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WO2025045837A1 - Pesticidally active indazole compounds - Google Patents

Pesticidally active indazole compounds Download PDF

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Publication number
WO2025045837A1
WO2025045837A1 PCT/EP2024/073845 EP2024073845W WO2025045837A1 WO 2025045837 A1 WO2025045837 A1 WO 2025045837A1 EP 2024073845 W EP2024073845 W EP 2024073845W WO 2025045837 A1 WO2025045837 A1 WO 2025045837A1
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formula
spp
compounds
hydrogen
methyl
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PCT/EP2024/073845
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French (fr)
Inventor
Camille LE CHAPELAIN
Roger Graham Hall
Andre Jeanguenat
Jagadeesh Prathap KILARU
Michel Muehlebach
Christopher Charles SCARBOROUGH
André Stoller
Matthias Weiss
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Publication of WO2025045837A1 publication Critical patent/WO2025045837A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to pesticidally active indazole compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active indazole compounds.
  • the invention also relates to the preparation of these indazole compounds, to intermediates useful in the preparation of these indazole compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these indazole compounds, to preparation of these compositions and to the use of these indazole compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina.
  • BACKGROUND [0002] WO 2023/037249, WO 2023/285175, WO 2022/157188 and WO 2019/197468 describe certain fused heterobicyclic carboxamide derivatives with pesticidal activity.
  • WO 2021/105334 describes certain 1H-indazole- 7-carboxamide derivatives which were evaluated for their cereblon binding affinity.
  • BRIEF SUMMARY [0003] It has now surprisingly been found that certain novel indazole compounds have pesticidal activity. More specifically, certain novel indazole-7-carboxamide compounds and aza analogues thereof, have pesticidal activity.
  • the present invention accordingly relates, in a first aspect, to a compound of the formula (I):
  • X is an oxygen atom or a sulfur atom; the staggered line represents the connection of Q to the rest of compound of the formula (I);
  • R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; 82994 FF
  • R 2a is hydrogen, halogen, -CN, C1-C4alkyl, C1-C3haloalkyl, C1-C4alkoxy, C1-C3haloalkoxy, C3- C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano;
  • R 2b
  • the present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I).
  • the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient.
  • the present invention makes available a method of combating and controlling pests, such as insects, acarines, nematodes, or molluscs, which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally, such as insecticidally, acaricidally, nematicidally, or molluscicidally, effective amount of a compound as defined in the first aspect or of a composition as defined in the second aspect.
  • pests such as insects, acarines, nematodes, or molluscs
  • the present invention makes available a method for the protection of plant propagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which 82994 FF comprises treating the propagation material or the site where the propagation material is planted, with an effective amount of a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect.
  • a pest such as insects, acarines, nematodes, or molluscs
  • the present invention makes available a plant propagation material, such as a seed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect.
  • the present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect.
  • the present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect.
  • the present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof.
  • Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1- C4alkane- or arylsulfonic acids
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-,
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • C1-Cnalkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- 82994 FF methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1-ethylbutyl, 2-ethy
  • C1-Cnhaloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoro
  • C1-C2fluoroalkyl refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.
  • C1-Cnalkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.
  • haloC1-Cnalkoxy refers to a C1-Cnalkoxy radical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different halo atom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy.
  • C1-Cncyanoalkyl refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1- (cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
  • C3-Cncycloalkyl refers to a saturated monocyclic hydrocarbon radical attached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cyanoC3-Cncycloalkyl refers to a C3-Cncycloalkyl where one of the hydrogen atoms in these radicals is replaced by a cyano group.
  • C3-C4cycloalkylC1-C2alkyl refers to a cyclopropyl or cyclobutyl radical bonded via a methylene or ethylene bridge to the rest of the molecule.
  • the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge.
  • C1-Cnalkylsulfanyl refers to a C1-Cnalkyl moiety linked through a sulfur atom.
  • C1-Cnhaloalkylthio or “C1-Cnhaloalkylsulfanyl” as used herein refers to a C1- Cnhaloalkyl moiety linked through a sulfur atom.
  • C3-Cncycloalkylsulfanyl refers to 3-n membered cycloalkyl moiety linked through a sulfur atom.
  • C2-Cnalkenyl refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl.
  • C2-Cnalkynyl refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.
  • Halogen or "halo" is generally fluorine, chlorine, bromine or iodine.
  • halogen in combination with other meanings, such as haloalkyl.
  • optionally substituted means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, "C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms" means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C 3 -C 4 cycloalkyl substituted with 2 halo atoms.
  • controlling refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
  • pest refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest.
  • the term “effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
  • an effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to 82994 FF be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
  • compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in formula (I*) below: where A, R 1 , R 2a , R 2b , R 3 , R 6 , Q and X are as defined in the first aspect.
  • the present invention contemplates both racemates and individual enantiomers.
  • Compounds of formula (I') having a preferred stereochemistry are set out below: [0036] Particularly preferred compounds of the present invention are compounds of formula (I’), where A, R 1 , R 2a , R 2b , R 3 , R 6 , Q and X are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I’), and agrochemically acceptable salts thereof.
  • Particularly preferred compounds of formula (I’) include compounds of formula (I’a) as shown below, where X is oxygen, and A, R 1 , R 2a , R 2b , R 3 , R 6 , and Q are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I*a), and agrochemically acceptable salts thereof: 82994 FF [0038] Compounds of formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A, R 1 , R 2a , R 2b , R 3 , R 6 , Q and X are as defined in the first aspect, may be depicted as compounds of formula (I-N1) and (I-N2): [0039] When R 6 is hydrogen, compounds of the formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a),
  • Particularly preferred compounds of the present invention are compounds of formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A is CH, and where R 1 , R 2a , R 2b , R 3 , R 6 , Q and X are as defined in the first aspect.
  • R 6 is hydrogen
  • these compounds may exist in different 82994 FF tautomeric forms, as represented above as the 1H-indazole (I”-1), 2H-indazole (I”-2), and 3H-indazole (I”-3). More preferably, X is oxygen.
  • Preferred compounds where A is CH, X is oxygen, and where R 1 , R 2a , R 2b , R 3 , R 6 , and Q are as defined in the first aspect may be depicted as compounds of formula (I-N1a) and (I-N2a): (I-N1a) (I-N2a) and preferably as compounds of formula (I’N1a) and (I’N2a): [0042] Embodiments according to the invention are provided as set out below. [0043] In an embodiment of each aspect of the invention, A is N. When A is N, the moiety containing A is a pyrazolo[4,3-b]pyridine group. In another embodiment of each aspect of the invention, A is CH.
  • A is CH.
  • X is oxygen (i.e. an oxygen atom).
  • X is S (i.e. a sulfur atom).
  • R 1 is as follows: A.
  • R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B.
  • R 1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; or C.
  • R 1 is hydrogen, methyl, or cyclopropylmethyl; or D.
  • R 1 is hydrogen or methyl; or E. R 1 is methyl; or F.
  • R 1 is hydrogen.
  • R 1 is hydrogen, methyl, or cyclopropylmethyl; or R 1 is hydrogen or methyl. Most preferably, R 1 is hydrogen.
  • R 2a is as follows: A. R 2a is hydrogen, halogen, C1-C3haloalkyl, C1-C4alkoxy, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; or B.
  • R 2a is hydrogen, halogen, C1-C3fluoroalkyl, cyclopropyl, cyclobutyl, or cyclopropyl substituted with a single fluoro or cyano; or C.
  • R 2a is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethyl, cyclopropyl, 1- fluorocyclopropyl, 1-cyanocyclopropyl, or isopropoxy; or D.
  • R 2a is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethyl, cyclopropyl, 1- fluorocyclopropyl, or 1-cyanocyclopropyl; or E. R 2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl; or F. R 2a is hydrogen, bromo, iodo, or cyclopropyl; or G. R 2a is hydrogen or cyclopropyl; or H. R 2a is cyclopropyl; or I. .R 2a is hydrogen.
  • R 2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl.
  • R 2a is hydrogen, iodo, or cyclopropyl.
  • R 2a is hydrogen or cyclopropyl.
  • R 2b is as follows: A.
  • R 2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1- C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, -CN, C1-C3alky
  • R 2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1- C2haloalkyl, C3-C4cycloalkylcarbonyl, cyclopropyl, or cyclopropyl substituted with one or two substituents independently selected from the group consisting of halogen, -CN, methyl, and triflu
  • R 2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl; or D.
  • R 2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3haloalkylsulfonyl, or cyclopropyl; or E.
  • R 2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; or F. R 2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; or G. R 2b is chloro, bromo, cyclopropyl, difluoromethyl, or trifluoromethyl; or H. R 2b is bromo, cyclopropyl, or trifluoromethyl; or 82994 FF I.
  • R 2b is bromo or trifluoromethyl; or J. R 2b is cyclopropyl.
  • R 2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl, such as R 2b is bromo or trifluoromethyl.
  • R 6 is connected to one of the two nitrogen atoms of the pyrazole ring of the indazole group (when A is CH) or of the pyrazolo[4,3-b]pyridine group (when A is N) of the compound of formula (I).
  • R 6 is connected to a nitrogen atom refers to one or the other nitrogen atom of said pyrazole ring. In particular, R 6 is not connected to A when A is nitrogen.
  • R 6 is as follows: A. R 6 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl or C1-C6alkoxycarbonyl; or B.
  • R 6 is hydrogen, C1-C4alkyl, C1-C3cyanoalkyl, C1-C2alkoxyC1-C2alkyl, C2-C3alkenyl, C2-C3alkynyl, C3- C4cycloalkylC1-C2alkyl or C1-C4alkoxycarbonyl; or C.
  • R 6 is hydrogen, C1-C4alkyl, C1-C2alkoxyC1-C2alkyl, or C3-C4cycloalkylC1-C2alkyl; or D.
  • R 6 is hydrogen, C1-C4alkyl, or C1-C2alkoxyC1-C2alkyl; or E.
  • R 6 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, 2-methoxyethyl, allyl, propargyl, cyclopropylmethyl, methoxycarbonyl, or ethoxycarbonyl; or F.
  • R 6 is hydrogen, methyl, or methoxymethyl; or G.
  • R 6 is hydrogen or methoxymethyl; or H.
  • R 6 is methoxymethyl; or I.
  • R 6 is hydrogen.
  • R 6 is hydrogen, methyl, or methoxymethyl.
  • R 6 is hydrogen or methoxymethyl.
  • R 6 is hydrogen or methoxymethyl.
  • R 6 is hydrogen.
  • compounds of formula (I) are compounds of formula (I-N1a), such as compounds of formula (I-N1a), where R 6 is hydrogen, and tautomers thereof. More preferably, compounds of formula (I) are compounds of formula (I’N1a), such as compounds of formula (I’N1a), where R 6 is hydrogen, and tautomers thereof.
  • R 3 is as follows: A. R 3 is C1-C3alkyl or C1-C3haloalkyl; or B. R 3 is methyl or trifluoromethyl; or C. R 3 is methyl.
  • R 3 is methyl.
  • Q is Q a .
  • R 5 is as follows: A. R 5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R 5 is hydrogen, halogen, or C1-C3alkyloxy; or C. R 5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or D. R 5 is hydrogen, halogen, or C1-C3alkyloxy; or 82994 FF E.
  • R 5 is hydrogen, halogen, or C1-C3alkyl; or F.
  • R 5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, 2-methoxyethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylcarbonyl, methoxycarbonyl, or 1,3,4-oxadiazol-2-yl; or G.
  • R 5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; or H.
  • R 5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or I. R 5 is hydrogen. [0058] In preferred embodiments where Q is Q a , R 5 is as follows: A. R 5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or B. R 5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; or C.
  • R 5 is hydrogen, cyclopropyl, or methoxy; or D. R 5 is hydrogen.
  • Q a is selected from Q a -1 to Q a -16: 82994 FF
  • Q a is Q a -1, Q a -4, Q a -5 Q a -6, Q a -7, Q a -10, or Q a -15; or Q a is selected from Q a -1, Q a - 6, Q a -7, Q a -10, and Q a -15.
  • Q is Q a -1, or Q a -15.
  • Q is Q a -1.
  • Q is Q b .
  • R 5a and R 5b are as follows: A. R 5a is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R 5a is hydrogen, halogen, or C1-C3alkyloxy; or C. R 5a is hydrogen, halogen, or C1-C3alkyl; or D. R 5a is hydrogen, chloro, fluoro, methyl, cyclopropyl, trifluoromethyl, methoxy, difluoromethoxy, or cyano; or E.
  • R 5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy; or F. R 5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy; or G. R 5a is hydrogen; and A. R 5b is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R 5b is hydrogen, halogen, or C1-C3alkyloxy; or C. R 5b is hydrogen, halogen, or C1-C3alkyl; or D. R 5b is hydrogen, chloro, fluoro, or methoxy; or E.
  • R 5b is hydrogen, fluoro, or methoxy; or F. R 5b is hydrogen.
  • Q is Q b : A. R 5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy and R 5b is hydrogen, fluoro, or methoxy; or B. R 5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy, and R 5b is hydrogen, chloro, fluoro, or methoxy; or C.
  • R 5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy
  • R 5b is hydrogen, fluoro, or methoxy
  • D is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy
  • R 5b is hydrogen
  • E is hydrogen
  • R 5a is hydrogen
  • R 5b is hydrogen, fluoro, or methoxy
  • R 5a and R 5b are hydrogen.
  • Q b is selected from Q b -1 to Q b -13: 82994 FF
  • Q b is Q b -1, Q b -2, Q b -3, Q b -5, Q b -6, Q b -8, Q b -9, Q b -10, or Q b -11; or Q b is selected from Q b -1, Q b -2, Q b -3, Q b -5, Q b -8, Q b -9, Q b -10, and Q b -11.
  • Q b is Q b -1, Q b -2, Q b -3, Q b -5, Q b -8, Q b -10, or Q b -11.
  • Q b is Q b -1, Q b -3, Q b -5, Q b -10, or Q b -11.
  • Q b is Q b -1.
  • R 4 is as follows: A.
  • R 4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R 4b ; or R 4 is oxo-pyridazinyl optionally N-substituted with a single substituent R 4c ; or B.
  • R 4 is Q c -1, Q c -2, Q c -3, Q c -4, Q c -5, Q c -6, Q c -7, Q c -8, or Q c -9: 82994 FF F.
  • R 4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 6- ethoxypyridazin-3-yl, 6-chloropyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl; or G.
  • R 4 is pyrazin-2-yl, pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl; or H.
  • R 4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl.
  • R 4 is Q c -1, Q c -2, Q c -3, Q c -4, or Q c -9. More preferably, R 4 is Q c -1, Q c -2, or Q c -3.
  • R 4 is Q c -1 or Q c -2, such as R 4 is Q c -2.
  • R 4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 6-ethoxypyridazin-3- yl, 6-chloropyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5-carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, such as preferably R 4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin
  • R 4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl. Even more preferably, R 4 is pyrimidin-2- yl or 5-cyano-2-pyridyl. [0067] In embodiments where Q is Q b , R 4a is as follows: 82994 FF A.
  • R 4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R 4b ; or R 4a is oxo- pyridazinyl optionally N-substituted with a single substituent R 4c ; or B.
  • R 4a is Q c -1, Q c -2, Q c -3, Q c -4, Q c -5, Q c -6, Q c -7, Q c -8, Q c -9, Q c -10, or Q c -11: C.
  • R 4a is Q c -1, Q c -2, Q c -3, Q c -4, or Q c -9; or D.
  • R 4a is Q c -1, Q c -2, or Q c -3; or E.
  • R 4a is Q c -1; or F.
  • R 4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; i.e.
  • R 4a is Q c -1, with cyano as R 4b .
  • R 4a is Q c -1, Q c -2, Q c -3, Q c -4, or Q c -9, such as R 4a is Q c -1, Q c -2, or Q c -3. More preferably, R 4a is Q c -1.
  • the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, and oxo-pyridazinyl rings of R 4 and R 4a are each connected to the remainder of the compound via a carbon atom.
  • R 4b is as follows: A. R 4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR 10 R 11 , -N(R 11 )C(O)OR 10 , or -N(R 11 )C(O)R 10 ; or B.
  • R 4b is hydrogen, halogen, cyano, hydroxy, C 1 -C 3 alkyl, C 1 -C 3 fluoroalkyl, C 1 -C 3 alkoxy, C 1 - C3fluoroalkoxy, -C(O)NR 10 R 11 , or -NHC(O)R 10 ; or C.
  • R 4b is hydrogen, fluoro, chloro, iodo, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR 10 R 11 , -NHC(O)R 10 or - N(CH3)C(O)R 10 ; or D.
  • R 4b is hydrogen, chloro, iodo, cyano, C1-C3alkyl, methoxy, -C(O)NR 10 R 11 , -NHC(O)R 10 or - N(CH3)C(O)R 10 ; or E.
  • R 4b is hydrogen, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR 10 R 11 , -NHC(O)R 10 or -N(CH3)C(O)R 10 ; or 82994 FF F.
  • R 4b is hydrogen, cyano, C1-C3alkyl, methoxy, -C(O)NHR 11 , -NHC(O)R 10 or -N(CH3)C(O)R 10 ; or G.
  • R 4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR 11 , -C(O)N(CH3)R 11 , - NHC(O)R 10 or -N(CH3)C(O)R 10 ; or H.
  • R 4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or I.
  • R 4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or J.
  • R 4b is hydrogen, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or K.
