Het-22 Het-23 Het-24 wherein # denotes the bond in formulae (I) and (l-A), and wherein R 6 and k are as defined above and where R 6a is hydrogen or has one of the meanings given for R 6 and where R 6b is hydrogen or a C-bound radical mentioned as R 6 and where R 6b is in particular hydrogen, C1-C4- alkyl or Ci-C4-haloalkyl.
  • k is 0, 1 or 2, especially 0 or 1 .
  • Het-1 , Het-2, Het-3, Het-4, Het-7, Het-8, Het-9, Het-10, Het-1 1 , Het-18 and Het-21 k is especially 1.
  • R 6a in formulae Het-12, Het-13, Het-14, Het-16, Het-17, Het-19, Het 20 and Het-22 is different from hydrogen.
  • R 6 is in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, C1-C4- haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoro- methyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci- C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2- difluoroeth
  • R 6a is in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluo- rine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoro
  • R 6b is in particular selected from the group consisting of hydrogen, Ci-C4-alkyl, such as methyl or ethyl, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably C1-C2- alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl.
  • Ci-C4-alkyl such as methyl or ethyl
  • Ci-C4-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethy
  • R 6 is selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlo- rine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-triflu
  • R 6a is selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, C1-C4- haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluo- romethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-
  • a particularly preferred group of embodiments relates to compounds of formulae (I) and (I-
  • a particular subgroup of embodiments relates to compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-1 a
  • R 6 is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, and C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl, and even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, tri- fluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl; R 6a is as defined above and in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine and Ci-C4-alkyl, such as methyl or ethyl, more
  • a special embodiment of the radical Het-1a is 6-chloropyridin-3-yl, i.e. R 6a is hydrogen and R 6 is chlorine.
  • a further special embodiment of the radical Het-1a is 6-(trifluoromethyl)pyridin-3- yl, i.e. R 6a is hydrogen and R 6 is trifluoromethyl.
  • Another particularly preferred group of embodiments relates to compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-11 , where k is 0, 1 or 2, in particular 0 or 1 , and where Het is in articular a radical of formula Het-11 a,
  • R 6a is as defined above and wherein R 6a is in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and C1-C4- haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluor
  • Another particularly preferred group of embodiments relates to compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-24, where k is 0, 1 or 2, in particular 0 or 1 , and where R 6 , if present, is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-
  • Preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and the salts thereof, wherein R 1 and R 2 may together be CR 13 R 14 .
  • R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, halogen, cyano, Ci-C3-alkyl, such as methyl ethyl or isopropyl, or C1-C3- haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl.
  • At least one of the radicals R 1 and R 2 is hydrogen.
  • compounds of formulae (I) and (l-A) and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and the salts thereof, wherein R 1 and R 2 are both hydrogen.
  • R 1 , R 2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1 -fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R 1 , R 2 are independently from each other
  • Het is selected from the group consisting of radicals of formulae Het-1 , Het-1 1 a and Het-24, wherein
  • R 6 is selected from the group consisting of halogen, such as chlorine or fluorine, C1-C4- alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, C1-C4- haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluo- roethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and C1-C2- haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-
  • R 6a is selected from the group consisting of hydrogen, halogen, such as chlorine or fluo- rine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy,
  • Ci-C4-haloalkoxy such as difluoromethoxy or trifluoromethoxy
  • Ci-C4-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci- C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl and
  • k is 0, 1 or 2 and wherein k is especially 1 or 2.
  • R 1 , R 2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1 -fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R 1 , R 2 are independently from each other
  • a particular subgroup of embodiments relates to compounds of formulae (I) and (I- A), and likewise to the compounds of groups (1 ), (2), (1 a), (1 b), (1 c), (1 d),(1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-1 a
  • halogen such as chlorine or fluorine
  • Ci-C4-alkyl such as methyl or ethyl
  • C1-C4- haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl, and even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl;
  • halogen such as chlorine or fluorine
  • Ci-C4-alkyl such as methyl or ethyl, more preferably is hydrogen
  • Het is especially 6-chloropyridin-3-yl, i.e. R 6a is hydrogen and R 6 is chlorine, or 6-(trifluoromethyl)pyridin-3-yl, i.e. R 6a is hydrogen and R 6 is trifluoromethyl.
  • R 1 , R 2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1 -fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R 1 , R 2 are independently from each other
  • R 6a is as defined above and wherein R 6a is in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and C1-C4- haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluor
  • R 1 , R 2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1- difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1-fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R 1 , R 2 are independently from each other in particular selected from the
  • R 1 , R 2 are independently from each other selected from the group consisting of hydrogen, halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C6-haloalkyl, C2-C6-halocycloalkyl;
  • R 1 and R 2 form, together with the carbon atom, which they attached to, a 3- to 5-membered saturated carbocyclic ring;
  • R 3 if present, are independently from each other selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R 7 ,
  • R 7a is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl
  • R 8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl;
  • R 15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloal- koxy;
  • R 16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
  • R 17a and R 17b are independently from each other selected from hydrogen, Ci- C6-alkyl and Ci-C6-haloalkyl; a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 5 , and
  • Het * is a 5- or 6- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 , and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
  • R 8b is Ci-C 6 -haloalkyl, C 3 -C 6 - cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, and
  • Q irrespectively of its occurrence is selected from a single bond, Chb, O, S, S(O) and S(0) 2 .
  • Het is a radical Het-1 a, Het-1 1 a or Het-24, as defined above, and wherein Het is in particular 6-chloropyridin-3-yl, 6-trifluoromethylpyridin-3-yl, 2-chlorothiazol-5-yl or tetrahydrofuran-3-yl;
  • R 1 is hydrogen or Ci-C4-alkyl, in particular hydrogen or methyl, especially hydrogen
  • Cyc is thiazol-2-yl, which is unsubstituted or which carries 1 or 2 radicals R 3 , which are as defined above and which are preferably selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR 8b , S(0) n R 8b , a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 5 , and a moiety Q-Het * , wherein Het * is 5- or 6- mem- bered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optional
  • Q is a single bond, Chb, O, S, S(O) or S(0)2and wherein R 3 , if present, is especially selected from the group consisting of halogen, cyano, Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci- C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, or pentafluoroethoxy, Ci-C4
  • R 3 is also especially preferred selected from the group consisting of formyl, COOH, Ci-C4-alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl, Ci-C4-alkylaminocarbonyl, such as methylaminocarbonyl or ethylaminocarbonyl and di-(Ci-C4-alkyl)aminocarbonyl, such as dimethylaminocarbonyl, diethylaminocarbonyl, N- methyl-N-ethylaminocarbonyl and Ci-C4-alkyl such as methyl or ethyl,which is substituted with 1 or 2 identical or different substituents R 7 , wherein R 7 is as defined above.
  • Ci-C4-alkoxycarbonyl such
  • R 7 is in particular
  • R 7a is hydrogen, Ci-C6-alkyl such as methyl or ethyl or Ci-C6-haloalkyl, especially C1-C4- haloalkyl such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl;
  • R 8 is hydrogen, Ci-C6-alkyl such as methyl or ethyl, Ci-C6-haloalkyl such as difluorome- thyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 1 ,1 ,
  • R 15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;
  • R 16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
  • R 17a and R 17b are independently from each other selected from hydrogen, Ci-C6-alkyl such as methyl or ethyl and Ci-C6-haloalkyl such as. difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl.
  • Ci-C6-alkyl such as methyl or ethyl
  • Ci-C6-haloalkyl such as. difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluor
  • N 16 are hydroxyimino, methoxyimino, ethoxyimino, acetoxy- imino and propanoylimino.
  • NNR 9a R 9b are methylcarbamoylhydrazono, ethylcarbamoylhydra- zono, 2,2,2-trifluoroethylcarbamoylhydrazono, acetylhydrazono, propanoylhydrazono and ben- zoylhydrazono
  • Het * , Q, R 5 and R 8b are preferably as follows:
  • Het * a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 het- eroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 ,
  • R 8b is Ci-C6-haloalkyl, in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, C3-C6-cycloalkyl, such as cyclobutyl, cyclopropyl, or cyclopentyl, Ci- C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, or C3-C6- halocycloalkyl, such as 1 -fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocycloprop
  • R 5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , C1-C6- haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl, C 3 -C 6 -halocycloalkyl, OR 8b and S(0) n R 8b , where R 8b is as defined herein and in particular Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or, C3-C6-halocycloalkyl, and especially Ci-C2-haloalkyl, such as difluoromethyl, trifluorome- thyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoro
  • Ci-C2-haloalkylthio such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 - difluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio
  • Ci-C4-alkylthio such methylthio or ethylthio
  • Ci-C2-haloalkylsulfonyl such as trifluoromethylsulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl, 1 ,1 ,2,2-tetrafluoroethylsul
  • Q irrespectively of its occurrence is selected from a single bond, CH2, O, S, S(O) and S(0) 2 .
  • Het is a radical Het-1 a, Het-1 1 a or Het-24, as defined above, and wherein Het is in particular 6-chloropyridin-3-yl, 6-trifluoromethylpyridin-3-yl, 2-chlorothiazol-5-yl or tetrahydrofuran-3- yi;
  • R 1 is hydrogen or Ci-C4-alkyl, in particular hydrogen or methyl, especially hydrogen; and Cyc is selected from 2,3-dihydrothiophen-5-yl and thiophen-2-yl, where the aforementioned two radicals are unsubstituted or carry 1 or 2 radicals R 3 , which are selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR 8b , S(0) n R 8b , a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R 5 , and a moiety Q-Het * ; and wherein
  • Het * a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R 5 ,
  • R 8b is d-Ce-haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl or C 3 -C 6 -halocycloalkyl;
  • R 5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF 5 , Ci- Ce-haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 6 -alkyl, C 3 -C 6 -halocycloalkyl, OR 8b and S(0) n R 8b , Q is selected from a single bond, Chb, O, S, S(O) and S(0)2.
  • R w irrespectively of its occurrence, is selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, C1-C4- alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-
  • R 6 irrespectively of its occurrence, is selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluormethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluo- rine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,
  • phenyl and phenoxy where the phenyl ring in the last two mentioned radicals is unsubstituted or carriers 1 , 2, 3, 4 or 5 radicals R 10 ,
  • R 7 may also be Ci-C4-alkyl, such as methyl or ethyl, or Ci-C4-haloalkyl, such as difluormethyl, trifluoromethyl, 2,2,2-trifluoroethyl or pentafluoroetyl, if the radical, to which R 7 is attached, is C3-C6-cycloalkyl.
  • R 7a hydrogen, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2- fluoro-1 -methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or heptafluoroisopropyl, C3-C6-cycl
  • R 7b is preferably selected from the group consisting of halogen, Ci-C4-alkyl, C1-C4- haloalkyl, C3-C6-cycloalkyl, and phenyl, it being possible for phenyl to be unsubstituted, partly or completely halogenated, and where R 7b is more particularly fluorine, chlorine, Ci-C4-alkyl, such as methyl, ethyl, propyl, isopropyl or n-butyl, Ci-C4-haloalkyl, especially Ci-C2-fluoroalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difl uoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl.
  • R 7c is preferably selected from the group consisting of Ci-C4-alkoxy, NH2, C1-C4- alkylamino and di-(Ci-C4-alkyl)amino
  • R 8 irrespectively of its occurrence, is selected from the group consisting of C1-C4- alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difl uoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2-fluoro-1 - methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or
  • R 8a irrespectively of its occurrence, is selected from the group consisting of C1-C4- alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2-fluoro-1 - methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or h
  • R 8b irrespectively of its occurrence, is selected from the group consisting of C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 - difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, C3-C6-cycloalkyl, such as cyclobutyl, cyclopropyl, or cyclopentyl, Ci-C6-alkyl, in particular C1-C4- alkyl, such as methyl, ethyl, n-propyl, or n-butyl, or C3-C6-halocycloalkyl, such as 1 - fluorocyclopropyl, 2-fluoro
  • R 9a and R 9b are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or isobutyl, and Ci-C4-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or NR 9a R 9b may also be a saturated N-bound 3-, 4-, 5- or 6-membered heterocycle, which in addition to the nitrogen atom may have 1 further heteroatom as ring members, which is selected from O and N and where the N-bound 3-, 4-, 5- or 6-membered heterocycle may be unsubstituted or carry 1 , 2, 3 or 4 radicals selected from Ci-C
  • radicals NR 9a R 9b include, but are not limited to methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2- butylamino, isobutylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, N- methyl-N-ethylamino, N-methyl-N-propylamino, N-methyl-N-n-propylamino, N-methyl-N- isopropylamino, N-methyl-N-n-butylamino, N-methyl-N-2-butylamino, N-methyl-N-isobutylamino, 1 -pyrrolidinyl, 1 -piperidinyl, 1 -piperazinly, 4-methyl-1 -piperazinly and 4-morpholinyl.
  • R 10 halogen, such as chlorine or fluorine, CN, OH, SH, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2- trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and C1-C4- haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-di
  • R 11 , R 12 independently of their occurrence, are selected from the group consisting of Ci- C6-alkyl, Ci-C6-alkoxy, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in last two radicals are unsubstituted or substituted with 1 , 2, or 3 identical or different radicals selected from fluorine, chlorine, Ci-C3-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy and Ci-C2-haloalkoxy.
  • R 13 , R 14 independently of their occurrence, are selected from the group consisting of hydrogen, fluorine, chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl or n-butyl, C3-C6- cycloalkyl, such as cyclopropyl, cyclobutyl or cyclopentyl, and phenyl.
  • Ci-C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl
  • Ci-C4-haloalkyl such as difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2-fluoro-1 - methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or heptafluoroisopropyl, phenyl which may be partially or fully
  • R 16 irrespectively of its occurrence, is selected from the group consisting of C1-C4- alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1 , 2 or 3 identical or different radicals selected from the group consisting of halogen, such as chlorine or fluorine, Ci- C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular C1-C2- haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,
  • R 17 irrespectively of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, Ci-C6-alkoxy, Ci-C4-haloalkoxy, C3-C6-alkenyl, C3-C6- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1 , 2 or 3 identical or different radicals selected from the group con- sisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-
  • R 17a and R 17b irrespectively of their occurrence, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or isobutyl, and Ci-C4-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, phenyl or benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1 , 2, 3 or 4 identical or different radicals R 10 , which are as defined above or preferably selected from the group consisting of halogen, such as chlorine or fluorine, CN, Ci-C4-alkyl, such as methyl,
  • NR 17a R 17b may also be a saturated N- bound 3-, 4-, 5- or 6-membered heterocycle, which in addition to the nitrogen atom may have 1 further heteroatom as ring members, which is selected from O and N and where the N-bound 3- , 4-, 5- or 6-membered heterocycle may be unsubstituted or carry 1 , 2, 3 or 4 radicals selected from Ci-C4-alkyl and Ci-C4-haloalkyl.
  • radicals NR 17a R 17b include, but are not limited to methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, isobutylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, N-methyl-N- ethylamino, N-methyl-N-propylamino, N-methyl-N-n-propylamino, N-methyl-N-isopropylamino, N-methyl-N-n-butylamino, N-methyl-N-2-butylamino, N-methyl-N-isobutylamino, 1-pyrrolidinyl, 1- piperidinyl, 1-piperazinly, 4-methyl-1-piperazinly and 4-morpholinyl.
  • R 17c irrespectively of its occurrence, is selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl- Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1, 2 or 3 identical or different radicals selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoro
  • R 17d irrespectively of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C3-C6-alkenyl and C3-C6-cycloalkyl-Ci-C4-alkyl
  • a special group of embodiments relates to the compounds of formula (l)-A.1 a, to their tau- tomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 a.1 to l-A.1a.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.2a.1 to l-A.2a.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.1 b, to their tautomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 b.1 to I- A.1b.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.2b.1 to l-A.2b.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.1c, to their tautomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 c.1 to I-A.1 c.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (com- pounds l-A.2c.1 to l-A.2c.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.1d, to their tautomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 d.1 to l-A.1d.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.2d.1 to l-A.2d.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.3a, to their tau- tomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3a.1 to l-A.3a.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.4a.1 to l-A.4a.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.3b, to their tau- tomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3b.1 to l-A.3b.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.4b.1 to l-A.4b.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.3c, to their tautomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3c.1 to l-A.3c.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.4c.1 to l-A.4c.428).
  • a special group of embodiments relates to the compounds of formula (l)-A.3d, to their tautomers, to their stereoisomers and to their salts, where R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3d.1 to l-A.3d.428).
  • R 1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R 1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (com- pounds l-A.4d.1 to l-A.4d.428).
  • Cyc-6 4-(cyclopropyl)thiazol-2-yl
  • Cyc-7 4-trifluoromethylthiazol-2-yl
  • Cyc-58 4-(3-trifluoromethyl-phenyoxy)oxazol-2-yl Cyc-59 4-(isoxazol-3-yl)oxazol
  • Cyc-63 4-(4-chlorophenyl)methyloxazol-2-yl
  • Cyc-64 4-benzyloxazol-2-yl
  • Cyc-1 13 5-(cyclopropyl)-1 ,2,4-thiadiazol-3-yl
  • Cyc- 194 4-(1 -acetoxyethyl)thiazol-2-yl
  • Cyc-195 4-(1 -methoxyethyl)thiazol-2-yl
  • the compounds of formula (I) according to the present invention can be prepared e.g. according the preparation methods and preparation schemes as described below.
  • Compounds of formula (I) according to the present invention can be prepared by standard methods of organic chemistry e.g. by the preparation methods and preparation schemes as described below.
  • the definitions of Het, Cyc, W, W 2 , W 3 , W 4 , R 1 and R 2 of the molecular structures given in schemes 1 to 5 are as defined above.
  • Room temperature means a temperature range between about 20 and 25 °C.
  • Suitable leaving groups LG 2 in the compounds of formula (V) include, but are not limited to: halogen, such as chlorine or bromine, Ci-C4-alkyl sulfonate such as methyl- or ethyl sulfonate, Ci-C4-haloalkyl sulfonate, such as trifluoromethyl sulfonate, aryl sulfonate, such as phenyl sulfonate or tolylsulfonate, Ci-C4-alkyl phosphonate, Ci-C4-haloalkyl phosphate.
  • halogen such as chlorine or bromine
  • Ci-C4-alkyl sulfonate such as methyl- or ethyl sulfonate
  • Ci-C4-haloalkyl sulfonate such as trifluoromethyl sulfonate
  • aryl sulfonate such as phenyl sulfonate or
  • Preparation of the compounds of formula (IV) can be achieved, for example, by alkylation of the appropriate 2-amino-heterocycle precursor compound (III) with the appropriate reagent of formula (II).
  • the reaction is preferably carried out in polar solvents such as acetonitrile, acetone, 1 ,4-dioxane, tetrahydrofuran, N,N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide, N- methylpyrolidinone or a C1-C6 alcohol or inert solvents such as: dichloromethane, 1 ,2- dichloroethane, 1 ,2-dimethoxyethane, carbon tetrachloride, tetrahydrofuran, toluene, xylenes, mesitylene, cymene, tetralone ranging between room temperature and the reflux temperature of the solvent.
  • polar solvents such as acetonitrile, acetone,
  • Compounds of formula (I) can also be prepared by reaction of an immonium compound of formula (IVa) with an amine substituted heterocyclic compound of formula (Va) as outlined in scheme 2.
  • Compounds of formula I can also be prepared as outlined in scheme 3 by reaction of a ketone of formula (IVb) with a compound (Va), as for example described by Stivers et al, WO 2006135763 or by Fattorusso et al, J. Med. Chem. 2008, 51 , 1333-1343.
  • Compounds of formula (IVb) can be prepared by reaction of a compound of formula II with a compound of formula Ilia in analogy to the methods described in schemes 1 or 2.
  • individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or the respective precursor.
  • certain compounds of formula (I) can advantageously be prepared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
  • reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel.
  • Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystalliza- tion or trituration with an appropriate solvent.
  • the term "compound(s) of the present invention” or “compound(s) accord- ing to the invention” refers to the compound(s) of formula (I) as defined above, which are also referred to as “compound(s) of formula I” or “compound(s) I” or “formula I compound(s)”, and includes their salts, tautomers and stereoisomers.
  • the compounds of the formula (I) and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
  • the compounds of the formula (I) are especially suitable for efficiently combating insects, in particular the following pests:
  • Insects from the order of the lepidopterans (Lepidoptera), for example Acronicta major, Adoxophyes orana, Aedia leucomelas, Agrotis spp. such as Agrotis fucosa, Agrotis segetum, Agrotis ypsilon; Alabama argillacea, Anticarsia gemmatalis, Anticarsia spp., Argyresthia con- sexuallla, Autographa gamma, Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius,
  • Cacoecia murinana Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp. such as Chilo suppressalis; Choristoneura fumiferana, Choristoneura occidental is, Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cydia pomonella, Dendro- limus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Ephestia cautella, Ephestia kuehniella, Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Feltia spp.
  • Feltia subterranean such as Feltia subterranean; Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Helicoverpa spp. such as Helicoverpa armigera, Helicoverpa zea; Heliothis spp.
  • Lymantria spp. such as Lymantria dispar, Lymantria monacha; Lyonetia clerkel- la, Malacosoma neustria, Mamestra spp. such as Mamestra brassicae; Mods repanda, Mythim- na separata, Orgyia pseudotsugata, Oria spp., Ostrinia spp.
  • Pseudoplusia includens, Pyrausta nubilalis, Rhyacionia frustrana, Scrobipalpula absolutea, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera spp. such as Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura;
  • Thaumatopoea pityocampa Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp. such as Trichoplusia ni; Tuta absoluta, and Zeiraphera canadensis;
  • Beetles ⁇ Coleoptera for example Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus sinuatus, Agriotes spp. such as Agriotes fuscicollis, Agriotes lineatus, Agriotes ob- scurus; Amphimallus solstitialis, Anisandrus dispar, Anobium punctatum, Anomala rufocuprea, Anoplophora spp. such as Anoplophora glabripennis; Anthonomus spp.
  • Anthonomus grandis such as Anthonomus grandis, Anthonomus pomorum; Anthrenus spp., Aphthona euphoridae, Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as Atomaria linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp.
  • Conoderus vespertinus such as Conoderus vespertinus; Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptorhynchus lapathi, Ctenicera ssp. such as Ctenicera destructor; Cur- culio spp., Dectes texanus, Dermestes spp., Diabrotica spp. such as Diabrotica 12-punctata Diabrotica speciosa, Diabrotica longicornis, Diabrotica semipunctata, Diabrotica virgifera; Epi- lachna spp. such as Epilachna varivestis, Epilachna vigintioctomaculata; Epitrix spp.
  • Leptinotarsa decemlineata such as Leptinotarsa decemlineata; Limonius californicus, Lissorhoptrus oryzophilus, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp. such as Lyctus bruneus; Melanotus communis, Meligethes spp. such as Meligethes aeneus; Melolon- tha hippocastani, Melolontha melolontha, Migdolus spp., Monochamus spp.
  • Phyllotreta chrysocephala such as Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata; Phyllophaga spp., Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis , Rhizopertha dominica, Sitona lineatus, Sitophilus spp. such as Sitophilus granaria, Sitophilus zeamais;
  • Sphenophorus spp. such as Sphenophorus levis; Sternechus spp. such as Sternechus sub- signatus; Symphyletes spp., Tenebrio molitor, Tribolium spp. such as Tribolium castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp., and Zabrus spp. such as Zabrus tenebri- oides;
  • Aedes spp. such as Aedes aegypti, Aedes albopictus, Aedes vexans; Anastrepha ludens, Anopheles spp.
  • Anopheles albimanus such as Anopheles albimanus, Anopheles crucians, Anopheles freebomi, Anopheles gambiae, Anopheles leucosphyrus, Anopheles macu- lipennis, Anopheles minimus, Anopheles quadrimaculatus, Anopheles sinensis; Bibio hor- tulanus, Calliphora erythrocephala, Calliphora vicina, Cerafitis capitata, Ceratitis capitata, Chrysomyia spp.
  • Chrysomya bezziana such as Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellar- ia; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as Cochli- omyia hominivorax; Contarinia spp. such as Contarinia sorghicola; Cordylobia anthropophaga, Culex spp.
  • Lucilia caprina such as Lucilia caprina, Lucilia cuprina, Lucilia sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as Mayetiola destructor; Musca spp. such as Musca autumnalis, Musca domestica; Muscina stabu- lans, Oestrus spp. such as Oestrus ovis; Opomyza florum, Oscinella spp. such as Oscinella frit; Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp.
  • Phorbia antiqua Phorbia brassicae, Phorbia coarctata
  • Prosimulium mixtum Psila rosae, Psorophora columbiae, Psoro- phora discolor, Rhagoletis cerasi, Rhagoletis pomonella
  • Sarcophaga spp. such as Sarcophaga haemorrhoidalis
  • Simulium vittatum Stomoxys spp. such as Stomoxys calcitrans
  • Tabanus atratus such as Tabanus atratus, Tabanus bovinus, Tabanus lineola, Tabanus similis; Tannia spp., Tip- ula oleracea, Tipula paludosa, and Wohlfahrtia spp.;
  • Thrips ⁇ Thysanoptera). e.g. Basothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp. such as Frankliniella fusca, Frankliniella occidental- is, Frankliniella tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp. such as Scirtothrips citri; Taeniothrips cardamoni, Thrips spp. such as Thrips oryzae, Thrips palmi, Thrips tabaci;
  • Termites e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Heterotermes longiceps, Heterotermes tenuis, Leucotermes flavipes, Odontotermes spp., Reticulitermes spp. such as Reticulitermes speratus, Reticulitermes flavipes, Reticulitermes grassei, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes virginicus; Termes natalensis;
  • Cockroaches (Blattaria - Blattodea), e.g. Acheta domesticus, Blatta orientalis, Blattella asahinae, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melano- plus spp., Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta japonica;
  • Hemiptera e.g. Acroster- num spp. such as Acrosternum hilare; Acyrthosipon spp.
  • Aphis fabae such as Aphis fabae, Aphis forbesi, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis sambuci, Aphis schneideri, Aphis spiraecola; Arboridia a pica lis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp. such as Bemisia argentifolii, Bemisia tabaci; Blissus spp.
  • Dysaphis plantaginea such as Dysaphis plantaginea, Dysaphis pyri, Dysaphis radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as Dysdercus cin- gulatus, Dysdercus intermedius; Dysmicoccus spp., Empoasca spp. such as Empoasca fabae, Empoasca solana; Eriosoma spp., Erythroneura spp., Eurygaster spp. such as Eurygaster in- tegriceps; Euscelis bilobatus, Euschistus spp.
  • Euschistuos heros such as Euschistuos heros, Euschistus impic- tiventris, Euschistus servus; Geococcus coffeae, Halyomorpha spp. such as Halyomorpha halys; Heliopeltis spp., Homalodisca coagulata, Horcias nobilellus, Hyalopterus pruni, Hy- peromyzus lactucae, lcerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Leca- nium spp., Lepidosaphes spp., Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp.
  • Macrosiphum spp. such as Macrosiphum rosae, Macrosiphum avenae, Macrosiphum euphorbi- ae; Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius,
  • Melanaphis sacchari Metcafiella spp., Metopolophium dirhodum, Miridae spp., Monellia cos- talis, Monelliopsis pecanis, Myzus spp. such as Myzus ascalonicus, Myzus cerasi, Myzus persi- cae, Myzus varians; Nasonovia ribis-nigri, Nephotettix spp. such as Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephotettix virescens; Nezara spp.
  • Nezara viridula such as Nezara viridula; Nilaparvata lugens, Oebalus spp., Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp. such as Pemphigus bursarius; Pen- tomidae, Peregrin us maidis, Perkinsiella saccharicida, Phenacoccus spp., Phloeomyzus pas- serinii, Phorodon humuli, Phylloxera spp., Piesma quadrata, Piezodorus spp.
  • Piezodo- rus guildinii Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Psallus seria- tus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as Pseudo- coccus comstocki; Psylla spp.
  • Psylla mail such as Psylla mail, Psylla piri; Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp.
  • Rhopalosiphum pseudobrassicas such as Rhopalosiphum pseudobrassicas, Rhopalosiphum insertum, Rhopalosiphum maidis, Rhopalosiphum padi; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mail, Scaphoides titanus, Schi- zaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobi- on avenae, Sogata spp., Sogatella furcifera, Solubea insularis , Stephanitis nashi, Stictocephala festina, Tenalaphara malayensis, Thyanta spp.
  • Thyanta perditor such as Thyanta perditor; Tibraca spp., Tinocal- lis caryaefoliae, Tomaspis spp., Toxoptera spp. such as Toxoptera aurantii; Trialeurodes spp. such as Trialeurodes vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as Unaspis yanonensis; and Viteus vitifolii;
  • Hoplocampa spp. such as Hoplocampa minuta, Hoplocampa testudinea; Lasius spp.
  • Crickets, grasshoppers, locusts e.g. Acheta domestica, Calliptamus italicus, Chortoicetes terminifera, Dociostaurus maroccanus, Gryllotalpa africana, Gryllotalpa gryllotalpa, Hieroglyphus daganensis, Kraussaria angulifera, Locusta migratoria, Locustana pardalina, Mel- anoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Oedaleus senegalensis, Schistocerca ameri- cana, Schistocerca gregaria, Tachycines asynamorus, and Zonozerus variegatus;
  • Lice ⁇ Phthiraptera e.g. Damalinia spp., Pediculus spp. such as Pediculus humanus capi- tis, Pediculus humanus corporis; Pthirus pubis, Haematopinus spp. such as Haematopinus eu- rysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.;
  • Fleas ⁇ Siphonaptera e.g. Ceratophyllus spp., Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus.
  • the compounds of the formula (I) are also suitable for efficiently combating arthropd pests different from insects such as, in particular the following pests:
  • arachnids ⁇ Arachnida such as acari,e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma spp. (e.g. Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum), Argas spp. (e.g. Argas persicus), Boophilus spp. (e.g. Boophilus an- nulatus, Boophilus decoloratus, Boophilus microplus), Dermacentor silvarum, Dermacentor an- dersoni, Dermacentor variabilis, Hyalomma spp.
  • acari e.g. of the families Argasidae, Ixodidae and Sar- coptidae
  • Amblyomma spp. e.g. Amblyomma americanum, Amblyomm
  • Ixodes spp. e.g. Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus
  • Orni- thodorus spp. e.g. Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata
  • Orni- thonyssus bacoti Otobius megnini, Dermanyssus gallinae, Psoroptes spp. (e.g. Psoroptes ovis), Rhipicephalus spp.
  • Rhizoglyphus spp. e.g. Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhip- icephalus evertsi
  • Rhizoglyphus spp. e.g. Sarcoptes scabiei
  • Eriophyidae spp. such as Acaria sheldoni, Aculops spp. (e.g. Aculops pelekassi) Aculus spp. (e.g. Aculus pointedendali), Epitrimerus pyri, Phyllocoptruta oleivora and Eriophyes spp. (e.g. Eriophyes sheldoni); Tarsonemidae spp.
  • Tenuipalpidae spp. such as Brevipalpus spp. (e.g. Brevipalpus phoenicis); Tetranychidae spp.
  • Eotetranychus spp. Eutetranychus spp., Oligonychus spp., Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacifi- cus, Tetranychus telarius and Tetranychus urticae
  • Bryobia praetiosa Panonychus spp. (e.g. Panonychus ulmi, Panonychus citri), Metatetranychus spp. and Oligonychus spp. (e.g. Oligo- nychus pratensis), Vasates lycopersici
  • Araneida e.g. Latrodectus mactans, and Loxosceles reclusa.