  • R 4b is hydrogen, cyano, -C(O)NH2, or -C(O)NHCH3; or L.
  • R 4b is hydrogen or cyano; or M.
  • R 4b is cyano, -C(O)NH2, or -C(O)NHCH3; or N.
  • R 4b is hydrogen.
  • R 10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or B.
  • R 10 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyclopropylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or C.
  • R 10 is hydrogen, C1-C3alkyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, cyanoC3- C4cycloalkyl, or C1-C3alkoxyC1-C3alkyl; or D.
  • R 10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; or E. R 10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl; or F. R 10 is hydrogen, methyl, ethyl, isopropyl, or cyclopropyl; or G. R 10 is hydrogen, methyl, or cyanomethyl; or H. R 10 is hydrogen or methyl and R 11 is as follows: A.
  • R 11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or B.
  • R 11 is hydrogen, hydroxy, C1-C3alkyl, C1-C3cyanoalkyl, cyanoC3-C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C3alkoxy; or C.
  • R 11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, C1-C3cyanoalkyl, or C1-C3alkoxy; or D. R 11 is hydrogen, C1-C3alkyl, cyanocyclopropyl, C1-C3alkoxyC1-C3alkyl, or methoxy; or E. R 11 is hydrogen, C1-C3alkyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, or C1-C3alkoxy; or F. R 11 is hydrogen, C1-C3alkyl, cyclopropyl, or C1-C3alkoxy; or G.
  • R 11 is hydrogen, C1-C3alkyl, cyclopropyl, or methoxy; or H.
  • R 11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or I.
  • R 11 is hydrogen or methyl; or 82994 FF J.
  • R 11 is hydrogen.
  • R 10 is hydrogen, methyl, or cyanomethyl, such as R 10 is hydrogen or methyl.
  • R 11 is hydrogen or methyl, such as R 11 is hydrogen.
  • R 4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3. More preferably, R 4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3.
  • R 4b is hydrogen, this means that the corresponding pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl group R 4 or R 4a is non-substituted.
  • the group R 4b is in the meta or para position with respect to the link of R 4 or R 4a to the remainder of the compound, i.e. to the Q a or Q b ring, respectively.
  • R 4c is as follows: A.
  • R 4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; or B. R 4c is C1-C3alkyl, C1-C3haloalkyl, or C3-C6cycloalkylC1-C4alkyl; or C. R 4c is methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, or cyclopropylmethyl; or D.
  • R 4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; or E. R 4c is methyl, ethyl, or cyclopropylmethyl; or F. R 4c is methyl or cyclopropylmethyl; or G. R 4c is methyl or ethyl; or H. R 4c is methyl. [0077] In preferred embodiments of each aspect of the invention, R 4c is methyl or ethyl. For instance, R 4c is methyl.
  • R 4 and R 4a are selected from QQ-1 to QQ-17, where the staggered line represents the connection to Q a or Q b : 82994 FF
  • R 4 and R 4a are selected from QQ-1, QQ-2, QQ-3, QQ-5, QQ-6, QQ- 9, QQ-13, QQ-14, QQ-15, QQ-16, and QQ-17. More preferably, Preferably, R 4 and R 4a are selected from QQ- 1 and QQ-2.
  • a preferred group of compounds of formula (I) is represented by compounds of formula (I-A): 82994 FF wherein A, R 1 , R 2a , R 2b , R 3 and Q are as defined for compound of formula (I); or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula (I-A). More preferably, A is CH.
  • Another preferred group of compounds of formula (I) is represented by compounds of formula (I-B): wherein A, R 1 , R 2a , R 2b , R 3 and Q are as defined for compound of formula (I); or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula (I-B). More preferably, A is CH.
  • the present invention makes available a compound of formula (I) having the substituents A, Q (i.e.
  • A is CH or N, preferably A is CH;
  • X is oxygen;
  • R 1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R 1 is hydrogen or methyl;
  • R 2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl;
  • R 2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl;
  • R 3 is methyl or trifluoromethyl;
  • Q is Q a , wherein R 5 is hydrogen, bromo, iodo, methoxy, 2- methoxyethoxy, such as Q a is Q a -1, Q a -6, Q a -7, Q a
  • A is CH or N, preferably A is CH; X is oxygen; R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R 1 is hydrogen, methyl, or cyclopropylmethyl; R 2a is hydrogen, halogen, C1-C3haloalkyl, C1-C4alkoxy, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R 2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1
  • A is CH or N, preferably A is CH;
  • X is oxygen;
  • R 1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R 1 is hydrogen or methyl;
  • R 2a is hydrogen, bromo, iodo, or cyclopropyl;
  • R 2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl;
  • R 3 is methyl or trifluoromethyl;
  • Q is Q b , wherein R 5a and R 5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl, such as R 5a and R 5b are hydrogen; such as Q b is Q b
  • A is CH or N, preferably A is CH; X is oxygen; R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R 1 is hydrogen, methyl, or cyclopropylmethyl; R 2a is hydrogen, halogen, C1-C3haloalkyl, C1-C4alkoxy, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R 2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1
  • A is CH or N;
  • X is an oxygen atom or a sulfur atom, such as X is oxygen;
  • R 1 is hydrogen;
  • R 2a is hydrogen or cyclopropyl;
  • R 2b is cyclopropyl;
  • R 3 is methyl;
  • Q is Q a -1, Q a -15, or Q b -1;
  • R 4 is pyrazin-2-yl, pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4- yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, such as R 4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6- carbamoyl
  • A is CH; X is oxygen; R 1 is hydrogen or methyl, such as R 1 is hydrogen; R 2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl, preferably R 2a is hydrogen, iodo, isopropoxy, or cyclopropyl; R 2b is bromo or trifluoromethyl; R 6 is hydrogen or methoxymethyl; R 3 is methyl; Q is Q a and Q a is Q a -1 or Q a -15, preferably Q a is Q a -1; and R 4 is Q c -1, Q c -2, Q c - 3, Q c -4, Q c -5, Q c -6, or Q c -9, such as R 4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl
  • A is CH; X is oxygen; R 1 is hydrogen or methyl, such as R 1 is hydrogen; R 2a is hydrogen, bromo, iodo, or cyclopropyl, such as R 2a is hydrogen; R 2b is bromo or trifluoromethyl, such as R 2b is bromo; R 6 is hydrogen; R 3 is methyl; Q is Q b and Q b is Q b -1, Q b -3, Q b - 5, Q b -10, or Q b -11, preferably Q b is Q b -1; and R 4a is Q c -1, Q c -2, Q c -3, Q c -4, or Q c -9, preferably R 4a is Q c -1, such as R 4a is 5-cyano-2-pyridyl or pyrimidin-2-yl.
  • A is CH; X is oxygen; R 1 is hydrogen or methyl, such as R 1 is hydrogen; R 2a is hydrogen, bromo, iodo, or cyclopropyl, such as R 2a is hydrogen; R 2b is bromo or trifluoromethyl, such as R 2b is bromo; R 6 is hydrogen; R 3 is methyl; Q is Q a -1 or Q b -1, and R 4 and R 4a , as the case may be, are selected from QQ-1 to QQ-17, such as from QQ-1, QQ-2, QQ-3, QQ-5, QQ-6, QQ-9, QQ-13, QQ-14, QQ-15, QQ-16, and QQ-17.
  • R 4 and R 4a are QQ-1 or QQ-2.
  • compounds of formula (I-A) are provided, where A is CH; X is oxygen; R 1 is hydrogen or methyl; R 2a is hydrogen, bromo, iodo, or cyclopropyl; R 2b is bromo or trifluoromethyl; R 3 is methyl; Q is Q a -1; R 4 is Q c -1, Q c -2, Q c -3, Q c -5, Q c -6, or Q c -9; R 4b is hydrogen, chloro, ethoxy, methoxy, C(O)NH2, or C(O)NHCH3; and R 4c is ethyl or methyl.
  • Compounds of the formula (I) can be made, for example, by reaction of a compound of the formula (II), wherein X 1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride, and wherein T has the meaning given above, with a compound of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R 1 , R 3 and Q have the same meaning as given above for compounds of the formula (I).
  • a compound of the formula (II) wherein X 1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride, and wherein T has the meaning given above
  • a compound of formula (III), or a salt thereof such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)- methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®).
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)- methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic an
  • Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic 82994 FF base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl
  • compounds of the formula (II) are either known, or they can be prepared by methods known to a person skilled in the art.
  • compounds of the formula (II) wherein X 1 is a leaving group, such as a halogen, for instance chloride can be formed by treatment of compounds of formula (II) wherein X 1 is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C.
  • DMF N,N-dimethylformamide
  • DCM dichloromethane
  • THF tetrahydrofuran
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • an organic base such as, for example, triethylamine.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid
  • a Lewis acid such as zinc bromide or titanium(IV) isopropoxide
  • compounds of formula (I) can be made, for example, by reaction of compound of the formula (IV), wherein T has the same meaning as given above in Scheme 1, and R 1 has the same meaning as given above for compounds of the formula (I), with a compound of the formula (V), wherein R 3 and Q have the same meaning as given above for compounds of the formula (I), and X 2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • organic base such as, for example, triethylamine.
  • a compound of the formula (I) can be made by reaction of a compound of the formula (IVa), wherein T has the same meaning as given above in Scheme 1, with a compound of the formula (VII), wherein R 3 and Q have the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula (VII) wherein R 3 and Q have the same meaning as given above for compounds of the formula (I)
  • a compound of the formula (V) can be treated with a reducing agent, followed by reaction with a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula (V), wherein the leaving group X 2 is a sulfonate, for instance a mesylate.
  • This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a base such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula (Ia), wherein T has the same meaning as given above in Scheme 1, and R 3 and Q have the same meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula (VI), 82994 FF wherein R 1 has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen, and wherein X 30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (Ia-1).
  • a leaving group such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base,
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride 82994 FF (T3P®).
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4- dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50 °C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane
  • a base such as an inorganic base, for instance sodium, potassium or cesium carbonate
  • an organic base such as, for example, triethylamine, diisopropylethylamine
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, or between ambient temperature and 80 °C.
  • a solvent such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid
  • Compounds of the formula (Ik) 82994 FF can be prepared by the reaction of an amine of the formula (IIIf), or a salt thereof wherein R 1 , R 3 , R 4 and R 5 are as described in formula (I), with a compound of the formula (IIa) wherein A, R 2a , R 2b and R 6 are as described in formula (I) and X 1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid, or a Lewis acid, such as zinc bromide
  • a solvent or without a solvent such as, for instance, methanol.
  • R 4a -M1 is a metal, such as for instance lithium, or –MgCl, or –ZnBr, or –B(OH)2; or R 4a -M1 represents a boronate, such as a pinacol ester of a boronic acid, or a stannane 82994 FF such as R 4a -Sn(n-Bu)3.
  • Such transformations are known to a person skilled in the art as Suzuki-, Kumada-, Negishi- or Stille-coupling reactions, respectively.
  • Such reactions are carried out in a temperature range of - 100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst (for example palladium(II) acetate, 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride or tetrakis(triphenyl-phosphine)palladium(0)), and optionally in the presence of an additional ligand, such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand.
  • a catalyst such as a metal catalyst, for instance a palladium catalyst (for example palladium(II) acetate
  • the reaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance CuI.
  • a base which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or tribasic potassium phosphate, or an organic base, such as an amine base, for instance triethyl amine.
  • This reaction is done with or without a solvent, preferentially in a solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, toluene or N.N-dimethylformamide, optionally in the presence of water.
  • reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath.
  • compound (XVII) can be reacted with a compound of the formula (XV) to give intermediate (XVIII). This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate (XIV) to the compound of formula (Ic).
  • the intermediate (XVIII) is reacted with a compound of the formula (IVb) to give a compound of the formula (Ic), wherein R 1 is hydrogen and A, R 2a , R 2b , R 3 , R 4a and R 6 have the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI).
  • the intermediate compound of the formula (XVIII) can be reacted with an amine of the formula (XIX), or a salt thereof, to give the intermediate of the formula (IIIa), or a salt thereof.
  • the intermediate compounds of formulas (XIV), (XVI), (XVIII) and (IIIa) can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.
  • Compounds of the formula (XVII) are known, or they can be prepared by methods known to a person skilled in the art.
  • Compounds of the formula (Id) 82994 FF can be prepared by the reaction of an amine of the formula (IIIb), or a salt thereof wherein R 1 , R 3 , R 4a , R 5a and R 5b are as described in formula (I), with a compound of the formula (IIa) wherein A, R 2a , R 2b and R 6 are as described in formula (I) and X 1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.
  • the chemistry is described in more detail in Scheme 8.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • Amines of formula (IIIc), or a salt thereof may be obtained by biocatalyzed deracemization of amines of formula (IIId), or a salt thereof. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • compounds of formula (IIIc), or a salt thereof can be obtained from compounds of the formula (XXII), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), following the synthesis described in Scheme 10.
  • Amines of formula (IIIc), or a salt thereof may be obtained from intermediates of formula (XXII), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in
  • Such intermediates of formula (XXII), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXI), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula (XXI) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine,
  • amines of formula (IIIc) may be obtained by reduction of azides of formula (XXIII), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen.
  • Azides of formula (XXIII) may be obtained by treatment of alcohols of formula (XXI), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • an azidation reagent such as diphenyl phosphoryl azide
  • a solvent such as toluene or THF
  • a base such as DBU
  • Alcohols of formula (XXI) may be obtained by enantioselective reduction of ketones of formula (XXIV), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I).
  • reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or 82994 FF RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • compounds of formula (IIIc) may also be prepared as outlined in Scheme 11.
  • Amines of formula (IIIc), or a salt thereof can be prepared by deprotection of amines of formula (XXV), wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), for instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane.
  • Amines of formula (XXV) can be obtained by condensation of diamines of formula (XLVII), wherein R 5a , and R 5b are as described in formula (I), on diketones of formula (XXVI), wherein R 3 and R 4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ.
  • Diketones of formula (XXVI) may be formed by oxidation of hydroxyketones of formula (XXVII), wherein R 3 and R 4a are as described in formula (I).
  • This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/Bu4NHSO4.
  • solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof
  • base for instance triethylamine or alternatively sodium hypochlorite
  • a catalyst such as TEMPO/Bu4NHSO4.
  • Hydroxyketones of formula (XXVII) may be synthesized by cross-benzoin condensation between aldehydes of formula (XXIX), wherein R 4a is as described in formula (I), and aldehydes of formula (XXVIII), wherein R 3 is as described in formula (I).
  • Aldehydes of formula (XXVIII) are commercially available in chiral form, like for instance Boc-L- alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36- 82994 FF 9).
  • Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt, in the presence of a base such as potassium tert-butoxide or N,N- isopropylethylamine, in a suitable solvent such as DCM or THF, at a temperature between -20 °C and the boiling point of the solvent.
  • organocatalyst such as a triazolium salt or a thiazolium salt
  • a base such as potassium tert-butoxide or N,N- isopropylethylamine
  • a suitable solvent such as DCM or THF
  • Amines of formula (XXXIV) can be prepared by deracemization procedure method, which involves for example, a selective acylation of one enantiomer. Such an example is described in Scheme 13 more in details.
  • Amines of formula (XXXIV) may be obtained by biocatalyzed deracemization of amines of formula (XXXIVa), wherein R 3 , R 5a , and R 5b are as in formula (I) and X07 is a leaving group such as bromine, chlorine or iodine. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • a lipase e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • Chiral auxiliaries of formula (XXXVI) are for instance mandelic acid or (1R)-menthylchloroformate.
  • Intermediates of formula (XXXVII) can be formed by coupling of a chiral auxiliary of formula (XXXVI), wherein X0 is a leaving group, such as chlorine, with amines of the formula (XXXIVa) following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493.
  • amines of formula (XXXIV), or a salt thereof can be formed as described in Scheme 15.
  • Amines of formula (XXXIV), or a salt thereof may be obtained from intermediates of formula (XXIIa), wherein R 3 , R 5a , and R 5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person
  • Such intermediates of formula (XXIIa), wherein R 3 , R 5a , and R 5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXIa), wherein R 3 , R 5a , and R 5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula (XXIa) with an azodicarboxylate, such as diethyl
  • amines of formula (XXXIV) may be obtained by reduction of azides of formula (XXIIIa), wherein R 3 , R 5a , and R 5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen.
  • Azides of formula (XXIIIa) may be obtained by treatment of alcohols of formula (XXIa) with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • Alcohols of formula (XXIa) may be obtained by enantioselective reduction of ketones of formula (XXIVa), wherein R 3 , R 5a , and R 5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide.
  • Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p- cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • catalysts for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p- cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a salt of the substrate compound of the formula (IIa-1), for instance a carboxylic acid sodium salt, can be used in this amide bond formation reaction to form the compounds of the formula (I- A).
  • Compounds of the formula (IIa-1), wherein A, R 2a and R 2b are as described in formula (I) can be prepared by saponification of compounds of the formula (IIa-2), wherein A, R 2a and R 2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under conditions known to a person skilled in the art (using for example conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane at room temperature, or up to refluxing conditions; or alternatively treating compounds of the formula (IIa-2) with an acid, such as for example a hydrohalide acid, preferably hydrochloride or hydrobro
  • the compounds of formula (XL) are reacted with carbon monoxide CO (usually under pressure, for example in the range of 5 to 200 bar), in the presence of a metal catalyst such as a palladium catalyst (for example: palladium(II) acetate, or 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride (Pd(dppf)Cl2, optionally as a dichloromethane complex)), optionally in the presence of a phosphine ligand, preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, in an alcohol RaOH solvent (optionally in presence of an inert organic co-solvent), and at temperatures ranging between 0 and 250°C, preferably between room temperature and 200°C.