  • Araneida e.g. Latrodectus mactans
  • Silverfish, firebrat ⁇ Thysanura e.g. Lepisma saccharina and Thermobia domestica;
  • Centipedes ⁇ Chilopoda e.g. Geophilus spp., Scutigera spp. such as Scutigera coleop- trata;
  • Millipedes e.g. Blaniulus guttulatus, Narceus spp.
  • nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species such as Aphelenchoides besseyi ; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus lignicolus Mamiya et Kiy
  • Xiphinema species and other plant parasitic nematode species.
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the class of the Bivalva, for example, Dreissena spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Di
  • pest species which may be controlled by compounds of formula (I) include: Anisoplia austriaca, Apamea spp., Austroasca viridigrisea, Baliothrips biformis, Caeno- rhabditis elegans, Cephus spp., Ceutorhynchus napi, Chaetocnema aridula, Chilo auricilius, Chilo indicus , Chilo polychrysus, Chortiocetes terminifera, Cnaphalocroci medinalis, Cnaphalo- crosis spp., Colias eurytheme, Collops spp., Cornitermes cumulans, Creontiades spp., Cy- clocephala spp., Dalbulus maidis, Deraceras reticulatum , Diatrea saccharalis, Dichelops furca- tus, Dicladispa armigera
  • Diloboderus abderus such as Diloboderus abderus; Edessa spp., Epino- tia spp., Formicidae, Geocoris spp., Globitermes sulfureus, Gryllotalpidae, Halotydeus destructor, Hipnodes bicolor, Hydrellia philippina, Julus spp., Laodelphax spp., Leptocorsia acuta , Lep- tocorsia oratorius , Liogenys fuscus, Lucillia spp., Lyogenys fuscus, Mahanarva spp., Ma lad era matrida, Marasmia spp., Mastotermes spp., Mealybugs, Megascelis ssp, Metamasius hemipter- us, Microtheca spp., Mods latipes, Murgantia spp., My
  • Orseolia oryzae such as Orseolia oryzae; Oxycaraenus hyalinipennis, Plusia spp., Pomacea canaliculata, Procornitermes ssp, Procornitermes triacifer , Psylloides spp., Ra- chiplusia spp., Rhodopholus spp., Scaptocoris castanea, Scaptocoris spp., Scirpophaga spp. such as Scirpophaga incertulas , Scirpophaga innotata; Scotinophara spp. such as Scotinopha- ra coarctata; Sesamia spp.
  • Sesamia inferens such as Sesamia inferens, Sogaella frucifera, Solenapsis geminata, Spissistilus spp., Stalk borer, Stenchaetothrips biformis, Steneotarsonemus spinki, Sylepta derogata, Telehin licus, Trichostrongylus spp..
  • Compounds of the formula (I) are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera.
  • the compounds of the formula (I) can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions.
  • the use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the formula (I) according to the present invention.
  • the formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq.
  • auxiliaries suitable for the formulation of agrochemicals such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, antifoaming agents, anti- freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
  • Solvents/carriers which are suitable, are e.g.:
  • solvents such as water, aromatic solvents (for example Solvesso products, xylene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-metyhl-pyrrolidone (NMP),N-octylpyrrolidone NOP), acetates (glycol diac- etate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid dimethylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modi- fied oils such as alkylated plant oils.
  • solvents such as water, aromatic solvents (for example Solvesso products, xylene and the like), paraffins (for example mineral fractions), alcohols (
  • solvent mixtures may also be used.
  • carriers such as ground natural minerals and ground synthetic minerals, such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sul- fate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • fertilizers such as, for example, ammonium sul- fate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • Suitable emulsifiers are nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates.
  • dispersants examples include lignin-sulfite waste liquors and methylcellulose.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of
  • naphthalenesulfonic acid with phenol and formaldehyde polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers,
  • tributylphenyl polyglycol ether tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
  • anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
  • Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
  • Suitable preservatives are for example dichlorophen und benzyl alcohol hemiformal
  • Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Mention may be made, in this context, for example, of commercial thickeners based on polysaccharides, such as Xanthan Gum ® (Kelzan ® from Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from R.T. Vanderbilt), or organic phyllosilicates, such as Attaclay ® (from Engelhardt).
  • polysaccharides such as Xanthan Gum ® (Kelzan ® from Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from R.T. Vanderbilt)
  • organic phyllosilicates such as Attaclay ® (from Engelhardt).
  • Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon ® SRE, Wacker or Rhodorsil ® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trade- marks Proxel ® from Avecia (or Arch) or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas.
  • Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound composition.
  • the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds.
  • buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N- methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, par
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, am- monium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient.
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0,01 to 60% by weight active compound by weight, preferably 0,1 to 40% by weight.
  • the compound of formula (I) can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.
  • Products for dilution with water may be applied to the seed diluted or undiluted.
  • the active compound 10 parts by weight of the active compound is dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added.
  • the active com- pound dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound is obtained.
  • a dispersant for example polyvinylpyrrolidone.
  • Dilu- tion with water gives a dispersion, whereby a formulation with 20% (w/w) of active compounds is obtained.
  • Emulsions EW, EO, ES
  • 25 parts by weight of the active compound is dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound is obtained.
  • an emulsifier machine e.g. Ultraturrax
  • Water-dispersible granules and water-soluble granules 50 parts by weight of the active compound is ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound, whereby a formulation with 50% (w/w) of active compound is obtained.
  • 75 parts by weight of the active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound, whereby a formulation with 75% (w/w) of active compound is obtained.
  • Products to be applied undiluted for foliar applications may be applied to the seed diluted or undiluted.
  • 0.5 part by weight of the active compound is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound is obtained.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • the active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
  • the active ingredients may also be used successfully in the ultra-low-volume process
  • compounds of formula (I) may be applied with other active ingredients, for example with other pesticides, in particular insecticides, nematicides and acaricides, fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, and safeners.
  • pesticides in particular insecticides, nematicides and acaricides, fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, and safeners.
  • Preferred mixing partners are insecticides, nematicides and fungicides.
  • compositions of this invention may be used sequentially or in combination with the above- described compositions, if appropriate also added only immediately prior to use (tank mix).
  • plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • Acetylcholine esterase (AChE) inhibitors from the class of
  • M.1A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetan- ate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
  • M.1 B organophosphates for example acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicroto- phos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxy- aminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, metha
  • GABA-gated chloride channel antagonists such as:
  • M.2A cyclodiene organochlorine compounds as for example endosulfan or chlordane
  • M.2B fiproles phenylpyrazoles
  • ethiprole phenylpyrazoles
  • fipronil flufiprole
  • pyrafluprole pyriprole
  • M.3A pyrethroids for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, be- ta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, del- tamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin,
  • M.4 Nicotinic acetylcholine receptor agonists from the class of M.4A neonico- tinoids, for example acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.2: (2E-)-1 -[(6-Chloropyridin-3-yl)methyl]- N'-nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7- methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;
  • M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
  • M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
  • M.8A alkyl halides as methyl bromide and other alkyl halides, or
  • M.9B pymetrozine, or M.9C flonicamid M.10 Mite growth inhibitors, for example
  • M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase for example
  • M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradifon;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers for example nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
  • benzoylureas as for example bis- trifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;
  • M.16 Inhibitors of the chitin biosynthesis type 1 as for example buprofezin;
  • Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
  • Octopamin receptor agonists as for example amitraz
  • M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
  • M.22 Voltage-dependent sodium channel blockers for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]- ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2- methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]- hydrazinecarboxamide;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid de- rivatives, for example spirodiclofen, spiromesifen or spirotetramat
  • M.24 Mitochondrial complex IV electron transport inhibitors for example M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide.
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile deriva- tives, for example cyenopyrafen or cyflumetofen;
  • M.28 Ryanodine receptor-modulators from the class of diamides, as for example flubendi- amide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1 : (R)-3-Chlor-N1 - ⁇ 2-methyl-4-[1 ,2,2,2 -tetrafluor-1 - (trifluormethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)phthalamid and M.28.2: (S)-3- Chlor-N1 - ⁇ 2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -(trifluormethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2- methylsulfonylethyl)phthalamid, or the compound M.28.3: 3-bromo-N- ⁇
  • insecticidal active compounds of unknown or uncertain mode of action as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflani- lide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butox- ide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the compounds
  • M.29.5 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H- 1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or
  • M.29.6a (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide
  • M.29.6b (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide
  • M.29.6c (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2- pyridylidene]acetamide
  • M.29.6d (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2
  • M.29.10 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 , 2,2,3,3,3- hexafluoro-1 -(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.29.1 1.c)
  • M.29.14a 1 -[(6-Chloro-3-pyridinyl)methyl]-1 , 2,3,5, 6,7-hexahydro-5-methoxy-7-methyl-8- nitro-imidazo[1 ,2-a]pyridine; or M.29.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or the compounds
  • M.29.16b 1 -(1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide
  • M.29.16c N,5-dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4- carboxamide
  • M.29.16d 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide
  • M.29.16e N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5-methyl-N-pyridazin-4- yl-pyrazole-4-carboxamide
  • M.29.16f 1 -(1 ,2-dimethylpropyl)-N,
  • the M.4 neonicotinoid cycloxaprid is known from WO2010/069266 and WO201 1/069456, the neonicotinoid M.4A.2, sometimes also to be named as guadipyr, is known from
  • WO2013/003977 and the neonicotinoid M.4A.3 (approved as paichongding in China) is known from WO2007/101369.
  • the metaflumizone analogue M.22B.1 is described in CN 10171577 and the analogue M.22B.2 in CN102126994.
  • the phthalamides M.28.1 and M.28.2 are both known from WO2007/101540.
  • the anthranilamide M.28.3 is described in WO2005/077934.
  • the hydra- zide compound M.28.4 is described in WO2007/043677.
  • the anthranilamides M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and
  • WO2013/024010 the anthranilamide ⁇ .28.5 ⁇ ) is described in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and M.28.5I) in WO2012/034403.
  • the diamide compounds M.28.6 and M.28.7 can be found in CN102613183.
  • the spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO2006/089633 and the biphenyl-substituted spiro- cyclic ketoenol derivative M.29.4 from WO2008/06791 1.
  • the triazoylphenylsulfide M.29.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are described in WO2009/124707.
  • the compounds M.29.6a) to ⁇ .29.6 ⁇ ) listed under M.29.6 are described in WO2012/029672, and M.29.6j) and M.29.6k) in WO2013/129688.
  • the nematicide M.29.8 is known from WO2013/055584.
  • the isoxazoline M.29.9.a) is described in
  • WO2013/050317 The isoxazoline M.29.9.b) is described in WO2014/126208.
  • the pyridalyl- type analogue M.29.10 is known from WO2010/060379.
  • M.29.1 1.b) to M.29.1 1 .h) are described in WO2010/018714, and the carboxamides M.29.1 1 i) to M.29.1 1 .P) in WO2010/127926.
  • the pyridylthiazoles M.29.12.a) to M.29.12.C) are known from WO2010/006713, M.29.12.d) and M.29.12.e) are known from WO2012/000896, and M.29.12. ⁇ ) to M.29.12. m) from WO2010/129497.
  • the compounds M.29.14a) and M.29.14b) are known from WO2007/101369.
  • the pyrazoles M.29.16.a) to M.29.16h) are described in
  • stereoisomers, salts, tautomers and N-oxides may also be applied with fungicides as compound II.
  • Inhibitors of complex III at Q 0 site e. g. strobilurins: azoxystrobin (A.1 .1 ), coumeth- oxystrobin (A.1.2), coumoxystrobin (A.1 .3), dimoxystrobin (A.1.4), enestroburin (A.1 .5), fenaminstrobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim- methyl (A.1 .9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxy- .strobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1 .15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17)
  • inhibitors of complex II e. g. carboxamides: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl- 2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole
  • respiration inhibitors e. g. complex I, uncouplers: diflumetorim (A.4.1 ), (5,8- difluoroquinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1 .1 ), biterta- nol (B.1 .2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1 .7), epoxiconazole (B.1.8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1 .12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1 .15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), pa

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Abstract

The present invention relates to N-acylimino compound of formula (I), wherein; Cyc is (i) a 3-, 4-, 5-, 6- or 7-membered, saturated, partially unsaturated or maximally unsaturated heteromonocycle having 1, 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(O)2, which is unsubstituted or carries one or more, in particular 1, 2, 3, 4, 5 or 6 subsitutents R3, or (ii) a 8-, 9- or 10-membered, saturated, partially unsaturated or maximally unsaturated heterobicycle having 1, 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(O)2, which is unsubstituted or carries one or more, in particular 1, 2, 3, 4, 5 or 6 subsitutents R4; Het is a 5- or 6-membered carbon-bound or nitrogen-bound heterocyclic ring, W1=W2-W3=W4 represents an unsaturated carbon chain group connected to N and C=N, and thus forming a unsaturated or partially unsaturated 5-or 6-membered nitrogen containing heterocycle, wherein W1, W2, W3 and W4 each individually represent CRV or one of W1=W2 or W3=W4 may also be CRVRW; R1, R2 may be hydrogen, halogen, C1-C6-alkyl etc. The invention also relates to the use of the N-acylimino heterocyclic compounds, their ste¬ reoisomers, their tautomers and their salts, for combating invertebrate pests. Furthermore the invention relates also to methods of combating invertebrate pests, which comprises applying such compounds.

Description

N-SUBSTITUTED IMINO HETEROCYCLIC COMPOUNDS
FOR COMBATING INVERTEBRATE PESTS
The present invention relates to N-substituted imino heterocyclic compounds, including their stereoisomers, tautomers and salts, and to compositions comprising such compounds. The invention also relates to the use of the N-substituted imino heterocyclic compounds, their stereoisomers, their tautomers and their salts, for combating invertebrate pests. Furthermore the invention relates also to methods of combating invertebrate pests, which comprises applying such compounds. Background of Invention
Invertebrate pests, such as insects, acaridae and nematode pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
EP 259738 discloses co ula A, which have insecticidal activity:
Figure imgf000003_0001
(A)
where W is a substituted pyridyl radical or a 5-or 6-membered heterocyclic radical, R is hydrogen or alkyl, T together with the atoms to which it is bound forms a 5- or 6-membered heterocyclic ring, Y is inter alia a nitrogen atom and Z is an electron withdrawing group selected from nitro and cyano.
Pesticidal compounds, which are similar to those of EP 259738, are known from
EP 639569, where the moiety electron withdrawing moiety Z is an electron withdrawing group such as alkoxcarbonyl, arylcarbonyl, heterocyclic carbonyl, Ci-C4-alkylsulfonyl, sulfamoyl or
US 2013/0150414 describe, inter alia, pesticidal compounds of the formula B
Figure imgf000004_0001
wherein Ar is an aryl or 5- or 6-membered heterocyclic group, Ra is hydrogen or alkyi, Y' is hydrogen, halogen, a hydroxyl group, an alkyi group or an alkoxy group and Rb is an alkyi group substituted with halogen or an alkoxy group, optionally substituted with halogen.
Pesticidal compounds, which are similar to those of US 2013/0150414, are known from WO 2013/129688.
EP 535227 describes N-substituted heterocyclic amidine compounds of the formula C
Figure imgf000004_0002
having insecticidal activity, wherein Ri represents optionally substituted nitrogen contain- ing hetaryl, R2 represents optionally substituted alkyi, alkenyl, alkynyl, cycloalkyi, cycloalkenyl, aryl etc., R3 represents represents optionally substituted alkyi, alkenyl, alkynyl, cycloalkyi, cycloalkenyl or R2 and R3 may be combined together to form a ring and R4 represents an optionally substituted nitrogenous heterocycle.
The pesticidal activity of the compounds is not satisfactory. It is therefore an object of the present invention to provide compounds having a good pesticidal activity, especially against difficult to control insects and acarid pests.
Summary of Invention
It has been found that these objects are solved by N-substituted imino compounds of the general formula (I) described below, by their stereoisomers, their tautomers and their salts. Therefore, the present invention relates to N-substituted imino compounds of formula (I):
Figure imgf000005_0001
wherein
Cyc is
(i) a 3-, 4-, 5-, 6- or 7-membered, saturated, partially unsaturated or maximally unsaturated heteromonocycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R3, or
(ϋ) a 8-, 9- or 10-membered, saturated, partially unsaturated or maximally unsaturated heterobicycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R4;
Het is a 5- or 6-membered carbon-bound or nitrogen-bound heterocyclic or heteroaro- matic ring, comprising 2, 3, 4 or 5 carbon atoms and 1 , 2 or 3 heteroatoms as ring members, which are independently selected from sulfur, oxygen or nitrogen, wherein the sulfur and nitrogen ring members can independently be partly or fully oxidized, and wherein each ring is optionally substituted by k identical or different substituents R6, wherein k is an integer selected from 0, 1 , 2, 3 or 4;
W1=W2-W3=W4 represents an unsaturated carbon chain group connected to N and C=N, and thus forming a unsaturated or partially unsaturated 5- or 6- membered nitrogen containing heterocycle, wherein
W1, W2, W3 and W4 each individually represent CRV or one of W1=W2 or W3=W4 may also be CRVRW wherein
each Rv independently from each other, is hydrogen, halogen, cyano, azido, nitro,
SCN, SF5, Ci-Cio-alkyl, C3-C8-cycloalkyl, C2-Cio-alkenyl or C2-Cio- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may be unsubstituted or may be partly or fully hal- ogenated and/or may optionally be substituted with 1 , 2 or 3 identical or different radicals R7,
or Rv is OR8, NR9aR9b, S(0)nR8a, S(0)nNR9aR9b, C(=0)R7a,
C(=0)NR9aR9b, C(=0)OR8, C(=S)R7a, C(=S)NR9aR9b, C(=S)OR8,
C(=S)SR8a, C(=NR 7)R7a, C(=NR 7)NR9aR9 and Si(R11)2R12,
each Rw independently from each other, are selected from the group consisting of hydrogen, halogen, cyano, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl and C2-Cio-alkynyl, wherein the carbon atoms of the aforementioned four aliphatic and cycloaliphatic radicals may be unsubstituted or may be partly or fully halogenated or may optionally be further substituted with 1 , 2 or 3 identical or different radicals R7; or
Rv and Rw present in one of the groups may together form =0, =CR13R14, =S,
=NR17, =NOR16, =NNR9aR9b;
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, CN, SCN, nitro, Ci-C6-alkyl, C3-C6-cycloalkyl, wherein each of the two aforementioned radicals are unsubstituted, partly or completely hal- ogenated or may carry any combination of 1 , 2 or 3 radicals R7,
Si(R11)2R12, OR8, OS02R8a, S(0)nR8a, S(0)nNR9aR9 , NR9aR9 , C(=0)NR9aR9 , C(=S)NR aR , C(=0)OR8, C(=0)R7a, C(=S)R7a,
phenyl, benzyl, where the phenyl ring in the last two radicals is unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10,
and a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 identical or different het- eroatoms as ring members, which are selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identi- cal or different substituents R10, and wherein the nitrogen and/or the sulfur at- om(s) of the heterocyclic ring may optionally be oxidized, or
R1 and R2 form, together with the carbon atom, which they attached to, a 3-, 4-, 5- or 6-membered saturated or partly unsaturated carbocyclic or heterocyclic ring, wherein each of the carbon atoms of said cycle are unsubstituted or may carry any combination of 1 or 2 identical or different radicals R7, or
R and R2 may together be =0, =CR13R14, =S, =NR17, =NOR16 or =NNR9aR9b; where, independently of their occurrence, n is 0, 1 or 2;
R3, R4 are independently from each other selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-C10- alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7, OR8b, NR17aR17b, S(0)nR8b, S(0)nNR 7aR 7 , NR 7dS(0)nR8b, C(=0)R7 , CH(=0), OC(=0)R7 , NR 7dC(=0)R7 , C(=0)NR 7aR 7 , NR 7dC(=0)NR 7aR 7 , C(=0)OR8 , C(=S)R7 , OC(=S)R7 , NR 7cC(=S)R7 , C(=S)NR 7aR 7 , NR 7dC(=S)NR 7aR 7 , C(=S)OR8a, C(=S)SR8a, C(=NR 7)R7a,
C(=NR 7)-C(0)R7c, C(=NR 7)NR 7aR 7 , Si(R11)2R12,
a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two of R3 or two of R4, which are present on one ring carbon may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b, R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN,
SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7, OR8b, NR17aR17b, S(0)nR8b, S(0)nNR7aR7b, NR7dS(0)nR8b, C(=0)R7 , OC(=0)R7 , NR7dC(=0)R7 , C(=0)NR7aR7 , NR7dC(=0)NR7aR7 , C(=0)OR8 , C(=S)R7 , OC(=S)R7 , NR7cC(=S)R7 , C(=S)NR7aR7 , NR7dC(=S)NR7aR7 , C(=S)OR8a, C(=S)SR8a, C(=NR7)R7a,
C(=NR7)-C(0)R7c, C(=NR7)NR7aR7 , Si(R11)2R12;
Q irrespectively of its occurrence is selected from a single bond, Ci-C4-alkylene, which is unsubstituted or partly or completely halogenated, O, S, S(O), S(0)2, NR7d, C(=0), OC(=0), C(=0)-0, NR7dC(=0), C(=0)NR7d, NR7dS(0)2, or S(0)2,NR7d;
R6 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci- Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or complete- ly halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7,
OR8, NR17aR17b, S(0)nR8a, S(0)nNR7aR7 , C(=0)R7a, C(=0)NR7aR7 , C(=0)OR8, C(=S)R7a, C(=S)NR7aR7 , C(=S)OR8, C(=S)SR8a, C(=NR7)R7a, C(=NR7)NR7aR7 , Si(R11)2R12;
phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents
R10,
and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two of R6 present on one ring carbon may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b,
or two R6 together form a linear C2-C7 alkylene chain, thus forming, together with the ring atom(s) to which they are bound, a 3-, 4-, 5-, 6-, 7- or 8-membered ring, where 1 or 2 CH2 moieties of the alkylene chain may be replaced by 1 or 2 heteroatom moieties selected from O, S and NR17c and/or 1 or 2 of the CH2 groups of the alkylene chain may be replaced by a group C=0, C=S and/or C=NR17; and where the alkylene chain is unsubstituted or may be substituted with 1 , 2, 3, 4, 5 or 6 radicals selected from the group consisting of halogen, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl which may be substituted with 1 , 2, 3, 4 or 5 radicals R10, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 radicals R10; independently of its occurrence, is selected from the group consisting of cyano, az- ido, nitro, -SCN, SF5, d-C6-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, Si(R11)2R12, OR8, OS02R8a, S(0)nR8a, S(0)nNR 7aR 7b, NR17aR17b, C(=0)NR 7aR 7b, C(=S)NR 7aR 7b, C(=0)OR8, C(=0)R15, C(=S)R15, C(=NR 7)R15, NR 7a-C(=0)R7a, NR 7a-C(=S)R7a, NR 7a-C(=0)OR8, NR 7a-C(=0)NR 7aR 7 ,
phenyl, phenoxy, phenyl-Ci-C4-alkyl, where the phenyl ring in the last three groups is optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two R7 present on one carbon atom may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b,
or two R7 may form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partly unsaturated carbocyclic or heterocyclic ring together with the carbon atoms to which the two R7 are bonded, where the heterocyclic ring comprises 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10; independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
R7b independently of its occurrence, is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized; R7c is OR8b or N R17aR17b;
R8 independently of its occurrence, is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, C(=0)R15, C(=0)N R 7aR 7b, C(=S)N R 7aR 7 , C(=0)OR16,
phenyl, phenyl-Ci-C-4-alkyl, where the phenyl ring in the last two mentioned radicals is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturat- ed heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
R8a independently of its occurrence, is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, phenyl-Ci-C-4-alkyl, where the phenyl ring in the last two mentioned radicals is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents
R10, and
a 5- or 6-membered aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 iden- tical or different substituents R10;
R8b independently of its occurrence is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6 haloal- kynyl;
R9a, R9b are each independently from one another selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C3- C8-cycloalkyl-Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-
C6-haloalkynyl,
S(0)nR16, -S(0)nNR 7aR 7 , C(=0)R15, C(=0)OR16, C(=0)NR 7aR 7 , C(=S)R15, C(=S)SR16, C(=S)NR 7aR 7 , C(=NR 7)R15;
phenyl, benzyl, 1 -phenethyl or 2-phenethyl, where the phenyl ring in the last four mentioned radicals is unsubstituted or may be substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10; and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated C-bound heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or,
R9a and R9b are together a C2-C7 alkylene chain and form a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partly unsaturated or maximally unsaturated ring together with the nitrogen atom they are bonded to, wherein the alkylene chain may contain one or two heteroatoms, which are, independently of each other, selected from oxygen, sulfur or nitrogen, and where the alkylene chain may optionally be substituted with 1 , 2, 3 or 4 radicals selected from halogen, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6- haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated C-bound heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or
R9a and R9b together may form =CR13R14, =NR17 or =NOR16 moiety;
R10 independently of its occurrence, is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-C10- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may optionally be substituted with 1 , 2, 3, 4 or 5 identical or different radicals R7,
Si(R11)2R12, OR16, OS(0)nR16a, -S(0)nR16a, S(0)nNR 7aR 7b, NR17aR17b, C(=0)R15, C(=S)R15, C(=0)OR16, -C(=NR 7)R15, C(=0)NR 7aR 7 , C(=S)NR 7aR 7 ,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different radicals selected from OH, halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heter- ocyclic ring is unsubstituted or may be substituted with 1 , 2, 3, 4 or 5 substituents selected independently from one another from halogen, cyano, NO2, Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
or
two R10 present together on one carbon ring atom of a saturated or partly unsaturated heterocyclic radical may form =0, =CR13R14, =S, =NR17, =NOR16,
=NNR17aR17b;
or,
two R10 on adjacent carbon ring atoms may also be a bivalent radical selected from CH2CH2CH2CH2, CH=CH-CH=CH, N=CH-CH=CH, CH=N-CH=CH, N=CH-N=CH, OCH2CH2CH2, OCH=CHCH2, CH2OCH2CH2, OCH2CH2O, OCH2OCH2, CH2CH2CH2, CH=CHCH2, CH2CH2O, CH=CHO, CH2OCH2, CH2C(=0)0, C(=0)OCH2, 0(CH2)0, SCH2CH2CH2, SCH=CHCH2, CH2SCH2CH2, SCH2CH2S, SCH2SCH2, CH2CH2S, CH=CHS, CH2SCH2, CH2C(=S)S, C(=S)SCH2, S(CH2)S, CH2CH2NR17, CH2CH=N, CH=CH-NR17, OCH=N, SCH=N and form together with the carbon atoms to which the two R10 are bonded a 5-membered or 6-membered partly unsaturated or unsaturated, aromatic carbocyclic or heterocyclic ring, wherein the ring may optionally be substituted with one or two substituents selected from =0, OH, CH3, OCH3, halogen, cyano, halomethyl and halomethoxy;
R11, R12 independently of their occurrence, are selected from the group consisting of d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkoxy-Ci-C4-alkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8-halocycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8-halocycloalkyl-Ci-C4- alkyl, Ci-C6-haloalkoxy-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals are unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different radicals selected from halogen, OH, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R13, R14 independently of their occurrence, are selected from the group consisting of hydrogen, halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4- alkyl, phenyl and benzyl; R15 independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;
C(=0)OR8b, C(=0)NR7aR7b,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
R16 independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-alkylcarbonyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3- C8-cycloalkyl-Ci-C4-alkyl, wherein the six last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino and di-(Ci-C6-alkyl)amino;
R16a independently of its occurrence, is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
R17 independently of its occurrence, is selected from the group consisting of hydrogen, trimethylsilyl, triethylsilyl, fer/butyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Cs-Cs-cycloalkoxy, C3-C8- cycloalkyl-Ci-C4-alkoxy, Ci-C6-alkylthio, wherein the 1 1 last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkoxy, phenyl, benzyl, pyridyl, phenoxy, benzyloxy and pyridyloxy, wherein the six last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl,
R17a, R17b are each independently from one another selected from the group consisting of hydrogen, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, ferfbutyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkoxy, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl,
or,
R17a and R17b may together be a C2-C6 alkylene chain forming a 3- to 7- membered saturated, partly unsaturated or unsaturated ring together with the nitrogen atom R17a and R17b are bonded to, wherein the alkylene chain may contain 1 or 2 heteroatoms selected, independently of each other, from oxygen, sulfur or nitrogen, and may optionally be substituted with halogen, C1-C4- haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized; or
R17a and R17b together may form =CR13R14, =NR17 or =NOR16 moiety; R17c independently of its occurrence, is selected from the group consisting of hydrogen, CN, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci- C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy, phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
R17d independently of its occurrence, is selected from the group consisting of hydrogen, CN, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci- C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy; the stereoisomers, tautomers and the salts thereof, except for those compounds of formula I, where Cyc is 2-hydroxycarbonyl-3,3-dimethyl-4-thia-1 -azabicyclo[3.2.0]heptan-7-on- 6-yl, if Het is 2-furyl, W =W2-W3=W4 represents CH=CH-CH=CH and R1 and R2 are hydrogen, and also except from the stereoisomers, tautomers and the salts thereof.
Moreover, the present invention relates to and includes the following embodiments:
agricultural and veterinary compositions comprising an amount of at least one compound of the formula (I) or a stereoisomer, tautomer or salt thereof;
the use of the compounds of formula (I), the stereoisomers, the tautomers or the salts thereof for combating invertebrate pests;
the use of the compounds of formula (I), the stereoisomers, the tautomers or the salts thereof for protecting growing plants from attack or infestation by invertebrate pests;
the use of the compounds of formula (I), the stereoisomers, the tautomers or the salts, thereof for protecting plant proparagation material, especially seeds, from soil insects; the use of the compounds of formula (I), the stereoisomers, the tautomers or the salts thereof for protecting the seedlings roots and shoots of plants from soil and foliar insects; a method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of the formula (I) or a stereoisomer, a tautomer or salt thereof;
a method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound of the formula (I) or a stereoisomer, a tautomer or salt thereof, in particular a method protecting crop plants from attack or infestation by animal pests, which comprises contacting the crop plants with a pesticidally effective amount of at least one compound of the formula (I) or stereoisomer, a tautomer or salt thereof;
- a method for the protection of plant propagation, especially seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pregermination with at least one compound of the formula (I) or stereoisomer, a tautomer or salt thereof;
seeds comprising a compound of the formula (I) or an enantiomer, diastereomer or salt thereof;
the use of compounds of formula (I), the stereoisomers, the tautomers or the salts, in particular the veterinary acceptable salts, thereof for combating parasites in and on animals, in particular for the use in the treatment of animals infested or infected by parasites, for preventing animals of getting infected or infested by parasites or for protecting animals against infestation or infection by parasites;
a method for treating animals infested or infected by parasites or preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites which comprises administering or applying to the animals a parasiticidal- ly effective amount of a compound of formula (I) or the stereoisomers and/or salts, in par- ticular veterinary acceptable salts, thereof;
a process for the preparation of a veterinary composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises formulating a compound of formula (I) or a stereoisomer, tautomer and/or veterinary acceptable salt thereof with a carrier composition suitable for veterinary use;
- the use of a compound of formula (I) or the stereoisomers, tautomers and/or veterinary acceptable salt thereof for the preparation of a medicament for treating, controlling, preventing or protecting animals against infestation or infection by parasites.
The present invention also relates to plant propagation materials, in particular as mentioned above to seeds, containing at least one compound of formula (I), a stereoisomer, a tau- tomer and/or an agriculturally acceptable salt thereof. Detailed Description of Invention
The present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers, diastereomers and E/Z-isomers as well as to mixtures thereof and also to the salts thereof. The present invention relates to each isomer alone, or mixtures or combinations of the isomers in any proportion to each other. In particular the radicals Cyc and W may be E or Z with respect to the C=N bond. Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (E/Z-isomers, cis/trans isomers) and mixtures thereof. Depending on the substitution pattern, the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. One center of chirality is the carbon ring atom carrying radical R1. The invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantiomers or diastereomers of the compound I or its mixtures.
The present invention also relates to potential tautomers of the compounds of formula (I) and also to the salts of such tautomers. The present invention relates to the tautomer as such as well as to mixtures or combinations of the tautomers in any proportion to each other. The term "tautomers" encompasses isomers, which are derived from the compounds of formula (I) by the shift of an H-atom involving at least one H-atom located at a nitrogen, oxygen or sulphur atom. Examples of tautomeric forms are keto-enol forms, imine-enamine forms, urea-isourea forms, thiourea-isothiourea forms, (thio)amide-(thio)imidate forms etc.
The compounds of the present invention, i.e. the compounds of formula (I), their stereoisomers, their tautomers as well as their salts, in particular their agriculturally acceptable salts and their veterinarily acceptable salts, may be amorphous or may exist in one ore more different crystalline states (polymorphs) or modifications which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the formula (I), mixtures of different crystalline states or modifications of the respective stereoisomers or tautomers, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula (I) are preferably agriculturally salts as well as veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.
Suitable agriculturally or veterinary useful salts are especially the salts of those cations or anions, in particular the acid addition salts of those acids, whose cations and anions, respec- tively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4+) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy- Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammo- nium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen car- bonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4- alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix
Cn-Cm indicates in each case the possible number of carbon atoms in the group.
"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.
The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in partic- ular by fluorine or chlorine. For example, partially or fully halogenated alkyl is also termed haloalkyl, partially or fully halogenated cycloalkyl is also termed halocycloalkyl, partially or fully halogenated alkylenyl is also termed haloalkenyl, partially or fully halogenated alkylynyl is also termed haloalkynyl, partially or fully halogenated alkoxy is also termed haloalkoxy, partially or fully halogenated alkylthio is also termed haloalkthio, partially or fully halogenated alkylsulfinyl is also termed haloalkylsulfinyl, partially or fully halogenated alkylsulfonyl is also termed haloalsulfonyl, partially or fully halogenated cycloalkylalkyl is also termed halocycloalkylalkyl.
The term "Cn-Cm-alkyl" as used herein, and also in Cn-Cm-alkylamino, di-Cn-Cm-alkylamino, Cn-Cm-alkylaminocarbonyl, di-(Cn-Cm-alkylamino)carbonyl, Cn-Cm-alkylthio , Cn-Cm-alkylsulfinyl and Cn-Cm-alkylsulfonyl, refers to a branched or unbranched saturated hydrocarbon group hav- ing n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 - methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 - dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. Ci-C4-alkyl means for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl.
The term "Cn-Cm-alkanediyl" as used herein is synonym to "Cn-Cm-alkylene" and refers to a linear or branched saturated bivalent hydrocarbon group having n to m, e.g. 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, for example methylene, ethane-1 ,1 -diyl, ethane-1 ,2-diyl, propane-1 ,1 -diyl, propane-1 ,2-diyl, propane-1 ,3-diyl, propane-2,2-diyl, butane-1 ,1 -diyl, butane- 1 ,2-diyl, butane-2,3-diyl, butane-2,2-diyl, butane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,1 -diyl, pen- tane-2,2-diyl, pentane-3,3-diyl, pentane-1 ,2-diyl, pentane-1 ,3-diyl, pentane-1 ,4-diyl, pentane- 1 ,5-diyl, pentane-2,3-diyl, pentane-2,4-diyl, 2-methylbutane-1 ,4-diyl, 2,2-dimethylpropane-1 ,3- diyl, hexane-1 ,6-diyl, hexane-1 ,5-diyl or 2,5-hexane-2,5-diyl. The term "linear Ci-C6-alkanediyl" refers to a linear saturated bivalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, for example methylen, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl and hexane-1 ,6-diyl.
The term "Cn-Cm-haloalkyl" as used herein, and also in Cn-Cm-haloalkylthio (= Cn-Cm- haloalkylsulfenyl), Cn-Cm-haloalkylsulfinyl and Cn-Cm-haloalkylsulfonyl, refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g. 1 to 10 in particular 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloro- methyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluorome- thyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2,2- difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2-fluoro-1 -methylethyl, 2,2- difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 -(trifluoromethyl)ethyl.
1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl and the like. The term Ci-Cio-haloalkyl in particular comprises Ci-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoro- methyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl. "Halomethyl" is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluo- romethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like.
Similarly, "Cn-Cm-alkoxy", "Cn-Cm-alkylthio", or "Cn-Cm-alkylsulfenyl", respectively, "Cn-Cm- alkylsulfinyl" or "Cn-Cm-alkylsulfonyl" refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through O, S, S(=0) or S(=0)2 linkages, respectively, at any bond in the alkyl group. Accordingly, the terms "Cn-Cm-haloalkoxy", "Cn-Cm-haloalkylthio" or "Cn-Cm-alkylsulfenyl", respectively, "Cn-Cm-haloalkylsulfinyl" or "Cn-Cm-haloalkylsulfonyl", refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through O, S, S(=0) or S(=0)2 linkages, respectively, at any bond in the haloalkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term "Cn-Cm-alkoxy" is a Cn-Cm-alkyl group, as defined above, attached via an oxygen atom. Ci-C2-Alkoxy is methoxy or ethoxy. Ci-C4-Alkoxy is, for example, methoxy, ethoxy, n- propoxy, 1 -methylethoxy (isopropoxy), butoxy, 1 -methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy). Ci-C6-Alkoxy includes the meanings given for Ci-C4-alkoxy and also includes, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3- methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 - dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethyl butoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2- trimethylpropoxy, 1 -ethyl-1 -methylpropoxy or 1 -ethyl-2-methylpropoxy. Ci-Cs-Alkoxy includes the meanings given for Ci-C6-alkoxy and also includes, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof. Ci-Cio-Alkoxy includes the meanings given for Ci- Ce-alkoxy and also includes, for example, nonyloxy, decyloxy and positional isomers thereof.
The term "Cn-Cm-alkylthio" is a Cn-Cm-alkyl group, as defined above, attached via a sulfur atom. Ci-C2-Alkylthio is methylthio or ethylthio. Ci-C4-Alkylthio is, for example, methylthio, ethylthio, n-propylthio, 1 -methylethylthio (isopropylthio), butylthio, 1 -methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1 -dimethylethylthio (tert-butylthio). Ci-C6-Alkylthio includes the meanings given for Ci-C4-alkylthio and also includes, for example, pentylthio, 1 - methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1 ,1 -dimethylpropylthio, 1 ,2- dimethylpropylthio, 2,2-dimethylpropylthio, 1 -ethylpropylthio, hexylthio, 1 -methylpentylthio, 2- methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2- dimethylbutylthio, 1 ,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 -ethylbutylthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2- trimethylpropylthio, 1 -ethyl-l -methylpropylthio or 1-ethyl-2-methylpropylthio. Ci-Cs-Alkylthio includes the meanings given for Ci-C6-alkylthio and also includes, for example, heptylthio, oc- tylthio, 2-ethylhexylthio and positional isomers thereof. Ci-Cio-Alkylthio includes the meanings given for Ci-Cs-alkylthio and also includes, for example, nonylthio, decylthio and positional isomers thereof.
The term "Cn-Cm-a I kylsu If i nyl" is a Cn-Cm-alkyl group, as defined above, attached via a S(=0) group. The term "Cn-Cm-alkylsulfonyl" is a Cn-Cm-alkyl group, as defined above, attached via a S(=0)2 group.
The term "Cn-Cm-haloalkyloxy" is a Cn-Cm-haloalkyl group, as defined above, attached via an oxygen atom. Examples include Ci-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluo- romethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1 -bromoethoxy, 1 - fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoro- ethoxy.
The term "Cn-Cm-haloalkylthio" is a Cn-Cm-haloalkyl group, as defined above, attached via a sulfur atom. Examples include Ci-C2-haloalkylthio, such as chloromethylthio, bromomethyl- thio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethyl- thio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1 -chloroethylthio, 1 -bromoethylthio, 1 -fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2- trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2- fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio and the like.
Similarly the terms Ci-C2-fluoroalkoxy and Ci-C2-fluoroalkylthio refer to Ci-C2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
The term "Cn-Cm-haloalkylsulfinyl" is a Cn-Cm-haloalkyl group, as defined above, attached via a S(=0) group. The term "Cn-Cm-haloalkylsulfonyl" is a Cn-Cm-haloalkyl group, as defined above, attached via a S(=0)2 group.
The term "C2-Cm-alkenyl" as used herein denotes a linear or branched ethylenically unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a C=C- double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 - butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2- methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2-methyl- 1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 - methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl- 1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl, 2- hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl-
1 - pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-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, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-
2- butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-
3- butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl- 3-butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 - ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2- propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2-methyl-1 -propenyl and 1 -ethyl-2-methyl-2- propenyl.
The term "C2-Cm-haloalkenyl" as used herein, which is also expressed as "C2-Cm-alkenyl which is partially or fully halogenated", refers to C2-Cm-alkenyl, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example 1 -fluoroethenyl, 2-fluoroethenyl, 2,2-difluoroethenyl, 1 ,2,2-trifluoroethenyl, 1 -fluoro-2-propenyl, 2-fluoro-2-propenyl, 3-fluoro-2-propenyl, 1 -fluoro-1 - propenyl, 1 ,2-difluoro-1 -propenyl, 3,3-difluoropropen-2-yl, 1 -chloroethenyl, 2-chloroethenyl, 2,2,- dichloroethenyl, 1 -chloro-2-propenyl, and the like.
The term "C2-Cm-alkynyl" as used herein refers to linear or branched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one C- C-triple bond, such as ethynyl, propynyl, 1 -butynyl, 2-butynyl, and the like.
The term "C2-Cm-haloalkynyl" as used herein, which is also expressed as "C2-Cm-alkynyl which is partially or fully halogenated", refers to C2-Cm-alkynyl, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine. Examples of C2-Cm-haloalkynyl include 1 -fluoro-2-propenyl, 2- fluoro-2-propenyl, 3-fluoro-2-propenyl, 1 -fluoro-2-propynyl and 1 ,1 -difluoro-2-propenyl, and the like.
The term "C3-Cm-cycloalkyl" as used herein refers to monocyclic and polycyclic 3- to m- membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohex- yl, cycloheptyl, cyclooctyl, cyclodecyl, bicyclo[2.2.1 ]heptyl, bicyclo[3.1 .1]heptyl, bicy- clo[2.2.2]octyl and bicyclo[3.2.1 ]octyl. Preferably, the term cycloalkyl denotes a monocyclic saturated hydrocarbon radical. The term "C3-Cm-cycloalkenyl" as used herein refers to monocyclic and polycyclic 3- to m- membered monounsaturated cycloaliphatic radicals, e.g. 1 -cyclopropenyl, 3-cyclopropenyl, 1 - cyclobutenyl, 3-cyclobutenyl, cyclopentenyl, 3-cyclopentenyl, 1 -cyclohexenyl, 3-cyclohexenyl, or 4-cyclohexenyl. Preferably, the term cycloalkenyl denotes a monocyclic mono-unsaturated hy- drocarbon radical.
The term "C3-Cm-halocycloalkyl" as used herein, which is also expressed as "cycloalkyl which is partially or fully halogenated", refers C3-Cm-cycloalkyl as mentioned above, in which some or all of the hydrogen atoms are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine. Examples of C3-Cm-halocycloalkyl include 1 - fluorocycloprpyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 1 -chlorocyclcopropyl, 2- chlorocyclopropyl, 2,2-dichlorocyclopropyl, 2,3-difluorocyclopropyl, 1 -fluorocycobutyl etc.
The term "C3-Cm-cycloalkyl-Ci-C4-alkyl" refers to a C3-Cm-cycloalkyl group as defined above, which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above. Examples for C3-Cm-cycloalkyl-Ci-C4-alkyl are cyclopropyl methyl, cyclopropylethyl, cy- clopropyl propyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclo- pentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl.
The term "C3-Cm-halocycloalkyl-Ci-C4-alkyl" refers to a C3-Cm-halocycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above.
The term "Ci-C4-alkoxy-Ci-C4-alkyl" as used herein refers to alkyl having 1 to 4 carbon atoms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an Ci-C4-alkoxy group. Examples are methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, isobutoxymethyl, tert- butoxymethyl, 1 -methoxyethyl, 1 -ethoxyethyl, 1 -propoxyethyl, 1 -isopropoxyethyl, 1 -n- butoxyethyl, 1 -sec-butoxyethyl, 1 -isobutoxyethyl, 1 -tert-butoxyethyl, 2-methoxyethyl, 2- ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 2-sec-butoxyethyl, 2- isobutoxyethyl, 2-tert-butoxyethyl, 1 -methoxypropyl, 1 -ethoxypropyl, 1 -propoxypropyl, 1 - isopropoxypropyl, 1 -n-butoxypropyl, 1 -sec-butoxypropyl, 1 -isobutoxypropyl, 1 -tert-butoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-propoxypropyl, 2-isopropoxypropyl, 2-n-butoxypropyl, 2- sec-butoxypropyl, 2-isobutoxypropyl, 2-tert-butoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3- propoxypropyl, 3-isopropoxypropyl, 3-n-butoxypropyl, 3-sec-butoxypropyl, 3-isobutoxypropyl, 3- tert-butoxypropyl and the like.
The term Ci-C4-haloalkoxy-Ci-C4-alkyl is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms, wherein one of the hydrogen atoms is replaced by a Ci-C4-alkoxy group and wherein at least one, e.g. 1 , 2, 3, 4 or all of the remaining hydrogen atoms, either in the alkoxy moiety or in the alkyl moiety or in both, are replaced by halogen atoms. Examples are difluoromethoxymethyl (CHF2OCH2), trifluoromethoxymethyl, 1 -difluoromethoxyethyl, 1 - trifluoromethoxyethyl, 2-difluoromethoxyethyl, 2-trifluoromethoxyethyl, difluoro-methoxy-methyl (CH3OCF2), 1 ,1 -difluoro-2-methoxyethyl, 2,2-difluoro-2-methoxyethyl and the like.
The term "Ci-Cm-alkoxycarbonyl" is a Ci-Cm-alkoxy group, as defined above, attached via a carbonyl group atom. Ci-C2-Alkoxycarbonyl is methoxycarbonyl or ethoxycarbonyl. C1-C4- Alkoxy is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1 - methylethoxycarbonyl, butoxycarbonyl, 1 -methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1 ,1 -dimethylethoxycarbonyl. Ci-C6-Alkoxycarbonyl includes the meanings given for C1-C4- alkoxycarbonyl and also includes, for example, pentoxycarbonyl, 1 -methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 1 ,1 -dimethylpropoxycarbonyl, 1 ,2- dimethylpropoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1 -ethylpropoxycarbonyl, hexoxycar- bonyl, 1 -methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4- methylpentoxycarbonyl, 1 ,1 -dimethylbutoxycarbonyl, 1 ,2-dimethylbutoxycarbonyl,
1 ,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl,
3,3-dimethylbutoxycarbonyl, 1 -ethylbutoxy, 2-ethylbutoxycarbonyl, 1 ,1 ,2- trimethylpropoxycarbonyl, 1 ,2,2-trimethylpropoxycarbonyl, 1 -ethyl-1 -methylpropoxycarbonyl or 1 -ethyl-2-methylpropoxycarbonyl.
The term "aryl" as used herein refers to an aromatic hydrocarbon radical such as naphthyl or in particular phenyl.
The term "3- to 6-membered carbocyclic ring" as used herein refers to cyclopropane, cy- clobutane, cyclopentane and cyclohexane rings. The term "3- to 7-membered carbocyclic ring" as used herein refers to cyclopropane, cyclobutane, cyclopentane, cyclohexane and cyclohep- tane rings.
The term "3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms" or "containing heteroatom groups", wherein those heteroatom(s) (group(s)) are selected from N, O, S, NO, SO and SO2 and are ring members, as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
Examples of 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic rings include: oxiranyl, aziridinyl, azetidinyl, 2 tetrahydrofuranyl, 3-tetrahydrofuranyl, 2 tetrahydrothienyl, 3 tetrahy- drothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3 pyrazolidinyl, 4 pyrazolidinyl, 5-pyrazolidinyl, 2 imidaz- olidinyl, 4 imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5 oxazolidinyl, 3-isoxazolidinyl, 4 isoxa- zolidinyl, 5 isoxazolidinyl, 2 thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3 isothiazolidinyl, 4- isothiazolidinyl, 5 isothiazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4 oxadiazolidin 5 yl, 1 ,2,4- thiadiazolidin-3-yl, 1 ,2,4 thiadiazolidin-5-yl, 1 ,2,4 triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4 thiadiazolidin-2-yl, 1 ,3,4 triazolidin-2-yl, 2-tetrahydropyranyl, 4 tetrahydropyranyl, 1 ,3-dioxan-5- yl, 1 ,4-dioxan-2-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4 hexahy- dropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5 hexahydropyrimidinyl, 2- piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4 hexahydrotriazin-3-yl, 2-morpholinyl, 3- morpholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1 -oxothiomorpholin-2-yl, 1 -oxothiomorpholin-
3- yl, 1 ,1 -dioxothiomorpholin-2-yl, 1 ,1 -dioxothiomorpholin-3-yl, hexahydroazepin-1 -, -2-, -3- or -4- yl, hexahydrooxepinyl, hexahydro-1 ,3-diazepinyl, hexahydro-1 ,4-diazepinyl, hexahydro-1 ,3- oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro-1 ,3-dioxepinyl, hexahydro-1 ,4-dioxepinyl and the like. Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3- dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2-pyrrolin-2- yl, 2-pyrrolin-3-yl, 3 pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4 isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2 isoxazolin-5-yl, 3-isoxazolin-5-yl, 4- isoxazolin-5-yl, 2-isothiazolin-3-yl, 3 isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3- isothiazolin-4-yl, 4 isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3 dihydropyrazol-1 -yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3 dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1 -yl, 3,4 dihydropyrazol-3-yl, 3,4-dihydropyrazol-4- yl, 3,4-dihydropyrazol-5-yl, 4,5 dihydropyrazol-1 -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-
4- yl, 4,5 dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3 dihydrooxazol- 4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4 dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 3,4-dihydrooxazol-5-yl, 3,4 dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4 di- or tetrahydro- pyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5 di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1 ,3,5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin- 3-yl, 2,3,4,5-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin- 2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7 tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7 tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5- tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7 tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7 tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1 ,3-diazepinyl, tet- rahydro-1 ,4-diazepinyl, tetrahydro-1 ,3-oxazepinyl, tetrahydro-1 ,4-oxazepinyl, tetrahydro-1 ,3- dioxepinyl and tetrahydro-1 ,4-dioxepinyl.
Examples of 5- or 6-membered maximally unsaturated heterocyclic rings, also termed heteroaromatic rings or hetaryl, include: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1 -pyrrolyl, 2-pyrrolyl, 3- pyrrolyl, 1 -pyrazolyl, 3-pyrazolyl, 4-pyrazo-"lyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4 thiazolyl, 5-thiazo-"lyl, 3-isoxazolyl, 3-isothiazolyl, 4-isoxazolyl, 4-isothiazolyl, 5- isoxazolyl, 5-isothiazolyl, 1 -imidazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4- thiadiazol-2-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,3,4-thiadiazol-2-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-oxadiazol-5-yl, 1 ,3,4-thiadiazol-5-yl, 1 ,2,4-triazol-1 -yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-4-yl, 2-pyridinyl, 3-pyridinyl,
4- pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2- pyrazinyl.
Examples of 8-, 9- or 10-membered, saturated, partially unsaturated heterobicycles having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members include 2- azabicyclo[2.2.1]heptyl, 5-azabicyclo[2.2.1 ]heptyl, 2,5-diazabicyclo[2.2.1 ]heptyl, 3- azabicyclo[3.2.1]octyl, 8-azabicyclo[3.2.1 ]octyl, 3,8-diazabicyclo[3.2.1]octyl, indolin-1 -yl, indolin- 2-yl, indolin-3-yl, 2,3-dihydroindazol-2-yl, 2,3-dihydroindazol-3-yl, 2,3-dihydroindazol-1 -yl, 3,4- dihydroquinolinyl, 1 ,2,3,4-tetrahydroquinolinyl, 3,4-dihydroisoquinolinyl, 1 ,2,3,4- tetrahydroisoquinolinyl, 3,4-dihydrocinnolinyl, 1 ,2,3,4-tetrahydrocinnolinyl, 5,6,7,8- tetrahydroquinolinyl, 5,6,7,8-tetrahydroisoquinolinyl, 5,6,7,8-tetrahydrocinnolinyl, chromenyl, chromanyl, 4,5,6,7-tetrahydroindole, 4,5,6,7-tetrahydroisoindole .
Examples of 8-, 9- or 10-membered maximally unsaturated heterobicycles, also termed bicyclic hetaryl, having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members include quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizynyl, isoindolyl, indazolyl, benzofuryl, ben- zothienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, pyrrolo[1 ,2- a]imidazolyl, imidazo[1 ,2-b]pyrazolyl, imidazo[1 ,2-a]pyridinyl, imidazo[1 ,2-a]pyrimidinyl, imidazo[1 ,2-a]pyridine-2-yl, thieno[3,2-b]pyridine-5-yl, imidazo-[2,1 -b]-thiazol-6-yl and 1 ,2,4- triazolo[1 ,5-a]pyridine-2-yl.
Embodiments of the present invention as well preferred compounds of the present inven- tion are outlined in the following paragraphs. The remarks made below concerning preferred embodiments of the variables of the compounds of formula (I), especially with respect to their substituents W, W2, W3, W4, Het, R1 ,R2 and Cyc and the variable k and m are valid both on their own and, in particular, in every possible combination with each other.
When # appears in a formula showing a preferred substructure of a compound of the pre- sent invention, it denotes the attachment bond in the remainder molecule.
In particular groups of embodiments, in the compounds of formula (I), the variables R3, R4 and R16, have the following meanings:
R3, R4 are independently from each other selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-C10- alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7,
OR8b, NR17aR17b, S(0)nR8b, S(0)nNR 7aR 7b, NR 7dS(0)nR8b, C(=0)R7 , OC(=0)R7 , NR 7dC(=0)R7 , C(=0)NR 7aR 7 , NR 7dC(=0)NR 7aR 7 , C(=0)OR8 , C(=S)R7 ,
OC(=S)R7 , NR 7cC(=S)R7 , C(=S)NR 7aR 7 , NR 7dC(=S)NR 7aR 7 , C(=S)OR8a,
C(=S)SR8a, C(=NR 7)R7a, C(=NR 7)-C(0)R7c, C(=NR 7)NR 7aR 7 , Si(R11)2R12, a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two of R3 or two of R4, which are present on one ring carbon may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b, R16 independently of its occurrence, is selected from the group consisting of hydrogen, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci- C4 alkoxy,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino; where n, R5, R7, R7a, R7 , R7c, R8a, R8 , R9a, R9 , R11, R12, R13, R14, R16, R 7, R 7a, R 7 , R 7c and R17d have one of the meanings given above.
In a particular group of embodiments (1 ), Cyc is 5- or 6-membered, partially unsaturated or maximally unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring mem- bers, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3.
In a particular group of embodiments (1 a), Cyc is 5-membered maximally unsaturated heteromonocycle, i.e. 5-membered monocyclic hetaryl, having 1 heteroatom as ring member, which is selected from O and S, and 1 or 2 nitrogen atoms as ring members, where the heter- omonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3. In particular, Cyc is selected from the group consisting of thiazol-2-yl, oxazol-2-yl, isoxazol-5-yl, isothiazol-5-yl, 1 ,3,4- thiadiazol-2-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-oxadiazol- 5-yl and 1 ,2,4-thiadiazol-5-yl, where the aforementioned 5-membered heterocycles are unsub- stituted or carry 1 , 2 or 3, in particular 1 or 2 radicals R3. In particular, Cyc is also selected from oxazol-5-yl.
In another particular group of embodiments (1 b), Cyc is 6-membered maximally unsaturated heteromonocycle, i.e. 6-membered monocyclic hetaryl, having 1 , 2 or 3 nitrogen atoms as heteroatom ring member, where the heteromonocycle is unsubstituted or carries 1 , 2, 3 or 4 subsitutents R3. In particular, Cyc is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4- pyridyl, 2-pyrimidinyl, 3-pyridazinyl and 4-pyridazinyl, where the aforementioned 6-membered heterocycles are unsubstituted or carry 1 , 2, 3 or 4, in particular 1 , 2 or 3 radicals R3.
In another particular group of embodiments (1 c), Cyc is 5-membered partially unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O and S, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3. In particular, Cyc is selected from 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,3- dihydrothiophen-2-yl, 2,3-dihydrothiophen-5-yl and 2,5-dihydrothiophen-2-yl, where the aforementioned 5-membered partially unsaturated heterocycles are unsubstituted or carry 1 , 2 or 3, in particular 1 or 2 radicals R3.
In another particular group of embodiments (1 d), Cyc is 5-membered partially unsaturated heteromonocycle, having 1 heteroatom as ring member, which is selected from O and S, and 1 or 2 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3. In particular, Cyc is selected from thiazolin-2-yl (4,5-dihydrothiazol-2-yl), and oxazolin-2-yl, where the aforementioned 5-membered heterocycles are unsubstituted or carry 1 , 2 or 3, in particular 1 or 2 radicals R3.
In another particular group of embodiments (1 e), Cyc is 5-membered maximally unsaturated heteromonocycle, i.e. 5-membered monocyclic hetaryl, having 1 heteroatom as ring member, which is selected from O and S, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3. In particular, Cyc is selected from furan-2-yl, furan-3-yl, thiophen- 2-yl and thiophen-3-yl, where the aforementioned 5-membered heterocycles are unsubstituted or carry 1 or 2 radicals R3.
In a special group of embodiments (1 a.1 ), Cyc is thiazol-2-yl, which is unsubstituted or which carries in particular 1 or 2 radicals R3.
In a further special group of embodiments (1 a.2), Cyc is oxazol-2-yl, which is unsubstitut- ed or which carries in particular 1 or 2 radicals R3. In yet a further special group of embodiments (1 a.3), Cyc is isothiazol-5-yl, which is un- substituted or which carries in particular 1 or 2 radicals R3.
In yet a further special group of embodiments (1 a.4), Cyc is isoxazol-5-yl, which is unsub- stituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.5), Cyc is 1 ,3,4-thiadiazol-2-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.6), Cyc is 1 ,3,4-oxadiazol-2-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.7), Cyc is 1 ,2,4-thiadiazol-3-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.8), Cyc is 1 ,2,4-oxadiazol-3-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.9), Cyc is 1 ,2,4-thiadiazol-5-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.10), Cyc is 1 ,2,4-oxadiazol-5-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 a.1 1 ), Cyc is oxazol-5-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 b.1 ), Cyc is 2-pyridyl, which is unsubsti- tuted and which carries in particular 1 , 2, 3 or 4 radical R3.
In yet a further special group of embodiments (1 b.2), Cyc is 3-pyridyl, which is unsubstituted and which carries in particular 1 , 2, 3 or 4 radical R3.
In yet a further special group of embodiments (1 b.3), Cyc is 4-pyridyl, which is unsubstituted or which carries in particular 1 , 2, 3 or 4 radical R3.
In yet a further special group of embodiments (1 b.4), Cyc is 2-pyrimidinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R3.
In yet a further special group of embodiments (1 b.5), Cyc is 4-pyrimidinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R3.
In yet a further special group of embodiments (1 b.6), Cyc is 5-pyrimidinyl, which is unsub- stituted or which carries in particular 1 , 2 or 3 radical R3.
In yet a further special group of embodiments (1 b.7), Cyc is 3-pyridazinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R3.
In yet a further special group of embodiments (1 b.8), Cyc is 4-pyridazinyl, which is unsubstituted or which carries in particular 1 , 2 or 3 radical R3. In yet a further special group of embodiments (1 c.1 ), Cyc is 2,3-dihydrothiophen-5-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 d .1 ), Cyc is thiazolin-2-yl which is unsubstituted or which carries 1 radical R3.
In yet a further special group of embodiments (1 d.2), Cyc is oxazolin-2-yl, which is unsubstituted or which carries in particular 1 radical R3.
In yet a further special group of embodiments (1 e.1 ), Cyc is thiophen-2-yl, which is unsubstituted or which carries in particular 1 radical R3.
In the compounds of formula (I), R3 and R4, if present, are preferably independently from each other selected from the group consisting of
halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3- C6-halocycloalkyl,
Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R7, C(=0)NR 7aR 7b, CHO, COOR8b, OR8b, S(0)nR8b,
where
R7 is OR8, NR17aR17b or NR 7a-C(=0)R7a or
two R7 present on one carbon atom may together form =NOR16, or =NNR9aR9b; R7a is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl;
R8 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or C(=0)R15;
R8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl;
R9a, R9b are independently of each other selected from hydrogen, Ci-C6-alkyl, C1-C6- haloalkyl, C(=0)NR 7aR 7 and C(=0)R15,
R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;
R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
R17a and R17b are independently from each other selected from hydrogen, Ci-C6-alkyl and d-Ce-haloalkyl; a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 5- or 6- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring mem- bers, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substitu- ents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two of R3 or two of R4, which are present on one ring carbon atom may together be =0, thereby forming a carbonyl group
wherein
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci- Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b and S(0)nR8b, where R8b is Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl, and
Q irrespectively of its occurrence is selected from a single bond, Chb, O, S, S(O) and
S(0)2.
In the context of the groups of embodiments (1 ), (1 a), (1 b), (1 c), (1 d), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ), the radical R3, if present, is prefer- ably selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, C1-C6- haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b, S(0)nR8b,
a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and a moiety Q-Het*, wherein Het* is a 3-, 4-, 5- or 6- mem- bered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two radicals R3, which are bound to the same carbon atom, may be =0, thereby form- ing a carbonyl group.
R3, if present, is in particular selected from the group consisting of halogen, cyano, C1-C6- haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b, S(0)nR8b,
a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2 or 3 identical or different substituents R5 and wherein Q is a single bond, Chb, O, S, S(O) or S(0)2, or two radicals R3, which are bound to the same carbon atom, may be =0, thereby forming a carbonyl group.