  • a metal catalyst such as a palladium catalyst (for example: palladium(II) acetate, or 1,1’- bis(diphen
  • compounds of the formula (IIa-1), wherein A, R 2a and R 2b are as described in formula (I) can be prepared by i) performing a lithium-halogen (Li-X 3 ) exchange on compounds of the formula (XL), wherein A, R 2a and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), followed by ii) quenching the formed organolithium species with carbon dioxide.
  • Li-X 3 lithium-halogen
  • Scheme 17 [0152] As shown above in Scheme 17, compounds of the formula (XL), wherein A and R 2b are as described in formula (I), R 2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by reacting compounds of the formula (XL-1), wherein A and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine) and X 4 is a halogen, preferably bromine or iodine, with a reagent of the formula R 2a -M2, wherein R 2a is C1-C4alkyl, C1-C3haloalkyl
  • transformations are known to a person skilled in the art as Kumada-, Negishi-, Stille-, and Suzuki-coupling reactions, respectively 82994 FF and are achieved in the presence of a palladium (alternatively nickel) catalyst as described in detail in Scheme 7 (transformation XIV + XV into Ic).
  • Compounds of the formula (XL-1), wherein A and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine) and X 4 is a halogen, preferably bromine or iodine, can be prepared by a halogenation reaction, which involves for example, reacting the compounds of the formula (XL-2), wherein A and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), with halogenating reagents such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), sulfuryl chloride or alternatively chlorine, bromine or iodine, optionally in presence of a base such as sodium, potassium or cesium carbon
  • Such halogenation reactions are carried out in an inert solvent, such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, sulfuric acid, ethers, N,N-dimethylformamide, methanol or methanol-water mixtures, acetonitrile or acetonitrile-water mixtures, at temperatures between 20-200°C, preferably between room temperature to 100°C.
  • an inert solvent such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, sulfuric acid, ethers, N,N-dimethylformamide, methanol or methanol-water mixtures, acetonitrile or acetonitrile-water mixtures
  • Compounds of the formula (XL-2), wherein A and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by diazotization/cyclization of the corresponding toluidine (ortho-tolylamine or 2-methyl- aniline) compounds of the formula (XL-3), wherein A and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), under conditions reported for example in Liebigs Ann.
  • a mixture of compounds (XL-3) in acetonitrile and aqueous hydrochloric (or hydrobromic) acid is diazotized (aqueous sodium nitrite) at 0°C, then treated with sodium or potassium acetate at temperatures between 0°C and room temperature to provide said indazole compounds (XL-2).
  • Compounds of the formula (XL-3), wherein A and R 2b are as described in formula (I), and in which X 3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by a halogenation reaction, which involves for example, reacting the compounds of the formula (XL- 4), wherein A and R 2b are as described in formula (I), with halogenating reagents such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), sulfuryl chloride or alternatively chlorine, bromine or iodine, optionally in presence of a base such as sodium, potassium or cesium carbonate, and optionally in the presence of a catalyst or an additive.
  • a halogenation reaction which involves for example, reacting the compounds of the formula (XL- 4), wherein A and R 2b are as described in formula (I), with
  • Such halogenation reactions are carried out in an inert solvent, such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, sulfuric acid, ethers, N,N- dimethylformamide, acetonitrile or acetonitrile-water mixtures, at temperatures between 20-200°C, preferably between room temperature to 100°C.
  • an inert solvent such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, sulfuric acid, ethers, N,N- dimethylformamide, acetonitrile or acetonitrile-water mixtures
  • a mixture of compounds (XL-5) in aqueous hydrochloric, hydrobromic or sulfuric acid (alternatively in concentrated acid), optionally in the presence of a solvent such as acetonitrile, is diazotized (aqueous sodium nitrite) at temperatures between 0°C and room temperature, followed by treatment of the reaction mixture comprising the formed diazonium intermediate with tin(II) chloride dihydrate, also known as stannous chloride, at temperatures between 0°C and room temperature, to provide the indazole compounds (XL).
  • Such photochemical aza-Fries rearrangement (a 1,3-acyl migration) of the corresponding acyl-aniline (XL-7) is conducted via irradiation at a given wavelength (e.g.254 nm) with appropriate lamps, in an appropriate photochemical reaction vessel, in solvents, preferably deoxygenated, such as cyclohexane, dichloromethane or acetonitrile, at temperatures preferably around room temperature, and optionally under flow conditions, characterized by parameters such as the reactor volume (e.g.55 mL), residence time (e.g.55 min), flow rate (e.g.1 mL/min), and the like.
  • a given wavelength e.g.254 nm
  • solvents preferably deoxygenated, such as cyclohexane, dichloromethane or acetonitrile
  • Anilide compounds of the formula (XL-7), wherein A and R 2b are as described in formula (I), and R 2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano can be made, for example, by reaction of aniline compounds of the formula (XL-8), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein A and R 2b are as described in formula (I), with acylating agents of the formula (XL-9), respectively (XL-9a), wherein R 2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, under conditions
  • Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydro-furan, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between 0 and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydro-furan, ethyl a
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethyl- amino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®).
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethyl- amino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium
  • T3P® propanephosphonic acid cyclic anhydride
  • compounds of the formula (XL-9a) can be formed by treatment of compounds of formula (XL-9) with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C.
  • DMF dichloromethane
  • THF tetrahydrofuran
  • a salt of the substrate compound of the formula (IIb-1), for instance a carboxylic acid sodium salt, can be used in this amide bond formation reaction to form the compounds of the formula (I- B).
  • Compounds of the formula (IIb-1), wherein A, R 2a and R 2b are as described in formula (I) can be prepared by saponification of compounds of the formula (IIb-2), wherein A, R 2a and R 2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under conditions already described in Scheme 16 above (transformation IIa-2 to IIa-1).
  • compounds of the formula (IIa-1), wherein A, R 2a and R 2b are as described in formula (I) can be prepared directly from compounds of the formula (IIb-2), wherein A, R 2a and R 2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, by a one-pot saponification / MOM group cleavage sequence, in which the respective conditions described above are sequentially applied.
  • Compounds of the formula (IIa-3), wherein A and R 2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl and X 4 is a halogen, preferably bromine or iodine, can be prepared by reacting compounds of the formula (IIa-4), wherein A and R 2b are as described in formula (I), and in which Ra is C1- C6alkyl or benzyl, with halogenating reagents, under conditions already described in Scheme 17 above (transformation XL-2 to XL-1).
  • compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above wherein R 1 , R 3 , R 4a , R 5a and R 5b are as described in formula (I), particularly those compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above, wherein R 3 and R 4a are as described in formula (I) and in which R 1 , R 5a and R 5b are hydrogen, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/069575, and WO 2022/258481.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium 82994 FF bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N- dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU).
  • DBU 1,8- diazabicyclo[5.4.0]undec-7-ene
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N- methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. [0182] The reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • an inorganic salt which forms, for example silver chloride is insoluble and thus precipitates from the reaction mixture.
  • the compounds of formula (I) which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each 82994 FF case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities,
  • N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2O2/urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • Tables A-1 to A-52 and Tables B-1 to B- 52 can be prepared according to the methods described above.
  • the examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I- A-1) and (I-B-1). 82994 FF Tables A-1 to A-52 (formula I-A-1) [0196]
  • Table A-1 provides 15 compounds A-1.001 to A-1.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • compound A-4.011 is [0197]
  • Table A-2 provides 15 compounds A-2.001 to A-2.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table A-3 provides 15 compounds A-3.001 to A-3.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table A-4 provides 15 compounds A-4.001 to A-4.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table A-5 provides 15 compounds A-5.001 to A-5.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table A-6 provides 15 compounds A-6.001 to A-6.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Table A-7 provides 15 compounds A-7.001 to A-7.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z.
  • Table A-8 provides 15 compounds A-8.001 to A-8.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table A-9 provides 15 compounds A-9.001 to A-9.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z. 82994 FF
  • Table A-10 provides 15 compounds A-10.001 to A-10.015 of formula I-A-1 wherein R 2a is CF3, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table A-11 provides 15 compounds A-11.001 to A-11.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table A-12 provides 15 compounds A-12.001 to A-12.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table A-13 provides 15 compounds A-13.001 to A-13.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table A-14 provides 15 compounds A-14.001 to A-14.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table A-15 provides 15 compounds A-15.001 to A-15.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table A-16 provides 15 compounds A-16.001 to A-16.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Table A-17 provides 15 compounds A-17.001 to A-17.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is CHF 2 , R 1 is H and Q are as defined in table Z.
  • Table A-18 provides 15 compounds A-18.001 to A-18.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table A-19 provides 15 compounds A-19.001 to A-19.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table A-20 provides 15 compounds A-20.001 to A-20.015 of formula I-A-1 wherein R 2a is CHF2, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table A-21 provides 15 compounds A-21.001 to A-21.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table A-22 provides 15 compounds A-22.001 to A-22.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is Cl, R 1 is CH 3 and Q are as defined in table Z.
  • Table A-23 provides 15 compounds A-23.001 to A-23.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table A-24 provides 15 compounds A-24.001 to A-24.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table A-25 provides 15 compounds A-25.001 to A-25.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table A-26 provides 15 compounds A-26.001 to A-26.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Table A-27 provides 15 compounds A-27.001 to A-27.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is CHF 2 , R 1 is H and Q are as defined in table Z.
  • Table A-28 provides 15 compounds A-28.001 to A-28.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table A-29 provides 15 compounds A-29.001 to A-29.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table A-30 provides 15 compounds A-30.001 to A-30.015 of formula I-A-1 wherein R 2a is Br, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table A-31 provides 15 compounds A-31.001 to A-31.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table A-32 provides 15 compounds A-32.001 to A-32.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table A-33 provides 15 compounds A-33.001 to A-33.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table A-34 provides 15 compounds A-34.001 to A-34.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table A-35 provides 15 compounds A-35.001 to A-35.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table A-36 provides 15 compounds A-36.001 to A-36.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is CF 3 , R 1 is CH 3 and Q are as defined in table Z.
  • Table A-37 provides 15 compounds A-37.001 to A-37.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z.
  • Table A-38 provides 15 compounds A-38.001 to A-38.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table A-39 provides 15 compounds A-39.001 to A-39.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table A-40 provides 15 compounds A-40.001 to A-40.015 of formula I-A-1 wherein R 2a is I, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table A-41 provides 15 compounds A-41.001 to A-41.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table A-42 provides 15 compounds A-42.001 to A-42.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table A-43 provides 15 compounds A-43.001 to A-43.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table A-44 provides 15 compounds A-44.001 to A-44.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table A-45 provides 15 compounds A-45.001 to A-45.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table A-46 provides 15 compounds A-46.001 to A-46.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is CF 3 , R 1 is CH 3 and Q are as defined in table Z.
  • Table A-47 provides 15 compounds A-47.001 to A-47.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z. 82994 FF
  • Table A-48 provides 15 compounds A-48.001 to A-48.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table A-49 provides 15 compounds A-49.001 to A-49.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table A-50 provides 15 compounds A-50.001 to A-50.015 of formula I-A-1 wherein R 2a is Cyp, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table A-51 provides 15 compounds A-51.001 to A-51.015 of formula I-A-1 wherein R 2a is isopropoxy, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table A-52 provides 15 compounds A-52.001 to A-52.015 of formula I-A-1 wherein R 2a is isopropoxy, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Tables B-1 to B-52 (formula I-B-1) [0248] Table B-1 provides 15 compounds B-1.001 to B-1.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • compound B-29.006 is (B-29.006) [0249]
  • Table B-2 provides 15 compounds B-2.001 to B-2.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table B-3 provides 15 compounds B-3.001 to B-3.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table B-4 provides 15 compounds B-4.001 to B-4.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table B-5 provides 15 compounds B-5.001 to B-5.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table B-6 provides 15 compounds B-6.001 to B-6.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Table B-7 provides 15 compounds B-7.001 to B-7.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z.
  • Table B-8 provides 15 compounds B-8.001 to B-8.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table B-9 provides 15 compounds B-9.001 to B-9.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table B-10 provides 15 compounds B-10.001 to B-10.015 of formula I-B-1 wherein R 2a is CF3, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table B-11 provides 15 compounds B-11.001 to B-11.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table B-12 provides 15 compounds B-12.001 to B-12.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table B-13 provides 15 compounds B-13.001 to B-13.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table B-14 provides 15 compounds B-14.001 to B-14.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table B-15 provides 15 compounds B-15.001 to B-15.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table B-16 provides 15 compounds B-16.001 to B-16.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is CF 3 , R 1 is CH 3 and Q are as defined in table Z.
  • Table B-17 provides 15 compounds B-17.001 to B-17.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z.
  • Table B-18 provides 15 compounds B-18.001 to B-18.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table B-19 provides 15 compounds B-19.001 to B-19.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table B-20 provides 15 compounds B-20.001 to B-20.015 of formula I-B-1 wherein R 2a is CHF2, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table B-21 provides 15 compounds B-21.001 to B-21.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table B-22 provides 15 compounds B-22.001 to B-22.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table B-23 provides 15 compounds B-23.001 to B-23.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table B-24 provides 15 compounds B-24.001 to B-24.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table B-25 provides 15 compounds B-25.001 to B-25.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table B-26 provides 15 compounds B-26.001 to B-26.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is CF 3 , R 1 is CH 3 and Q are as defined in table Z.
  • Table B-27 provides 15 compounds B-27.001 to B-27.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z. 82994 FF
  • Table B-28 provides 15 compounds B-28.001 to B-28.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table B-29 provides 15 compounds B-29.001 to B-29.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table B-30 provides 15 compounds B-30.001 to B-30.015 of formula I-B-1 wherein R 2a is Br, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table B-31 provides 15 compounds B-31.001 to B-31.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table B-32 provides 15 compounds B-32.001 to B-32.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table B-33 provides 15 compounds B-33.001 to B-33.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table B-34 provides 15 compounds B-34.001 to B-34.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table B-35 provides 15 compounds B-35.001 to B-35.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is CF 3 , R 1 is H and Q are as defined in table Z.
  • Table B-36 provides 15 compounds B-36.001 to B-36.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Table B-37 provides 15 compounds B-37.001 to B-37.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z.
  • Table B-38 provides 15 compounds B-38.001 to B-38.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table B-39 provides 15 compounds B-39.001 to B-39.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table B-40 provides 15 compounds B-40.001 to B-40.015 of formula I-B-1 wherein R 2a is I, A is CH, R 2b is Cyp, R 1 is CH 3 and Q are as defined in table Z.
  • Table B-41 provides 15 compounds B-41.001 to B-41.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is Cl, R 1 is H and Q are as defined in table Z.
  • Table B-42 provides 15 compounds B-42.001 to B-42.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is Cl, R 1 is CH3 and Q are as defined in table Z.
  • Table B-43 provides 15 compounds B-43.001 to B-43.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is Br, R 1 is H and Q are as defined in table Z.
  • Table B-44 provides 15 compounds B-44.001 to B-44.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is Br, R 1 is CH3 and Q are as defined in table Z.
  • Table B-45 provides 15 compounds B-45.001 to B-45.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is CF 3 , R 1 is H and Q are as defined in table Z.
  • Table B-46 provides 15 compounds B-46.001 to B-46.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z. 82994 FF
  • Table B-47 provides 15 compounds B-47.001 to B-47.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is CHF2, R 1 is H and Q are as defined in table Z.
  • Table B-48 provides 15 compounds B-48.001 to B-48.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is CHF2, R 1 is CH3 and Q are as defined in table Z.
  • Table B-49 provides 15 compounds B-49.001 to B-49.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is Cyp, R 1 is H and Q are as defined in table Z.
  • Table B-50 provides 15 compounds B-50.001 to B-50.015 of formula I-B-1 wherein R 2a is Cyp, A is CH, R 2b is Cyp, R 1 is CH3 and Q are as defined in table Z.
  • Table B-51 provides 15 compounds B-51.001 to B-51.015 of formula I-B-1 wherein R 2a is isopropoxy, A is CH, R 2b is CF3, R 1 is H and Q are as defined in table Z.
  • Table B-52 provides 15 compounds B-52.001 to B-52.015 of formula I-B-1 wherein R 2a is isopropoxy, A is CH, R 2b is CF3, R 1 is CH3 and Q are as defined in table Z.
  • Table Z Substituent definitions of Q 82994 FF [0300] In Tables A-1 to A-52 and Tables B-1 to B-52, Cyp represents cyclopropyl.
  • a compound of formula IIa-1 as shown below, where A, R 2a , and R 2b are as defined for compounds of formula (I); for instance where A, R 2a , and R 2b are as described in Tables A-1 to A-52; in particular where A is CH, R 2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl and R 2b is bromo, cyclopropyl, or trifluoromethyl; preferably A is CH, R 2a is cyclopropyl and R 2b is trifluoromethyl ⁇ A compound of formula IIa-2, as shown below, where A, R 2a , and R 2b are as defined for compounds of formula (I), R a is C 1 -C 6 alkyl or benzyl, preferably R a is methyl or ethyl; for instance where A
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate.
  • Examples of the above mentioned animal pests are: 82994 FF ⁇ from the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptrut
  • ⁇ from the order Anoplura for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.