R3, if present, is especially selected from the group consisting of halogen, cyano, C1-C2- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoroethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, or tert.butoxy, Ci-C2-haloalkylthio, such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 -difluoroethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci- C4-alkylthio, such methylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethyl- sulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 1 ,1 ,2,2- tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, Ci-C4-alksulfonyl, such as methylsulfonyl or ethylsulfonyl, phenyl, benzyl, phenoxy and phenylsulfonyl, wherein phenyl is the last 4 groups is unsubstituted or substituted with 1 , 2 or 3 identical or different substituents R5 as defined above and preferably selected from Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoro- ethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, or tert.butoxy, Ci-C2-haloalkylthio, such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 -difluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci-C4-alkylthio, such methylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethylsulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl, 1 ,1 ,2,2-tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, C1-C4- alksulfonyl, such as methylsulfonyl or ethylsulfonyl.
In the context of the groups of embodiments (1 ), (1 a), (1 b), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4),
(1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2), and (1 e.1 ), the radical R3, if present, is also preferably selected from the group consisting of C(=0)N R17aR17b, CHO, COOR8b and d-Ce-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R7.
R3, if present, is also especially selected from the group consisting of formyl, COOH , Ci-
C6-alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl, Ci-C4-alkylaminocarbonyl, such as methylaminocarbonyl or ethylaminocarbonyl and di-(Ci-C4-alkyl)aminocarbonyl, such as dimethylaminocarbonyl, diethylaminocarbonyl, N- methyl-N-ethylaminocarbonyl and Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R7. In the context of R3, R7 is as defined above and preferably selected from OR8, N R17aR17b and N R17a-C(=0)R7a or two R7 present on one carbon atom may together form =NOR16 or =N N R9aR9b; wherein R7a is hydrogen, Ci-Ce-alkyl such as methyl or ethyl or Ci- C6-haloalkyl, especially Ci-C4-haloalkyl such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoro- ethyl; R8 is hydrogen, Ci-C6-alkyl such as methyl or ethyl, Ci-C6-haloalkyl such as difluorome- thyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl or C(=0)R15; R9a, R9b are each independently of each other selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C(=0)NR17aR17b and C(=0)R15; in particu- lar R9b is hydrogen; R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy; R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or Ci-C6-haloalkylcarbonyl; R17a and R17b are independently from each other selected from hydrogen, Ci-C6-alkyl such as methyl or ethyl and Ci-C6-haloalkyl such as difluo- romethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl. Particular examples of =NOR16 are, but are not limited to, hydroxyimino, methoxyimino, ethoxyimino, acetoxyimino and propanoylimino. Particular examples of =NNR9aR9b are, but are not limited to, methylcarbamoylhydrazono, ethylcar- bamoylhydrazono, 2,2,2-trifluoroethylcarbamoylhydrazono, acetylhydrazono, propanoylhydra- zono and benzoylhydrazono.
In the context of R3, the radicals Het*, Q, R8b and R5 are as defined above and in particular as follows:
Het* a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 het- eroatoms as ring members, which are identical or different and selected from oxygen, ni- trogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5;
R8b is Ci-C6-haloalkyl, in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, C3-C6-cycloalkyl, such as cyclobutyl, cyclopropyl, or cyclopentyl, Ci- C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, or C3-C6- halocycloalkyl, such as 1 -fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 1 - chlorocyclopropyl, 2-chlorocyclopropyl, 2,2-dichlorocyclopropyl, 1 -fluorocyclobutyl, or 1 - fluorocyclopentyl; R8b is in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl, or Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n- butyl.
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, C1-C6- haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b and S(0)nR8b, where R8b is as defined herein and in particular Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or, C3-C6-halocycloalkyl, and especially Ci-C2-haloalkyl, such as difluoromethyl, trifluorome- thyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl, or Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n- butyl; R5 is in particular selected from the group consisting of halogen, cyano, C1-C2- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, tri- fluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoroethoxy, C1-C4- alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, or tert.butoxy, Ci-C2-haloalkylthio, such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 - difluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci-C4-alkylthio, such methylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethylsulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl, 1 ,1 ,2,2-tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, C1-C4- alksulfonyl, such as methylsulfonyl or ethylsulfonyl;
Q irrespectively of its occurrence is selected from a single bond, CH2, O, S, S(O) and S(0)2.
In another particular group of embodiments (2), Cyc is a 8-, 9- or 10-membered, saturated, partially unsaturated or maximally unsaturated heterobicycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R4, in particular an 8-, 9- or 10 membered maximally unsaturated fused heterobicycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring members, where the heterobicycle is unsubstituted or carries 1 , 2 or 3 subsitutents R4. Particular examples of Cyc in the groups of embodiments (2) include: quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizynyl, isoindolyl, indazolyl, benzofuryl, ben- zothienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, pyrrolo[1 ,2- a]imidazolyl, imidazo[1 ,2-b]pyrazolyl, imidazo[1 ,2-a]pyridinyl, imidazo[1 ,2-a]pyrimidinyl, imid- azo[1 ,2-a]pyridine-2-yl, thieno[3,2-b]pyridine-5-yl, imidazo-[2,1 -b]-thiazol-6-yl and 1 ,2,4- triazolo[1 ,5-a]pyridine-2-yl, where the aformentioned fused heterobicylces are unsubsituteted or carry 1 , 2, 3 or 4 radicals R4 as defined herein.
The radicals R4, if present, are preferably selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl, OR8b and S(0)nR8b.
R4, if present, is in particular selected from the group consisting of halogen, cyano, C1-C6- haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b and S(0)nR8b. R4, if present, is especially selected from the group consisting of halogen, cyano, C1-C2- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoroethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, or tert.butoxy, Ci-C2-haloalkylthio, such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 -difluoroethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci- C4-alkylthio, such methylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethyl- sulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 1 ,1 ,2,2- tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, Ci-C4-alksulfonyl, such as methylsulfonyl or ethylsulfonyl.
Preferred are compounds of formula (I), and likewise the compounds of groups (1 ), (2), (1 a), (1 b), (1 c), (1 d), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2), and (1 e.1 ) embodiments, wherein W1=W2-W3=W4 represents a carbon chain group connected to N and C=N, which is selected from the group consisting of CRw6=CRw5-CRw4=CRw3, CRw6=CRw5- CHRw4, CHRw6-CRw4=CRw3 , CRw6=CRw5-C(0) and C(0)-CRw4=CRw3, where in the five aforementioned radicals the carbon atom which carries Rw6 is bound to the nitrogen atom and where Rw3, Rw4, Rw5 and Rw6, independently of each other, have one of the meanings given for Rw. In this context, Rw is preferably selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, C1-C4- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as meth- oxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy. Preferably, at most one of Rw3, Rw4, Rw5 and Rw6 is different from hydrogen.
In particularly preferred groups of embodiments Rw3, Rw4 and Rw6 are hydrogen while Rw5 has one of the meanings given for Rw, and where Rw5 is in particular selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2- trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and C1-C4- haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy.
In other particularly preferred groups of embodiments Rw3, Rw4 and Rw5 are hydrogen while Rw6 has one of the meanings given for Rw, and where Rw6 is in particular selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluo- romethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci- C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluo- romethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy.
Especially, all of Rw3, Rw4, Rw5 and Rw6 are hydrogen.
Preferred are compounds of formula (l-A), their stereoisomers, their tautomers and the salts thereof
Figure imgf000037_0001
(l-A)
wherein Cyc, R1, R2 and Het are as defined herein, and wherein p is 0 or 1 and R™ has one of the meanings given for Rw different from hydrogen, and wherein R™ is preferably selected from the group consisting of halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluo- romethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci- C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluo- romethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy.
If p is 1 , R™ is preferably located in para-position with respect to the carbon atom that carries the imino-nitrogen.
In formula (l-A), Cyc is preferably as defined for group (1 ) of embodiments, in particular as defined for groups (1 a) and (1 b) of embodiments and especially as defined for groups (1 a), (1 b), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7) and (1 b.8) of embodiments. Also preferred are compounds of formula (l-A), wherein Cyc is as defined for groups (1c) and (1d) of embodiments and especially as defined for groups (1c.1), (1d.1), (1 d.2) and (1e.1) of embodiments.
Preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein Het is selected from the group consisting of radicals of formulae Het-1 to Het- 24, with preference given to compounds of the formulae (I) and (l-A), their stereoisomers, there tautomers and their salts, where Het is selected from the radicals of the formulae Het-1 , Het-11 and Het-24:
Figure imgf000038_0001
Het-1 Het-2 Het-3 Het- Het-5
Figure imgf000038_0002
Het-6 Het-7 Het-8 Het-9 Het-10
Figure imgf000038_0003
Het-11 Het-12 Het-13 Het-14 Het-15
Figure imgf000038_0004
Het-16 Het-17 Het-18 Het-19 Het-20
Figure imgf000039_0001
Het-21 Het-22 Het-23 Het-24 wherein # denotes the bond in formulae (I) and (l-A), and wherein R6 and k are as defined above and where R6a is hydrogen or has one of the meanings given for R6 and where R6b is hydrogen or a C-bound radical mentioned as R6 and where R6b is in particular hydrogen, C1-C4- alkyl or Ci-C4-haloalkyl. In particular k is 0, 1 or 2, especially 0 or 1 . In formulae Het-1 , Het-2, Het-3, Het-4, Het-7, Het-8, Het-9, Het-10, Het-1 1 , Het-18 and Het-21 , k is especially 1. In particular R6a in formulae Het-12, Het-13, Het-14, Het-16, Het-17, Het-19, Het 20 and Het-22 is different from hydrogen.
Irrespectively of its occurrence, R6 is preferably selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6-alkinyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may optionally be partly or completely halogenated, in particular by fluorine or chlorine, or may further substituted independently from one another with one or more R7, or R6 may also be a radical selected from the group consisting of OR8, NR17aR17b, S(0)nR8, S(0)nNR 7aR 7b, C(=0)R7a, C(=0)NR 7aR 7 , C(=0)OR8, C(=S)R7a, C(=S)NR 7aR 7 , C(=NR 7)R7a, and C(=NR 7)NR 7aR 7 . Irrespectively of its occurrence, R6 is in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, C1-C4- haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoro- methyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci- C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl.
Irrespectively of its occurrence, R6a is preferably selected from the group consisting of hy- drogen, halogen, cyano, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl and C2-C6-alkinyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may optionally be partly or completely halogenated, in particular by fluorine or chlorine, or may further substituted independently from one another with one or more R7, or R6a may also be a radical selected from the group consisting of OR8, NR17aR17b, S(0)nR8, S(0)nNR 7aR 7 , C(=0)R7a, C(=0)NR 7aR 7 , C(=0)OR8, C(=S)R7a, C(=S)NR 7aR 7 , C(=NR 7)R7a, and C(=NR 7)NR 7aR 7 . Irrespectively of its occurrence, R6a is in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluo- rine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl.
Irrespectively of its occurrence, R6b is in particular selected from the group consisting of hydrogen, Ci-C4-alkyl, such as methyl or ethyl, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably C1-C2- alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl.
Particularly preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1 ), (2), (1 a), (1 b), (1 c), (1 d), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein Het is selected from the group consisting of radicals of formulae Het-1 , Het-1 1 a and Het-24,
Figure imgf000040_0001
Het-1 Het-11a Het-24 where
R6 is selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlo- rine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl; and where
R6a is selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, C1-C4- haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluo- romethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl and k is 0, 1 or 2.
A particularly preferred group of embodiments relates to compounds of formulae (I) and (I-
A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1.a11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-1 , where k is 0, 1 or 2, in particular 1 or 2 and especially 1 and where R6 is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoro- methoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl. Amongst the compounds of this particular group of embodiments, a particular subgroup of embodiments relates to compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-1 a
Figure imgf000041_0001
where
R6 is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, and C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl, and even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, tri- fluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl; R6a is as defined above and in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine and Ci-C4-alkyl, such as methyl or ethyl, more preferably is hydrogen.
A special embodiment of the radical Het-1a is 6-chloropyridin-3-yl, i.e. R6a is hydrogen and R6 is chlorine. A further special embodiment of the radical Het-1a is 6-(trifluoromethyl)pyridin-3- yl, i.e. R6a is hydrogen and R6 is trifluoromethyl.
Another particularly preferred group of embodiments relates to compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-11 , where k is 0, 1 or 2, in particular 0 or 1 , and where Het is in articular a radical of formula Het-11 a,
Figure imgf000042_0001
where R6a is as defined above and wherein R6a is in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and C1-C4- haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl. A special embodiment of the radical Het-11a is 2-chlorothiazol-5-yl, i.e. R6a is chlorine.
Another particularly preferred group of embodiments relates to compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-24, where k is 0, 1 or 2, in particular 0 or 1 , and where R6, if present, is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, and even more preferably from fluorine, chlorine, C1-C2- alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl. Preferred are compounds of compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and the salts thereof, wherein R1 and R2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci- C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, Ci-C6-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, orC3-C6- halocycloalkyl such as 1-fluorocyclopropyl or 2,2-difluorocyclopropyl.
Preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and the salts thereof, wherein R1 and R2 may together be =CR13R14.
Preferred are also compounds of formulae (I) and (l-A), wherein R1 and R2 form, together with the carbon atom, which they attached to, a 3- to 5 membered saturated carbocyclic ring such as cyclopropyl, cyclobutyl or cyclopentyl.
Even more preferred are compounds of formulae (I) and (l-A), and likewise the com- pounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6),
(1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and the salts thereof, wherein R1 and R2 are independently from each other selected from the group consisting of hydrogen, halogen, cyano, Ci-C3-alkyl, such as methyl ethyl or isopropyl, or C1-C3- haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl.
Preferably at least one of the radicals R1 and R2 is hydrogen.
Especially more preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, to the stereoisomers, the tautomers and the salts thereof, wherein R1 and R2 are both hydrogen.
Particularly preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1 -fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R1, R2 are independently from each other in particular selected from the group consisting of hydrogen, halogen, cyano, Ci-C3-alkyl, such as methyl ethyl or isopropyl, or Ci-C3-haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl; wherein preferably at least one of R1 and R2 is hydrogen and wherein R1, R2 are more especially hydrogen; and
Het is selected from the group consisting of radicals of formulae Het-1 , Het-1 1 a and Het-24, wherein
R6 is selected from the group consisting of halogen, such as chlorine or fluorine, C1-C4- alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, C1-C4- haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluo- roethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and C1-C2- haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl;
R6a is selected from the group consisting of hydrogen, halogen, such as chlorine or fluo- rine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy,
Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci- C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl and
k is 0, 1 or 2 and wherein k is especially 1 or 2.
Particularly preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1 ), (2), (1 a), (1 b), (1 c), (1 d), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1 -fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R1, R2 are independently from each other in particular selected from the group consisting of hydrogen, halogen, cyano, Ci-C3-alkyl, such as methyl ethyl or isopropyl, or Ci-C3-haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl; and wherein R1, R2 are more especially hydrogen; and wherein Het is a radical of formula Het-1 , where k is 0, 1 or 2, in particular 1 or 2 and especially 1 and where R6 is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, C1-C4- alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci- C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl. Amongst the compounds of this particular group of embodiments, a particular subgroup of embodiments relates to compounds of formulae (I) and (I- A), and likewise to the compounds of groups (1 ), (2), (1 a), (1 b), (1 c), (1 d),(1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ) of embodiments, to the stereoisomers, the tautomers and to the salts thereof, wherein Het is a radical of formula Het-1 a
Figure imgf000045_0001
where
is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, and C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl or pentafluoroethyl, and even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl;
is as defined above and in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine and Ci-C4-alkyl, such as methyl or ethyl, more preferably is hydrogen;
and wherein Het is especially 6-chloropyridin-3-yl, i.e. R6a is hydrogen and R6 is chlorine, or 6-(trifluoromethyl)pyridin-3-yl, i.e. R6a is hydrogen and R6 is trifluoromethyl.
Particularly preferred are also compounds of formulae (I) and (l-A), and likewise the compounds of groups (1 ), (2), (1 a), (1 b), (1 c), (1 d), (1 a.1 ), (1 a.2), (1 a.3), (1 a.4), (1 a.5), (1 a.6), (1 a.7), (1 a.8), (1 a.9), (1 a.10), (1 a.1 1 ), (1 b.1 ), (1 b.2), (1 b.3), (1 b.4), (1 b.5), (1 b.6), (1 b.7), (1 b.8), (1 c.1 ), (1 d.1 ), (1 d.2) and (1 e.1 ) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1 -fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R1, R2 are independently from each other in particular selected from the group consisting of hydrogen, halogen, cyano, Ci-C3-alkyl, such as methyl ethyl or isopropyl, or Ci-C3-haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl; and wherein R1, R2 are more especially hydrogen; and wherein Het is a radical of formula Het- 1 1 , where k is 0, 1 or 2, in particular 0 or 1 , and where Het is in particular a radical of formula Het-1 1 a,
Figure imgf000046_0001
where R6a is as defined above and wherein R6a is in particular selected from the group consisting of hydrogen, halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and C1-C4- haloalkyl, even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, and wherein Het is especially 2-chlorothiazol-5-yl. Particularly preferred are also compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C3-C6-cycloalkyl, such as cyclopropyl or cyclobutyl, C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1- difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or C3-C6-halocycloalkyl such as 1-fluorocyclopropyl or 2,2-difluorocyclopropyl; wherein especially R1, R2 are independently from each other in particular selected from the group consisting of hydrogen, halogen, cyano, Ci-C3-alkyl, such as methyl ethyl or isopropyl, or Ci-C3-haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl; and wherein R1, R2 are more especially hydrogen; and wherein Het is a radical of formula Het- 24, where k is 0, 1 or 2, in particular 0 or 1 , and where R6, if present, is as defined above and in particular selected from the group consisting of halogen, such as chlorine or fluorine, C1-C4- alkyl, such as methyl or ethyl, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, and even more preferably from fluorine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl.
Particularly preferred are compounds of formulae (I) and (l-A), and likewise the compounds of groups (1), (2), (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments, the stereoisomers thereof, the tautomers thereof and the salts thereof, wherein
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C6-haloalkyl, C2-C6-halocycloalkyl;
or
R1 and R2 may together be =CR13R14;
or
R1 and R2 form, together with the carbon atom, which they attached to, a 3- to 5-membered saturated carbocyclic ring; and
Cyc is
(i) 5- or 6-membered, partially unsaturated or maximally unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3,
wherein
R3 if present, are independently from each other selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R7,
C(=0)NR 7aR 7b, CHO, COOR8b, OR8b, S(0)nR8b,
wherein
R7 is OR8, NR17aR17b or NR 7a-C(=0)R7a or
two R7 present on one carbon atom may together form =NOR16 or =NNR9aR9b;
R7a is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl;
R8 is hydrogen, Ci-C6-alkyl, d-C6-haloalkyl or C(=0)R15;
R8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl;
R9a, R9b are each independently of each other selected from hydrogen, Ci- Ce-alkyl, Ci-C6-haloalkyl, C(=0)NR 7aR 7 and C(=0)R15,
R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloal- koxy;
R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
R17a and R17b are independently from each other selected from hydrogen, Ci- C6-alkyl and Ci-C6-haloalkyl; a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 5- or 6- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
wherein is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, d-Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl, OR8b and S(0)nR8b, where R8b is Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, and
Q irrespectively of its occurrence is selected from a single bond, Chb, O, S, S(O) and S(0)2.
Especiallyl preferred are compounds of formula (l-Aa), their stereoisomers, their tauto- mers and the salts thereof
Figure imgf000049_0001
(l-Aa)
wherein
Het is a radical Het-1 a, Het-1 1 a or Het-24, as defined above, and wherein Het is in particular 6-chloropyridin-3-yl, 6-trifluoromethylpyridin-3-yl, 2-chlorothiazol-5-yl or tetrahydrofuran-3-yl;
R1 is hydrogen or Ci-C4-alkyl, in particular hydrogen or methyl, especially hydrogen; and
Cyc is thiazol-2-yl, which is unsubstituted or which carries 1 or 2 radicals R3, which are as defined above and which are preferably selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b, S(0)nR8b, a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and a moiety Q-Het*, wherein Het* is 5- or 6- mem- bered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, or two radicals R3, which are bound to the same carbon atom, may be =0, thereby forming a carbonyl group; and wherein
Q is a single bond, Chb, O, S, S(O) or S(0)2and wherein R3, if present, is especially selected from the group consisting of halogen, cyano, Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci- C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, or pentafluoroethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2- propoxy, n-butoxy, 2-butoxy, or tert.butoxy, Ci-C2-haloalkylthio, such as difluoromethylthio, tri- fluoromethylthio, 1 -fluoroethylthio, 1 ,1 -difluoroethylthio, 2,2-difluoroethylthio, 2,2,2- trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci-C4-alkylthio, such me- thylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethylsulfonyl, 1 ,1 - difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 1 ,1 ,2,2- tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, Ci-C4-alksulfonyl, such as methylsulfonyl or ethylsulfonyl, phenyl, benzyl, phenoxy and phenylsulfonyl, wherein phenyl is the last 4 groups is unsubstituted or substituted with 1 , 2 or 3 identical or different substituents R5 as defined above and preferably selected from Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoro- ethoxy, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, or tert.butoxy, Ci-C2-haloalkylthio, such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 -difluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci-C4-alkylthio, such methylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethylsulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl, 1 ,1 ,2,2-tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, C1-C4- alksulfonyl, such as methylsulfonyl or ethylsulfonyl.
In an alternative specific embodiment of the compounds of formula (l-Aa), R3, if present, is also in particular selected from CHO, COOR8b, C(=0)NR17aR17b and d-Ce-alkyl which is substituted with 1 or 2 identical or different substituents R7.
R3, if present, is also especially preferred selected from the group consisting of formyl, COOH, Ci-C4-alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl, Ci-C4-alkylaminocarbonyl, such as methylaminocarbonyl or ethylaminocarbonyl and di-(Ci-C4-alkyl)aminocarbonyl, such as dimethylaminocarbonyl, diethylaminocarbonyl, N- methyl-N-ethylaminocarbonyl and Ci-C4-alkyl such as methyl or ethyl,which is substituted with 1 or 2 identical or different substituents R7, wherein R7 is as defined above.
In this context, R7 is in particular
OR8, NR17aR17b or NR 7a-C(=0)R7a; or
two R7 present on one carbon atom may together form =NOR16 or =NNR9aR9b;
wherein
R7a is hydrogen, Ci-C6-alkyl such as methyl or ethyl or Ci-C6-haloalkyl, especially C1-C4- haloalkyl such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl; R8 is hydrogen, Ci-C6-alkyl such as methyl or ethyl, Ci-C6-haloalkyl such as difluorome- thyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl or C(=0)R15;
R9a, R9b are each independently of each other selected from hydrogen, Ci-C6-alkyl, Ci- Ce-haloalkyl, C(=0)NR17aR17b and C(=0)R15; in particular R9b is hydrogen;
R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;
R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
R17a and R17b are independently from each other selected from hydrogen, Ci-C6-alkyl such as methyl or ethyl and Ci-C6-haloalkyl such as. difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl.
Particular examples of =NOR16 are hydroxyimino, methoxyimino, ethoxyimino, acetoxy- imino and propanoylimino.
Particular examples of =NNR9aR9b are methylcarbamoylhydrazono, ethylcarbamoylhydra- zono, 2,2,2-trifluoroethylcarbamoylhydrazono, acetylhydrazono, propanoylhydrazono and ben- zoylhydrazono
In this context Het*, Q, R5 and R8b are preferably as follows:
Het* a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 het- eroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5,
R8b is Ci-C6-haloalkyl, in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 - fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, C3-C6-cycloalkyl, such as cyclobutyl, cyclopropyl, or cyclopentyl, Ci- C6-alkyl, in particular Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, or C3-C6- halocycloalkyl, such as 1 -fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 1 - chlorocyclopropyl, 2-chlorocyclopropyl, 2,2-dichlorocyclopropyl, 1 -fluorocyclobutyl, or 1 - fluorocyclopentyl; R8b is in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl, or Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n- butyl.
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, C1-C6- haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b and S(0)nR8b, where R8b is as defined herein and in particular Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or, C3-C6-halocycloalkyl, and especially Ci-C2-haloalkyl, such as difluoromethyl, trifluorome- thyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2- tetrafluoroethyl or pentafluoroethyl, or Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n- butyl; R5 is in particular selected from the group consisting of halogen, cyano, C1-C2- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl, Ci-C2-haloalkoxy, such as difluoromethoxy, tri- fluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, or pentafluoroethoxy, C1-C4- alkoxy, such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, or tert.butoxy,
Ci-C2-haloalkylthio, such as difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 1 ,1 - difluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 1 ,1 ,2,2-tetrafluoroethylthio or pentafluoroethylthio, Ci-C4-alkylthio, such methylthio or ethylthio, Ci-C2-haloalkylsulfonyl, such as trifluoromethylsulfonyl, 1 ,1 -difluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl, 1 ,1 ,2,2-tetrafluoroethylsulfonyl or pentafluoroethylsulfonyl, C1-C4- alksulfonyl, such as methylsulfonyl or ethylsulfonyl;
Q irrespectively of its occurrence is selected from a single bond, CH2, O, S, S(O) and S(0)2.
Especiallyl preferred are also compounds of formula (l-Aa), their stereoisomers, their tau- tomers and the salts thereof, wherein
Het is a radical Het-1 a, Het-1 1 a or Het-24, as defined above, and wherein Het is in particular 6-chloropyridin-3-yl, 6-trifluoromethylpyridin-3-yl, 2-chlorothiazol-5-yl or tetrahydrofuran-3- yi;
R1 is hydrogen or Ci-C4-alkyl, in particular hydrogen or methyl, especially hydrogen; and Cyc is selected from 2,3-dihydrothiophen-5-yl and thiophen-2-yl, where the aforementioned two radicals are unsubstituted or carry 1 or 2 radicals R3, which are selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b, S(0)nR8b, a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and a moiety Q-Het*; and wherein
Het* a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5,
R8b is d-Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl;
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci- Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b and S(0)nR8b, Q is selected from a single bond, Chb, O, S, S(O) and S(0)2.
Apart from that, the variables Rv, Rw, R6, R7, R7a, R7b, R7c, R8, R8a, R8b, R9a, R9b, R10, R11 , R12, R13, R14, R15, R16, R17, R17a, R17b, R17c and R17d, irrespectively of their occurrence, in particular have the following meanings, if not stated otherwise:
Rv is hydrogen or together with an Rv, which is bound to an adjacent carbon atom, forms together with the existing bound a C=C-double bond.
Rw irrespectively of its occurrence, is selected from the group consisting of hydrogen, halogen, such as fluorine or chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, C1-C4- alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy. Rw is more particularly hydrogen, chlorine, fluorine or methyl and especially hydrogen.
R6 irrespectively of its occurrence, is selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl or ethyl, Ci-C4-alkoxy, such as methoxy or ethoxy, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluormethoxy, and Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, more preferably from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl, even more preferably from fluo- rine, chlorine, Ci-C2-alkyl, such as methyl or ethyl and Ci-C2-haloalkyl such as difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl.
R7 irrespectively of its occurrence, is selected from the group consisting of CN, OH , Ci- C4-alkoxy, such as methoxy or ethoxy, Ci-C4-alkylthio, such as methylsulfanyl or ethylsulfanyl, Ci-C4-haloalkoxy, such as difluoromethoxy or trifluoromethoxy, S(0)nR8a, S(0)nNR17aR17b, NR17aR17b, C(=0)NR 7aR 7 , C(=S)NR 7aR 7 , C(=0)OR8, C(=0)R15, NR 7a-C(=0)R7a, NR 7a- C(=0)OR8a, NR 7a-C(=0)NR 7aR 7 ,
phenyl and phenoxy, where the phenyl ring in the last two mentioned radicals is unsubstituted or carriers 1 , 2, 3, 4 or 5 radicals R10,
it being possible that R7 may also be Ci-C4-alkyl, such as methyl or ethyl, or Ci-C4-haloalkyl, such as difluormethyl, trifluoromethyl, 2,2,2-trifluoroethyl or pentafluoroetyl, if the radical, to which R7 is attached, is C3-C6-cycloalkyl.
R7a hydrogen, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2- fluoro-1 -methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or heptafluoroisopropyl, C3-C6-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and phenyl, where the phenyl ring in the last radicalsis unsubstitued or substituted by 1 , 2 or 3 identical or different radicals R10, which are as defined above or preferably selected from the group consisting of halogen, such as chlorine or fluorine, CN, C1-C4- alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular C1-C2- haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 , 1 -d if I uoroethyl , 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluo- romethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2- trifluoroethoxy.
R7b is preferably selected from the group consisting of halogen, Ci-C4-alkyl, C1-C4- haloalkyl, C3-C6-cycloalkyl, and phenyl, it being possible for phenyl to be unsubstituted, partly or completely halogenated, and where R7b is more particularly fluorine, chlorine, Ci-C4-alkyl, such as methyl, ethyl, propyl, isopropyl or n-butyl, Ci-C4-haloalkyl, especially Ci-C2-fluoroalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difl uoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl.
R7c is preferably selected from the group consisting of Ci-C4-alkoxy, NH2, C1-C4- alkylamino and di-(Ci-C4-alkyl)amino
R8 irrespectively of its occurrence, is selected from the group consisting of C1-C4- alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difl uoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2-fluoro-1 - methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or heptafluoroisopropyl, Ci-C4-alkylcarbonyl, such as acetyl or propionyl, Ci-C4-haloalkylcarbonyl, such as difluoroacetyl or trifluoroacetyl, Ci-C4-alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, 2- butoxycarbonyl, isobutoxycarbonyl or tert.-butoxycarbonyl, NH2-C(0), Ci-C4-alkylamino- carbonyl, such as methylaminocarbonyl or ethylaminocarbonyl, di-(Ci-C4-alkyl)aminocarbonyl, such as dimethylaminocarbonyl, diethylaminocarbonyl, N-methyl-N-ethylaminocarbonyl and the like, phenyl, benzyl, phenylcarbonyl, phenoxycarbonyl and phenylaminocarbonyl, where the phenyl ring in the last five radicals is unsubstitued or substituted by 1 , 2 or 3 identical or different radicals selected from the group consisting of halogen, such as chlorine or fluorine, CN, Ci- C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular C1-C2- haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluo- romethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2- trifluoroethoxy.
R8a irrespectively of its occurrence, is selected from the group consisting of C1-C4- alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, C1-C4- haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2-fluoro-1 - methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or heptafluoroisopropyl, phenyl which is unsubstitued or substituted by 1 , 2, 3 or 4 identical or different radicals R10, which are as defined above or preferably selected from the group consisting of halogen, such as chlorine or fluorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoro- methyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2- trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and C1-C4- haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy.
R8b irrespectively of its occurrence, is selected from the group consisting of C1-C6- haloalkyl, in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 - difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, C3-C6-cycloalkyl, such as cyclobutyl, cyclopropyl, or cyclopentyl, Ci-C6-alkyl, in particular C1-C4- alkyl, such as methyl, ethyl, n-propyl, or n-butyl, or C3-C6-halocycloalkyl, such as 1 - fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 1 -chlorocyclopropyl, 2- chlorocyclopropyl, 2,2-dichlorocyclopropyl, 1 -fluorocyclobutyl, or 1 -fluorocyclopentyl; R8b is in particular Ci-C2-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 1 ,1 -difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl or pentafluoroethyl, or Ci-C4-alkyl, such as methyl, ethyl, n-propyl, or n-butyl.