  • ⁇ from the order Coleoptera for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna s
  • Trogoderma spp. ⁇ from the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., O
  • ⁇ from the order Hemiptera for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocor
  • Thyanta spp Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysom
  • Vespa spp. ⁇ from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminata; ⁇ from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chry
  • Trichodectes spp. 82994 FF ⁇ from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp., and Schistocerca spp.; ⁇ from the order Psocoptera, for example, Liposcelis spp.; ⁇ from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp.
  • Orthoptera for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. ,
  • Thysanoptera for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; ⁇ from the order Thysanura, for example, Lepisma saccharina.
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria 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; Sting nematodes, Bel
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H.
  • the active ingredients according to the invention can be used for controlling, i.e.
  • pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and
  • compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I.
  • Iresines spp. Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.
  • the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the compounds of formula (I) are particularly suitable for control of ⁇ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in sunflower, vegetables, soybeans, and sugarcane);
  • ⁇ a pest of the order Lepidoptera for example, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn);
  • ⁇ a pest of the order Thysanoptera such as the family
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vip1, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, 82994 FF such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1FA 2 , Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • CP4 EPSPS obtained from Agrobacterium sp. strain CP4
  • Roundup® contains glyphosate
  • Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0392225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related proteins" (PRPs; see e.g. EP-A-0392225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1, KP4 or KP6 toxins stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related
  • compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention provides a compound of the first aspect for use in therapy.
  • the present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal.
  • the present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal.
  • present invention further provides a compound of the first aspect, for use in preventing and/or treating diseases transmitted by ectoparasites.
  • the present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal.
  • the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal.
  • the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and/or treating diseases transmitted by ectoparasites.
  • the present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal.
  • the present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal.
  • controlling when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation.
  • treating when used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease. 82994 FF
  • preventing when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal.
  • animal when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal.
  • Non-human mammals include, but are not limited to, livestock animals and companion animals.
  • Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses.
  • Companion animals include, but are not limited to, dogs, cats and rabbits.
  • a "parasite” is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense.
  • An "endoparasite” is a parasite which lives in the host animal.
  • Ectoparasite is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice).
  • the Acari (or Acarina) sub-class comprises ticks and mites.
  • Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros.
  • Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates.
  • Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera.
  • Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis.
  • Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes.
  • Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola ovis and Bovicola bovis.
  • the term "effective amount" when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal.
  • the effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • the compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally ' and subcutaneously. Topical administration is preferred.
  • Formulations suitable for topical administration include, for example, solutions, 82994 FF emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip.
  • the compounds of the invention may be administered by means of an ear tag or collar.
  • Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts.
  • Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS indoor residual spraying
  • a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005/113886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees. 82994 FF
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g.
  • Ataenius spp. e.g. Black turfgrass ataenius, A. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls (Margarodes spp.)
  • mole crickets tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two- lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Examples of such parasites are: ⁇ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomy
  • Siphonapta for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. ⁇
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. ⁇
  • Blattarida for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests : beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocer
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • a compound TX controls one 82994 FF or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp.
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.
  • a compound TX controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilapar
  • a compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • TX means "one compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P”
  • TX means "one compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P”
  • TX Muscodor roseus A3-5 (NRRL Accession No.30548) + TX, Myrothecium verrucaria composition + TX, nabam + TX, NC-184 + TX, Neem tree based products + TX, Neodiprion sertifer NPV and N.
  • lecontei NPV + TX nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp.
  • TX trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc- call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp.
  • acridum + TX Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020/193387) + TX, methyl (
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • TX Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX
  • NRRL 305408 + TX, Mycorrhizae spp. (AMykor®, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp.
  • TX Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, P
  • TX Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp.
  • Rhizobia Distal®, Vault®
  • Rhizoctonia + TX Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • TX Trichoderma atroviride
  • Trichoderma gamsii TX
  • Trichoderma hamatum TH 382 + TX Trichoderma harzianum rifai (Mycostar®) + TX
  • Trichoderma harzianum T-22 Trianum-P®, PlantShield HC®, RootShield®, Trianum-G® + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp.
  • TX maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus,
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, CAS Number: 2643947-26-4 + TX, Chondroster
  • NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX
  • Bacillus pumilus in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No.71840-19) + TX
  • Bacillus subtilis CX-9060 from Certis USA LLC
  • Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S.
  • Patent No.7,094,592 + TX Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S.
  • Patent No.6,060,051 available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US
  • TX Paenibacillus polymyxa
  • strain 82994 FF AC-1 e.g. TOPSEED® from Green Biotech Company Ltd.
  • TX Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX
  • Pantoea agglomerans in particular strain E325 (Accession No.
  • NRRL B-21856 (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No.
  • CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX; Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX, Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREENTM from University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No.
  • Agrobacterium radiobacter strain K84 e.g. GALLTROL-A® from AgBioChem, CA
  • Bacillus amyloliquefaciens isolate B246 e.g. AVOGREENTM from University of Pretoria
  • Bacillus amyloliquefaciens strain F727 also known as strain MBI110
  • Patent No. 5,061,495 + TX Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.
  • NRRL B-50897, WO 2017/019448 e.g., HOWLERTM and ZIO® from AgBiome Innovations, US
  • TX Pseudomonas chlororaphis
  • strain MA342 e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert
  • TX Pseudomonas fluorescens strain A506 (e.g. BLIGHTBAN® A506 by NuFarm) + TX
  • Pseudomonas proradix e.g.
  • PRORADIX® from Sourcon Padena + TX
  • Streptomyces griseoviridis strain K61 also known as Streptomyces galbus strain K61
  • DSM 7206 Streptomyces galbus strain K61
  • MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf.
  • BIOKUPRUMTM by AgriLife + TX
  • Chaetomium globosum available as RIVADIOM® by Rivale
  • TX Cladosporium cladosporioides
  • strain H39 having Accession No. CBS122244, US 2010/0291039 (by Stichting Moowgrass Onderzoek) + TX
  • Coniothyrium minitans in particular strain CON/M/91-8 (Accession No. DSM9660, e.g.
  • strain ICC 080 having Accession No. IMI 392151 (e.g., BIO-TAMTM from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938, CNCM No.1- 82994 FF 3939 (WO 2010/086790) from Lesaff
  • T-Gro from Andermatt Biocontrol + TX
  • Trichoderma atroviride strain 77B T77 from Andermatt Biocontrol
  • Trichoderma atroviride strain ATCC 20476 IMI 206040
  • Trichoderma atroviride strain LC52 e.g. Tenet by Agrimm Technologies Limited
  • Trichoderma atroviride strain LU132 e.g. Sentinel from Agrimm Technologies Limited
  • TX Trichoderma atroviride strain NMI no. V08/002388 + TX
  • Trichoderma atroviride strain NMI no. V08/002389 + TX Trichoderma atroviride strain NMI no.
  • Trichoderma atroviride strain CNCM 1-1237 e.g. Esquive® WP from Agrauxine, FR
  • Trichoderma fertile e.g. product TrichoPlus from BASF
  • Trichoderma gamsii (formerly T. viride) + TX
  • Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.)
  • + TX Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g.
  • Trianum-P from Koppert TX
  • Trichoderma harzianum strain T-22 e.g. Trianum-P from Andermatt Biocontrol or Koppert
  • Trichoderma harzianum strain TH35 e.g. Root-Pro by Mycontrol
  • Trichoderma polysporum strain IMI 206039 e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden
  • Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX
  • Trichoderma virens also known as Gliocladium virens
  • strain GL-21 e.g.
  • Trichoderma virens strain G-41 formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No.
  • NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
  • TX Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No.
  • WCS850 deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; 82994 FF a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IFTM from TerraMax, Inc.) + TX, Azotobacter chroococcum
  • NRRL B-5015 + TX
  • Bacillus amyloliquefaciens in particular strain FZB42 e.g. RHIZOVITAL® from ABiTEP, DE
  • Bacillus amyloliquefaciens in particular strain IN937a + TX Bacillus amyloliquefaciens pm414 (LOLI- PEPTA® from Biofilm Crop Protection) + TX
  • Bacillus amyloliquefaciens SB3281 ATCC # PTA-7542, WO 2017/205258
  • Bacillus amyloliquefaciens TJ1000 available as QUIKROOTS® from Novozymes
  • Bacillus cereus family member EE128 NRRL No.
  • YIELD SHIELD® from Bayer Crop Science, DE
  • + TX Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B-50421 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No. 13/330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g.
  • BIOBOOST® from Brett Young Seeds + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g.
  • PRORADIX® from Sourcon Padena + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g.
  • Trichoderma atroviride strain SC1 (described in WO2009/116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g.
  • aizawai in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp.
  • serotype H-7 e.g. FLORBAC® WG from Valent BioSciences, US
  • TX Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX
  • israeltaki strain ABTS 351 + TX Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp.
  • BMP 123 from Becker Microbial Products, IL, BARITONE from Bayer CropScience
  • TX Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX
  • israeltaki strain PB 54 + TX Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var.
  • SD-5428 e.g. NOVODOR® FC from BioFa DE
  • Bacillus thuringiensis var. Colmeri e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory
  • MBI206 TGAI and ZELTO® from Marrone Bio Innovations + TX
  • Chromobacterium subtsugae in particular strain PRAA4-1T e.g. MBI-203, e.g. GRANDEVO® from Marrone Bio Innovations
  • TX Chromobacterium subtsugae in particular strain PRAA4-1T
  • MBI-203 e.g. GRANDEVO® from Marrone Bio Innovations
  • TX Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX
  • Paenibacillus popilliae (formerly Bacillus 82994 FF popilliae, e.g. MILKY SPORE POWDERTM or MILKY SPORE GRANULARTM from St. Gabriel Laboratories) + TX
  • Serratia entomophila e.g.
  • ATCC74250 e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation
  • TX Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017/066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX; Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, of Adoxophyes orana (summer fruit tortrix) granul
  • Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp.
  • the designation is not a "common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name”, a “traditional name”, a “compound name” or a “development code” is used or, if neither one of those designations nor a "common name” is used, an "alternative name” is employed.
  • "CAS Reg. No” means the Chemical Abstracts Registry Number.
  • the active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-52, Tables B-1 to B-52, and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-52, Tables B-1 to B-52, and Table P, 82994 FF and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2
  • the compounds and mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.
  • the mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-52, Tables B-1 to B-52, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention.
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface- active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethyl-formamide, dimethyl sulfoxide, 1,4-dioxane, dipropyl
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of 82994 FF sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula-tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: ⁇ active ingredient: 1 to 95 %, preferably 60 to 90 % ⁇ surface-active agent: 1 to 30 %, preferably 5 to 20 % ⁇ liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts: ⁇ active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % 82994 FF ⁇ solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: ⁇ active ingredient: 5 to 75 %, preferably 10 to 50 % ⁇ water: 94 to 24 %, preferably 88 to 30 % ⁇ surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: ⁇ active ingredient: 0.5 to 90 %, preferably 1 to 80 % ⁇ surface-active agent: 0.5 to 20 %, preferably 1 to 15 % ⁇ solid carrier: 5 to 95 %,
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • the mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity.
  • Suitable additions to active ingredients are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or 82994 FF tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or 82994 FF tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides,
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredi-ent can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application).
  • systemic action systemic action
  • the active ingredient in solid form into the locus of the plants for example into the soil, for example in the form of granules (soil application).
  • paddy rice crops such granules can be metered into the flooded paddy-field.
  • the compounds of formula (I) of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula (I).
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • the compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m 2 .
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - [0395] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % [0397] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Coated granules Active ingredients 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % [0400] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % [0401]
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % 82994 FF Water 45.3 % [0402] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • the characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion [M+H] + or [M-H]-.
  • Method 1 [0405] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • Method 2 [0406] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from 82994 FF Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • an electrospray source Polarity: Positive and Negative Polarity Switch
  • Method 3 [0407] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • SQD SQDII or QDA Single quadrupole mass spectrometer
  • Capillary 0.8-3.00 kV
  • Cone 5-30 V
  • Source Temperature 120-150°C
  • Desolvation Temperature 350- 600°C
  • Cone Gas Flow 50-150
  • Example E1 Preparation of 5-bromo-N-[(1S)-1-[3-(5-cyano-2-pyridyl)pyrazin-2-yl]ethyl]-3-iodo-1H-indazole-7- carboxamide (compound P4)
  • Step 1 Preparation of 5-bromo-3-iodo-1H-indazole-7-carboxylic acid (I-16) (I-16) [0408]
  • To a solution of 5-bromo-1H-indazole-7-carboxylic acid (CAS 953409-99-9) (1.00 g, 4.15 mmol) in N,N-dimethylformamide (12.4 mL) at 0°C were added potassium hydroxide (0.419 g, 7.47 mmol), followed after 5 min by iodine (1.16 g, 4.56 mmol).
  • Step 2 Preparation of 5-bromo-N-[(1S)-1-[3-(5-cyano-2-pyridyl)pyrazin-2-yl]ethyl]-3-iodo-1H-indazole-7- carboxamide (P4) [0410] To a solution of 6-[3-[(1S)-1-aminoethyl]pyrazin-2-yl]pyridine-3-carbonitrile (CAS 2497659-69-3) (1.2 g, 4.6 mmol) in ethyl acetate (15 mL) were added propanephosphonic acid cyclic anhydride (T3P®, 50 wt.% in ethyl acetate, 4.2 mmol), 5-bromo-3-iodo-1H-indazole-7-carboxylic acid (I-16) (1.4 g, 3.8 mmol) and N,N- diisopropylethylamine (2.6 mL, 15 mmol) at
  • Step 2 Preparation of methyl 5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-2) (I-2) [0414] A pressure vessel was charged with 7-bromo-5-(trifluoromethyl)-1H-indazole (I-1) (5.7 g, 21.5 mmol), 1,1’-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (Pd(dppf)Cl2 ⁇ CH2Cl2; 1.79 g, 2.15 mmol), triethylamine (4.39 g, 43 mmol) and methanol (57 mL).
  • Step 3 Preparation of methyl 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-3) 82994 FF (I-3) [0416] To a solution of methyl 5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-2) (4.3 g, 17.6 mmol) in acetic acid (43 mL) was added N-iodosuccinimide (5.94 g, 26.41 mmol) at room temperature.
  • Step 4 Preparation of methyl 3-iodo-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-4) (I-4) [0418] To a suspension of sodium hydride (0.51 g, 12.97 mmol, 60 mass%) in tetrahydrofuran (32 mL) cooled to 0-5°C under nitrogen was added a solution of methyl 3-iodo-5-(trifluoromethyl)-1H-indazole-7- carboxylate (I-3) (3.2 g, 8.64 mmol) in tetrahydrofuran (32 mL) dropwise at 0-5°C (effervescence observed).
  • Step 5 Preparation of methyl 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-5) and 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) 82994 FF
  • the reaction mixture was heated to 85°C and a solution of tribasic potassium phosphate (3.23 g, 14.4 mmol) in degassed water (28 mL) was added dropwise at 80°C.
  • the mixture was heated at 85°C for 5 h, cooled to room temperature, diluted with water and the product extracted with EtOAc. The layers were separated and the aqueous phase kept aside. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo.
  • Step 6 Preparation of 3-cyclopropyl-N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-(trifluoromethyl)-1H- indazole-7-carboxamide (P8) 82994 FF
  • I-6 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid
  • N,N-diisopropylethylamine 0.432 g, 3.33 mmol
  • propane- phosphonic acid cyclic anhydride T3P®, 50 wt.% in ethyl acetate, 2.22 mmol
  • 3-iodo-N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-(trifluoromethyl)-1H-indazole- 7-carboxamide (P7) can be obtained from 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-15) and [(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]ammonium 2,2,2-trifluoroacetate (CAS 2641011-44-9) with above protocol in analogy.
  • Step 2 Preparation of N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-N-methyl-5-(trifluoromethyl)indazole-7-carboxamide (P20) [0430] To a mixture of 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7) (0.08 g, 0.25 mmol) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-methyl-ammonium chloride (0.108 g, 0.38 mmol), prepared as described in WO 2023/247360, in acetonitrile (1.6 mL) was added propane-phosphonic acid cyclic anhydr
  • 3-cyclopropyl-2-(methoxymethyl)-N-[(1S)-1-[2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2,4- triazol-3-yl]ethyl]-5-(trifluoromethyl)indazole-7-carboxamide (P17) can be obtained from 3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7) and [(1S)-1-[2-[6-(methyl- carbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]ammonium chloride (prepared in analogy to CAS 2694010-27- 8 as described for example in WO 2021/224323) with the above protocol in analogy.
  • N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P25) can be obtained from 3-cyclopropyl-5-(trifluoromethyl)-1H- 82994 FF indazole-7-carboxylic acid (I-6) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2694010-27-8) with above protocol in analogy.
  • Step 2 Preparation of [2-amino-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-9)
  • a solution of N-[4-(trifluoromethyl)phenyl]cyclopropanecarboxamide (I-8) (16 g, 69.81 mmol) in acetonitrile (4600 mL) was passed through a 55 mL-photo flow reactor (254 nm; flow: 1ml/minute; residence 82994 FF time: 55 min) at room temperature.
  • Step 3 Preparation of [2-amino-3-bromo-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-10) [0440] To a solution of [2-amino-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-9) (5.8 g, 25 mmol) in acetonitrile (120 mL) was added N-bromosuccinimide (5.6 g, 30 mmol) and reaction mixture was stirred at RT for 15 h. The mixture was diluted with an aqueous saturated sodium bicarbonate solution and the product extracted with ethyl acetate.