R9a and R9b irrespectively of their occurrence, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or isobutyl, and Ci-C4-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or NR9aR9b may also be a saturated N-bound 3-, 4-, 5- or 6-membered heterocycle, which in addition to the nitrogen atom may have 1 further heteroatom as ring members, which is selected from O and N and where the N-bound 3-, 4-, 5- or 6-membered heterocycle may be unsubstituted or carry 1 , 2, 3 or 4 radicals selected from Ci-C4-alkyl and Ci-C4-haloalkyl. Examples of such radicals NR9aR9b include, but are not limited to methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2- butylamino, isobutylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, N- methyl-N-ethylamino, N-methyl-N-propylamino, N-methyl-N-n-propylamino, N-methyl-N- isopropylamino, N-methyl-N-n-butylamino, N-methyl-N-2-butylamino, N-methyl-N-isobutylamino, 1 -pyrrolidinyl, 1 -piperidinyl, 1 -piperazinly, 4-methyl-1 -piperazinly and 4-morpholinyl.
R10 halogen, such as chlorine or fluorine, CN, OH, SH, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2- trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and C1-C4- haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy, C1-C4- alkylcarbonyl, such as acetyl or propionyl, Ci-C4-haloalkylcarbonyl, such as difluoroacetyl or trifluoroacetyl, Ci-C4-alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, 2-butoxycarbonyl, isobutoxycarbonyl or tert.-butoxycarbonyl, NH2-C(0), Ci-C4-alkylaminocarbonyl, such as methylaminocarbonyl or ethylaminocarbonyl, di-(Ci-C4-alkyl)aminocarbonyl, such as dimethylaminocarbonyl, diethyla- minocarbonyl, N-methyl-N-ethylaminocarbonyl and the like.
R11, R12 independently of their occurrence, are selected from the group consisting of Ci- C6-alkyl, Ci-C6-alkoxy, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in last two radicals are unsubstituted or substituted with 1 , 2, or 3 identical or different radicals selected from fluorine, chlorine, Ci-C3-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy and Ci-C2-haloalkoxy.
R13, R14 independently of their occurrence, are selected from the group consisting of hydrogen, fluorine, chlorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl or n-butyl, C3-C6- cycloalkyl, such as cyclopropyl, cyclobutyl or cyclopentyl, and phenyl.
R15 Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl, Ci-C4-haloalkyl, such as difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1 ,1 ,2,2-tetrafluoroethyl, pentafluoroethyl, 2-fluoro-1 - methylethyl, 2,2-difluoro-1 -methylethyl, 2,2,2-trifluoro-1 -methylethyl, 2,2,2-trifluoro-1 - (trifluoromethyl)ethyl or heptafluoroisopropyl, phenyl which may be partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci- C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 - difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy. R16 irrespectively of its occurrence, is selected from the group consisting of C1-C4- alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1 , 2 or 3 identical or different radicals selected from the group consisting of halogen, such as chlorine or fluorine, Ci- C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular C1-C2- haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluo- romethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2- trifluoroethoxy.
R17 irrespectively of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, Ci-C6-alkoxy, Ci-C4-haloalkoxy, C3-C6-alkenyl, C3-C6- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1 , 2 or 3 identical or different radicals selected from the group con- sisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, C1-C4- alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy.
R17a and R17b irrespectively of their occurrence, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or isobutyl, and Ci-C4-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 - difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, phenyl or benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1 , 2, 3 or 4 identical or different radicals R10, which are as defined above or preferably selected from the group consisting of halogen, such as chlorine or fluorine, CN, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 -difluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, C1-C4- alkoxy, such as methoxy, ethoxy, n-propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 ,1 -difluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy. NR17aR17b may also be a saturated N- bound 3-, 4-, 5- or 6-membered heterocycle, which in addition to the nitrogen atom may have 1 further heteroatom as ring members, which is selected from O and N and where the N-bound 3- , 4-, 5- or 6-membered heterocycle may be unsubstituted or carry 1 , 2, 3 or 4 radicals selected from Ci-C4-alkyl and Ci-C4-haloalkyl. Examples of such radicals NR17aR17b include, but are not limited to methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, isobutylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, N-methyl-N- ethylamino, N-methyl-N-propylamino, N-methyl-N-n-propylamino, N-methyl-N-isopropylamino, N-methyl-N-n-butylamino, N-methyl-N-2-butylamino, N-methyl-N-isobutylamino, 1-pyrrolidinyl, 1- piperidinyl, 1-piperazinly, 4-methyl-1-piperazinly and 4-morpholinyl.
R17c irrespectively of its occurrence, is selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl- Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals is unsubstitued or substituted by 1, 2 or 3 identical or different radicals selected from the group consisting of halogen, such as chlorine or fluorine, Ci-C4-alkyl, such as methyl, ethyl, n-propyl and isopropyl, Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, Ci-C4-alkoxy, such as methoxy, ethoxy, n- propoxy and isopropoxy, and Ci-C4-haloalkoxy, in particular Ci-C2-haloalkoxy, such as fluoro- methoxy, difluoromethoxy, trifluoromethoxy, 1,1-difluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy or 2,2,2-trifluoroethoxy.
R17d irrespectively of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C3-C6-alkenyl and C3-C6-cycloalkyl-Ci-C4-alkyl
A special group of embodiments relates to the compounds of formula (l)-A.1 a, to their tau- tomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 a.1 to l-A.1a.428).
Another special group of embodiments relates to the compounds of formula (l)-A.2a, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1d.1), (1d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.2a.1 to l-A.2a.428).
A special group of embodiments relates to the compounds of formula (l)-A.1 b, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 b.1 to I- A.1b.428).
Another special group of embodiments relates to the compounds of formula (l)-A.2b, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.2b.1 to l-A.2b.428).
A special group of embodiments relates to the compounds of formula (l)-A.1c, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 c.1 to I-A.1 c.428).
Another special group of embodiments relates to the compounds of formula (l)-A.2c, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (com- pounds l-A.2c.1 to l-A.2c.428).
A special group of embodiments relates to the compounds of formula (l)-A.1d, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds I-A.1 d.1 to l-A.1d.428).
Another special group of embodiments relates to the compounds of formula (l)-A.2d, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.2d.1 to l-A.2d.428).
A special group of embodiments relates to the compounds of formula (l)-A.3a, to their tau- tomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3a.1 to l-A.3a.428).
Another special group of embodiments relates to the compounds of formula (l)-A.4a, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.4a.1 to l-A.4a.428).
A special group of embodiments relates to the compounds of formula (l)-A.3b, to their tau- tomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3b.1 to l-A.3b.428).
Another special group of embodiments relates to the compounds of formula (l)-A.4b, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.4b.1 to l-A.4b.428).
A special group of embodiments relates to the compounds of formula (l)-A.3c, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3c.1 to l-A.3c.428).
Another special group of embodiments relates to the compounds of formula (l)-A.4c, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.4c.1 to l-A.4c.428).
A special group of embodiments relates to the compounds of formula (l)-A.3d, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (compounds l-A.3d.1 to l-A.3d.428).
Another special group of embodiments relates to the compounds of formula (l)-A.4d, to their tautomers, to their stereoisomers and to their salts, where R1 and Cyc are as defined above, in particular as defined for groups (1a), (1b), (1c), (1d), (1a.1), (1a.2), (1a.3), (1a.4), (1a.5), (1a.6), (1a.7), (1a.8), (1a.9), (1a.10), (1a.11), (1b.1), (1b.2), (1b.3), (1b.4), (1b.5), (1b.6), (1b.7), (1b.8), (1c.1), (1 d.1 ), (1 d.2) and (1e.1) of embodiments and where R1 and Cyc have in particular one of the meanings given in any of lines 1 to 428 of the following table A (com- pounds l-A.4d.1 to l-A.4d.428).
Figure imgf000061_0001
I-A.1a l-A.2a
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000062_0003
Figure imgf000062_0004
Figure imgf000062_0005
l-A.3b l-A.4b
Figure imgf000063_0001
Figure imgf000063_0002
l-A.3d l-A.4d
Table A
# R Cyc
1 H Cyc-1
2 H Cyc-2
3 H Cyc-3
4 H Cyc-4
5 H Cyc-5
6 H Cyc-6
7 H Cyc-7
8 H Cyc-8
9 H Cyc-9
10 H Cyc-10
1 1 H Cyc-1 1
12 H Cyc-12
13 H Cyc-13
14 H Cyc-14
15 H Cyc-15
16 H Cyc-16
17 H Cyc-17
18 H Cyc-18
Figure imgf000063_0003
Figure imgf000063_0004
19 H Cyc-19 R Cyc # R Cyc # R Cyc
H Cyc-56 89 H Cyc-89 122 H Cyc-122
H Cyc-57 90 H Cyc-90 123 H Cyc-123
H Cyc-58 91 H Cyc-91 124 H Cyc-124
H Cyc-59 92 H Cyc-92 125 H Cyc-125
H Cyc-60 93 H Cyc-93 126 H Cyc-126
H Cyc-61 94 H Cyc-94 127 H Cyc-127
H Cyc-62 95 H Cyc-95 128 H Cyc-128
H Cyc-63 96 H Cyc-96 129 H Cyc-129
H Cyc-64 97 H Cyc-97 130 H Cyc-130
H Cyc-65 98 H Cyc-98 131 H Cyc-131
H Cyc-66 99 H Cyc-99 132 H Cyc-132
H Cyc-67 100 H Cyc-100 133 H Cyc-133
H Cyc-68 101 H Cyc-101 134 H Cyc-134
H Cyc-69 102 H Cyc- 102 135 H Cyc-135
H Cyc-70 103 H Cyc-103 136 H Cyc-136
H Cyc-71 104 H Cyc- 104 137 H Cyc-137
H Cyc-72 105 H Cyc-105 138 H Cyc-138
H Cyc-73 106 H Cyc-106 139 H Cyc-139
H Cyc-74 107 H Cyc-107 140 H Cyc-140
H Cyc-75 108 H Cyc-108 141 H Cyc-141
H Cyc-76 109 H Cyc-109 142 H Cyc-142
H Cyc-77 1 10 H Cyc-1 10 143 H Cyc-143
H Cyc-78 1 1 1 H Cyc-1 1 1 144 H Cyc-144
H Cyc-79 1 12 H Cyc-1 12 145 H Cyc-145
H Cyc-80 1 13 H Cyc-1 13 146 H Cyc-146
H Cyc-81 1 14 H Cyc-1 14 147 H Cyc-147
H Cyc-82 1 15 H Cyc-1 15 148 H Cyc-148
H Cyc-83 1 16 H Cyc-1 16 149 H Cyc-149
H Cyc-84 1 17 H Cyc-1 17 150 H Cyc-150
H Cyc-85 1 18 H Cyc-1 18 151 H Cyc-151
H Cyc-86 1 19 H Cyc-1 19 152 H Cyc-152
H Cyc-87 120 H Cyc-120 153 H Cyc-153
H Cyc-88 121 H Cyc-121 154 H Cyc-154 # R Cyc # R Cyc # R Cyc
155 H Cyc-155 188 H Cyc-188 221 CHs Cyc-7
156 H Cyc- 156 189 H Cyc- 189 222 CHs Cyc-8
157 H Cyc- 157 190 H Cyc-190 223 CHs Cyc-9
158 H Cyc- 158 191 H Cyc-191 224 CHs Cyc-10
159 H Cyc- 159 192 H Cyc-192 225 CHs Cyc-1 1
160 H Cyc- 160 193 H Cyc-193 226 CHs Cyc-12
161 H Cyc-161 194 H Cyc-194 227 CHs Cyc-13
162 H Cyc- 162 195 H Cyc-195 228 CHs Cyc-14
163 H Cyc-163 196 H Cyc-196 229 CHs Cyc-15
164 H Cyc- 164 197 H Cyc-197 230 CHs Cyc-16
165 H Cyc- 165 198 H Cyc-198 231 CHs Cyc-17
166 H Cyc-166 199 H Cyc-199 232 CHs Cyc-18
167 H Cyc- 167 200 H Cyc-200 233 CHs Cyc-19
168 H Cyc-168 201 H Cyc-201 234 CHs Cyc-20
169 H Cyc-169 202 H Cyc-202 235 CHs Cyc-21
170 H Cyc- 170 203 H Cyc-203 236 CHs Cyc-22
171 H Cyc-171 204 H Cyc-204 237 CHs Cyc-23
172 H Cyc-172 205 H Cyc-205 238 CHs Cyc-24
173 H Cyc- 173 206 H Cyc-206 239 CHs Cyc-25
174 H Cyc-174 207 H Cyc-207 240 CHs Cyc-26
175 H Cyc- 175 208 H Cyc-208 241 CHs Cyc-27
176 H Cyc- 176 209 H Cyc-209 242 CHs Cyc-28
177 H Cyc-177 210 H Cyc-210 243 CHs Cyc-29
178 H Cyc- 178 21 1 H Cyc-21 1 244 CHs Cyc-30
179 H Cyc- 179 212 H Cyc-212 245 CHs Cyc-31
180 H Cyc- 180 213 H Cyc-213 246 CHs Cyc-32
181 H Cyc-181 214 H Cyc-214 247 CHs Cyc-33
182 H Cyc- 182 215 CHs Cyc-1 248 CHs Cyc-34
183 H Cyc- 183 216 CHs Cyc-2 249 CHs Cyc-35
184 H Cyc- 184 217 CHs Cyc-3 250 CHs Cyc-36
185 H Cyc- 185 218 CHs Cyc-4 251 CHs Cyc-37
186 H Cyc- 186 219 CHs Cyc-5 252 CHs Cyc-38
187 H Cyc- 187 220 CHs Cyc-6 253 CHs Cyc-39 # R Cyc # R Cyc # R Cyc
254 CHs Cyc-40 287 CHs Cyc-73 320 CHs Cyc-106
255 CHs Cyc-41 288 CHs Cyc-74 321 CHs Cyc-107
256 CHs Cyc-42 289 CHs Cyc-75 322 CHs Cyc-108
257 CHs Cyc-43 290 CHs Cyc-76 323 CHs Cyc-109
258 CHs Cyc-44 291 CHs Cyc-77 324 CHs Cyc-1 10
259 CHs Cyc-45 292 CHs Cyc-78 325 CHs Cyc-1 1 1
260 CHs Cyc-46 293 CHs Cyc-79 326 CHs Cyc-1 12
261 CHs Cyc-47 294 CHs Cyc-80 327 CHs Cyc-1 13
262 CHs Cyc-48 295 CHs Cyc-81 328 CHs Cyc-1 14
263 CHs Cyc-49 296 CHs Cyc-82 329 CHs Cyc-1 15
264 CHs Cyc-50 297 CHs Cyc-83 330 CHs Cyc-1 16
265 CHs Cyc-51 298 CHs Cyc-84 331 CHs Cyc-1 17
266 CHs Cyc-52 299 CHs Cyc-85 332 CHs Cyc-1 18
267 CHs Cyc-53 300 CHs Cyc-86 333 CHs Cyc-1 19
268 CHs Cyc-54 301 CHs Cyc-87 334 CHs Cyc-120
269 CHs Cyc-55 302 CHs Cyc-88 335 CHs Cyc-121
270 CHs Cyc-56 303 CHs Cyc-89 336 CHs Cyc-122
271 CHs Cyc-57 304 CHs Cyc-90 337 CHs Cyc-123
272 CHs Cyc-58 305 CHs Cyc-91 338 CHs Cyc-124
273 CHs Cyc-59 306 CHs Cyc-92 339 CHs Cyc-125
274 CHs Cyc-60 307 CHs Cyc-93 340 CHs Cyc-126
275 CHs Cyc-61 308 CHs Cyc-94 341 CHs Cyc-127
276 CHs Cyc-62 309 CHs Cyc-95 342 CHs Cyc-128
277 CHs Cyc-63 310 CHs Cyc-96 343 CHs Cyc-129
278 CHs Cyc-64 31 1 CHs Cyc-97 344 CHs Cyc-130
279 CHs Cyc-65 312 CHs Cyc-98 345 CHs Cyc-131
280 CHs Cyc-66 313 CHs Cyc-99 346 CHs Cyc-132
281 CHs Cyc-67 314 CHs Cyc-100 347 CHs Cyc-133
282 CHs Cyc-68 315 CHs Cyc-101 348 CHs Cyc-134
283 CHs Cyc-69 316 CHs Cyc-102 349 CHs Cyc-135
284 CHs Cyc-70 317 CHs Cyc-103 350 CHs Cyc-136
285 CHs Cyc-71 318 CHs Cyc-104 351 CHs Cyc-137
286 CHs Cyc-72 319 CHs Cyc-105 352 CHs Cyc-138 # R Cyc # R Cyc # R Cyc
353 CHs Cyc-' 139 379 CHs Cyc- 165 405 CHs Cyc-191
354 CHs Cyc-' 140 380 CHs Cyc- 166 406 CHs Cyc-192
355 CHs Cyc-' 141 381 CHs Cyc- 167 407 CHs Cyc-193
356 CHs Cyc-' 142 382 CHs Cyc- 168 408 CHs Cyc-194
357 CHs Cyc-' 143 383 CHs Cyc- 169 409 CHs Cyc-195
358 CHs Cyc-' 144 384 CHs Cyc- 170 410 CHs Cyc-196
359 CHs Cyc-' 145 385 CHs Cyc-171 41 1 CHs Cyc-197
360 CHs Cyc-' 146 386 CHs Cyc-172 412 CHs Cyc-198
361 CHs Cyc-' 147 387 CHs Cyc- 173 413 CHs Cyc-199
362 CHs Cyc-' 148 388 CHs Cyc-174 414 CHs Cyc-200
363 CHs Cyc-' 149 389 CHs Cyc- 175 415 CHs Cyc-201
364 CHs Cyc-' 150 390 CHs Cyc- 176 416 CHs Cyc-202
365 CHs Cyc-' 151 391 CHs Cyc-177 417 CHs Cyc-203
366 CHs Cyc-' 152 392 CHs Cyc- 178 418 CHs Cyc-204
367 CHs Cyc-' 153 393 CHs Cyc- 179 419 CHs Cyc-205
368 CHs Cyc-' 154 394 CHs Cyc- 180 420 CHs Cyc-206
369 CHs Cyc-' 155 395 CHs Cyc-181 421 CHs Cyc-207
370 CHs Cyc-' 156 396 CHs Cyc- 182 422 CHs Cyc-208
371 CHs Cyc-' 157 397 CHs Cyc- 183 423 CHs Cyc-209
372 CHs Cyc-' 158 398 CHs Cyc- 184 424 CHs Cyc-210
373 CHs Cyc-' 159 399 CHs Cyc- 185 425 CHs Cyc-21 1
374 CHs Cyc-' 160 400 CHs Cyc- 186 426 CHs Cyc-212
375 CHs Cyc-' 161 401 CHs Cyc- 187 427 CHs Cyc-213
376 CHs Cyc-' 162 402 CHs Cyc- 188 428 CHs Cyc-214
377 CHs Cyc-' 163 403 CHs Cyc- 189
378 CHs Cyc-' 164 404 CHs Cyc-190
In table A, the following abbreviations for radicals Cyc are used:
Cyc-1 thiazol-2-yl
Cyc-2 thiazolin-2-yl
Cyc-3 4-methylthiazol-2-yl
Cyc-4 4-ethylthiazol-2-yl
Cyc-5 4-(2-propyl)thiazol-2-yl
Cyc-6 4-(cyclopropyl)thiazol-2-yl Cyc-7 4-trifluoromethylthiazol-2-yl
Cyc-8 4-(2,2,2-trifluoroethyl)thiazol-2-yl
Cyc-9 4-nitrothiazol-2-yl
Cyc-10 4-chlorothiazol-2-yl
Cyc-1 1 4-methylsulfanylthiazol-2-yl
Cyc-12 4-(4-chlorophenyl)thiazol-2-yl
Cyc-13 4-(3-chlorophenyl)thiazol-2-yl
Cyc-14 4-(3-trifluoromethyl-phenyl)thiazol-2-yl
Cyc-15 4-(3-trifluoromethyl-phenyoxy)thiazol-2-yl
Cyc-16 4-(isoxazol-3-yl)thiazol
Cyc-17 4-phenylthiazol-2-yl
Cyc-18 4-(4-chlorophenoxy)thiazol-2-yl
Cyc-19 4-phenoxythiazol-2-yl
Cyc-20 4-(4-chlorophenyl)methylthiazol-2-yl
Cyc-21 4-benzylthiazol-2-yl
Cyc-22 4-(4-chlorophenyl)sulfonylthiazol-2-yl
Cyc-23 4,5-dimethylthiazol-2-yl
Cyc-24 5-methylthiazol-2-yl
Cyc-25 5-ethylthiazol-2-yl
Cyc-26 5-(2-propyl)thiazol-2-yl
Cyc-27 5-(cyclopropyl)thiazol-2-yl
Cyc-28 5-trifluoromethylthiazol-2-yl
Cyc-29 5-(2,2,2-trifluoroethyl)thiazol-2-yl
Cyc-30 5-nitrothiazol-2-yl
Cyc-31 5-chlorothiazol-2-yl
Cyc-32 5-methylsulfanylthiazol-2-yl
Cyc-33 5-(4-chlorophenyl)thiazol-2-yl
Cyc-34 5-(3-trifluoromethyl-phenyl)thiazol-2-yl
Cyc-35 5-(3-trifluoromethyl-phenoxy)thiazol-2-yl
Cyc-36 5-(isoxazol-3-yl)thiazol
Cyc-37 5-phenylthiazol-2-yl
Cyc-38 5-(4-chlorophenoxy)thiazol-2-yl
Cyc-39 5-phenoxythiazol-2-yl
Cyc-40 5-(4-chlorophenyl)-methylthiazol-2-yl
Cyc-41 5-benzylthiazol-2-yl
Cyc-42 5-(3-chlorophenyl)thiazol-2-yl
Cyc-43 5-(4-chlorophenyl)sulfonylthiazol-2-yl
Cyc-44 oxazol-2-yl Cyc-45 oxazolin-2-yl
Cyc-46 4-methyloxazol-2-yl
Cyc-47 4-ethyloxazol-2-yl
Cyc-48 4-(2-propyl)oxazol-2-yl
Cyc-49 4-(cyclopropyl)oxazol-2-yl
Cyc-50 4-trifluoromethyloxazol-2-yl
Cyc-51 4-(2,2,2-trifluoroethyl)oxazol-2-yl
Cyc-52 4-nitrooxazol-2-yl
Cyc-53 4-chlorooxazol-2-yl
Cyc-54 4-methylsulfanyloxazol-2-yl
Cyc-55 4-(4-chlorop enyl)oxazol-2-yl
Cyc-56 4-(3-chlorophenyl)oxazol-2-yl
Cyc-57 4-(3-trifluoromethyl-phenyl)oxazol-2-yl
Cyc-58 4-(3-trifluoromethyl-phenyoxy)oxazol-2-yl Cyc-59 4-(isoxazol-3-yl)oxazol
Cyc-60 4-phenyloxazol-2-yl
Cyc-61 4-(4-chlorophenoxy)oxazol-2-yl
Cyc-62 4-phenoxyoxazol-2-yl
Cyc-63 4-(4-chlorophenyl)methyloxazol-2-yl Cyc-64 4-benzyloxazol-2-yl
Cyc-65 4-(4-chlorophenyl)sulfonyloxazol-2-yl
Cyc-66 4,5-dimethyloxazol-2-yl
Cyc-67 5-methyloxazol-2-yl
Cyc-68 5-ethyloxazol-2-yl
Cyc-69 5-(2-propyl)oxazol-2-yl
Cyc-70 5-(cyclopropyl)oxazol-2-yl
Cyc-71 5-trifluoromethyloxazol-2-yl
Cyc-72 5-(2,2,2-trifluoroethyl)oxazol-2-yl
Cyc-73 5-nitrooxazol-2-yl
Cyc-74 5-chlorooxazol-2-yl
Cyc-75 5-methylsulfanyloxazol-2-yl
Cyc-76 5-(4-chlorophenyl)oxazol-2-yl
Cyc-77 5-(3-trifluoromethyl-phenyl)oxazol-2-yl
Cyc-78 5-(3-trifluoromethyl-phenoxy)oxazol-2-yl Cyc-79 5-(isoxazol-3-yl)oxazol
Cyc-80 5-phenyloxazol-2-yl
Cyc-81 5-(4-chlorop enoxy)oxazol-2-yl
Cyc-82 5-phenoxyoxazol-2-yl Cyc-83 5-(4-chlorophenyl)-methyloxazol-2-yl
Cyc-84 5-benzyloxazol-2-yl
Cyc-85 5-(3-chlorophenyl)oxazol-2-yl
Cyc-86 5-(4-chlorophenyl)sulfonyloxazol-2-yl
Cyc-87 1 ,3,4-thiadiazol-2-yl
Cyc-88 5-methyl-1 ,3,4-thiadiazol-2-yl
Cyc-89 5-ethyl-1 ,3,4-thiadiazol-2-yl
Cyc-90 5-(2-propyl)-1 ,3,4-thiadiazol-2-yl
Cyc-91 5-(cyclopropyl)-1 ,3,4-thiadiazol-2-yl
Cyc-92 5-trifluoromethyl-1 ,3,4-thiadiazol-2-yl
Cyc-93 5-(2,2,2-trifluoroethyl)-1 ,3,4-thiadiazol-2-yl
Cyc-94 5-nitro-1 ,3,4-thiadiazol-2-yl
Cyc-95 5-chloro-1 ,3,4-thiadiazol-2-yl
Cyc-96 5-methyl-1 ,3,4-thiadiazol-2-yl
Cyc-97 5-methylsulfanyl-1 ,3,4-thiadiazol-2-yl
Cyc-98 5-(4-chlorophenyl)-1 ,3,4-thiadiazol-2-yl
Cyc-99 5-(3-trifluoromethylphenyl)-1 ,3,4-thiadiazol-2-yl
Cyc-100 5-(3-trifluoromethyl-phenoxy)-1 ,3,4-thiadiazol-2-yl
Cyc-101 5-(isoxazol-3-yl)-1 ,3,4-thiadiazol-2-yl
Cyc-102 5-phenyl-1 ,3,4-thiadiazol-2-yl
Cyc-103 5-(4-chlorophenoxy)-1 ,3,4-thiadiazol-2-yl
Cyc-104 5-phenoxy-1 ,3,4-thiadiazol-2-yl
Cyc-105 5-(4-chlorophenyl)-methyl-1 ,3,4-thiadiazol-2-yl
Cyc-106 5-benzyl-1 ,3,4-thiadiazol-2-yl
Cyc-107 5-(3-chlorophenyl)-1 ,3,4-thiadiazol-2-yl
Cyc-108 5-(4-chlorophenyl)sulfonyl-1 ,3,4-thiadiazol-2-yl
Cyc-109 1 ,2,4-thiadiazol-3-yl
Cyc-1 10 5-methyl-1 ,2,4-thiadiazol-3-yl
Cyc-1 1 1 5-ethyl-1 ,2,4-thiadiazol-3-yl
Cyc-1 12 5-(2-propyl)-1 ,2,4-thiadiazol-3-yl
Cyc-1 13 5-(cyclopropyl)-1 ,2,4-thiadiazol-3-yl
Cyc-1 14 5-trifluoromethyl-1 ,2,4-thiadiazol-3-yl
Cyc-1 15 5-(2,2,2-trifluoroethyl)-1 ,2,4-thiadiazol-3-yl
Cyc-1 16 5-nitro-1 ,2,4-thiadiazol-3-yl
Cyc-1 17 5-chloro-1 ,2,4-thiadiazol-3-yl
Cyc-1 18 5-methyl-1 ,2,4-thiadiazol-3-yl
Cyc-1 19 5-methylsulfanyl-1 ,2,4-thiadiazol-3-yl
Cyc-120 5-(4-chlorophenyl)-1 ,2,4-thiadiazol-3-yl Cyc-' 21 5-(3-trifluoromethylphenyl)-1 ,2,4-thiadiazol-3-yl
Cyc-' 22 5-(3-trifluoromethyl-phenoxy)-1 ,2,4-thiadiazol-3-yl
Cyc-' 23 5-(isoxazol-3-yl)-1 ,2,4-thiadiazol-3-yl
Cyc-' 24 5-phenyl-1 ,2,4-thiadiazol-3-yl
Cyc-' 25 5-(4-chlorop enoxy)-1 ,2,4-thiadiazol-3-yl
Cyc-' 26 5-phenoxy-1 ,2,4-thiadiazol-3-yl
Cyc-' 127 5-(4-chlorophenyl)-methyl-1 ,2,4-thiadiazol-3-yl
Cyc-' 128 5-benzyl-1 ,2,4-thiadiazol-3-yl
Cyc-' 129 5-(3-chlorophenyl)-1 ,2,4-thiadiazol-3-yl
Cyc-' 130 5-(4-chlorophenyl)sulfonyl-1 ,2,4-thiadiazol-3-yl
Cyc-' 131 1 ,3,4-oxadiazol-2-yl
Cyc-' 132 5-methyl-1 ,3,4-oxadiazol-2-yl
Cyc-' 133 5-ethyl-1 ,3,4-oxadiazol-2-yl
Cyc- 134 5-(2-propyl)-1 ,3,4-oxadiazol-2-yl
Cyc- 135 5-(cyclopropyl)-1 ,3,4-oxadiazol-2-yl
Cyc- 136 5-trifluoromethyl-1 ,3,4-oxadiazol-2-yl
Cyc- 137 5-(2,2,2-trifluoroethyl)-1 ,3,4-oxadiazol-2-yl
Cyc- 138 5-nitro-1 ,3,4-oxadiazol-2-yl
Cyc- 139 5-chloro-1 ,3,4-oxadiazol-2-yl
Cyc- 140 5-methyl-1 ,3,4-oxadiazol-2-yl
Cyc- 141 5-methylsulfanyl-1 ,3,4-oxadiazol-2-yl
Cyc- 142 5-(4-chlorophenyl)-1 ,3,4-oxadiazol-2-yl
Cyc- 143 5-(3-trifluoromethylphenyl)-1 ,3,4-oxadiazol-2-yl
Cyc- 144 5-(3-trifluoromethyl-phenoxy)-1 ,3,4-oxadiazol-2-yl
Cyc- 145 5-(isoxazol-3-yl)-1 ,3,4-oxadiazol-2-yl
Cyc- 146 5-phenyl-1 ,3,4-oxadiazol-2-yl
Cyc- 147 5-(4-chlorop enoxy)-1 ,3,4-oxadiazol-2-yl
Cyc- 148 5-phenoxy-1 ,3,4-oxadiazol-2-yl
Cyc- 149 5-(4-chlorophenyl)-methyl-1 ,3,4-oxadiazol-2-yl
Cyc- 150 5-benzyl-1 ,3,4-oxadiazol-2-yl
Cyc- 151 5-(3-chlorophenyl)-1 ,3,4-oxadiazol-2-yl
Cyc- 152 5-(4-chlorop enyl)sulfonyl-1 ,3,4-oxadiazol-2-yl
Cyc- 153 1 ,2,4-oxadiazol-3-yl
Cyc- 154 5-methyl- ,2,4-oxadiazol-3-yl
Cyc- 155 5-ethyl-1 ,2,4-oxadiazol-3-yl
Cyc- 156 5-(2-propyl)-1 ,2,4-oxadiazol-3-yl
Cyc- 157 5-(cyclopropyl)-1 ,2,4-oxadiazol-3-yl
Cyc- 158 5-trifluoromethyl-1 ,2,4-oxadiazol-3-yl Cyc-' 59 5-(2,2,2-trifluoroethyl)-1 ,2,4-oxadiazol-3-yl
Cyc-' 60 5-nitro-1 ,2,4-oxadiazol-3-yl
Cyc-' 61 5-chloro-1 ,2,4-oxadiazol-3-yl
Cyc-' 62 5-methyl-1 ,2,4-oxadiazol-3-yl
Cyc-' 63 5-methylsulfanyl-1 ,2,4-oxadiazol-3-yl
Cyc-' 64 5-(4-chlorop enyl)-1 ,2,4-oxadiazol-3-yl
Cyc-" 165 5-(3-trifluoromethylphenyl)-1 ,2,4-oxadiazol-3-yl
Cyc-' 166 5-(3-trifluoromethyl-phenoxy)-1 ,2,4-oxadiazol-3-yl
Cyc-' 167 5-(isoxazol-3-yl)-1 ,2,4-oxadiazol-3-yl
Cyc-' 168 5-phenyl-1 ,2,4-oxadiazol-3-yl
Cyc-' 169 5-(4-chlorophenoxy)-1 ,2,4-oxadiazol-3-yl
Cyc-' 170 5-phenoxy-1 ,2,4-oxadiazol-3-yl
Cyc-' 171 5-(4-chlorop enyl)-methyl-1 ,2,4-oxadiazol-3-yl
Cyc- 172 5-benzyl-1 ,2,4-oxadiazol-3-yl
Cyc- 173 5-(3-chlorophenyl)-1 ,2,4-oxadiazol-3-yl
Cyc- 174 5-(4-chlorophenyl)sulfonyl-1 ,2,4-oxadiazol-3-yl
Cyc- 175 4-ethoxycarbonylthiazol-2-yl
Cyc- 176 4-carboxythiazol-2-yl
Cyc- 177 4-formylthiazol-2-yl
Cyc- 178 4-(hydroxyiminomethyl)thiazol-2-yl
Cyc- 179 4-(methoxyiminomethyl)thiazol-2-yl
Cyc - 180 4-(diethylcarbamoyl)thiazol-2-yl
Cyc- 181 4-(methylcarbamoyl)thiazol-2-yl
Cyc- 182 4-(methylaminomethyl)thiazol-2-yl
Cyc- 183 4-(hydroxymethyl)thiazol-2-yl
Cyc- 184 4-(acetoxyiminomethyl)thiazol-2-yl
Cyc- 185 4-cyanothiazol-2-yl
Cyc- 186 4-[[methyl-(2,2,2-trifluoroacetyl)amino]methyl]thiazol-2-yl
Cyc- 187 4-(1 -hydroxyethyl)thiazol-2-yl
Cyc- 188 4-(acetoxymethyl)thiazol-2-yl
Cyc- 189 4-(methoxymethyl)thiazol-2-yl
Cyc- 190 4-[(methylcarbamoylhydrazono)methyl]thiazol-2-yl
Cyc- 191 4-[[acetyl(methyl)amino]methyl]thiazol-2-yl
Cyc- 192 4-[(2,2,2-trifluoroethylcarbamoylhydrazono)methyl]thiazol-2-yl
Cyc- 193 4-(acetamidomethyl)thiazol-2-yl
Cyc- 194 4-(1 -acetoxyethyl)thiazol-2-yl Cyc-195 4-(1 -methoxyethyl)thiazol-2-yl
Cyc-196 4-[(acetylhydrazono)methyl]thiazol-2-yl
Cyc-197 4-[(benzoylhydrazono)methyl]thiazol-2-yl
Cyc-198 4,5-di hyd rothi azol-2-yl
Cyc-199 5-(trifluoromethyl)-1 ,3,4-thiadiazol-2-yl
Cyc-200 1 ,2,4-thiadiazol-5-yl
Cyc-201 3-bromo-1 ,2,4-thiadiazol-5-yl
Cyc-202 3-chloro-1 ,2,4-thiadiazol-5-yl
Cyc-203 3-methyl-1 ,2,4-thiadiazol-5-yl
Cyc-204 4-cyanopyrimidin-2-yl
Cyc-205 4,6-dichloropyrimidin-2-yl
Cyc-206 4,6-dimethoxypyrimidin-2-yl
Cyc-207 5-methoxy-2-methylsulfonyl-pynmidin-4-yl
Cyc-208 5-chloro-6-ethyl-2-methylsulfonyl-pyrimidin-4-yl
Cyc-209 oxazol-2-yl
Cyc-210 4-cyanooxazol-5-yl
Cyc-21 1 5-(4-chlorophenyl)-1 ,3,4-oxadiazol-2-yl
Cyc-212 5-ethyl-1 ,2,4-oxadiazol-3-yl
Cyc-213 3-phenyl-1 ,2,4-oxadiazol-5-yl
Cyc-214 4-cyano-2,3-dihydrothiophen-5-yl
The compounds of formula (I) according to the present invention can be prepared e.g. according the preparation methods and preparation schemes as described below. Compounds of formula (I) according to the present invention can be prepared by standard methods of organic chemistry e.g. by the preparation methods and preparation schemes as described below. The definitions of Het, Cyc, W, W2, W3, W4, R1 and R2 of the molecular structures given in schemes 1 to 5 are as defined above. Room temperature means a temperature range between about 20 and 25 °C.
An examples of a general method for the preparation of compounds of formula (I) is shown below in Scheme 1 . The synthesis of compounds of formula (I) can be achieved by reac- tion of the imine functionality in compounds of formula (IV) with a heterocyclic compound of formula (V) by analogy to the method described in Anderson, K.W. et al., Angew.Chem.lnt.Ed. 2006, 45, 6523-6527. Examples of suitable leaving groups LG2 in the compounds of formula (V) include, but are not limited to: halogen, such as chlorine or bromine, Ci-C4-alkyl sulfonate such as methyl- or ethyl sulfonate, Ci-C4-haloalkyl sulfonate, such as trifluoromethyl sulfonate, aryl sulfonate, such as phenyl sulfonate or tolylsulfonate, Ci-C4-alkyl phosphonate, Ci-C4-haloalkyl phosphate.
Preparation of the compounds of formula (IV) can be achieved, for example, by alkylation of the appropriate 2-amino-heterocycle precursor compound (III) with the appropriate reagent of formula (II). The reaction is preferably carried out in polar solvents such as acetonitrile, acetone, 1 ,4-dioxane, tetrahydrofuran, N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N- methylpyrolidinone or a C1-C6 alcohol or inert solvents such as: dichloromethane, 1 ,2- dichloroethane, 1 ,2-dimethoxyethane, carbon tetrachloride, tetrahydrofuran, toluene, xylenes, mesitylene, cymene, tetralone ranging between room temperature and the reflux temperature of the solvent. Representative reaction conditions for the alkylation of compounds analogous to compounds of formula (III) are given in Tett. Lett. 201 1 , 52(23), 3033-3037. Examples of suitable leaving groups LG in formula (II) include, but are not limited to: halogen, such as chlorine or bromine, In compounds of formula (II).
Scheme 1 :
Figure imgf000074_0001
Compounds of formula (I) can also be prepared by reaction of an immonium compound of formula (IVa) with an amine substituted heterocyclic compound of formula (Va) as outlined in scheme 2. In formula (IVa), D may be a leaving group as for example S-Ci-C6-alkyl, S(=0)2-Ci- C6-alkyl, halogen. Analogous reactions have been disclosed in US 5,328,915. Compounds of formula (IVa) can be prepared by reaction of an alkylation reagent of formula (II) with a compound of formula (Ilia), as for example described by Bennasar, M.-Lluisa et al, Chemical Communications (Cambridge), (24), 2459-2460; 2000 (for D = halogen) or in EP 390099 (for D = S- d-Ce-alkyl). Scheme 2:
Figure imgf000075_0001
Compounds of formula I can also be prepared as outlined in scheme 3 by reaction of a ketone of formula (IVb) with a compound (Va), as for example described by Stivers et al, WO 2006135763 or by Fattorusso et al, J. Med. Chem. 2008, 51 , 1333-1343. Compounds of formula (IVb) can be prepared by reaction of a compound of formula II with a compound of formula Ilia in analogy to the methods described in schemes 1 or 2.
Scheme 3
Figure imgf000075_0002
Compounds of formula I, where Cyc is an optionally substituted 2-thiazolyl radical can also be prepared as outlined in scheme 4 starting from the compounds of formula (IV). Reaction of the compound of formula (IV) with the isothiocyanate compound (VI) results in a car- bamoiylthiocarbamate compound of formula (VII), which can be hydrolyzed to the corresponding thio-urea compound of formula (Vila). Compound of formula (Vila) can be cyclized by reaction with an alpha-halomethyl ketone of formula (VIII), wherein R3' and R3" are hydrogen or have one of the meanings given for R3. Suitable reaction conditions can be taken from Madsen et al., J.Med. Chem 2009, 52, 2989-3000; Liebscher, J. et al. Synthesis, 1989, 968-970.
Scheme 4:
Figure imgf000076_0001
\r (vii)
Figure imgf000076_0002
Compounds of the formula (I), where Cyc is substituted 2,3-dihydrothiophen-5-yl can be prepared as outlined in scheme 5 by reacting a compound of the formula (IV) with a 1 - cyclopropanecarboxylic acid of the formula (IX) wherein each R3a, independently of its occurrence, is hydrogen or has one of the meanings given for R3 to obtain a compound of formula (X). The reaction is preferably carried out in the presence of a coupling reagent such as propylphosphonic acid or propyl phosphonic anhydride. Compound of formula (X) is treated with a thionating agent such as P4S10 to give the compound of formula (I), where Cyc is substituted 2,3-dihydrothiophen-5-yl.
Scheme 5:
Figure imgf000076_0003
(I) Compounds of the formula (I), where Cyc is optionally substituted thiophen-2-yl can be prepared by aromatization of compounds of formula (I), wherein Cyc is substituted 2,3- dihydrothiophen-5-yl, with DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) as for example described by Flynn, Bernard L; Flynn, Guy P; Hamel, Ernest; Jung; Bioorganic and Medicinal Chemistry Letters; vol. 1 1 ; nb. 17; (2001 ); p. 2341 - 2343.
If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or the respective precursor. For example, in individual cases, certain compounds of formula (I) can advantageously be prepared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystalliza- tion or trituration with an appropriate solvent.
As used herein, the term "compound(s) of the present invention" or "compound(s) accord- ing to the invention" refers to the compound(s) of formula (I) as defined above, which are also referred to as "compound(s) of formula I" or "compound(s) I" or "formula I compound(s)", and includes their salts, tautomers and stereoisomers.The compounds of the formula (I) and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
The compounds of the formula (I) are especially suitable for efficiently combating insects, in particular the following pests:
Insects from the order of the lepidopterans (Lepidoptera), for example Acronicta major, Adoxophyes orana, Aedia leucomelas, Agrotis spp. such as Agrotis fucosa, Agrotis segetum, Agrotis ypsilon; Alabama argillacea, Anticarsia gemmatalis, Anticarsia spp., Argyresthia con- jugella, Autographa gamma, Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius,
Cacoecia murinana, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp. such as Chilo suppressalis; Choristoneura fumiferana, Choristoneura occidental is, Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cydia pomonella, Dendro- limus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Ephestia cautella, Ephestia kuehniella, Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Feltia spp. such as Feltia subterranean; Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Helicoverpa spp. such as Helicoverpa armigera, Helicoverpa zea; Heliothis spp. such as Heliothis armigera, Heliothis virescens, Heliothis zea; Hellula un- dalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homona magnanima, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fis- cellaria, Laphygma spp. such as Laphygma exigua; Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lithophane antennata, Lobesia botrana, Loxagrotis albicosta, Loxo- stege sticticalis, Lymantria spp. such as Lymantria dispar, Lymantria monacha; Lyonetia clerkel- la, Malacosoma neustria, Mamestra spp. such as Mamestra brassicae; Mods repanda, Mythim- na separata, Orgyia pseudotsugata, Oria spp., Ostrinia spp. such as Ostrinia nubilalis; Oulema oryzae, Panolis flammea, Pectinophora spp. such as Pectinophora gossypiella; Peridroma sau- cia, Phalera bucephala, Phthorimaea spp. such as Phthorimaea operculella; Phyllocnistis citrel- la, Pieris spp. such as Pieris brassicae, Pieris rapae; Plathypena scabra, Plutella maculipennis, Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera spp. such as Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura;
Thaumatopoea pityocampa, Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp. such as Trichoplusia ni; Tuta absoluta, and Zeiraphera canadensis;
Beetles {Coleoptera), for example Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus sinuatus, Agriotes spp. such as Agriotes fuscicollis, Agriotes lineatus, Agriotes ob- scurus; Amphimallus solstitialis, Anisandrus dispar, Anobium punctatum, Anomala rufocuprea, Anoplophora spp. such as Anoplophora glabripennis; Anthonomus spp. such as Anthonomus grandis, Anthonomus pomorum; Anthrenus spp., Aphthona euphoridae, Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as Atomaria linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as Bruchus lentis, Bruchus pisorum, Bruchus rufimanus; Byctiscus betulae, Callosobruchus chinensis, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as Ceuthorrhynchus assimilis, Ceuthorrhynchus napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as Conoderus vespertinus; Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptorhynchus lapathi, Ctenicera ssp. such as Ctenicera destructor; Cur- culio spp., Dectes texanus, Dermestes spp., Diabrotica spp. such as Diabrotica 12-punctata Diabrotica speciosa, Diabrotica longicornis, Diabrotica semipunctata, Diabrotica virgifera; Epi- lachna spp. such as Epilachna varivestis, Epilachna vigintioctomaculata; Epitrix spp. such as Epitrix hirtipennis; Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Heter- onychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera brunneipen- nis, Hypera postica, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lema bilineata, Lema melanopus, Leptinotarsa spp. such as Leptinotarsa decemlineata; Limonius californicus, Lissorhoptrus oryzophilus, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp. such as Lyctus bruneus; Melanotus communis, Meligethes spp. such as Meligethes aeneus; Melolon- tha hippocastani, Melolontha melolontha, Migdolus spp., Monochamus spp. such as Monocha- mus alternatus; Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzae- philus surinamensis, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema oryzae, Oxycetonia jucunda, Phaedon cochleariae, Phyllobius pyri, Phyllopertha horti- cola, Phyllophaga spp., Phyllotreta spp. such as Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata; Phyllophaga spp., Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis , Rhizopertha dominica, Sitona lineatus, Sitophilus spp. such as Sitophilus granaria, Sitophilus zeamais;
Sphenophorus spp. such as Sphenophorus levis; Sternechus spp. such as Sternechus sub- signatus; Symphyletes spp., Tenebrio molitor, Tribolium spp. such as Tribolium castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp., and Zabrus spp. such as Zabrus tenebri- oides;
Flies, mosquitoes {Diptera), e.g. Aedes spp. such as Aedes aegypti, Aedes albopictus, Aedes vexans; Anastrepha ludens, Anopheles spp. such as Anopheles albimanus, Anopheles crucians, Anopheles freebomi, Anopheles gambiae, Anopheles leucosphyrus, Anopheles macu- lipennis, Anopheles minimus, Anopheles quadrimaculatus, Anopheles sinensis; Bibio hor- tulanus, Calliphora erythrocephala, Calliphora vicina, Cerafitis capitata, Ceratitis capitata, Chrysomyia spp. such as Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellar- ia; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as Cochli- omyia hominivorax; Contarinia spp. such as Contarinia sorghicola; Cordylobia anthropophaga, Culex spp. such as Culex nigripalpus, Culex pipiens, Culex quinquefasciatus, Culex tarsalis, Culex tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia spp. such as Delia antique, Delia coarctata, Delia platura, Delia radicum; Dermatobia hominis, Drosophila spp., Fannia spp. such as Fannia canicularis; Gastraphilus spp. such as Gasterophilus intestinalis; Geomyza Tripunctata, Glossina fuscipes, Glossina morsitans, Glossina palpalis, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as Hylemyia platura; Hypoderma spp. such as Hypoderma lineata; Hyppobosca spp., Leptoconops torrens, Liriomyza spp. such as Liriomyza sativae, Liriomyza trifolii; Lucilia spp. such as Lucilia caprina, Lucilia cuprina, Lucilia sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as Mayetiola destructor; Musca spp. such as Musca autumnalis, Musca domestica; Muscina stabu- lans, Oestrus spp. such as Oestrus ovis; Opomyza florum, Oscinella spp. such as Oscinella frit; Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as Phorbia antiqua, Phorbia brassicae, Phorbia coarctata; Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psoro- phora discolor, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga spp. such as Sarcophaga haemorrhoidalis; Simulium vittatum, Stomoxys spp. such as Stomoxys calcitrans; Tabanus spp. such as Tabanus atratus, Tabanus bovinus, Tabanus lineola, Tabanus similis; Tannia spp., Tip- ula oleracea, Tipula paludosa, and Wohlfahrtia spp.;
Thrips {Thysanoptera). e.g. Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp. such as Frankliniella fusca, Frankliniella occidental- is, Frankliniella tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp. such as Scirtothrips citri; Taeniothrips cardamoni, Thrips spp. such as Thrips oryzae, Thrips palmi, Thrips tabaci;
Termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Heterotermes longiceps, Heterotermes tenuis, Leucotermes flavipes, Odontotermes spp., Reticulitermes spp. such as Reticulitermes speratus, Reticulitermes flavipes, Reticulitermes grassei, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes virginicus; Termes natalensis;
Cockroaches (Blattaria - Blattodea), e.g. Acheta domesticus, Blatta orientalis, Blattella asahinae, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melano- plus spp., Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta japonica;
Bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acroster- num spp. such as Acrosternum hilare; Acyrthosipon spp. such as Acyrthosiphon onobrychis, Acyrthosiphon pisum; Adelges laricis, Aeneolamia spp., Agonoscena spp., Aleurodes spp., Al- eurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anu- raphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as Aphis fabae, Aphis forbesi, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis sambuci, Aphis schneideri, Aphis spiraecola; Arboridia a pica lis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp. such as Bemisia argentifolii, Bemisia tabaci; Blissus spp. such as Blissus leucopterus; Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Cameocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Cercopidae, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis ju- glandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as Cimex hemipterus, Ci- mex lectularius; Coccomytilus halli, Coccus spp., Creontiades dilutus, Cryptomyzus ribis, Cryp- tomyzus ribis, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurades spp., Diaphorina spp., Diaspis spp., Dichelops eatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmanni- anae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as Dysaphis plantaginea, Dysaphis pyri, Dysaphis radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as Dysdercus cin- gulatus, Dysdercus intermedius; Dysmicoccus spp., Empoasca spp. such as Empoasca fabae, Empoasca solana; Eriosoma spp., Erythroneura spp., Eurygaster spp. such as Eurygaster in- tegriceps; Euscelis bilobatus, Euschistus spp. such as Euschistuos heros, Euschistus impic- tiventris, Euschistus servus; Geococcus coffeae, Halyomorpha spp. such as Halyomorpha halys; Heliopeltis spp., Homalodisca coagulata, Horcias nobilellus, Hyalopterus pruni, Hy- peromyzus lactucae, lcerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Leca- nium spp., Lepidosaphes spp., Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as Lygus hesperus, Lygus lineolaris, Lygus pratensis; Macropes excavatus, Macrosiphum spp. such as Macrosiphum rosae, Macrosiphum avenae, Macrosiphum euphorbi- ae; Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius,
Melanaphis sacchari, Metcafiella spp., Metopolophium dirhodum, Miridae spp., Monellia cos- talis, Monelliopsis pecanis, Myzus spp. such as Myzus ascalonicus, Myzus cerasi, Myzus persi- cae, Myzus varians; Nasonovia ribis-nigri, Nephotettix spp. such as Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephotettix virescens; Nezara spp. such as Nezara viridula; Nilaparvata lugens, Oebalus spp., Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp. such as Pemphigus bursarius; Pen- tomidae, Peregrin us maidis, Perkinsiella saccharicida, Phenacoccus spp., Phloeomyzus pas- serinii, Phorodon humuli, Phylloxera spp., Piesma quadrata, Piezodorus spp. such as Piezodo- rus guildinii, Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Psallus seria- tus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as Pseudo- coccus comstocki; Psylla spp. such as Psylla mail, Psylla piri; Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as Rhopalosiphum pseudobrassicas, Rhopalosiphum insertum, Rhopalosiphum maidis, Rhopalosiphum padi; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mail, Scaphoides titanus, Schi- zaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobi- on avenae, Sogata spp., Sogatella furcifera, Solubea insularis , Stephanitis nashi, Stictocephala festina, Tenalaphara malayensis, Thyanta spp. such as Thyanta perditor; Tibraca spp., Tinocal- lis caryaefoliae, Tomaspis spp., Toxoptera spp. such as Toxoptera aurantii; Trialeurodes spp. such as Trialeurodes vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as Unaspis yanonensis; and Viteus vitifolii;
Ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta capiguara, Atta ceph- alotes, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Bombus spp., Camponotus floridanus, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Doli- chovespula maculata, Hoplocampa spp. such as Hoplocampa minuta, Hoplocampa testudinea; Lasius spp. such as Lasius niger, Linepithema humile, Monomorium pharaonis, Paravespula germanica, Paravespula pennsylvanica, Paravespula vulgaris, Pheidole megacephala, Pogo- nomyrmex barbatus, Pogonomyrmex californicus, Polistes rubiginosa, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Vespa spp. such as Vespa crabro, and Vespula squamosal;
Crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Calliptamus italicus, Chortoicetes terminifera, Dociostaurus maroccanus, Gryllotalpa africana, Gryllotalpa gryllotalpa, Hieroglyphus daganensis, Kraussaria angulifera, Locusta migratoria, Locustana pardalina, Mel- anoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Oedaleus senegalensis, Schistocerca ameri- cana, Schistocerca gregaria, Tachycines asynamorus, and Zonozerus variegatus;
[Earwigs {Dermaptera), e.g. forficula auricularia,
Lice {Phthiraptera), e.g. Damalinia spp., Pediculus spp. such as Pediculus humanus capi- tis, Pediculus humanus corporis; Pthirus pubis, Haematopinus spp. such as Haematopinus eu- rysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.;
Fleas {Siphonaptera), e.g. Ceratophyllus spp., Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus.
The compounds of the formula (I) are also suitable for efficiently combating arthropd pests different from insects such as, in particular the following pests:
arachnids {Arachnida), such as acari,e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma spp. (e.g. Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum), Argas spp. (e.g. Argas persicus), Boophilus spp. (e.g. Boophilus an- nulatus, Boophilus decoloratus, Boophilus microplus), Dermacentor silvarum, Dermacentor an- dersoni, Dermacentor variabilis, Hyalomma spp. (e.g. Hyalomma truncatum), Ixodes spp. (e.g. Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus), Orni- thodorus spp. (e.g. Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata), Orni- thonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. (e.g. Psoroptes ovis), Rhipicephalus spp. (e.g. Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhip- icephalus evertsi), Rhizoglyphus spp., Sarcoptes spp. (e.g. Sarcoptes scabiei), and Eriophyidae spp. such as Acaria sheldoni, Aculops spp. (e.g. Aculops pelekassi) Aculus spp. (e.g. Aculus schlechtendali), Epitrimerus pyri, Phyllocoptruta oleivora and Eriophyes spp. (e.g. Eriophyes sheldoni); Tarsonemidae spp. such as Hemitarsonemus spp., Phytonemus pallidus and Po- lyphagotarsonemus latus, Stenotarsonemus spp.; Tenuipalpidae spp. such as Brevipalpus spp. (e.g. Brevipalpus phoenicis); Tetranychidae spp. such as Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacifi- cus, Tetranychus telarius and Tetranychus urticae; Bryobia praetiosa, Panonychus spp. (e.g. Panonychus ulmi, Panonychus citri), Metatetranychus spp. and Oligonychus spp. (e.g. Oligo- nychus pratensis), Vasates lycopersici; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa. And Acarus siro, Chorioptes spp., Scorpio maurus;
Silverfish, firebrat {Thysanura), e.g. Lepisma saccharina and Thermobia domestica;
Centipedes {Chilopoda), e.g. Geophilus spp., Scutigera spp. such as Scutigera coleop- trata;
Millipedes (Diplopoda), e.g. Blaniulus guttulatus, Narceus spp.,
Springtails (Collembola ), e.g. Onychiurus ssp. such as Onychiurus armatus,
They are also suitable for controlling nematodes: plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species such as Aphelenchoides besseyi ; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus lignicolus Mamiya et Kiyohara, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocricone- ma species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylen- chus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemi- cycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nema- todes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus brachy- urus, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primi- tivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species such as Tylenchulus semipenetrans; Dagger nematodes,
Xiphinema species; and other plant parasitic nematode species.
Examples of further pest species which may be controlled by compounds of fomula (I) include: from the class of the Bivalva, for example, Dreissena spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enter- obius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schisto- somen spp., Strongyloides fuellebomi, Strongyloides stercora lis, Stronyloides spp., Taenia sag- inata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; from the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; from the order of the Symphyla, for example, Scutigerella immaculata.
Further examples of pest species which may be controlled by compounds of formula (I) include: Anisoplia austriaca, Apamea spp., Austroasca viridigrisea, Baliothrips biformis, Caeno- rhabditis elegans, Cephus spp., Ceutorhynchus napi, Chaetocnema aridula, Chilo auricilius, Chilo indicus , Chilo polychrysus, Chortiocetes terminifera, Cnaphalocroci medinalis, Cnaphalo- crosis spp., Colias eurytheme, Collops spp., Cornitermes cumulans, Creontiades spp., Cy- clocephala spp., Dalbulus maidis, Deraceras reticulatum , Diatrea saccharalis, Dichelops furca- tus, Dicladispa armigera , Diloboderus spp. such as Diloboderus abderus; Edessa spp., Epino- tia spp., Formicidae, Geocoris spp., Globitermes sulfureus, Gryllotalpidae, Halotydeus destructor, Hipnodes bicolor, Hydrellia philippina, Julus spp., Laodelphax spp., Leptocorsia acuta , Lep- tocorsia oratorius , Liogenys fuscus, Lucillia spp., Lyogenys fuscus, Mahanarva spp., Ma lad era matrida, Marasmia spp., Mastotermes spp., Mealybugs, Megascelis ssp, Metamasius hemipter- us, Microtheca spp., Mods latipes, Murgantia spp., Mythemina separata , Neocapritermes opa- cus, Neocapritermes parvus, Neomegalotomus spp., Neotermes spp., Nymph ula depunctalis, Oebalus pugnax, Orseolia spp. such as Orseolia oryzae; Oxycaraenus hyalinipennis, Plusia spp., Pomacea canaliculata, Procornitermes ssp, Procornitermes triacifer , Psylloides spp., Ra- chiplusia spp., Rhodopholus spp., Scaptocoris castanea, Scaptocoris spp., Scirpophaga spp. such as Scirpophaga incertulas , Scirpophaga innotata; Scotinophara spp. such as Scotinopha- ra coarctata; Sesamia spp. such as Sesamia inferens, Sogaella frucifera, Solenapsis geminata, Spissistilus spp., Stalk borer, Stenchaetothrips biformis, Steneotarsonemus spinki, Sylepta derogata, Telehin licus, Trichostrongylus spp..
Compounds of the formula (I) are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera.
For use in a method according to the present invention, the compounds of the formula (I) can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions. The use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the formula (I) according to the present invention.
The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, antifoaming agents, anti- freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
Solvents/carriers, which are suitable, are e.g.:
solvents such as water, aromatic solvents (for example Solvesso products, xylene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-metyhl-pyrrolidone (NMP),N-octylpyrrolidone NOP), acetates (glycol diac- etate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid dimethylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modi- fied oils such as alkylated plant oils. In principle, solvent mixtures may also be used. carriers such as ground natural minerals and ground synthetic minerals, such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sul- fate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Suitable emulsifiers are nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates.
Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of
naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers,
tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
Suitable preservatives are for example dichlorophen und benzyl alcohol hemiformal
Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Mention may be made, in this context, for example, of commercial thickeners based on polysaccharides, such as Xanthan Gum® (Kelzan® from Kelco), Rhodopol®23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), or organic phyllosilicates, such as Attaclay® (from Engelhardt). Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trade- marks Proxel® from Avecia (or Arch) or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas. Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound composition. If appropriate, the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N- methylpyrrolidone and water.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, am- monium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0,01 to 60% by weight active compound by weight, preferably 0,1 to 40% by weight.
The compound of formula (I) can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.
The following are examples of formulations:
1 . Products for dilution with water. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A) Water-soluble concentrates (SL, LS)
10 parts by weight of the active compound is dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active com- pound dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound is obtained.
B) Dispersible concentrates (DC)
20 parts by weight of the active compound is dissolved in 70 parts by weight of cyclohex- anone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilu- tion with water gives a dispersion, whereby a formulation with 20% (w/w) of active compounds is obtained.
C) Emulsifiable concentrates (EC)
15 parts by weight of the active compounds is dissolved in 7 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compounds is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound is dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound is obtained.
E) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compound is comminuted with ad- dition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound, whereby a formulation with 20% (w/w) of active compound is obtained.
F) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of the active compound is ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound, whereby a formulation with 50% (w/w) of active compound is obtained.
G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound, whereby a formulation with 75% (w/w) of active compound is obtained.
H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound is comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound, whereby a formulation with 20% (w/w) of active compound is obtained.
2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
I) Dustable powders (DP, DS)
5 parts by weight of the active compound are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound.
J) Granules (GR, FG, GG, MG)
0.5 part by weight of the active compound is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
K) ULV solutions (UL)
10 parts by weight of the active compound is dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound, which is applied undiluted for foliar use.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to pre- pare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
The active ingredients may also be used successfully in the ultra-low-volume process
(ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
In the method of this invention compounds of formula (I) may be applied with other active ingredients, for example with other pesticides, in particular insecticides, nematicides and acaricides, fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, and safeners. Preferred mixing partners are insecticides, nematicides and fungicides.
These additional ingredients may be used sequentially or in combination with the above- described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
The following list M of pesticides, grouped and numbered according the Mode of Action Classification of the Insecticide Resistance Action Committee (IRAC), together with which the compounds of the present invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation:
M.1 Acetylcholine esterase (AChE) inhibitors from the class of
M.1A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetan- ate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
M.1 B organophosphates, for example acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicroto- phos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxy- aminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methida- thion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion- methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupi- rimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothi- on;
M.2. GABA-gated chloride channel antagonists such as:
M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
M.3 Sodium channel modulators from the class of
M.3A pyrethroids, for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, be- ta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, del- tamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthnn, tetramethrin, tralomethrin and transfluthrin; or
M.3B sodium channel modulators such as DDT or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neonico- tinoids, for example acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.2: (2E-)-1 -[(6-Chloropyridin-3-yl)methyl]- N'-nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7- methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;
M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, for example spinosad or spinetoram;
M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
M.7 Juvenile hormone mimics, such as
M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
M.8 miscellaneous non-specific (multi-site) inhibitors, for example
M.8A alkyl halides as methyl bromide and other alkyl halides, or
M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
M.9 Selective homopteran feeding blockers, for example
M.9B pymetrozine, or M.9C flonicamid; M.10 Mite growth inhibitors, for example
M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
M.12 Inhibitors of mitochondrial ATP synthase, for example
M.12A diafenthiuron, or
M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradifon;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, for example chlorfenapyr, DNOC or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example bis- trifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , as for example buprofezin;
M.17 Moulting disruptors, Dipteran, as for example cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
M.19 Octopamin receptor agonists, as for example amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, for example
M.20A hydramethylnon, or M.20B acequinocyl, or M.20C fluacrypyrim;
M.21 Mitochondrial complex I electron transport inhibitors, for example
M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
M.22 Voltage-dependent sodium channel blockers, for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]- ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2- methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]- hydrazinecarboxamide;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid de- rivatives, for example spirodiclofen, spiromesifen or spirotetramat; M.24 Mitochondrial complex IV electron transport inhibitors, for example M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide.