  • Step 4 Preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11)
  • Step 5 Preparation of methyl 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-12) (I-12) [0444]
  • a pressure vessel was charged with 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11) (0.10 g, 0.327 mmol), 1,1’-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (Pd(dppf)Cl2 ⁇ CH2Cl2; 0.027 g, 0.0328 mmol), triethylamine (0.0335 g, 0.327 mmol) and methanol (3 mL).
  • Step 6 Preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) [0446] To a solution of methyl 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-12) (0.1 g, 0.352 mmol) in methanol (1.00 mL) and water (1.00 mL) was added lithium hydroxide (0.01 g, 0.422 mmol). The reaction mixture was stirred at room temperature for 12 hours, then concentrated under reduced pressure. The residue was diluted with ice cold water and acidified with concentrated hydrochloric acid.
  • Step 7 Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P10) [0448] To a mixture 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) (0.06 g, 0.222 mmol), and [(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2378554-38-0) (0.066 g, 0.266 mmol) in acetonitrile (1.2 mL) was added N,N-diisopropylethylamine (0.114 mL, 0.666 mmol), followed by propanephosphonic acid cycl
  • N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-iodo-5-(trifluoromethyl)-1H- indazole-7-carboxamide (P9) can be obtained from 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I- 15) and [(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2378554-38-0) with above protocol in analogy.
  • N-[(1S)-1-[2-(6-chloropyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxamide (P22) can be obtained from 3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7) and [(1S)-1-[2-(6-chloropyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 3039973-68-4) with above protocol in analogy.
  • Step 2 Preparation of methyl 3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 20) (I-20) [0460] To a solution of methyl 3-hydroxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-19) (0.05 g, 0.164 mmol) in toluene (1.25 mL) was added silver carbonate (0.328 mmol). The reaction mixture was heated to 100°C, then 2-iodopropane (0.493 mmol) was slowly added and stirring continued at 100°C for 5 hours. The mixture was diluted with water and the product extracted with ethyl acetate.
  • Step 3 Preparation of sodium 3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 21) (I-21) [0462] To a solution of methyl 3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 20) (0.047 g, 0.14 mmol) in methanol (0.94 mL) and water (0.94 mL) was added sodium hydroxide (8.1 mg, 0.20 mmol) at room temperature.
  • Example E6 Preparation of 3-cyclopropyl-2-(methoxymethyl)-N-[(1S)-1-[2-(6-methoxypyridazin-3-yl)-1,2,4- triazol-3-yl]ethyl]-5-(trifluoromethyl)indazole-7-carboxamide (compound P21) [0466] To a mixture of N-[(1S)-1-[2-(6-chloropyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxamide (P22) (280 mg, 0.54 mmol) in methanol (5 mL) was 82994 FF added potassium carbonate (187.6 mg, 1.34 mmol).
  • 3-cyclopropyl-N-[(1S)-1-[2-(6-ethoxypyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P30) can be obtained from N-[(1S)-1-[2-(6-chloropyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxamide (P29) and ethanol with above protocol in analogy.
  • Step 2 Preparation of 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-15) [0472] To a solution of 5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-14) (0.8 g, 3.48 mmol) in acetic acid (8 mL) was added N-iodosuccinimide (0.82 g, 3.65 mmol) at room temperature. After addition the reaction mixture was heated at 60°C for 16 h. The mixture was diluted with an aqueous solution of sodium metabisulfite (100 mL) and the precipitated solid isolated by filtration.
  • Example PI-2 Alternative preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) [0474] To a solution of methyl 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 5) (1.8 g, 5.48 mmol) in methanol (36 mL) and water (36 mL) was added NaOH (0.329 g, 8.22 mmol) at room temperature. After addition the reaction mixture was stirred at room temperature for 15 h, then concentrated under reduced pressure and the residue diluted with water.
  • Example PI-3 Alternative preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11) Step 1: Preparation of 7-bromo-3-iodo-5-(trifluoromethyl)-1H-indazole (I-13) [0476] To a solution of 7-bromo-5-(trifluoromethyl)-1H-indazole (I-1) (1.0 g, 3.8 mmol) and NaOH (0.45 g, 11 mmol) in methanol (11 mL) and water (11 mL) was added iodine (1.0 g, 4.0 mmol) portionwise keeping the internal temperature around room temperature.
  • iodine 1.0 g, 4.0 mmol
  • Step 2 Preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11) [0478] A solution of 7-bromo-3-iodo-5-(trifluoromethyl)-1H-indazole (I-13) (5.5 g, 14.07 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.83 g, 0.70 mmol) in tetrahydrofuran (28 mL) was flushed with argon and cooled to 0°C.
  • Example PI-4 Alternative preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) [0480] A solution of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11) (0.212 g, 0.69 mmol) in tetrahydrofuran (4.6 mL) under argon was cooled to -78°C.
  • Example B1 Activity against Chilo suppressalis (Striped rice stemborer) [0484] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well).
  • the samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation.
  • Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • the following compounds resulted in at least 80% control at an application rate of 200 ppm: P2, P6, P7, P8, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P23, P25, P26, P27, P28, P31.
  • Example B2 Activity against Diabrotica balteata (Corn root worm) [0486] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
  • Example B6 Activity against Myzus persicae (Green peach aphid). Feeding/Contact activity [0494] Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.
  • Example B7 Activity against Myzus persicae (Green peach aphid).
  • Intrinsic activity Test compounds prepared from 10'000 ppm DMSO stock solutions were applied by pipette into 24- well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.
  • Example B9 Activity against Plutella xylostella (Diamond back moth) [0500] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.
  • Example B10 Activity against Spodoptera littoralis (Egyptian cotton leaf worm) 82994 FF
  • Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0503] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P6, P8, P11, P12, P16, P17, P20, P25, P26, P27, P31.

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Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

Description

82994 FF 1 PESTICIDALLY ACTIVE INDAZOLE COMPOUNDS TECHNICAL FIELD [0001] The present invention relates to pesticidally active indazole compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active indazole compounds. The invention also relates to the preparation of these indazole compounds, to intermediates useful in the preparation of these indazole compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these indazole compounds, to preparation of these compositions and to the use of these indazole compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina. BACKGROUND [0002] WO 2023/037249, WO 2023/285175, WO 2022/157188 and WO 2019/197468 describe certain fused heterobicyclic carboxamide derivatives with pesticidal activity. WO 2021/105334 describes certain 1H-indazole- 7-carboxamide derivatives which were evaluated for their cereblon binding affinity. BRIEF SUMMARY [0003] It has now surprisingly been found that certain novel indazole compounds have pesticidal activity. More specifically, certain novel indazole-7-carboxamide compounds and aza analogues thereof, have pesticidal activity. [0004] Hence, the present invention accordingly relates, in a first aspect, to a compound of the formula (I):
Figure imgf000002_0001
X is an oxygen atom or a sulfur atom;
Figure imgf000002_0002
the staggered line represents the connection of Q to the rest of compound of the formula (I); R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; 82994 FF R2a is hydrogen, halogen, -CN, C1-C4alkyl, C1-C3haloalkyl, C1-C4alkoxy, C1-C3haloalkoxy, C3- C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3- C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, -CN, C1-C3alkyl, and C1-C3haloalkyl; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10 ; R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R6 is connected to a nitrogen atom, and R6 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1- C3alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl or C1-C6alkoxycarbonyl; R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of the compound of formula (I). [0005] The present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I). [0006] In a second aspect, the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient. [0007] In a third aspect, the present invention makes available a method of combating and controlling pests, such as insects, acarines, nematodes, or molluscs, which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally, such as insecticidally, acaricidally, nematicidally, or molluscicidally, effective amount of a compound as defined in the first aspect or of a composition as defined in the second aspect. [0008] In a fourth aspect, the present invention makes available a method for the protection of plant propagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which 82994 FF comprises treating the propagation material or the site where the propagation material is planted, with an effective amount of a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect. [0009] In a fifth aspect, the present invention makes available a plant propagation material, such as a seed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect. [0010] The present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof. DETAILED DESCRIPTION [0011] Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1- C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. [0012] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form. [0013] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. [0014] The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation. [0015] The term "C1-Cnalkyl" as used herein refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- 82994 FF methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl. [0016] The term "C1-Cnhaloalkyl" as used herein refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro- 2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3- difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3- trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3- pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2- fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4- bromobutyl or nonafluorobutyl. Accordingly "C1-C2fluoroalkyl" refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. [0017] The term "C1-Cnalkoxy" as used herein refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. The term "haloC1-Cnalkoxy" as used herein refers to a C1-Cnalkoxy radical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different halo atom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy. [0018] The term "C1-Cncyanoalkyl" as used herein refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1- (cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like. [0019] The term "C3-Cncycloalkyl" as used herein refers to a saturated monocyclic hydrocarbon radical attached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. [0020] The term "cyanoC3-Cncycloalkyl" as used herein refers to a C3-Cncycloalkyl where one of the hydrogen atoms in these radicals is replaced by a cyano group. [0021] The term "C3-Cncycloalkylcarbonyl" as used herein refers to a C3-Cncycloalkyl radical bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. Similarly the terms "C1- Cnalkylcarbonyl", "C1-Cnalkoxycarbonyl", "phenyloxycarbonyl" and "benzyloxycarbonyl" as used herein refers to an C1-Cnalkyl, C1-Cnalkoxy, phenyloxy and benzyloxy group bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. [0022] The term "C3-C4cycloalkylC1-C2alkyl" as used herein refers to a cyclopropyl or cyclobutyl radical bonded via a methylene or ethylene bridge to the rest of the molecule. When the C3-C4cycloalkylC1-C2alkyl 82994 FF radical is substituted, the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge. [0023] The term "C1-Cnalkylsulfanyl" as used herein refers to a C1-Cnalkyl moiety linked through a sulfur atom. Similarly, the term "C1-Cnhaloalkylthio" or "C1-Cnhaloalkylsulfanyl" as used herein refers to a C1- Cnhaloalkyl moiety linked through a sulfur atom. Similarly, the term "C3-Cncycloalkylsulfanyl" refers to 3-n membered cycloalkyl moiety linked through a sulfur atom. [0024] The term "C1-Cnalkylsulfinyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, the term "C1-Cnhaloalkylsulfinyl " or "C1-Cnhaloalkylsulfinyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, the term "C3- Cncycloalkylsulfinyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom of the S(=O) group. [0025] The term "C1-Cnalkylsulfonyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly, the term "C1-Cnhaloalkylsulfonyl " or "C1-Cnhaloalkylsulfonyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly, the term "C3-Cncycloalkylsulfonyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom of the S(=O)2 group. [0026] The term "C2-Cnalkenyl" as used herein refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl. [0027] The term "C2-Cnalkynyl" as used herein refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl. [0028] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl. [0029] The term "optionally substituted" as used herein means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, "C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms" means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3-C4cycloalkyl substituted with 2 halo atoms. [0030] As used herein, the term "controlling" refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced. [0031] As used herein, the term "pest" refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest. [0032] As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect. [0033] An effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to 82994 FF be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances. [0034] As one of ordinary skill in the art will appreciate, compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in formula (I*) below:
Figure imgf000007_0001
where A, R1, R2a, R2b, R3, R6, Q and X are as defined in the first aspect. [0035] The present invention contemplates both racemates and individual enantiomers. Compounds of formula (I') having a preferred stereochemistry are set out below:
Figure imgf000007_0002
[0036] Particularly preferred compounds of the present invention are compounds of formula (I’), where A, R1, R2a, R2b, R3, R6, Q and X are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I’), and agrochemically acceptable salts thereof. [0037] Particularly preferred compounds of formula (I’) include compounds of formula (I’a) as shown below, where X is oxygen, and A, R1, R2a, R2b, R3, R6, and Q are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I*a), and agrochemically acceptable salts thereof:
Figure imgf000007_0003
82994 FF [0038] Compounds of formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A, R1, R2a, R2b, R3, R6, Q and X are as defined in the first aspect, may be depicted as compounds of formula (I-N1) and (I-N2):
Figure imgf000008_0001
[0039] When R6 is hydrogen, compounds of the formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A, R1, R2a, R2b, R3, Q and X are as defined in the first aspect, may exist in different tautomeric forms, represented as the 1H-indazole (I”-1), 2H-indazole (I”-2), and, 3H-indazole (I”-3):
Figure imgf000008_0002
where the staggered line represents the connection to the remainder of said compounds of the formula (I), (I*), (I*a), (I’) and (I’a). This invention covers all such tautomers and mixtures thereof in all proportions. [0040] Particularly preferred compounds of the present invention are compounds of formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and (I’a), where A is CH, and where R1, R2a, R2b, R3, R6, Q and X are as defined in the first aspect. When R6 is hydrogen, these compounds may exist in different 82994 FF tautomeric forms, as represented above as the 1H-indazole (I”-1), 2H-indazole (I”-2), and 3H-indazole (I”-3). More preferably, X is oxygen. [0041] Preferred compounds where A is CH, X is oxygen, and where R1, R2a, R2b, R3, R6, and Q are as defined in the first aspect may be depicted as compounds of formula (I-N1a) and (I-N2a):
Figure imgf000009_0001
(I-N1a) (I-N2a) and preferably as compounds of formula (I’N1a) and (I’N2a):
Figure imgf000009_0002
[0042] Embodiments according to the invention are provided as set out below. [0043] In an embodiment of each aspect of the invention, A is N. When A is N, the moiety containing A is a pyrazolo[4,3-b]pyridine group. In another embodiment of each aspect of the invention, A is CH. In a preferred embodiment of each aspect of the invention, A is CH. When A is CH, the moiety containing A is an indazole group. [0044] In an embodiment of each aspect of the invention, X is oxygen (i.e. an oxygen atom). In an embodiment of each aspect of the invention, X is S (i.e. a sulfur atom). Preferably, in embodiments of each aspect of the invention, X is oxygen. [0045] In an embodiment of each aspect of the invention, R1 is as follows: A. R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B. R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; or C. R1 is hydrogen, methyl, or cyclopropylmethyl; or D. R1 is hydrogen or methyl; or E. R1 is methyl; or F. R1 is hydrogen. 82994 FF [0046] In preferred embodiments of each aspects of the invention, R1 is hydrogen, methyl, or cyclopropylmethyl; or R1 is hydrogen or methyl. Most preferably, R1 is hydrogen. [0047] In an embodiment of each aspect of the invention, R2a is as follows: A. R2a is hydrogen, halogen, C1-C3haloalkyl, C1-C4alkoxy, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; or B. R2a is hydrogen, halogen, C1-C3fluoroalkyl, cyclopropyl, cyclobutyl, or cyclopropyl substituted with a single fluoro or cyano; or C. R2a is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethyl, cyclopropyl, 1- fluorocyclopropyl, 1-cyanocyclopropyl, or isopropoxy; or D. R2a is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethyl, cyclopropyl, 1- fluorocyclopropyl, or 1-cyanocyclopropyl; or E. R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl; or F. R2a is hydrogen, bromo, iodo, or cyclopropyl; or G. R2a is hydrogen or cyclopropyl; or H. R2a is cyclopropyl; or I. .R2a is hydrogen. [0048] In preferred embodiments of each aspect of the invention, R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl. For instance, R2a is hydrogen, iodo, or cyclopropyl. In more preferred embodiments of each aspect of the invention, R2a is hydrogen or cyclopropyl. [0049] In an embodiment of each aspect of the invention, R2b is as follows: A. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1- C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, -CN, C1-C3alkyl, and C1-C3haloalkyl; or B. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1- C2haloalkyl, C3-C4cycloalkylcarbonyl, cyclopropyl, or cyclopropyl substituted with one or two substituents independently selected from the group consisting of halogen, -CN, methyl, and trifluoromethyl; or C. R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl; or D. R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3haloalkylsulfonyl, or cyclopropyl; or E. R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; or F. R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; or G. R2b is chloro, bromo, cyclopropyl, difluoromethyl, or trifluoromethyl; or H. R2b is bromo, cyclopropyl, or trifluoromethyl; or 82994 FF I. R2b is bromo or trifluoromethyl; or J. R2b is cyclopropyl. [0050] In preferred embodiments of each aspect of the invention, R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl, such as R2b is bromo or trifluoromethyl. [0051] As shown above, R6 is connected to one of the two nitrogen atoms of the pyrazole ring of the indazole group (when A is CH) or of the pyrazolo[4,3-b]pyridine group (when A is N) of the compound of formula (I). For the sake of clarity, “R6 is connected to a nitrogen atom” refers to one or the other nitrogen atom of said pyrazole ring. In particular, R6 is not connected to A when A is nitrogen. [0052] In an embodiment of each aspect of the invention, R6 is as follows: A. R6 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl or C1-C6alkoxycarbonyl; or B. R6 is hydrogen, C1-C4alkyl, C1-C3cyanoalkyl, C1-C2alkoxyC1-C2alkyl, C2-C3alkenyl, C2-C3alkynyl, C3- C4cycloalkylC1-C2alkyl or C1-C4alkoxycarbonyl; or C. R6 is hydrogen, C1-C4alkyl, C1-C2alkoxyC1-C2alkyl, or C3-C4cycloalkylC1-C2alkyl; or D. R6 is hydrogen, C1-C4alkyl, or C1-C2alkoxyC1-C2alkyl; or E. R6 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, 2-methoxyethyl, allyl, propargyl, cyclopropylmethyl, methoxycarbonyl, or ethoxycarbonyl; or F. R6 is hydrogen, methyl, or methoxymethyl; or G. R6 is hydrogen or methoxymethyl; or H. R6 is methoxymethyl; or I. R6 is hydrogen. [0053] In preferred embodiments of each aspect of the invention, R6 is hydrogen, methyl, or methoxymethyl. Preferably, R6 is hydrogen or methoxymethyl. Most preferably, R6 is hydrogen. [0054] In preferred embodiments of each aspect of the invention, compounds of formula (I) are compounds of formula (I-N1a), such as compounds of formula (I-N1a), where R6 is hydrogen, and tautomers thereof. More preferably, compounds of formula (I) are compounds of formula (I’N1a), such as compounds of formula (I’N1a), where R6 is hydrogen, and tautomers thereof. [0055] In an embodiment of each aspect of the invention, R3 is as follows: A. R3 is C1-C3alkyl or C1-C3haloalkyl; or B. R3 is methyl or trifluoromethyl; or C. R3 is methyl. [0056] In preferred embodiments of each aspect of the invention, R3 is methyl. [0057] In an embodiment of each aspect of the invention, Q is Qa. In embodiments where Q is Qa, R5 is as follows: A. R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R5 is hydrogen, halogen, or C1-C3alkyloxy; or C. R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or D. R5 is hydrogen, halogen, or C1-C3alkyloxy; or 82994 FF E. R5 is hydrogen, halogen, or C1-C3alkyl; or F. R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, 2-methoxyethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylcarbonyl, methoxycarbonyl, or 1,3,4-oxadiazol-2-yl; or G. R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; or H. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or I. R5 is hydrogen. [0058] In preferred embodiments where Q is Qa, R5 is as follows: A. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or B. R5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; or C. R5 is hydrogen, cyclopropyl, or methoxy; or D. R5 is hydrogen. [0059] For instance, Qa is selected from Qa-1 to Qa-16:
Figure imgf000012_0001
82994 FF
Figure imgf000013_0001
[0060] As an example, Qa is Qa-1, Qa-4, Qa-5 Qa-6, Qa-7, Qa-10, or Qa-15; or Qa is selected from Qa-1, Qa- 6, Qa-7, Qa-10, and Qa-15. Preferably, Q is Qa-1, or Qa-15. Most preferably, Q is Qa-1. [0061] In another embodiment of each aspect of the invention, Q is Qb. In embodiments where Q is Qb, R5a and R5b are as follows: A. R5a is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R5a is hydrogen, halogen, or C1-C3alkyloxy; or C. R5a is hydrogen, halogen, or C1-C3alkyl; or D. R5a is hydrogen, chloro, fluoro, methyl, cyclopropyl, trifluoromethyl, methoxy, difluoromethoxy, or cyano; or E. R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy; or F. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy; or G. R5a is hydrogen; and A. R5b is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R5b is hydrogen, halogen, or C1-C3alkyloxy; or C. R5b is hydrogen, halogen, or C1-C3alkyl; or D. R5b is hydrogen, chloro, fluoro, or methoxy; or E. R5b is hydrogen, fluoro, or methoxy; or F. R5b is hydrogen. [0062] In preferred embodiments where Q is Qb: A. R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy and R5b is hydrogen, fluoro, or methoxy; or B. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy, and R5b is hydrogen, chloro, fluoro, or methoxy; or C. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy, and R5b is hydrogen, fluoro, or methoxy; or D. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy and R5b is hydrogen; or E. R5a is hydrogen, and R5b is hydrogen, fluoro, or methoxy; or F. R5a and R5b are hydrogen. [0063] For instance, Qb is selected from Qb-1 to Qb-13: 82994 FF
Figure imgf000014_0001
[0064] As an example, Qb is Qb-1, Qb-2, Qb-3, Qb-5, Qb-6, Qb-8, Qb-9, Qb-10, or Qb-11; or Qb is selected from Qb-1, Qb-2, Qb-3, Qb-5, Qb-8, Qb-9, Qb-10, and Qb-11. For instance, Qb is Qb-1, Qb-2, Qb-3, Qb-5, Qb-8, Qb-10, or Qb-11. Preferably, Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11. Most preferably, Qb is Qb-1. [0065] In embodiments where Q is Qa, R4 is as follows: A. R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; or B. R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9: 82994 FF
Figure imgf000015_0001
F. R4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 6- ethoxypyridazin-3-yl, 6-chloropyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl; or G. R4 is pyrazin-2-yl, pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl; or H. R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl. [0066] In preferred embodiments of each aspect of the invention, R4 is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9. More preferably, R4 is Qc-1, Qc-2, or Qc-3. Even more preferably, R4 is Qc-1 or Qc-2, such as R4 is Qc-2. For instance, R4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 6-ethoxypyridazin-3- yl, 6-chloropyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5-carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, such as preferably R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl. More preferably, R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl. Even more preferably, R4 is pyrimidin-2- yl or 5-cyano-2-pyridyl. [0067] In embodiments where Q is Qb, R4a is as follows: 82994 FF A. R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; or B. R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11:
Figure imgf000016_0001
C. R4a is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9; or D. R4a is Qc-1, Qc-2, or Qc-3; or E. R4a is Qc-1; or F. R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; i.e. R4a is Qc-1, with cyano as R4b. [0068] In preferred embodiments of each aspect of the invention, R4a is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9, such as R4a is Qc-1, Qc-2, or Qc-3. More preferably, R4a is Qc-1. [0069] In preferred embodiments of each aspect of the invention, the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, and oxo-pyridazinyl rings of R4 and R4a are each connected to the remainder of the compound via a carbon atom. In other words, a carbon atom of the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, or oxo-pyridazinyl rings of R4 and R4a is linked to Qa or Qb, respectively. [0070] In an embodiment of each aspect of the invention, R4b is as follows: A. R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10 ; or B. R4b is hydrogen, halogen, cyano, hydroxy, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1- C3fluoroalkoxy, -C(O)NR10R11, or -NHC(O)R10; or C. R4b is hydrogen, fluoro, chloro, iodo, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or - N(CH3)C(O)R10; or D. R4b is hydrogen, chloro, iodo, cyano, C1-C3alkyl, methoxy, -C(O)NR10R11, -NHC(O)R10 or - N(CH3)C(O)R10; or E. R4b is hydrogen, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or -N(CH3)C(O)R10; or 82994 FF F. R4b is hydrogen, cyano, C1-C3alkyl, methoxy, -C(O)NHR11, -NHC(O)R10 or -N(CH3)C(O)R10; or G. R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, - NHC(O)R10 or -N(CH3)C(O)R10; or H. R4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or I. R4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or J. R4b is hydrogen, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3; or K. R4b is hydrogen, cyano, -C(O)NH2, or -C(O)NHCH3; or L. R4b is hydrogen or cyano; or M. R4b is cyano, -C(O)NH2, or -C(O)NHCH3; or N. R4b is hydrogen. [0071] In an embodiment of each aspect of the invention, for instance where Q is Qa-1 or Qb-1, R10 is as follows: A. R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or B. R10 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyclopropylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; or C. R10 is hydrogen, C1-C3alkyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, cyanoC3- C4cycloalkyl, or C1-C3alkoxyC1-C3alkyl; or D. R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; or E. R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl; or F. R10 is hydrogen, methyl, ethyl, isopropyl, or cyclopropyl; or G. R10 is hydrogen, methyl, or cyanomethyl; or H. R10 is hydrogen or methyl and R11 is as follows: A. R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or B. R11 is hydrogen, hydroxy, C1-C3alkyl, C1-C3cyanoalkyl, cyanoC3-C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C3alkoxy; or C. R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, C1-C3cyanoalkyl, or C1-C3alkoxy; or D. R11 is hydrogen, C1-C3alkyl, cyanocyclopropyl, C1-C3alkoxyC1-C3alkyl, or methoxy; or E. R11 is hydrogen, C1-C3alkyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, or C1-C3alkoxy; or F. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or C1-C3alkoxy; or G. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or methoxy; or H. R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or I. R11 is hydrogen or methyl; or 82994 FF J. R11 is hydrogen. [0072] In preferred embodiments of each aspect of the invention, R10 is hydrogen, methyl, or cyanomethyl, such as R10 is hydrogen or methyl. Also in embodiments of each aspect of the invention, R11 is hydrogen or methyl, such as R11 is hydrogen. [0073] In preferred embodiments of each aspect of the invention, R4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3. More preferably, R4b is hydrogen, chloro, cyano, methoxy, -C(O)NH2, or -C(O)NHCH3. [0074] When R4b is hydrogen, this means that the corresponding pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl group R4 or R4a is non-substituted. [0075] In preferred embodiments of each aspect of the invention, the group R4b is in the meta or para position with respect to the link of R4 or R4a to the remainder of the compound, i.e. to the Qa or Qb ring, respectively. [0076] In an embodiment of each aspect of the invention, R4c is as follows: A. R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; or B. R4c is C1-C3alkyl, C1-C3haloalkyl, or C3-C6cycloalkylC1-C4alkyl; or C. R4c is methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, or cyclopropylmethyl; or D. R4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; or E. R4c is methyl, ethyl, or cyclopropylmethyl; or F. R4c is methyl or cyclopropylmethyl; or G. R4c is methyl or ethyl; or H. R4c is methyl. [0077] In preferred embodiments of each aspect of the invention, R4c is methyl or ethyl. For instance, R4c is methyl. [0078] In more preferred embodiments of each aspect of the invention, R4 and R4a, as the case may be, are selected from QQ-1 to QQ-17, where the staggered line represents the connection to Qa or Qb:
Figure imgf000018_0001
82994 FF
Figure imgf000019_0001
[0079] Preferably, R4 and R4a, as the case may be, are selected from QQ-1, QQ-2, QQ-3, QQ-5, QQ-6, QQ- 9, QQ-13, QQ-14, QQ-15, QQ-16, and QQ-17. More preferably, Preferably, R4 and R4a are selected from QQ- 1 and QQ-2. [0080] A preferred group of compounds of formula (I) is represented by compounds of formula (I-A):
Figure imgf000019_0002
82994 FF wherein A, R1, R2a, R2b, R3 and Q are as defined for compound of formula (I); or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula (I-A). More preferably, A is CH. [0081] Another preferred group of compounds of formula (I) is represented by compounds of formula (I-B):
Figure imgf000020_0001
wherein A, R1, R2a, R2b, R3 and Q are as defined for compound of formula (I); or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula (I-B). More preferably, A is CH. [0082] Accordingly, the present invention makes available a compound of formula (I) having the substituents A, Q (i.e. Qa with R4 and R5, or Qb with R4a, R5a and R5b), R1, R2a, R2b, R3, R6, R10, R11, and X as defined above, in all combinations and each permutation. [0083] For instance, compounds of formula (I) are made available, where A is CH or N, preferably A is CH; X is oxygen; R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1 is hydrogen or methyl; R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl; R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl or trifluoromethyl; Q is Qa, wherein R5 is hydrogen, bromo, iodo, methoxy, 2- methoxyethoxy, such as Qa is Qa-1, Qa-6, Qa-7, Qa-10, or Qa-15; R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9, such as R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl; wherein R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10 or -N(CH3)C(O)R10; R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2- cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; and R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or R4c is methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, or cyclopropylmethyl; and R6 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, 2-methoxyethyl, allyl, propargyl, cyclopropylmethyl, methoxycarbonyl, or ethoxycarbonyl. [0084] Compounds of formula (I) are made available, where A is CH or N, preferably A is CH; X is oxygen; R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R1 is hydrogen, methyl, or cyclopropylmethyl; R2a is hydrogen, halogen, C1-C3haloalkyl, C1-C4alkoxy, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl, such as R2b is chloro, bromo, 82994 FF iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; R3 is methyl or trifluoromethyl; Q is Qa and Qa is Qa-1 or Qa-15; R4 is Qc-1, Qc-2, or Qc-3, such as R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl; wherein R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10 or -N(CH3)C(O)R10; R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2- cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; and R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; and R6 is hydrogen, methyl, or methoxymethyl. [0085] For instance, compounds of formula (I) are made available, where A is CH or N, preferably A is CH; X is oxygen; R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1 is hydrogen or methyl; R2a is hydrogen, bromo, iodo, or cyclopropyl; R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl; R3 is methyl or trifluoromethyl; Q is Qb, wherein R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl, such as R5a and R5b are hydrogen; such as Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11; and R4a is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9; wherein R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, - C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10 or -N(CH3)C(O)R10; R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2- methoxyethyl, or ethoxymethyl; and R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1- cyanocyclopropyl, or methoxy; and R6 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl or C1-C6alkoxycarbonyl. [0086] Compounds of formula (I) are made available, where A is CH or N, preferably A is CH; X is oxygen; R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R1 is hydrogen, methyl, or cyclopropylmethyl; R2a is hydrogen, halogen, C1-C3haloalkyl, C1-C4alkoxy, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl, such as R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; R3 is methyl or trifluoromethyl; Q is Qb and Qb is Qb-1; R4a is Qc-1, Qc-2, or Qc-3, such as R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; wherein R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10 or -N(CH3)C(O)R10; R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2- cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; and R6 is hydrogen, C1-C4alkyl, or C1-C2alkoxyC1-C2alkyl. [0087] Compounds of formula (I) are made available, where A is CH; X is oxygen; R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1 is hydrogen; R2a is hydrogen or cyclopropyl; R2b is cyclopropyl; R3 is methyl; Q is Qa-1 or Qb-1; R4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin- 3-yl, 6-ethoxypyridazin-3-yl, 6-chloropyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- 82994 FF carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, or R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; and R6 is hydrogen, methyl, or methoxymethyl. [0088] Compounds of formula (I) are also made available, where A is CH; X is oxygen; R1 is hydrogen;R2a is hydrogen or cyclopropyl; R2b is cyclopropyl; R3 is methyl; Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11, such as Qb is Qb-1; R4a is Qc-1, Qc-2, or Qc-3; R4b is hydrogen, chloro, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, - C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; and R6 is hydrogen or methoxymethyl. [0089] Compounds of formula (I) are also made available, where A is CH or N; X is an oxygen atom or a sulfur atom, such as X is oxygen; R1 is hydrogen; R2a is hydrogen or cyclopropyl; R2b is cyclopropyl; R3 is methyl; Q is Qa-1, Qa-15, or Qb-1; R4 is pyrazin-2-yl, pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4- yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, such as R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6- cyanopyrimidin-4-yl; R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl; and R6 is hydrogen or methoxymethyl. [0090] Compounds of formula (I) are also made available, where A is CH; X is oxygen; R1 is hydrogen or methyl, such as R1 is hydrogen; R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl, preferably R2a is hydrogen, iodo, isopropoxy, or cyclopropyl; R2b is bromo or trifluoromethyl; R6 is hydrogen or methoxymethyl; R3 is methyl; Q is Qa and Qa is Qa-1 or Qa-15, preferably Qa is Qa-1; and R4 is Qc-1, Qc-2, Qc- 3, Qc-4, Qc-5, Qc-6, or Qc-9, such as R4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6- methoxypyridazin-3-yl, 6-ethoxypyridazin-3-yl, 6-chloropyridazin-3-yl, 5-cyano-2-pyridyl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6- cyanopyrimidin-4-yl, 5-carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl. [0091] Compounds of formula (I) are also made available, where A is CH; X is oxygen; R1 is hydrogen or methyl, such as R1 is hydrogen; R2a is hydrogen, bromo, iodo, or cyclopropyl, such as R2a is hydrogen; R2b is bromo or trifluoromethyl, such as R2b is bromo; R6 is hydrogen; R3 is methyl; Q is Qb and Qb is Qb-1, Qb-3, Qb- 5, Qb-10, or Qb-11, preferably Qb is Qb-1; and R4a is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9, preferably R4a is Qc-1, such as R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl. [0092] Compounds of formula (I) are also made available, where A is CH; X is oxygen; R1 is hydrogen or methyl, such as R1 is hydrogen; R2a is hydrogen, bromo, iodo, or cyclopropyl, such as R2a is hydrogen; R2b is bromo or trifluoromethyl, such as R2b is bromo; R6 is hydrogen; R3 is methyl; Q is Qa-1 or Qb-1, and R4 and R4a, as the case may be, are selected from QQ-1 to QQ-17, such as from QQ-1, QQ-2, QQ-3, QQ-5, QQ-6, QQ-9, QQ-13, QQ-14, QQ-15, QQ-16, and QQ-17. Preferably R4 and R4a are QQ-1 or QQ-2. [0093] Preferably, compounds of formula (I-A) are provided, where A is CH; X is oxygen; R1 is hydrogen or methyl; R2a is hydrogen, bromo, iodo, or cyclopropyl; R2b is bromo or trifluoromethyl; R3 is methyl; Q is Qa-1; R4 is Qc-1, Qc-2, Qc-3, Qc-5, Qc-6, or Qc-9; R4b is hydrogen, chloro, ethoxy, methoxy, C(O)NH2, or C(O)NHCH3; and R4c is ethyl or methyl. [0094] Compounds of formula (I-A) are provided, where A is CH; X is oxygen; R1 is hydrogen or methyl; R2a is hydrogen or cyclopropyl; R2b is bromo or trifluoromethyl; R3 is methyl; Q is Qa-1; R4 is pyrimidin-2-yl, 5-cyano- 2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, or 5-cyanothiazol-2-yl. 82994 FF Synthesis [0095] Compounds of formula (I) can be prepared by those skilled in the art following known methods. More specifically compounds of formulae (I), and (I’a), and intermediates therefor can be prepared as described below in the schemes and examples. Certain stereogenic centers have been left unspecified for the clarity and are not intended to limit the teaching of the schemes in any way. [0096] Compounds of formula (I), wherein Q, R1 and R3 are as defined in the first aspect, can be made, for example, as shown in scheme 1.