M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile deriva- tives, for example cyenopyrafen or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides, as for example flubendi- amide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1 : (R)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1 - (trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid and M.28.2: (S)-3- Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2- methylsulfonylethyl)phthalamid, or the compound M.28.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1 - cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide (proposed ISO name: cyclaniliprole), or the compound M.28.4: methyl-2-[3,5-dibromo-2-({[3-bromo- 1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1 ,2- dimethylhydrazinecarboxylate; or a compound selected from M.28.5a) to M.28.5d) and M.28.5h) to M.28.5I): M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5b) N-[4-chloro-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4- sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6- dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; M.28.5i) N-[2-(5-Amino-1 ,3,4-thiadiazol-2-yl)-4-chloro- 6-methylphenyl]-3-bromo-1 -(3-chloro-2-pyridinyl)-1 H-pyrazole-5-carboxamide; M.28.5j) 3- Chloro-1 -(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1 -cyano-1 - methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole-5-carboxamide; M.28.5k) 3-Bromo-N-[2,4- dichloro-6-(methylcarbamoyl)phenyl]-1 -(3,5-dichloro-2-pyridyl)-1 H-pyrazole-5-carboxamide; M.28.5I) N-[4-Chloro-2-[[(1 ,1 -dimethylethyl)amino]carbonyl]-6-methylphenyl]-1 -(3-chloro-2- pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide; or a compound selected from M.28.6: N-(2-cyanopropan-2-yl)-N-(2,4-dimethylphenyl)-3-iodobenzene-1 ,2-dicarboxamide; or M.28.7: 3-Chloro-N-(2-cyanopropan-2-yl)-N-(2,4-dimethylphenyl)-benzene-1 ,2-dicarboxamide;
M.29. insecticidal active compounds of unknown or uncertain mode of action, as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflani- lide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butox- ide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the compounds
M.29.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]- tetradec-1 1 -en-10-one, or the compound
M.29.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2- one, or the compound
M.29.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H- 1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or
a compound selected from the group of M.29.6, wherein the compound is selected from M.29.6a) to M.29.6k): M.29.6a) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6b) (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide; M.29.6c) (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2- pyridylidene]acetamide; M.29.6d) (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6e) (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6f) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide; M.29.6g) (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide; M.29.6h) (E/Z)-N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide; M.29.6i) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro- propanamide.); M.29.6j) N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- thioacetamide; or M.29.6k) N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'- isopropyl-acetamidine; or the compounds
M.29.8: 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2- a]pyridine-2-carboxamide; or the compounds
M.29.9.a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or M.29.9.b): 4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4,5- dihydroisoxazol-3-yl]-N-[(methoxyimino)methyl]-2-methylbenzamide; or
M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 , 2,2,3,3,3- hexafluoro-1 -(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.29.1 1.c)
3- (benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]-benzamide; M.29.1 1 .d) N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1 .e) N-[3-[[[2-bromo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4-fluoro-N-methyl-benzamide; M.29.1 1 .f)
4- fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1 .g) 3-fluoro-N-[2- fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1 .h) 2-chloro-N-[3- [[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide; M.29.1 1 .i) 4-cyano-N- [2-cyano-5-[[2,6-dibromo-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1 .j) 4-cyano-3-[(4-cyano-2-methyl- benzoyl)amino]-N-[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]-2- fluoro-benzamide; M.29.1 1.k) N-[5-[[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hexafluoro-1 - (trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;
M.29.1 1 .1) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1 -hydroxy-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;
M.29.1 1 .m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.29.1 1 .n) 4-cyano-N- [2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1.o) 4-cyano-N-[2-cyano-5-[[2,6- dichloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)eth^
benzamide; M.29.1 1 .p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 -
(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; or
a compound selected from the group of M.29.12, wherein the compound is selected from M.29.12a) to M.29.12m): M.29.12.a) 2-(1 ,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.29.12.b) 2-[6-[2-(5-Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.29.12.C) 2-[6-[2- (3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.29.12.d) N-Methylsulfonyl-6-[2-(3- pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.29.12. e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol- 5-yl]pyridine-2-carboxamide; M.29.12.f) N-Ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12. g) N-Methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12.h) N,2-Dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; Μ.29.12.Ϊ) N-Ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12.j) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3- methylthio-propanamide; M.29.12. k) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3- methylthio-propanamide; M.29.12.1) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio- propanamide; M.29.12. m) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio- propanamide; or the compounds
M.29.14a) 1 -[(6-Chloro-3-pyridinyl)methyl]-1 , 2,3,5, 6,7-hexahydro-5-methoxy-7-methyl-8- nitro-imidazo[1 ,2-a]pyridine; or M.29.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or the compounds
M.29.16a) 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or
M.29.16b) 1 -(1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16c) N,5-dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4- carboxamide; M.29.16d) 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide; M.29.16e) N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5-methyl-N-pyridazin-4- yl-pyrazole-4-carboxamide; M.29.16f) 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl- pyrazole-4-carboxamide; M.29.16g) 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4- yl-pyrazole-4-carboxamide; M.29.16h) N-methyl-1-(2-fluoro-1 -methyl-propyl]-5-methyl-N- pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16i) 1 -(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N- pyridazin-4-yl-pyrazole-4-carboxamide; or M.29.16j) 1 -(4,4-difluorocyclohexyl)-N,5-dimethyl-N- pyridazin-4-yl-pyrazole-4-carboxamide.
The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 16th Edition, C. MacBean, British Crop Protection Council (2013) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html.
Another online data base for pesticides providing the ISO common names is
http://www.alanwood.net/pesticides.
The M.4 neonicotinoid cycloxaprid is known from WO2010/069266 and WO201 1/069456, the neonicotinoid M.4A.2, sometimes also to be named as guadipyr, is known from
WO2013/003977, and the neonicotinoid M.4A.3 (approved as paichongding in China) is known from WO2007/101369. The metaflumizone analogue M.22B.1 is described in CN 10171577 and the analogue M.22B.2 in CN102126994. The phthalamides M.28.1 and M.28.2 are both known from WO2007/101540. The anthranilamide M.28.3 is described in WO2005/077934. The hydra- zide compound M.28.4 is described in WO2007/043677. The anthranilamides M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and
WO2013/024010, the anthranilamide Μ.28.5Ϊ) is described in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and M.28.5I) in WO2012/034403. The diamide compounds M.28.6 and M.28.7 can be found in CN102613183. The spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO2006/089633 and the biphenyl-substituted spiro- cyclic ketoenol derivative M.29.4 from WO2008/06791 1. The triazoylphenylsulfide M.29.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are described in WO2009/124707. The compounds M.29.6a) to Μ.29.6Ϊ) listed under M.29.6 are described in WO2012/029672, and M.29.6j) and M.29.6k) in WO2013/129688. The nematicide M.29.8 is known from WO2013/055584. The isoxazoline M.29.9.a) is described in
WO2013/050317. The isoxazoline M.29.9.b) is described in WO2014/126208. The pyridalyl- type analogue M.29.10 is known from WO2010/060379. The carboxamides broflanilide and
M.29.1 1.b) to M.29.1 1 .h) are described in WO2010/018714, and the carboxamides M.29.1 1 i) to M.29.1 1 .P) in WO2010/127926. The pyridylthiazoles M.29.12.a) to M.29.12.C) are known from WO2010/006713, M.29.12.d) and M.29.12.e) are known from WO2012/000896, and M.29.12.†) to M.29.12. m) from WO2010/129497. The compounds M.29.14a) and M.29.14b) are known from WO2007/101369. The pyrazoles M.29.16.a) to M.29.16h) are described in
WO2010/034737, WO2012/084670, and WO2012/143317, respectively, and the pyrazoles Μ.29.16Ϊ) and M.29.16j) are described in US 61/891437.
In another embodiment of the invention, the compounds of formula (I), or their
stereoisomers, salts, tautomers and N-oxides, may also be applied with fungicides as compound II.
The following list of fungicides, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
Inhibitors of complex III at Q0 site (e. g. strobilurins): azoxystrobin (A.1 .1 ), coumeth- oxystrobin (A.1.2), coumoxystrobin (A.1 .3), dimoxystrobin (A.1.4), enestroburin (A.1 .5), fenaminstrobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim- methyl (A.1 .9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxy- .strobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1 .15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)- phenyl)-2-methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1 .19), triclopy- ricarb/chlorodincarb (A.1 .20), famoxadone (A.1.21 ), fenamidone (A.1 .21 ), methyl-A/-[2-[(1 ,4- dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1 .22), 1 -[3-chloro- 2-[[1 -(4-chlorophenyl)-1 H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.23), 1 -[3- bromo-2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .24), 1 - [2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one
(A.1.25), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5- one (A.1.26), 1 -[2-[[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl- tetrazol-5-one (A.1 .27), 1 -[2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phenyl]-4- methyl-tetrazol-5-one (A.1.28), 1 -[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyl- tetrazol-5-one (A.1 .29), 1 -[3-cyclopropyl-2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]- methyl]phenyl]-4-methyl-tetrazol-5-one (A.1.30), 1-[3-(difluoromethoxy)-2-[[2-methyl-4- (1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .31 ), 1 -methyl-4-[3- methyl-2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]tetrazol-5-one (A.1 .32), 1 - methyl-4-[3-methyl-2-[[1 -[3-(trifluoromethyl)phenyl]-ethylideneamino]oxymethyl]phenyl]tetrazol- 5-one (A.1.33), (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-A/,3-dimethyl- pent-3-enamide (A.1 .34), (Z,2E)-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-A/,3- dimethyl-pent-3-enamide (A.1 .35), (Z,2E)-5-[1 -(4-chloro-2-fluoro-phenyl)pyrazol-3-yl]oxy-2- methoxyimino-A/,3-dimethyl-pent-3-enamide (A.1.36),
inhibitors of complex III at Q, site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9- dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy- pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-car- bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.6); (3S,6S,7R,8R)- 3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5- dioxonan-7-yl 2-methylpropanoate (A.2.7), (3S,6S,7R,8R)-8-benzyl-
3-[3-[(isobutyryloxy)methoxy]-4-methoxypicolinamido]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl isobutyrate (A.2.8);
inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl- 2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1 - methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 - methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl- pyrazole-4-carboxamide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3- (difluoromethyl)-l -methyl-pyrazole-4-carboxamide (A.3.27);
other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8- difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam
(A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1 .1 ), biterta- nol (B.1 .2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1 .7), epoxiconazole (B.1.8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1 .12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1 .15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1 .20), penconazole (B.1.21 ), propiconazole (B.1 .22), prothioconazole
(B.1.23), simeconazole (B.1 .24), tebuconazole (B.1.25), tetraconazole (B.1 .26), triadimefon (B.1.27), triadimenol (B.1 .28), triticonazole (B.1.29), uniconazole (B.1 .30), 1 -[re/-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo (B.1 .31 ), 2- [re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-th (B.1.32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazoM -yl)pentan-2-ol (B.1 .33) , 1 -[4- (4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.36), 2-[4-(4-chloro- phenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .37), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .38), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .39), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.40), 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .41 ), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1.51 ); imidazoles: imazalil (B.1.42), pefurazoate (B.1.43), prochloraz (B.1 .44), triflumizol (B.1.45); pyrimidines, pyridines and piperazines: fenarimol (B.1.46), nuarimol (B.1 .47), pyrifenox (B.1 .48), triforine (B.1 .49), [3- (4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1 .50);
Delta14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph- acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8);
- Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1.6), oxadixyl (C.1.7);
- others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate
(C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro- 2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
D) Inhibitors of cell division and cytoskeleton
tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1 ), car- bendazim (D1.2), fuberidazole (D1 .3), thiabendazole (D1 .4), thiophanate-methyl (D1 .5); tria- zolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);
other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
E) Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
protein synthesis inhibitors: blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1.4), fenpiclonil (F.1 .5), fludioxonil (F.1 .6);
G protein inhibitors: quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazo- phos (G.1.3), isoprothiolane (G.1 .4);
lipid peroxidation: dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos- methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
- phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph
(G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);
compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 );
fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(di- fluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesul- fonate (G.5.3);
H) Inhibitors with Multi Site Action
inorganic active substances: Bordeaux mixture (H.1 .1 ), copper acetate (H.1.2), copper hydroxide (H.1 .3), copper oxychloride (H.1.4), basic copper sulfate (H.1.5), sulfur (H.1.6);
thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12); guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin (1.1.1 ), polyoxin B (1.1 .2);
melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1.1 ), probenazole (J.1 .2), isotianil (J.1 .3), tiadinil (J.1.4), prohexadione-calcium (J.1.5); phosphonates: fosetyl (J.1 .6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1 .9);
K) Unknown mode of action
bronopol (K.1.1 ), chinomethionat (K.1 .2), cyflufenamid (K.1.3), cymoxanil (K.1 .4), dazomet (K.1 .5), debacarb (K.1.6), diclomezine (K.1 .7), difenzoquat (K.1 .8), difenzoquat- methylsulfate (K.1 .9), diphenylamin (K.1.10), fenpyrazamine (K.1.1 1 ), flumetover (K.1.12), flusulfamide (K.1 .13), flutianil (K.1 .14), methasulfocarb (K.1 .15), nitrapyrin (K.1 .16), nitrothal- isopropyl (K.1.18), oxathiapiprolin (K.1 .19), tolprocarb (K.1.20), oxin-copper (K.1.21 ), pro- quinazid (K.1 .22), tebufloquin (K.1.23), tecloftalam (K.1.24), triazoxide (K.1.25), 2-butoxy-6- iodo-3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2- (prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1 .27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yl- oxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1 .28), 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.29), N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine (K.1.32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6- tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester (K.1 .35), 3-[5-(4-methylphenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine (K.1 .36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine (pyrisoxazole) (K.1.37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1 .39), 2-(4- chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)- [(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1 .42), 2-[2- [(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1 .43), 2-[2-fluoro-6-[(8- fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan-2-ol (K.1 .44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihydroisoquinolin-1 -yl)quinoline (K.1 .45), 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 - yl)quinoline (K.1.46), 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1.47), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4-benzoxazepine (K.1 .48).
The fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
The fungicides described by lUPAC nomenclature, their preparation and their pesticidal activity is also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197;
DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657, WO2012/168188, WO 2007/006670, WO 201 1/77514; WO13/047749, WO
10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/024010 and WO 13/047441 , WO 13/162072,
WO 13/092224, WO 1 1/135833).
Suitable mixing partners for the compounds of the present invention also include biopesti- cides.
Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular. (2) Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence activators (e.g. induced resistance) and are relatively non-toxic to mammals.
Biopesticides for use against crop diseases have already established themselves on a variety of crops. For example, biopesticides already play an important role in controlling downy mildew diseases. Their benefits include: a 0-Day Pre-Harvest Interval, the ability to use under moderate to severe disease pressure, and the ability to use in mixture or in a rotational program with other registered pesticides.
A major growth area for biopesticides is in the area of seed treatments and soil amendments. Biopesticidal seed treatments are e.g. used to control soil borne fungal pathogens that cause seed rots, damping-off, root rot and seedling blights. They can also be used to control internal seed borne fungal pathogens as well as fungal pathogens that are on the surface of the seed. Many biopesticidal products also show capacities to stimulate plant host defenses and other physiological processes that can make treated crops more resistant to a variety of biotic and abiotic stresses or can regulate plant growth. Many biopesticidal products also show capacities to stimulate plant health, plant growth and/or yield enhancing activity.
The following list of biopesticides, in conjunction with which the compounds of the present invention can be used, is intended to illustrate the possible combinations but does not limit them:
L) Biopesticides
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. sai- toana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Micro- sphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beau- veria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonel- la granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bac- teriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopli- ae, Metarhizium anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paeci- lomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomy- ces galbus, S. microflavus;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)- 2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)-2,13-octadecadien-1 -ol acetate, (E,Z)-3,13- octadecadien-1 -ol, R-1 -octen-3-ol, pentatermanone, (E,Z,Z)-3,8,1 1 -tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1 -yl acetate, Z-1 1 - tetradecenal, Z-1 1 -tetradecen-1 -ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipofer- um, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liao- ningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti.
The biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http ://www. wf cc. i nfo/cci nf o/col I ection/by_acronym/) , are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pullu- lans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g. blastospores in Blossom Protect® from bio-ferm GmbH, Austria), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331 ; US 8,445,255); B. amyloliquefaciens spp. plantarum D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1 ; FERM BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. amyloliquefaciens ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 231 17; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. amyloliquefaciens ssp. plantarum MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1 ; e. g. Integral® from BASF Corp., USA), B. amyloliquefaciens spp. plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ 1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1 BE; ATCC BAA-390; CA 2471555 A1 ; e. g. QuickRoots™ from TJ Technologies, Watertown, SD, USA), B. firmus CNCM 1-1582, a variant of parental strain EIP- N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01 ; e. g. PRO-MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B- 50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Fed- erated States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA- 1 1857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 201 1/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wiscon- sin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent Biosciences, IL, USA), B. t. ssp. tenebrionis NB-176-1 , a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 B1 ; e. g. Novodor® from Valent Biosciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium m/n/fans CON/M/91 -08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha-beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care pic, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 1 12-126, 201 1 ; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF Agricultural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol. 22(7), 747-761 , 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizi- um anisopliae var. anisopliae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. formerly Shemer® from Agrogreen, Israel), Paecilomyces Hacinus 25'\ isolated from infected nematode eggs in the Philippines (AGAL 89/030550; W01991/02051 ; Crop Protection 27, 352-361 , 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Pasteuria nishizawae Pn1 isolated from a soybean field in the mid-2000s in Illinois, U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 201 1 ; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1 ), 91 -102, 1998; US 5,026,417, WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 B1 ; e. g. Regalia® SC from Marrone Biolnnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinemema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae (e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Streptomyces microflavus NRRL B-50550
(WO 2014/124369; Bayer CropScience, Germany), T. harzianum J-22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
The invertebrate pest, e.g. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compounds of formula (I), including their stereoisomers and tautomers, as well the salts thereof, or composition(s) contain- ing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
The compounds of formula (I), including their stereoisomers and tautomers, as well the salts thereof, or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of formula (I). The term "crop" refers both to growing and harvested crops.
The compounds of the present invention and the compositions comprising them are par- ticularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sug- arbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a insecticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
The present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one active compound of the formula (I), a stereoisomers, a tautomere or a salt thereof.
Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula (I), a stereoisomer, a tautomere or a salt thereof. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
The compounds of the invention can also be applied preventively to places at which oc- currence of the pests is expected.
The compounds of formula (I), including their stereoisomers and their tautomers, as well as their salts may be also used to protect growing plants from attack or infestation by pests. The use includes contacting the plant with a pesticidally effective amount of compounds of formula (I), a stereoisomer, a tautomere or a salt thereof. As such, "contacting" includes both direct con- tact, i.e. applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant, and indirect contact, i.e. applying the compounds/compositions to the locus of the pest and/or plant.
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenyl- ated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 Jul-Aug;17(4):720-8., Protein Eng Des Sel. 2004 Jan;17(1 ):57-66, Nat Protoc. 2007;2(5):1225-35., Curr Opin Chem Biol. 2006 Oct;10(5):487-91. Epub 2006 Aug 28., Bio- materials. 2001 Mar;22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1 ):1 13-21 ).
The term "cultivated plants" is to be understood also including plants that have been ren- dered tolerant to applications of specific classes of herbicides, such as hydroxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526,
WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names Round- upReady® (glyphosate) and LibertyLink® (glufosinate).
The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for ex- ample, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878,
WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
The term "cultivated plants" is to be understood also including plants that are, e.g. by the use of recombinant DNA techniques, capable of synthesizing one or more proteins in order to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Ex- amples of such proteins are the so-called "pathogenesis-related proteins", also termed PR proteins - see, for example EP-A 0 392 225 -, or plant disease resistance genes - for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum - or T4-lysozym - e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
The term "cultivated plants" is to be understood also including plants that are, e.g. by the use of recombinant DNA techniques, capable of synthesizing one or more proteins to increase the productivity, e. g. bio mass production, grain yield, starch content, oil content or protein content, or to improve tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new sub- stances of content, specifically to improve human or animal nutrition, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).
The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new sub- stances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato).
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically contain from
0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 5 g to 500 g per hec- tare, more desirably from 5 g to 200 g per hectare.
The compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, are effective through both contact, e.g. via soil, glass, wall, bed net, carpet, plant parts or animal parts, and ingestion, e.g. via ingestion of bait or plant part.
The compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non- crop pests, compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, are preferably used in a bait composition.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
Formulations of compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, as aerosols, e.g in spray cans, oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols, e.g. methanol, ethanol, propanol or butanol, ketones, e.g. acetone, methyl ethyl ketone, paraffin hydrocarbons, e.g. kerosenes or mineral oils, having boiling ranges of approximately 50 to 250°C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
The compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects, such as malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis, with compounds of formula (I) or the stereoisomers, tautomers or salts thereof, and with their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-Diethyl-meta-toluamide (DEET), Ν,Ν-diethylphenylacetamide (DEPA), 1 -(3- cyclohexan-1 -yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2- ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbio- thrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)- Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
The compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being, e.g. when the pests invade into houses and public facilities. The compounds of formula (I), their stereoisomers, their tautomers or their salts are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
The compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects. The compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects. The protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula (I), a tautomer, a stereosi- omer or a salt thereof. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.
The term seed includes seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
The term seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
The present invention also relates to seeds coated with or containing the active compound of the present invention, i.e. containing a compound of formula (I), a stereoisomer, a tautomer or a salt thereof.
The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, may also be used for the treatment seeds from plants, which tolerate the ac- tion of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
For example, the compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate- ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat. No. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thurin- giensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259),
Furthermore, the compounds of formula (I), including the tautomers and stereoisomers, as well as their salts, can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant proce- dures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/1 1376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).
The seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
Compositions which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW, EO, ES)
E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS)
H Gel-Formulations (GF)
I Dustable powders (DP, DS)
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l anti- freezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of a compound of formula (I), a stereoisomer, a tau- tomer or a salt, for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the the compound of formula (I), including its tautomers and stereoisomers, or a salt thereof, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
Seed Treatment formulations may additionally also comprise binders and optionally color- ants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pig- ment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of a gelling agent is carrageen (Satiagel®)
In the treatment of seed, the application rates of the compounds of formula (I) are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed. The invention therefore also relates to seed comprising a compound of the formula (I), a tautomer, a stereoisomer or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the formula (I) or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in partic- ular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
The compounds of formula (I), including their stereoisomers and their tautomers, and the veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
An object of the present invention is therefore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
The invention also relates to compositions containing a parasiticidally effective amount of a compound of formula (I) or a stereoisomer or a tautomer or a veterinarily acceptable salt thereof and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) or a stereoisomer or a tautomer or a veterinarily acceptable salt thereof or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula (I) or a stereoisomer or a tautomer or a veterinarily acceptable salt thereof or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly it has now been found that compounds of formula (I), including their stereoisomers and tautomers, and the salts thereof, are suitable for combating endo- and ectoparasites in and on animals.
Compounds of formula (I), including their stereoisomers and their tautomers, and the vet- erinarily acceptable salts thereof, and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals, including humans, and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Compounds of formula (I), including their stereoisomers and their tautomers, and the veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.
The compounds of formula (I), including their stereoisomers and their tautomers, and the veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds of formula (I) including their stereoisomers and their tautomers, and the veterinarily acceptable salts thereof are especially useful for combating ectoparasites.
The compounds of formula (I), including their stereoisomers and their tautomers, and the veterinarily acceptable salts thereof are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides cams, Xenopsylla che- opis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus;
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Peri- planeta australasiae, and Blatta orientalis;
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quad- rimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinque- fasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia ca- nicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoi- dalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atra- tus, Tabanus lineola, and Tabanus similis;
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Me- nopon gallinae, Menacanthus stramineus and Solenopotes capillatus;
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma macu latum, Ornithodorus hermsi, Ornithodo- rus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae;
Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp.,
Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterol- ichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp;
Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus;
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.;
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp;
Roundworms Nematoda:
Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Tri- churidae Trichuris spp., Capillaria spp.;
Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp;
Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp. , Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Steph- anurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Al- eurostrongylus abstrusus, and Dioctophyma renale;
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi;
Camallanida, e.g. Dracunculus medinensis (guinea worm);
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp.;
Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhyn- chus hirudinaceus and Oncicola spp;
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp;
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesoces- toides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplo- cephala spp., and Hymenolepis spp.
The compounds of formula (I), including their stereoisomers and their tautomers, and the salts thereof and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of the compounds of formula (I), including their stereoisomers and their tautomers, and the salts thereof and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formula (I), including their stereoisomers and their tautomers, and the salts thereof and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of formula (I), including their stereoisomers and their tautomers, and the salts thereof and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formula (I), including their stereoisomers and their tautomers, and the salts thereof and compositions containing them for combating ticks is a further preferred embodiment of the present invention. The compounds of formula (I), including their stereoisomers and their tautomers, and the salts thereof also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the compounds of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the com- pounds of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention may be formulated into an implant for subcutaneous administration. In addition the compounds of the present invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of a compound of the present invention.
The compounds of the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds of the present invention. In addition, the compounds of the present invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are:
Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
Emulsions and suspensions for oral or dermal administration; semi-solid preparations; Formulations in which the active compound is processed in an ointment base or in an oil-in- water or water-in-oil emulsion base; Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methyl- pyrrolidone, 2-pyrrolidone, and mixtures thereof.
The compounds of the present invention can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being nec- essary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are pre- pared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, ad- hesives are added.
Suitable solvents are, for example, water, alkanols, glycols, polyethylene glycols, poly- propylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxy- ethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are, for example, sulfites or metabisulfites such as potassium meta- bisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are, for example: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs- Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs- Cio fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipro- pylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.
Suitable hydrophilic phases are, for example, water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are, for example,
- non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan
monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, al- kylphenol polyglycol ether;
ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, an- tioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries, which may be mentioned, are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity. For the production of solid preparations, the active compound is mixed with suitable excip- ients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, car- bonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the composi- tions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of a compound of formula (I), a stereoisomer, a tautomer or a salt thereof.
Generally it is favorable to apply the compounds of the present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations for controlling endoparasites comprise a compound of the present invention usually in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight. In a preferred embodiment of the present invention, the compositions comprising the a compound of the present invention are applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release compounds of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of the present invention. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
The present invention is now illustrated in further details by the following examples, with imposing any limitation thereto.
The following abbreviations are used:
TFA: trifluoroacetic acid
EtOAc: ethyl acetate
HPLC: High Performance Liquid Chromatography
MS: Mass spectrometry
MeOH: Methanol
MeCN: Acetonitrile
DMSO: Dimethyl sulfoxide
RT: retention time
h: hour(s)
min: minute(s)
calc'd. for: calculated for
The characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
Method Analytical HPLC column: Phenomenex Kinetex 1 ,7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0,8-1 ,0ml_/min in 1 ,50 minutes at 60°C.
MS-method: ESI positive.
1H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.
In the examples, the term "room temperature" is understood as a temperature in the range from 20-25°C.
A. Synthesis examples Example 1 :
1 -[(6-chloro-3-pyridyl)methyl]-N-thiazol-2-yl-pyridin-2-imine (Compound 1-1 )
To a solution of tris(dibenzylideneacetone) dipalladium(O) (8 mg) and 2-di-tert-butylphosphino- 2',4',6'-triisopropylbiphenyl ("tert-butyl xphos", 15mg) in 5 ml toluene were added 1 -[(6-chloro-3- pyridyl)methyl]pyridin-2-imine hydrochloride (100mg, 0,45 mmol), 2-bromothiazole (75 mg, 0,45 mmol) and sodium tert-butoxide (130 mg, 1 ,36 mmol). The solution was stirred for 20 h at 80°C and then diluted with ethyl acetate. The organic layer was washed with water, dried (Na2S04), filtered, and concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane). The product was obtained as amorphous white foam (22 mg). HPLC-MS: RT 0.717min , M= 302.7 Example 2:
1 -[(6-chloro-3-pyridyl)methyl]-N-(4-methylthiazol-2-yl)pyridin-2-imine (Compound I-2)
Step 1 Ethyl N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]carbamothioyl-carbamate
To a solution of 1 -[(6-chloro-3-pyridyl)methyl]pyridin-2-imine hydrochloride (2 g, 0.01 mol) and triethylamine (0,8 g, 0.01 mol) in 20 ml of toluene was added ethoxycarbonyl isothiocyanate (1 g, 0.01 mol). The solution was stirred for 18h at room temperature. After dilution with methyl tert. -butyl ether the product was collected by filtration. The product was used in the next step without further purification.
Yield: 3.1 g
HPLC-MS: RT= 0.742min, M= 351.5 Step 2 [1 -[(6-chloro-3-pyridyl)methyl]-2-pyndylidene]thiourea
To the product from step 1 (2,88 g, 8.21 mmol) was added 2 M sodium hydroxide (28.7 ml) and the mixture was stirred at 70°C for 3h. The product was collected by filtration, washed with wa- ter and dried under vacuum. The product was used in the next step without further purification. Yield: 1.26 g
HPLC-MS: RT= 0.580 min, M= 278.7
Step 3 1 -[(6-chloro-3-pyridyl)methyl]-N-(4-methylthiazol-2-yl)pyridin-2-imine
To a solution of the product from step 2 (200 mg, 0.72 mmol) in 15 ml of ethanol were added 100 mg of potassium carbonate and 70 mg of chloroacetone. The mixture was stirred at reflux for 5 h. After 48 h additional stirring at room temperature the solution was decanted from the solid and concentrated to afford a residue that was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane) to yield 100mg of the abovementioned product.
HPLC-MS: RT 0.746min, M= 317.5
Example 3:
5-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]amino]-2,3-dihydrothiophene-4-carbonitrile (Compound 1-16)
Step 1 N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1 -cyano - cyclopropanecarboxamide To a suspension of 1 -[(6-chloro-3-pyridyl)methyl]pyridin-2-imine hydrochloride (6.00 g, 23.43 mmol), 1 -cyanocyclopropanecarboxylic acid (3.12 g, 28.10 mmol), and triethylamine (5.93g, 58.71 mmol) in CH2CI2 (80 mL) at room temperature was added a solution of propyl phosphonic anhydride (8.95 g, 28.10 mmol, a 50% wt solution in EtOAc was used). The reaction was then heated in the mircrowave at 100 C for 3 h. The reaction was then dilluted with EtOAc (200 mL), washed with saturated aqueous NaHCO3 (200 mL) and water (200mL), layers were separated, and the organic layer was dried over Na2S04 and concentrated in vacuo to afford a residue, which was purified using column chromatography over silica gel (0->30% MeOH/EtOAc), followed by preparative HPLC using 5%-95% MeCN/H20 to afford the desired product as a beige solid (0.130 g, 2% yield).