Figure imgf000023_0001
given for compounds of formula (I), and the staggered line represents the connection to the remainder of the compound T is attached to, such as the compounds of the formula (I), (Ia), (Ia-1), (Ib), (II), (IV), (IVa), (X), (XI) in Schemes 1 to 6. [0098] Compounds of the formula (I) can be made, for example, by reaction of a compound of the formula (II), wherein X1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride, and wherein T has the meaning given above, with a compound of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R1, R3 and Q have the same meaning as given above for compounds of the formula (I). In the case that X1 is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)- methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®). Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic 82994 FF base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. Compounds of the formula (II) are either known, or they can be prepared by methods known to a person skilled in the art. In particular, compounds of the formula (II) wherein X1 is a leaving group, such as a halogen, for instance chloride, can be formed by treatment of compounds of formula (II) wherein X1 is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C. Such methods are known to those skilled in the art and described for example in Tetrahedron 2005, 61 (46), 10827- 10852.
Figure imgf000024_0001
Scheme 2 [0099] Compounds of formula (III), or a salt thereof, wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I), can be made, for example, as shown in scheme 2. Treatment of a compound of the formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I) and X2 is a leaving group, such as a halogen or sulfonate, for instance bromide, with an amine of the formula (XIX), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), gives compounds of the formula (III), wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. [0100] Alternatively, treatment of a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), with an amine of the formula (XIX), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), gives compounds of the formula (III), wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, for the alkylation of amines and for the reductive alkylation of amines (e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic 82994 FF acid, at room temperature, analogous to WO2002/088073; or alternatively, by the use of a combination of Ti(i- OiPr)4 and NaBH4 as described in Synthesis 2003 (14), 2206) are well known to a person skilled in the art. The amines of formula (XIX), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000025_0001
Scheme 3 [0101] Alternatively, compounds of formula (I) can be made, for example, by reaction of compound of the formula (IV), wherein T has the same meaning as given above in Scheme 1, and R1 has the same meaning as given above for compounds of the formula (I), with a compound of the formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), and X2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide. The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art. [0102] Alternatively, a compound of the formula (I) can be made by reaction of a compound of the formula (IVa), wherein T has the same meaning as given above in Scheme 1, with a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods for the reductive alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art.
Figure imgf000025_0002
Scheme 4 82994 FF [0103] Compounds of formula (V), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), and X2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide, can be made, for example, as shown in scheme 4. Treatment of a compound of the formula (VIII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), with a halogenating agent, such as chlorine, bromine, N-chlorosuccinimide or N-bromosuccinimide, for example, gives compound of the formula (V), wherein the leaving group X2 is a halogen, for instance chloride or bromide. This reaction is done with or without a solvent, preferably in a solvent, with or without an additive, such as a radical starter, such as, for example, benzoyl peroxide or azoisobutyronitrile. The reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. [0104] Alternatively, a compound of the formula (VII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), can be treated with a reducing agent, followed by reaction with a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula (V), wherein the leaving group X2 is a sulfonate, for instance a mesylate. This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. A suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods for the halogenation, the reduction of carbonyl compounds and the sulfonylation of alcohols, and the range of conditions to perform them, are well known to a person skilled in the art. The compounds of the formula (VII) and the compounds of formula (VIII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000026_0001
Scheme 5 [0105] Alternatively, compounds of formula (Ia-1), wherein T has the same meaning as given above in Scheme 1, and R1, R3 and Q have the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, can be made, for example, as shown in scheme 5. A compound of the formula (Ia), wherein T has the same meaning as given above in Scheme 1, and R3 and Q have the same meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula (VI), 82994 FF wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (Ia-1). This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art and are described for example in WO2021/083936. Compounds of the formula (VI), wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000027_0001
[0106] Compounds of formula (Ib), wherein T has the same meaning as given above in Scheme 1, and R3, R4 and R5 have the same meaning as given above for compounds of the formula (I), can be made, for example, as shown in scheme 6. Reaction of a compound of the formula (II), wherein T has the same meaning as given above in Scheme 1 and wherein X1 is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride, with a compound of the formula (IX), or a salt thereof, wherein R3 has the same meaning as given above for compounds of the formula (I), gives a compound of the formula (X), wherein T has the same meaning as given above in Scheme 1, and wherein R3 has the same meaning as given above for compounds of the formula (I). In the case that X1 is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride 82994 FF (T3P®). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4- dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0107] Subsequent treatment of compound of the formula (X), wherein T has the same meaning as given above in Scheme 1, R3 has the same meaning as given above for compounds of the formula (I), with the known compound (XIII), wherein R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl (e.g. XIII is N,N-dimethylformamide dimethyl acetal, also named DMF-DMA), gives a compound of the formula (XI), wherein T has the same meaning as given above in Scheme 1, and wherein R3 has the same meaning as given above for compounds of the formula (I), and R5 is hydrogen, C1-C3alkyl, or C3-C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50 °C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0108] Further reaction of compound of the formula (XI), wherein T has the same meaning as given above in Scheme 1, R3 has the same meaning as given above for compounds of the formula (I), and R5 is hydrogen, C1-C3alkyl, or C3-C4cycloalkyl, with a hydrazine compound of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 has the same meaning as given above for compounds of the formula (I), gives the compound of the formula (Ib), wherein T has the same meaning as given above in Scheme 1, R3 and R4 have the same meaning as given above for compounds of the formula (I), and R5 is hydrogen, C1-C3alkyl, or C3- C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, or between ambient temperature and 80 °C. Within this sequence of transformations, the intermediate compounds of formula (X) and of formula (XI) can be used as crude products for the subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation. [0109] Compounds of the formula (IX), or a salt thereof, wherein R3 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. Hydrazine compounds of formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. [0110] Compounds of the formula (Ik) 82994 FF
Figure imgf000029_0001
can be prepared by the reaction of an amine of the formula (IIIf), or a salt thereof
Figure imgf000029_0002
wherein R1, R3, R4 and R5 are as described in formula (I), with a compound of the formula (IIa)
Figure imgf000029_0003
wherein A, R2a, R2b and R6 are as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.
82994 FF
Figure imgf000030_0001
Scheme 7 [0111] Compounds of formula (Ic) can be made, for example, as shown in scheme 7. Reaction of a compound of the formula (XVII) (wherein X05 is a leaving group such as chlorine, bromine, iodine, arysulfonate, alkylsulfonate or trifluoromethanesulfonate) with an amine of the formula (XIX), or a salt thereof, gives compounds of the formula (XVI) , or a salt thereof. This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, for the reductive alkylation of amines are well known to a person skilled in the art. [0112] Subsequent reaction of the intermediate of the formula (XVI) , or a salt thereof, with a compound of the formula (IIa) gives a compound of the formula (XIV). This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. [0113] Subsequently, the intermediate of the formula (XIV) is reacted with a compound of the formula (XV) to give the compound of formula (Ic), wherein A, R2a, R2b, R1, R3, R4a and R6 have the same meaning as given above for compounds of the formula (I), and M1 in R4a-M1 is a metal, such as for instance lithium, or –MgCl, or –ZnBr, or –B(OH)2; or R4a-M1 represents a boronate, such as a pinacol ester of a boronic acid, or a stannane 82994 FF such as R4a-Sn(n-Bu)3. Such transformations are known to a person skilled in the art as Suzuki-, Kumada-, Negishi- or Stille-coupling reactions, respectively. Such reactions are carried out in a temperature range of - 100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst (for example palladium(II) acetate, 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride or tetrakis(triphenyl-phosphine)palladium(0)), and optionally in the presence of an additional ligand, such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand. The reaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance CuI. The reaction is done with or without a base, which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or tribasic potassium phosphate, or an organic base, such as an amine base, for instance triethyl amine. This reaction is done with or without a solvent, preferentially in a solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, toluene or N.N-dimethylformamide, optionally in the presence of water. Where the reaction mixture is heated, the reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath. [0114] By an alternative route, compound (XVII) can be reacted with a compound of the formula (XV) to give intermediate (XVIII). This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate (XIV) to the compound of formula (Ic). [0115] Subsequently, the intermediate (XVIII) is reacted with a compound of the formula (IVb) to give a compound of the formula (Ic), wherein R1 is hydrogen and A, R2a, R2b, R3, R4a and R6 have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI). [0116] By yet another alternative route, the intermediate compound of the formula (XVIII) can be reacted with an amine of the formula (XIX), or a salt thereof, to give the intermediate of the formula (IIIa), or a salt thereof. This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI). [0117] Subsequently, the intermediate of the formula (IIIa), or a salt thereof, is reacted with a compound of the formula (IIa) to give the compound of the formula (Ic), wherein A, R2a, R2b, R1, R3, R4a and R6 have the same meaning as given above for compounds of the formula (I). This reaction is done essentially under the same conditions as described above for the transformation of intermediate (XVI) to intermediate (XIV). [0118] Within these different multistep sequences, the intermediate compounds of formulas (XIV), (XVI), (XVIII) and (IIIa) can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation. Compounds of the formula (XVII) are known, or they can be prepared by methods known to a person skilled in the art. [0119] Compounds of the formula (Id) 82994 FF
Figure imgf000032_0001
can be prepared by the reaction of an amine of the formula (IIIb), or a salt thereof
Figure imgf000032_0002
wherein R1, R3, R4a, R5a and R5b are as described in formula (I), with a compound of the formula (IIa)
Figure imgf000032_0003
wherein A, R2a, R2b and R6 are as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1. [0120] The chemistry is described in more detail in Scheme 8.
Figure imgf000032_0004
Scheme 8 [0121] Reaction of a compound of the formula (IIa), wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, with a compound of formula (IIIb), or a salt thereof, gives a compound of the formula (Id), wherein A, R2a, R2b, R1, R3, R4a, R5a, R5b and R6 have the same meaning as given above for 82994 FF compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. [0122] The formation of compounds of formula (IIIb) is outlined in Scheme 9.
Figure imgf000033_0001
Scheme 9 [0123] Compounds of formula (IIIb), or a salt thereof, can be prepared by treatment of compounds of formula (IIIc), or a salt thereof, wherein R3, R4a, R5a, and R5b are as described in formula (I), with compounds of formula (XX) wherein R1a is for example H, methyl or cyclopropyl, e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid at room temperature analogous to WO2002/088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206). [0124] Amines of formula (IIIc), or a salt thereof, may be obtained by biocatalyzed deracemization of amines of formula (IIId), or a salt thereof. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert- butyl ether at temperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem. 2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem.1991, 56, 2656-2665 or J. Am. Chem. Soc.2015, 137, 3996−4009. [0125] In an alternative process, compounds of formula (IIIc), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be obtained from compounds of the formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I), following the synthesis described in Scheme 10. 82994 FF
Figure imgf000034_0001
Scheme 10 [0126] Amines of formula (IIIc), or a salt thereof, may be obtained from intermediates of formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9. [0127] Such intermediates of formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXI), wherein R3, R4a, R5a, and R5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula (XXI) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide (HNPhth) or bis(tert-butoxycarbonyl)amine(HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed with inversion of the stereocenter, as described for instance in Chem. Rev.2009, 109, 2551-2651. [0128] Alternatively, amines of formula (IIIc) may be obtained by reduction of azides of formula (XXIII), wherein R3, R4a, R5a, and R5b are as described in formula (I), by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula (XXIII) may be obtained by treatment of alcohols of formula (XXI), wherein R3, R4a, R5a, and R5b are as described in formula (I), with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU. Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literature for instance in Adv. Synth. Catal.2018, 360, 2157–2165. [0129] Alcohols of formula (XXI) may be obtained by enantioselective reduction of ketones of formula (XXIV), wherein R3, R4a, R5a, and R5b are as described in formula (I). Such reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or 82994 FF RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607. [0130] Alternatively, compounds of formula (IIIc) may also be prepared as outlined in Scheme 11.
Figure imgf000035_0001
[0131] Amines of formula (IIIc), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be prepared by deprotection of amines of formula (XXV), wherein R3, R4a, R5a, and R5b are as described in formula (I), for instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane. [0132] Amines of formula (XXV) can be obtained by condensation of diamines of formula (XLVII), wherein R5a, and R5b are as described in formula (I), on diketones of formula (XXVI), wherein R3 and R4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ. [0133] Diketones of formula (XXVI) may be formed by oxidation of hydroxyketones of formula (XXVII), wherein R3 and R4a are as described in formula (I). This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/Bu4NHSO4. Examples of such oxidations can be found in the literature, for instance in Synlett, 2014, 25, 596 or J. Am. Chem. Soc.1990, 112, 5290-5313. [0134] Hydroxyketones of formula (XXVII) may be synthesized by cross-benzoin condensation between aldehydes of formula (XXIX), wherein R4a is as described in formula (I), and aldehydes of formula (XXVIII), wherein R3 is as described in formula (I). [0135] Aldehydes of formula (XXVIII) are commercially available in chiral form, like for instance Boc-L- alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36- 82994 FF 9). Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt, in the presence of a base such as potassium tert-butoxide or N,N- isopropylethylamine, in a suitable solvent such as DCM or THF, at a temperature between -20 °C and the boiling point of the solvent. Examples of catalysts for such transformations have been described in the literature for instance in J. Am. Chem. Soc.2014, 136, 7539-7542 or in Org. Lett.2016, 18, 4518-4521.
Figure imgf000036_0001
Scheme 12 [0136] As shown in Scheme 12, compounds of formula (Id) can be alternatively prepared by reaction of compounds of formula (XXX) (wherein A, R2a, R2b, R1, R3, R5a, R5b and R6 are as defined in formula (I) and X07 is a leaving group like, for example, chlorine, bromine, iodine) with compounds of formula (XXXI) (Stille reaction; R4a in XXXI is as defined in formula I) or compounds of formula (XXXII) (Suzuki-Miyaura reaction; R4a in XXXII is as defined in formula (I) and W is a boronic acid B(OH)2 group, or a corresponding boronate, such as a pinacol ester of said boronic acid) in the presence of a palladium catalyst as described in detail in Scheme 7. [0137] Compounds of formula (XXX) can be prepared by coupling of amines of formula (XXXIII) and compounds of formula (IIa), wherein A, R2a, R2b, R6 and X1 are described in Scheme 1, under the conditions described in detail in Scheme 1. Under the same conditions, if R1 = H, compounds of formula (XXX) may be obtained directly from compounds of formula (XXXIV). 82994 FF [0138] Compounds of formula (XXXIII) can be prepared by treatment of compounds of formula (XXXIV), with compounds of formula (XX) (wherein R1a is for example H, methyl or cyclopropyl), e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid at room temperature analogous to WO2002/088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206). [0139] Amines of formula (XXXIV) can be prepared by deracemization procedure method, which involves for example, a selective acylation of one enantiomer. Such an example is described in Scheme 13 more in details.
Figure imgf000037_0001
Scheme 13 [0140] Amines of formula (XXXIV) may be obtained by biocatalyzed deracemization of amines of formula (XXXIVa), wherein R3, R5a, and R5b are as in formula (I) and X07 is a leaving group such as bromine, chlorine or iodine. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem.2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem.1991, 56, 2656-2665 or J. Am. Chem. Soc.2015, 137, 3996−4009. [0141] Alternatively, resolution of amines of formula (XXXIVa) to give amines of formula (XXXIV) may be achieved using a chiral auxiliary, as described in Scheme 14.
Figure imgf000037_0002
Scheme 14 82994 FF [0142] Amines of formula (XXXIV) can be prepared from intermediates of formula (XXXVII), wherein R3, R5a, and R5b are as in compounds of the formula (I), X07 is a leaving group such as bromine, chlorine or iodine, and X12* is a chiral auxiliary, by treatment with acids such as HCl or bases such as NaOH. Chiral auxiliaries of formula (XXXVI) are for instance mandelic acid or (1R)-menthylchloroformate. Intermediates of formula (XXXVII) can be formed by coupling of a chiral auxiliary of formula (XXXVI), wherein X0 is a leaving group, such as chlorine, with amines of the formula (XXXIVa) following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493. [0143] Alternatively, amines of formula (XXXIV), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be formed as described in Scheme 15.
Figure imgf000038_0001
Scheme 15 [0144] Amines of formula (XXXIV), or a salt thereof, may be obtained from intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9. [0145] Such intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXIa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula (XXIa) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide(HNPhth) or bis(tert-butoxycarbonyl)amine (HNBoc2). 82994 FF Mitsunobu reactions are known by those skilled in the art to proceed with inversion of the stereocenter, as described for instance in Chem. Rev.2009, 109, 2551-2651. [0146] Alternatively, amines of formula (XXXIV) may be obtained by reduction of azides of formula (XXIIIa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula (XXIIIa) may be obtained by treatment of alcohols of formula (XXIa) with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU. Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literature for instance in Adv. Synth. Catal.2018, 360, 2157–2165. [0147] Alcohols of formula (XXIa) may be obtained by enantioselective reduction of ketones of formula (XXIVa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide. Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p- cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607.