LC-MS: mass calc'd. for Ci6Hi4N4OCI [M+H]+ 313.1 , found 313.1 ; RT= 0.788 min.
Step2 5-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]amino]-2,3-dihydrothiophene-4- carbonitrile To a solution of the compound from step 1 (0.200 g, 0.590 mmol) in pyridine (5 mL) was added P4S10 (0.170 g, 0.380 mmol) and the resulting suspension was heated to reflux for one hour. The reaction was then cooled to room temperature and then water (5 mL), sat. aqueous NaHCOs (50 mL) and CH2CI2 (100 mL) were consecutively added. The layers were separated, and the organic layer was washed with water (2 x 50 mL) The organic phase was dried over Na2S04, and concentrated in vacuo to afford a residue. The residue was purified to via preparative High Performanc Liquid Chromatography (Method : Waters Sunfire Prep C-18 OBD B · m 50x100 mm column. Elution: acetonitrile / water in a ratio of from 15:85 7.5 minutes, then 55:45 0.1 minutes, then 96:4 0.4 minutes.) to yield the title product as a brown solid (38 mg, 22% yield).
LC-MS: mass calc'd. for Ci6Hi4CIN4S [M+H]+ 328.1 , found 328.7; RT= 0.676 min.
By the methods described above for examples 1 , 2 and 3, the compounds of formula (I-A.1 a) summarized in table B can be prepared:
yc
Figure imgf000129_0001
Table B:
Figure imgf000129_0002
Figure imgf000130_0001
Figure imgf000131_0001
B Biological Examples
The biological activity of the compounds of formula I of the present invention may be evaluated in biological tests as described in the following.
General conditions: If not otherwise specified, most test solutions are to be prepared as follows: The active compound is to be dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled watenacteon. Further, the test solutions are to be prepared at the day of use (and, if not otherwised specified, in general at concentrations wt/vol).
B.1 Boll weevil (Anthonomus grandis)
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96- well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v
DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at
5 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 25 + 1 °C and about 75 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, compounds 1-1 , I-8, I-9, 1-10, 1-14, 1-21 , I-22, I-23, I-24, I-27, I-28, I-29, 1-31 ,
I-32, I-33, I-34, I-35, I-37, I-38, and I-43 at 2500 ppm showed over 75 % mortality in comparison with untreated controls.
Mediterranean fruitfly (Ceratitis capitate)
For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consisted of microtiter plates containing an insect diet and 50-80 C. capitata eggs. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 28 + 1 °C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, compounds 1-1 , I-2, I-3, I-4, I-6, I-8, 1-10, 1-1 1 , 1-15, 1-17, 1-18, 1-19, 1-21 , I-22, I-23, I-24, I-27, I-28, I-29, I-30, 1-31 , I-32, I-33, I-34, I-35, I-37, I-38, I-43 and I-45 at 2500 ppm showed over 75 % mortality in comparison with untreated controls. Tobacco budworm (Heliothis virescens)
For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 28 + 1 °C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, compounds I-2, I-3, I-6, I-8, I-9, 1-10, 1-1 1 , 1-14, 1-15, 1-18, 1-21 , I-23, I-24, I-27, 1-31 , I-32, I-35, I-37, I-38, I-43 and I-45 at 2500 ppm showed over 75% mortality in comparison with untreated controls.
Green Peach Aphid (Myzus persicae) For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.
After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed. In this test, compounds 1-1 , I-2, I-3, I-4, I-5, I-6, I-8, I-9, 1-10, 1-1 1 , 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, I-20, 1-21 , I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-30, 1-31 , I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, 1-41 , I-42, I-43, I-44, I-45, I-47 and I-48 at 2500 ppm showed over 75 % mortality in comparison with untreated controls.
Vetch aphid (Megoura viciae)
For evaluating control of vetch aphid {Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v
DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μΙ, using a custom built micro atomizer, at two replications.
After application, the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 ± 1 °C and about 50 ± 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.
In this test, compounds 1-1 , I-2, l-3,l-4, I-5, I-6, I-8, I-9 , 1-10, 1-1 1 , 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-21 , I-22, I-23, I-24, I-26, I-27, I-28, I-29, I-30, 1-31 , I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, 1-41 , I-42, I-43, I-45, I-46, I-47 and I-48 at 2500 ppm showed over 75 % mortality in comparison with untreated controls.

Claims

Claims
1 . A compound of formula (I):
Figure imgf000134_0001
wherein
Cyc is
(i) a 3-, 4-, 5-, 6- or 7-membered, saturated, partially unsaturated or maximally unsaturated heteromonocycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R3, or
(ii) a 8-, 9- or 10-membered, saturated, partially unsaturated or maximally
unsaturated heterobicycle having 1 , 2, 3 or 4 heteroatoms or heteroatom groups as ring members, which are selected from O, S, N, NO, S(O) and S(0)2, which is unsubstituted or carries one or more, in particular 1 , 2, 3, 4, 5 or 6 subsitutents R4;
Het is a 5- or 6-membered carbon-bound or nitrogen-bound heterocyclic or
heteroaromatic ring, comprising 2, 3, 4 or 5 carbon atoms and 1 , 2 or 3 heteroatoms as ring members, which are independently selected from sulfur, oxygen or nitrogen, wherein the sulfur and nitrogen ring members can independently be partly or fully oxidized, and wherein each ring is optionally substituted by k identical or different substituents R6, wherein k is an integer selected from 0, 1 , 2, 3 or 4;
W1=W2-W3=W4 represents an unsaturated carbon chain group connected to N and C=N, and thus forming a unsaturated or partially unsaturated 5- or 6- membered nitrogen containing heterocycle, wherein W1, W2, W3 and W4 each individually represent CRV or one of W1=W2 or W3=W4 may also be CRVRW wherein
each Rv independently from each other, is hydrogen, halogen, cyano, azido, nitro,
SCN, SF5, Ci-Cio-alkyl, C3-C8-cycloalkyl, C2-Cio-alkenyl or C2-Cio- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may be unsubstituted or may be partly or fully halogenated and/or may optionally be substituted with 1 , 2 or 3 identical or different radicals R7,
or Rv is OR8, NR9aR9b, S(0)nR8a, S(0)nNR9aR9b, C(=0)R7a, C(=0)NR9aR9b, C(=0)OR8, C(=S)R7a, C(=S)NR9aR9b, C(=S)OR8,
C(=S)SR8a, C(=NR 7)R7a, C(=NR 7)NR9aR9 and Si(R11)2R12,
each Rw independently from each other, are selected from the group consisting of hydrogen, halogen, cyano, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl and C2-Cio-alkynyl, wherein the carbon atoms of the aforementioned four aliphatic and cycloaliphatic radicals may be unsubstituted or may be partly or fully halogenated or may optionally be further substituted with 1 ,
2 or 3 identical or different radicals R7; or
Rv and Rw present in one of the groups may together form =0, =CR13R14, =S,
=NR17, =NOR16, =NNR9aR9 ;
R1, R2 are independently from each other selected from the group consisting of
hydrogen, halogen, CN, SCN, nitro, Ci-C6-alkyl, C3-C6-cycloalkyl, wherein each of the two aforementioned radicals are unsubstituted, partly or completely halogenated or may carry any combination of 1 , 2 or 3 radicals R7,
Si(R11)2R12, OR8, OS02R8a, S(0)nR8a, S(0)nNR9aR9 , NR9aR9 , C(=0)NR9aR9 , C(=S)NR aR , C(=0)OR8, C(=0)R7a, C(=S)R7a, phenyl, benzyl, where the phenyl ring in the last two radicals is unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents
R10, and a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 identical or different heteroatoms as ring members, which are selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sul- sulfur atom(s) of the heterocyclic ring may optionally be oxidized, or
R1 and R2 form, together with the carbon atom, which they attached to, a 3-, 4-, 5- or 6-membered saturated or partly unsaturated carbocyclic or heterocyclic ring, wherein each of the carbon atoms of said cycle are unsubstituted or may carry any combination of 1 or 2 identical or different radicals R7, or
R and R2 may together be =0, =CR13R14, =S, =NR17, =NOR16 or =NNR9aR9b; where, independently of their occurrence, n is 0, 1 or 2; R3, R4 are independently from each other selected from the group consisting of
halogen, cyano, azido, nitro, SCN, SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-C10- alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7,
OR8b, NR17aR17b, S(0)nR8b, S(0)nNR 7aR 7 , NR 7dS(0)nR8b, C(=0)R7 , CH(=0), OC(=0)R7 , NR 7dC(=0)R7 , C(=0)NR 7aR 7 , NR 7dC(=0)NR 7aR 7 , C(=0)OR8 , C(=S)R7 , OC(=S)R7 , NR 7cC(=S)R7 , C(=S)NR 7aR 7 , NR 7dC(=S)NR 7aR 7 , C(=S)OR8a, C(=S)SR8a, C(=NR 7)R7a,
C(=NR 7)-C(0)R7c, C(=NR 7)NR 7aR 7 , Si(R11)2R12;
a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may op- optionally be oxidized,
or two of R3 or two of R4, which are present on one ring carbon may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b,
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN,
SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7,
OR8b, NR17aR17b, S(0)nR8b, S(0)nNR7aR7 , NR7dS(0)nR8b, C(=0)R7 , OC(=0)R7 , NR7dC(=0)R7 , C(=0)NR7aR7 , NR7dC(=0)NR7aR7 , C(=0)OR8 , C(=S)R7 , OC(=S)R7 , NR7cC(=S)R7 , C(=S)NR7aR7 , NR7dC(=S)NR7aR7 , C(=S)OR8a, C(=S)SR8a, C(=NR7)R7a,
C(=NR7)-C(0)R7c, C(=NR7)NR7aR7 , Si(R11)2R12;
Q irrespectively of its occurrence is selected from a single bond, Ci-C4-alkylene, which is unsubstituted or partly or completely halogenated, O, S, S(O), S(0)2, NR7d, C(=0), OC(=0), C(=0)-0, NR7dC(=0), C(=0)NR7d, NR7dS(0)2, or
S(0)2,NR7d;
R6 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci- Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, and wherein the carbon atoms of the last 4 aliphatic and cycloaliphatic radicals may be partially or completely halogenated and/or further substituted independently from one another with 1 , 2 or 3 radicals R7,
OR8, NR17aR17b, S(0)nR8a, S(0)nNR7aR7 , C(=0)R7a, C(=0)NR7aR7 , C(=0)OR8, C(=S)R7a, C(=S)NR7aR7 , C(=S)OR8, C(=S)SR8a, C(=NR7)R7a, C(=NR7)NR7aR7 , Si(R11)2R12;
phenyl, optionally substituted with 1, 2, 3, 4 or 5 identical or different substituents R10,
and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocy- heterocyclic ring may optionally be oxidized,
or two of R6 present on one ring carbon may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b,
or two R6 together form a linear C2-C7 alkylene chain, thus forming, together with the ring atom(s) to which they are bound, a 3-, 4-, 5-, 6-, 7- or 8-membered ring, where 1 or 2 CH2 moieties of the alkylene chain may be replaced by 1 or 2 heteroatom moieties selected from O, S and NR17c and/or 1 or 2 of the CH2 groups of the alkylene chain may be replaced by a group C=0, C=S and/or C=NR17; and where the alkylene chain is unsubstituted or may be substituted with 1 , 2, 3, 4, 5 or 6 radicals selected from the group consisting of halogen, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3- Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6- haloalkynyl, phenyl which may be substituted with 1 , 2, 3, 4 or 5 radicals R10, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 radicals R10; independently of its occurrence, is selected from the group consisting of cyano, azido, nitro, -SCN, SF5, d-C6-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, Si(R11)2R12, OR8, OS02R8a, S(0)nR8a, S(0)nNR 7aR 7b, NR17aR17b, C(=0)NR 7aR 7b, C(=S)NR 7aR 7 , C(=0)OR8, C(=0)R15, C(=S)R15, C(=NR 7)R15, NR 7a-C(=0)R7a, NR 7a-C(=S)R7a, NR 7a-C(=0)OR8, NR 7a-C(=0)NR 7aR 7 ,
phenyl, phenoxy, phenyl-Ci-C4-alkyl, where the phenyl ring in the last three groups is optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two R7 present on one carbon atom may together form =0, =CR13R14, =S, =NR17, =NOR16, =NNR9aR9b,
or two R7 may form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partly unsaturated carbocyclic or heterocyclic ring together with the carbon atoms to which the two R7 are bonded, where the heterocyclic ring comprises 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10;
R7a independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents
R10, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
R7b independently of its occurrence, is selected from the group consisting of halogen, d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized;
OR8b or NR17aR17b; R8 independently of its occurrence, is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, C(=0)R15, C(=0)NR 7aR 7b, C(=S)NR 7aR 7b, C(=0)OR16,
phenyl, phenyl-Ci-C-4-alkyl, where the phenyl ring in the last two mentioned radicals is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
R8a independently of its occurrence, is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6 haloalkynyl, phenyl, phenyl-Ci-C-4-alkyl, where the phenyl ring in the last two mentioned radicals is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and
a 5- or 6-membered aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10;
R8b independently of its occurrence, is selected from the group consisting of hydrogen, d-Ce-alkyl, Ci-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6
haloalkynyl;
R9a, R9b are each independently from one another selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy,
Ci-C6-alkylthio, Ci-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C3- C8-cycloalkyl-Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2- C6 haloalkynyl,
S(0)nR16, -S(0)nNR 7aR 7 , C(=0)R15, C(=0)OR16, C(=0)NR 7aR 7 , C(=S)R15, C(=S)SR16, C(=S)NR 7aR 7 , C(=NR 7)R15; phenyl, benzyl, 1 -phenethyl or 2-phenethyl, where the phenyl ring in the last four mentioned radicals is unsubstituted or may be substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10; and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated C-bound heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized, or,
R9a and R9b are together a C2-C7 alkylene chain and form a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partly unsaturated or maximally unsaturated ring together with the nitrogen atom they are bonded to, wherein the alkylene chain may contain one or two heteroatoms, which are, independently of each other, selected from oxygen, sulfur or nitrogen, and where the alkylene chain may optionally be substituted with 1 , 2, 3 or 4 radicals selected from halogen, Ci- C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci- C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different substituents R10, and a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally unsaturated C-bound heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R10, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or
R9a and R9b together may form =CR13R14, =N R17 or =NOR16 moiety; R10 independently of its occurrence, is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-C10- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cycloaliphatic radicals may optionally be substituted with 1 , 2, 3, 4 or 5 identical or different radicals R7,
Si(R11)2R12, OR16, OS(0)nR16a, -S(0)nR16a, S(0)nNR 7aR 7b, NR17aR17b, C(=0)R15,
C(=S)R15, C(=0)OR16, -C(=NR 7)R15, C(=0)NR 7aR 7 , C(=S)NR 7aR 7 , phenyl, optionally substituted with 1 , 2, 3, 4 or 5 identical or different radicals selected from OH, halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and
a 3-, 4-, 5-, 6- or 7- membered saturated, partly unsaturated or maximally
unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is unsubstituted or may be substituted with 1 , 2, 3, 4 or 5 substituents selected independently from one another from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized; or
two R10 present together on one carbon ring atom of a saturated or partly unsaturated heterocyclic radical may form =0, =CR13R14, =S, =NR17, =NOR16, =NNR17aR17b;
or,
two R10 on adjacent carbon ring atoms may also be a bivalent radical selected from CH2CH2CH2CH2, CH=CH-CH=CH, N=CH-CH=CH, CH=N-CH=CH, N=CH-N=CH, OCH2CH2CH2, OCH=CHCH2, CH2OCH2CH2, OCH2CH2O, OCH2OCH2, CH2CH2CH2, CH=CHCH2, CH2CH2O, CH=CHO, CH2OCH2, CH2C(=0)0, C(=0)OCH2, 0(CH2)0, SCH2CH2CH2, SCH=CHCH2, CH2SCH2CH2, SCH2CH2S, SCH2SCH2, CH2CH2S, CH=CHS, CH2SCH2, CH2C(=S)S, C(=S)SCH2, S(CH2)S, CH2CH2NR17, CH2CH=N, CH=CH-NR17, OCH=N, SCH=N and form together with the carbon atoms to which the two R10 are bonded a 5-membered or 6-membered partly unsaturated or unsaturated, aromatic carbocyclic or heterocyclic ring, wherein the ring may optionally be substituted with one or two substituents selected from =0, OH, CH3, OCH3, halogen, cyano, halomethyl and halomethoxy;
R11, R12 independently of their occurrence, are selected from the group consisting of d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkoxy-Ci-C4-alkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl,
C3-C8-halocycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, C3-C8-halocycloalkyl-Ci-C4- alkyl, Ci-C6-haloalkoxy-Ci-C4-alkyl, phenyl and benzyl, where the phenyl ring in the last two radicals are unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different radicals selected from halogen, OH, cyano, NO2, C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy; R13, R14 independently of their occurrence, are selected from the group consisting of hydrogen, halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4- alkyl, phenyl and benzyl; R15 independently of its occurrence, is selected from the group consisting of hydrogen,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;
C(=0)OR8b, C(=0)NR 7aR 7b,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or maycarry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
R16 independently of its occurrence, is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-alkylcarbonyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3- C8-cycloalkyl-Ci-C4-alkyl, wherein the six last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino and di-(Ci-C6-alkyl)amino;
R16a independently of its occurrence, is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy,
phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
R17 independently of its occurrence, is selected from the group consisting of hydrogen, trimethylsilyl, triethylsilyl, fer/butyldimethylsilyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C4- alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C3-Cs-cycloalkoxy, C3-C8- cycloalkyl-Ci-C4-alkoxy, Ci-C6-alkylthio, wherein the 1 1 last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkoxy, phenyl, benzyl, pyridyl, phenoxy, benzyloxy and pyridyloxy, wherein the six last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl,
R17a, R17b are each independently from one another selected from the group consisting of hydrogen, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, ferfbutyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkoxy, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl,
or,
R17a and R17b may together be a C2-C6 alkylene chain forming a 3- to 7- membered saturated, partly unsaturated or unsaturated ring together with the nitrogen atom R17a and R17b are bonded to, wherein the alkylene chain may contain 1 or 2 heteroatoms selected, independently of each other, from oxygen, sulfur or nitrogen, and may optionally be substituted with halogen, Ci- C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized; or
R17a and R17b together may form =CR13R14, =NR17 or =NOR16 moiety; R17c independently of its occurrence, is selected from the group consisting of hydrogen, CN, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci- C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy, phenyl, benzyl and pyridyl, wherein the last three radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino or di-(Ci-C6-alkyl)amino;
R17d independently of its occurrence, is selected from the group consisting of hydrogen, CN, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci- C4-alkyl, wherein the five last mentioned aliphatic and cycloaliphatic radicals may be unsubstituted, partially or fully halogenated and/or oxygenated and/or may carry
1 or 2 radicals selected from C1-C4 alkoxy; the stereoisomers, tautomers and the salts thereof, except for those compounds of formula I, where Cyc is 2-hydroxycarbonyl-3,3-dimethyl-4-thia-1 - azabicyclo[3.2.0]heptan-7-on-6-yl, if Het is 2-furyl, R1 and R2 are hydrogen and W1=W2- W3=W4 represents CH=CH-CH=CH, and also except from the stereoisomers, tautomers and the salts thereof.
The compound of claim 1 , wherein
Het is selected from the group consisting of radicals of the following formula Het-1 to Het-24:
Figure imgf000145_0001
Figure imgf000146_0001
Het-11 Het-12 Het-13 Het-14 Het-15
Figure imgf000146_0002
Het-16 Het-17 Het-18 Het-19 Het-20
Figure imgf000146_0003
Het-21 Het-22 Het-23 Het-24 wherein # denotes the bond in formula (I), and wherein
k is 0, 1 or 2; and
R6A is hydrogen or has one of the meanings given for R6 and
R6B is hydrogen, Ci-C4-alkyl or Ci-C4-haloalkyl.
The compound of claim 2, wherein
Het is selected from the group consisting of radicals of formulae Het-1 , Het-1 1 a and Het-24,
Figure imgf000146_0004
Het-1 Het-11a Het-24 wherein # denotes the bond in formula (I), and wherein
R6 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and C1-C4- haloalkyl;
R6A is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and
Ci-C4-haloalkyl; and
k is 0, 1 or 2. The compound of claim 3, wherein Het is Het-1 a
Figure imgf000147_0001
Het-1a
wherein # denotes the bond in formula (I),
R6 is selected from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl and
R6a is hydrogen or halogen, in particular hydrogen.
The compound of any of the preceding claims, wherein
R1, R2 are independently from each other selected from the group consisting of hydrogen, halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C6-haloalkyl, C3-C6- halocycloalkyl;
or
R1 and R2 may together be =CR13R14;
or
R1 and R2 form, together with the carbon atom, which they attached to, a 3- to 5-membered saturated carbocyclic ring.
The compound of claim 5, wherein both R1 and R2 are hydrogen. The compound of any of the preceding claims, wherein Cyc is
(i) 5- or 6-membered, partially unsaturated or maximally unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3.
The compound of claim 7, wherein Cyc is
(i) 5-membered monocyclic hetaryl having 1 heteroatom as ring member, which is selected from O and S, and 1 or 2 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3.
The compound of claim 8, wherein Cyc is selected from the group consisting of thiazol-2- yl, oxazol-2-yl, oxazol-5-yl, isoxazol-5-yl, isothiazol-5-yl, 1 ,3,4-thiadiazol-2-yl, 1 ,3,4- oxadiazol-2-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4- thiadiazol-5-yl, where the aforementioned 5-membered heterocycles are unsubstituted or carry 1 or 2 radicals R3.
The compound of claim 7, wherein Cyc is a 5- or 6-membered, partially unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 or 2 subsitutents R3.
The compound of claim 10, wherein Cyc is selected from 4,5-dihydrothiazol-2-yl and 2,3- dihydrothiophen-5-yl, where the aforementioned 5-membered heterocycles are
unsubstituted or carry 1 or 2 radicals R3.
The compound of claim 7, wherein Cyc is 6-membered monocyclic hetaryl having 1 , 2 or 3 nitrogen atoms as ring member, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 radicals R3.
The compound of claim 12, wherein Cyc is selected form the group consisting of 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl or 4- pyridazinyl, where the aforementioned 6-membered heterocycles are unsubstituted or carry 1 , 2, or 3 radicals R3.
14. The compound of any of the preceding claims, wherein R3, R4 are independently from each other selected from the group consisting of
halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci- C6-alkyl, C3-C6-halocycloalkyl, Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R7,
C(=0)NR 7aR 7b, CHO, COOR8b, OR8b, S(0)nR8b,
where
R7 is OR8, NR17aR17b or NR 7a-C(=0)R7a or
two R7 present on one carbon atom may together form =NOR16, or
=NNR9aR9b;
R7a is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl;
R8 is hydrogen, d-C6-alkyl, Ci-C6-haloalkyl or C(=0)R15;
R8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6- halocycloalkyl; R9a, R9b are each independently of each other selected from hydrogen, Ci- Ce-alkyl, Ci-C6-haloalkyl, C(=0)N R 7aR 7 and C(=0)R15,
R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;
R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
R17a and R17b are independently from each other selected from hydrogen, Ci- C6-alkyl and Ci-C6-haloalkyl; a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 5- or 6- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
or two of R3 or two of R4, which are present on one ring carbon atom may together be =0,
wherein
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN , SF5, d-Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl, OR8b and S(0)nR8b, where R8b is Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl, and
Q irrespectively of its occurrence is selected from a single bond, Chb, O, S, S(O) and S(0)2.
15. The compound of any of the preceding claims, which is a compound of the formula (l-A), a stereoisomer, tautomer or salt thereof
Figure imgf000150_0001
(l-A) wherein Cyc, R1 , R2 and Het are as defined in any of claims 1 to 14, and wherein p is 0 or 1 and is selected from the group consisting of halogen, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkyl and Ci-C4-haloalkyl.
6. The compound of claim 15, wherein Het is selected from the group consisting of radicals of formulae Het-1 Het-1 1 a and Het-24,
Figure imgf000150_0002
Het-1 Het-11a Het-24
wherein # denotes the bond in formula (I), and wherein
R6 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and C1-C4- haloalkyl;
R6a is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and
Ci-C4-haloalkyl; and
k is 0, 1 or 2.
7. The compound of any of claims 15 to 16, wherein
R , R2 are independently from each other selected from the group consisting of hydrogen, halogen, CN , Ci-C6-alkyl, C3-C6-cycloalkyl, Ci-C6-haloalkyl, C2-C6- halocycloalkyl;
or
R1 and R2 may together be =CR13R14;
or
R1 and R2 form, together with the carbon atom, which they attached to, a 3- to 5-membered saturated carbocyclic ring; and
Cyc is (i) 5- or 6-membered, partially unsaturated or maximally unsaturated heteromonocycle having 1 heteroatom as ring member, which is selected from O, S and N, and which additionally may have 1 , 2 or 3 nitrogen atoms as ring members, where the heteromonocycle is unsubstituted or carries 1 , 2 or 3 subsitutents R3,
wherein
R3 if present, are independently from each other selected from the group
consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, Ci-C6-alkyl which is substituted with 1 , 2, 3 or 4 identical or different substituents R7,
C(=0)NR 7aR 7b, CHO, COOR8b, OR8b, S(0)nR8b, wherein
R7 is OR8, NR17aR17b or NR 7a-C(=0)R7a or
two R7 present on one carbon atom may together form =NOR16 or =NNR9aR9b;
R7a is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl;
R8 is hydrogen, d-C6-alkyl, Ci-C6-haloalkyl or C(=0)R15;
R8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl;
R9a, R9b are each independently of each other selected from hydrogen, Ci- Ce-alkyl, Ci-C6-haloalkyl, C(=0)NR 7aR 7 and C(=0)R15,
R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;
R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkylcarbonyl;
R17a and R17b are independently from each other selected from hydrogen, Ci- C6-alkyl and Ci-C6-haloalkyl; a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and
a moiety Q-Het*, wherein Het* is a 5- or 6- membered saturated, partly unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5, and wherein the nitrogen and/or the sulfur atom(s) of the heterocyclic ring may optionally be oxidized,
wherein R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, d-Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6- halocycloalkyl, OR8b and S(0)nR8b, where R8b is Ci-C6-haloalkyl, C3-C6- cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, and
Q irrespectively of its occurrence is selected from a single bond, Chb, O, S, S(O) and S(0)2.
The compound of claim 1 , which is a compound of formula (l-Aa), a tautomer,
stereoisomer or a salt thereof:
Figure imgf000152_0001
wherein
Het is a radical Het-1 a, Het-1 1 a or Het-24,
Figure imgf000152_0002
Het-1a Het-11a Het-24
wherein # denotes the bond in formula (I), and wherein
R6 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and C1-C4- haloalkyl;
R6a is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and
Ci-C4-haloalkyl;
k is O, 1 or 2;
R1 is hydrogen or Ci-C4-alkyl; and
Cyc is thiazol-2-yl, which is unsubstituted or which carries 1 or 2 radicals R3, which are selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, Ci-C6-alkyl which carries 1 or 2 radicals R7, C3-C6-halocycloalkyl, C(=0)NR 7aR 7 , CH(=0), C(=0)OR8 , OR8 , S(0)nR8b, a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and a moiety Q-Het*, or two radicals R3, which are bound to the same carbon atom, may be =0, thereby forming a carbonyl group; and wherein
Het* a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5;
R7 is OR8, NR17aR17b or NR17a-C(=0)R7a or two R7 present on one carbon atom may together form =NOR16 or =NNR9aR9b;
R7a is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl;
R8 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or C(=0)R15;
R8b is hydrogen, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl; R9a, R9b are each independently of each other selected from hydrogen, Ci-C6-alkyl, Ci-
Ce-haloalkyl, C(=0)NR 7aR 7 and C(=0)R15,
R15 is Ci-C6-alkyl, Ci-C6-haloalkyl or phenyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 substituents selected from C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
R16 is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylcarbonyl or C1-C6- haloalkyl carbonyl;
R17a and R17b are independently from each other selected from hydrogen, Ci-C6-alkyl and Ci-C6-haloalkyl;R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3- Ce-halocycloalkyl, OR8 and S(0)nR8b,
Q is selected from a single bond, CH2, O, S, S(O) and S(0)2.
The compound of claim 1 , which corresponds to a compound of formula (l-Aa), tautomer, a stereoisomer or a salt thereof:
Figure imgf000153_0001
wherein
Het is a radical Het-1 a, Het-1 1 a or Het-24,
Figure imgf000154_0001
Het-1a Het-11a Het-24
wherein # denotes the bond in formula (I), and wherein
R6 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and C1-C4- haloalkyl;
R6a is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and
Ci-C4-haloalkyl;
k is O, 1 or 2;
R1 is hydrogen or Ci-C4-alkyl;
Cyc is selected from 2,3-dihydrothiophen-5-yl and thiophen-2-yl, where the
aforementioned two radicals are unsubstituted or carry 1 or 2 radicals R3, which are selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, C1-C6- haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b, S(0)nR8b, a moiety Q-phenyl, wherein phenyl is unsubstituted or substituted with 1 , 2, 3, 4 or 5 identical or different substituents R5, and a moiety Q-Het*; and
wherein
Het* a 5- or 6- membered maximally unsaturated heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms as ring members, which are identical or different and selected from oxygen, nitrogen and sulfur, where the heterocyclic ring is optionally substituted with 1 , 2, 3 or 4 identical or different substituents R5,
R8b is Ci-C6-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl or C3-C6-halocycloalkyl;
R5 is selected from the group consisting of halogen, cyano, azido, nitro, SCN, SF5, d-Ce-haloalkyl, C3-C6-cycloalkyl, Ci-C6-alkyl, C3-C6-halocycloalkyl, OR8b and S(0)nR8b,
Q is selected from a single bond, CH2, O, S, S(O) and S(0)2.
20. An agricultural or veterinary composition for combating animal pests comprising at least one compound as defined in any of claims 1 to 19 and at least one inert liquid and/or solid acceptable carrier and optionally, if desired, at least one surfactant.
21 . The use of a compound as defined in any of claims 1 to 19 for combating or controlling invertebrate pests, for protecting growing plants from attack or infestation by invertebrate pests, for protecting plant propagation material, especially seeds, from soil insects, or for protect the seedlings roots and shoots of plants from soil and foliar insects.
22. A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound as defined in any one of claims 1 to 19.
A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 19.
A method for the protection of plant propagation material, especially seeds, from soil insects and of the seedlings roots and shoots from soil and foliar insects comprising contacting the plant propagation material before sowing and/or after pregermination with at least one compound as defined in any one of claims 1 to 19.
A method for treating animals infested or infected by parasites or preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites which comprises administering or applying to the animals a parasiticidally effective amount of a compound as defined in any of claims 1 to 19. 26. The compound as defined in any of claims 1 to 19 for the use in the treatment animals infested or infected by parasites, for preventing animals of getting infected or infested by parasites or for protecting animals against infestation or infection by parasites.
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US10440953B2 (en) 2015-08-07 2019-10-15 Basf Se Control of pests in maize by ginkgolides and bilobalide
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US10206397B2 (en) 2013-09-19 2019-02-19 Basf Se N-acylimino heterocyclic compounds
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EP3771714A1 (en) 2019-07-30 2021-02-03 Bayer AG Nitrogen-containing heterocycles as pesticides

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