Figure imgf000039_0001
Scheme 16 [0148] As shown above in Scheme 16, compounds of the formula (I-A), a subset of compounds of the formula (I), wherein A, R1, R2a, R2b, R3 and Q are as defined for compounds of the formula (I), can be prepared by reaction of compounds of the formula (IIa-1), a subset of compounds of the formula (II) wherein A, R2a and R2b are as described in formula (I) and X1 is hydroxy, with either compounds of the formula (IIIf) or (IIIb), or a salt thereof, under conditions already described above (transformations IIa + IIIf to Ik, and IIa + IIIb to Id) and in Scheme 1. Alternatively, a salt of the substrate compound of the formula (IIa-1), for instance a carboxylic acid sodium salt, can be used in this amide bond formation reaction to form the compounds of the formula (I- A). [0149] Compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I), can be prepared by saponification of compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under conditions known to a person skilled in the art (using for example conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane at room temperature, or up to refluxing conditions; or alternatively treating compounds of the formula (IIa-2) with an acid, such as for example a hydrohalide acid, preferably hydrochloride or hydrobromide acid, or trifluoroacetic acid, optionally in presence of a solvent, such as tetrahydrofuran, dioxane or dichloromethane, at temperatures between 0 and 150°C). 82994 FF [0150] Compounds of the formula (IIa-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by means of a carbonylation reaction on compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), in the presence of an alcohol RaOH, wherein Ra is C1-C6alkyl or benzyl. Typically in such a carbonylation reaction, the compounds of formula (XL) are reacted with carbon monoxide CO (usually under pressure, for example in the range of 5 to 200 bar), in the presence of a metal catalyst such as a palladium catalyst (for example: palladium(II) acetate, or 1,1’- bis(diphenylphosphino)ferrocene-palladium(II)dichloride (Pd(dppf)Cl2, optionally as a dichloromethane complex)), optionally in the presence of a phosphine ligand, preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, in an alcohol RaOH solvent (optionally in presence of an inert organic co-solvent), and at temperatures ranging between 0 and 250°C, preferably between room temperature and 200°C. [0151] Alternatively, compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I), can be prepared by i) performing a lithium-halogen (Li-X3) exchange on compounds of the formula (XL), wherein A, R2a and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), followed by ii) quenching the formed organolithium species with carbon dioxide. Such lithium-halogen exchange reactions can be performed using, for example, organolithium compounds such as butyllithium (BuLi), in an anhydrous aprotic solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran or N,N′-dimethylpropylene-urea (DMPU), and at temperatures ranging from -120 to 0°C, preferably between -78 and 0°C. The formed lithiated intermediate is preferably quenched in situ with carbon dioxide (gaseous, or alternatively solid carbon dioxide known as dry ice) to generate the compounds of the formula (IIa-1). Similar reactions are reported in literature for example in WO 2006/013048.
Figure imgf000040_0001
Scheme 17 [0152] As shown above in Scheme 17, compounds of the formula (XL), wherein A and R2b are as described in formula (I), R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by reacting compounds of the formula (XL-1), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine) and X4 is a halogen, preferably bromine or iodine, with a reagent of the formula R2a-M2, wherein R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano and M2 is a metal, such as for instance –MgCl, or –ZnBr, or –Sn(n-Bu)3, or –B(OH)2 (alternatively the corresponding boronic ester, also named boronate ester, such as the pinacol ester). Such transformations are known to a person skilled in the art as Kumada-, Negishi-, Stille-, and Suzuki-coupling reactions, respectively 82994 FF and are achieved in the presence of a palladium (alternatively nickel) catalyst as described in detail in Scheme 7 (transformation XIV + XV into Ic). [0153] Compounds of the formula (XL-1), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine) and X4 is a halogen, preferably bromine or iodine, can be prepared by a halogenation reaction, which involves for example, reacting the compounds of the formula (XL-2), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), with halogenating reagents such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), sulfuryl chloride or alternatively chlorine, bromine or iodine, optionally in presence of a base such as sodium, potassium or cesium carbonate, or sodium or potassium hydroxide, and optionally in the presence of a catalyst or an additive. Such halogenation reactions are carried out in an inert solvent, such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, sulfuric acid, ethers, N,N-dimethylformamide, methanol or methanol-water mixtures, acetonitrile or acetonitrile-water mixtures, at temperatures between 20-200°C, preferably between room temperature to 100°C. [0154] Compounds of the formula (XL-2), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by diazotization/cyclization of the corresponding toluidine (ortho-tolylamine or 2-methyl- aniline) compounds of the formula (XL-3), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), under conditions reported for example in Liebigs Ann. Chem.1980, 6, 908−927, Tetrahedron 2002, 58, 6061-6067 or Bioorg. Med. Chem. Lett. 2005, 15, 2752 −2757. Typically, a solution of compounds (XL-3) in acetic acid is diazotized (aqueous sodium nitrite) at temperatures between 0°C and room temperature to provide the indazole compounds (XL-2). Alternatively, a mixture of compounds (XL-3) in acetonitrile and aqueous hydrochloric (or hydrobromic) acid is diazotized (aqueous sodium nitrite) at 0°C, then treated with sodium or potassium acetate at temperatures between 0°C and room temperature to provide said indazole compounds (XL-2). [0155] Compounds of the formula (XL-3), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared by a halogenation reaction, which involves for example, reacting the compounds of the formula (XL- 4), wherein A and R2b are as described in formula (I), with halogenating reagents such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), sulfuryl chloride or alternatively chlorine, bromine or iodine, optionally in presence of a base such as sodium, potassium or cesium carbonate, and optionally in the presence of a catalyst or an additive. Such halogenation reactions are carried out in an inert solvent, such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, sulfuric acid, ethers, N,N- dimethylformamide, acetonitrile or acetonitrile-water mixtures, at temperatures between 20-200°C, preferably between room temperature to 100°C. [0156] Compounds of the formula (XL-4), or a salt thereof, wherein A and R2b are as described in formula (I),are either known, commercially available or may be prepared by methods known to a person skilled in the art. 82994 FF
Figure imgf000042_0001
[0157] Alternatively, as outlined in Scheme 18 above, compounds of the formula (XL), wherein A and R2b are as described in formula (I), R2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be be prepared by diazotization/reduction/cyclization of compounds of the formula (XL-5), or a salt thereof, wherein A and R2b are as described in formula (I), R2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), under conditions reported for example in WO 2012/169649 or JP 2014/133739. Typically, a mixture of compounds (XL-5) in aqueous hydrochloric, hydrobromic or sulfuric acid (alternatively in concentrated acid), optionally in the presence of a solvent such as acetonitrile, is diazotized (aqueous sodium nitrite) at temperatures between 0°C and room temperature, followed by treatment of the reaction mixture comprising the formed diazonium intermediate with tin(II) chloride dihydrate, also known as stannous chloride, at temperatures between 0°C and room temperature, to provide the indazole compounds (XL). [0158] Compounds of the formula (XL-5), or a salt thereof, wherein A and R2b are as described in formula (I), R2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), can be prepared from compounds of the formula (XL-6), or a salt thereof, wherein A and R2b are as described in formula (I), and R2a is hydrogen, C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, by a halogenation reaction following conditions already described in Scheme 17 (transformation XL-4 into XL-3).
Figure imgf000042_0002
Scheme 19 [0159] As shown in Scheme 19 above, Compounds of the formula (XL-6), or a salt thereof, wherein A and R2b are as described in formula (I), and R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, can be prepared by photochemical aza-Frie rearrangement of anilide compounds of the formula (XL-7), wherein A and R2b are as described in formula (I), and R2a is 82994 FF C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, under similar conditions described for example in J. Org. Chem.2006, 71, 24, 9217-9220 or Photochem. Photobiol. Sci.2016, 15, 105-116. [0160] Such photochemical aza-Fries rearrangement (a 1,3-acyl migration) of the corresponding acyl-aniline (XL-7) is conducted via irradiation at a given wavelength (e.g.254 nm) with appropriate lamps, in an appropriate photochemical reaction vessel, in solvents, preferably deoxygenated, such as cyclohexane, dichloromethane or acetonitrile, at temperatures preferably around room temperature, and optionally under flow conditions, characterized by parameters such as the reactor volume (e.g.55 mL), residence time (e.g.55 min), flow rate (e.g.1 mL/min), and the like. [0161] Anilide compounds of the formula (XL-7), wherein A and R2b are as described in formula (I), and R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, can be made, for example, by reaction of aniline compounds of the formula (XL-8), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein A and R2b are as described in formula (I), with acylating agents of the formula (XL-9), respectively (XL-9a), wherein R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, under conditions known to a person skilled in the art. Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydro-furan, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between 0 and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0162] Typically, when using (XL-9), the reaction is performed in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethyl- amino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®). [0163] Compounds of the formula (XL-9a) are either known, or they can be prepared by methods known to a person skilled in the art. In particular, compounds of the formula (XL-9a) can be formed by treatment of compounds of formula (XL-9) with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C. Such methods are known to those skilled in the art and described for example in Tetrahedron 2005, 61 (46), 10827-10852. [0164] Compounds of the formula (XL-9), wherein R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and compounds of the formula (XL-8), or a salt thereof, wherein A and R2b are as described in formula (I), are either known, commercially available or may be prepared by methods known to a person skilled in the art. 82994 FF
Figure imgf000044_0001
Scheme 20 [0165] Alternatively, as shown in Scheme 20, compounds of the formula (I-A), wherein A, R1, R2a, R2b, R3 and Q are as defined under formula (I) above, can be prepared by cleavage of the methoxymethyl (MOM) group in compounds of the formula (I-B), wherein A, R1, R2a, R2b, R3 and Q are as defined under formula (I) above, typically by treatment with acids (including a range of Lewis and Bronsted acids), for instance hydrochloric acid, in solvents such as methanol, ethanol, isopropanol, tetrahydrofuran, 2- methyltetrahydrofuran, water or mixtures thereof, under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Wuts, Peter G. M.; Greene, Theodora W. (2006). Greene's Protective Groups in Organic Synthesis, Fourth Edition - Wuts - Wiley Online Library; doi:10.1002/0470053488. [0166] Compounds of the formula (I-B), wherein A, R2a, R2b, R3 and Q are as defined under formula (I) above, and in which R1 is different from hydrogen, can be prepared by reaction of compounds of the formula (I-B), wherein A, R2a, R2b, R3 and Q are as defined under formula (I) above, and in which R1 is hydrogen, with a compound of the formula (VI), wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X30 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, under conditions already described in Scheme 5 (transformation Ia + VI into Ia-1).
Figure imgf000044_0002
Scheme 21 [0167] As outlined in Scheme 21, compounds of the formula (I-B), another subset of compounds of the formula (I), wherein A, R1, R2a, R2b, R3 and Q are as defined under formula (I) above, can be prepared by reaction of compounds of the formula (IIb-1), a subset of compounds of the formula (II) wherein A, R2a 82994 FF and R2b are as described in formula (I) and X1 is hydroxy, with either compounds of the formula (IIIf) or (IIIb), or a salt thereof, under conditions already described above (transformations IIa + IIIf to Ik, and IIa + IIIb to Id) and in Scheme 1. Alternatively, a salt of the substrate compound of the formula (IIb-1), for instance a carboxylic acid sodium salt, can be used in this amide bond formation reaction to form the compounds of the formula (I- B). [0168] Compounds of the formula (IIb-1), wherein A, R2a and R2b are as described in formula (I), can be prepared by saponification of compounds of the formula (IIb-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, under conditions already described in Scheme 16 above (transformation IIa-2 to IIa-1). [0169] Cleavage of the methoxymethyl (MOM) group in such compounds of the formula (IIb-1), by treatment with acids under conditions already described above in Scheme 20 (transformation I-B into I-A), does provide compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I). [0170] Alternatively, compounds of the formula (IIa-1), wherein A, R2a and R2b are as described in formula (I), can be prepared directly from compounds of the formula (IIb-2), wherein A, R2a and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, by a one-pot saponification / MOM group cleavage sequence, in which the respective conditions described above are sequentially applied. [0171] Compounds of the formula (IIb-2), wherein A and R2b are as described in formula (I), R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (IIb-3), wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl and X4 is a halogen, preferably bromine or iodine, with a reagent of the formula R2a-M2, wherein R2a is C1-C4alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano, and M2 is a metal, such as for instance –MgCl, or – ZnBr, or –Sn(n-Bu)3, or –B(OH)2 (alternatively the corresponding boronic ester, also named boronate ester, such as the pinacol ester), under conditions already described in Scheme 17 and Scheme 7 above.
Figure imgf000045_0001
Scheme 22 [0172] As outlined in Scheme 22 above, compounds of the formula (IIb-3), wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl and X4 is a halogen, preferably bromine or iodine, can be prepared by protecting position N2 in indazole compounds of the formula (IIa-3), wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl and X4 is a halogen, preferably bromine or iodine, with the methoxymethyl (MOM) group, for example by treatment with CH3OCH2Cl (MOM- Cl; alternatively with the corresponding iodide MOM-I), typically in the presence of a base such as sodium hydride or diisopropylethylamine, preferably sodium hydride, optionally in the presence of an additive such as 82994 FF sodium iodide or tetrabutylammonium iodide, in solvents such as dichloromethane, tetrahydrofuran or 2- methyltetrahydrofuran, at temperatures between 0 and 80°C, preferably between 0 and 40°C, under protection conditions known to a person skilled in the art, and described in the literature, such as for example in: Wuts, Peter G. M.; Greene, Theodora W. (2006). Greene's Protective Groups in Organic Synthesis, Fourth Edition - Wuts - Wiley Online Library; doi:10.1002/0470053488. [0173] Compounds of the formula (IIa-3), wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl and X4 is a halogen, preferably bromine or iodine, can be prepared by reacting compounds of the formula (IIa-4), wherein A and R2b are as described in formula (I), and in which Ra is C1- C6alkyl or benzyl, with halogenating reagents, under conditions already described in Scheme 17 above (transformation XL-2 to XL-1). [0174] Compounds of the formula (IIa-4), wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by means of a carbonylation reaction on compounds of the formula (XL-2), wherein A and R2b are as described in formula (I), and in which X3 is a halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), in the presence of an alcohol RaOH, wherein Ra is C1-C6alkyl or benzyl, under conditions already described in Scheme 16 above (transformation XL to IIa-2).
Figure imgf000046_0001
Scheme 23 [0175] As shown in Scheme 23, compounds of the formula (IIb-2), wherein A and R2b are as described in formula (I), R2a is C1-C4alkoxy and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (IIb-4), or a tautomer thereof, wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, with reagents of the formula C1-C4alkyl-X31, wherein X31 is a halogen (or a pseudo halogen) leaving group, preferably bromo or iodo, in the presence of a carbonate base, preferably silver carbonate, in an inert solvent such as hexane, dioxane or toluene, at temperatures ranging from room temperature to 200°C, preferably between 80 and 150°C, optionally under microwave irradiation, in analogy to descriptions found for example in Synthesis 2009, 16, 2725-2728. [0176] Compounds of the formula (IIb-4), or a tautomer thereof, wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (IIb-3), wherein A and R2b are as described in formula (I), and in which Ra is C1-C6alkyl or benzyl and X4 is a halogen, preferably bromine or iodine, with for example benzaldoxime PhC=NOH, preferably (E)-benzaldehyde oxime, in the presence of a base, such as potassium or cesium carbonate, optionally in the presence of a palladium catalyst such as RockPhos-G3-palladacycle ([(2-Di-tert-butylphosphino-3-methoxy-6-methyl-2′,4′,6′- triisopropyl-1,1′-biphenyl)-2-(2-aminobiphenyl)]palladium(II) methanesulfonate), in an aprotic solvent such as 82994 FF acetonitrile or N,N-dimethylformamide DMF, at temperatures between 0 and 100°C, preferably between room temperature and 80°C, as described, for example, in Angew. Chem. Int. Ed.56 (16), 4478–4482, 2017. [0177] Certain compounds of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or any other equivalent salt), wherein R1, R3 and Q have the same meaning as given above for compounds of the formula (I), are known in the literature. [0178] For example, compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above, wherein R1, R3, R4a, R5a and R5b are as described in formula (I), particularly those compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above, wherein R3 and R4a are as described in formula (I) and in which R1, R5a and R5b are hydrogen, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/069575, and WO 2022/258481.
Figure imgf000047_0001
[0179] Similarly, compounds of the formula (IIIe) and (IIIf), or a salt thereof as defined above, wherein R1, R3, R4 and R5 are as described in formula (I), particularly those compounds of the formula (IIIe) and (IIIf), or a salt thereof as defined above, wherein R3 and R4 are as described in formula (I) and in which R1 is hydrogen or methyl and R5 is hydrogen, methyl or cyclopropyl, can be prepared in analogy to descriptions found for example in WO 2021/083936, WO 2021/099303, WO 2021/105091, WO 2021/165195, WO 2021/224323, WO 2022/268648, WO 2023/104714, WO 2023/247360 and WO 2024/110554.
Figure imgf000047_0002
[0180] Depending on the procedure or the reaction conditions, the reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium 82994 FF bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N- dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU). [0181] The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N- methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. [0182] The reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C. [0183] Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step. [0184] Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent. [0185] Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent. [0186] Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture. [0187] Depending on the procedure or the reaction conditions, the compounds of formula (I), which have salt-forming properties can be obtained in free form or in the form of salts. [0188] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each 82994 FF case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case. [0189] Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography. [0190] Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents. [0191] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry. [0192] N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000/15615. [0193] It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity. [0194] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form. [0195] The compounds of formula (I) according to the following Tables A-1 to A-52 and Tables B-1 to B- 52 can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I- A-1) and (I-B-1). 82994 FF
Figure imgf000050_0001
Tables A-1 to A-52 (formula I-A-1) [0196] Table A-1 provides 15 compounds A-1.001 to A-1.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. For example, compound A-4.011 is
Figure imgf000050_0002
[0197] Table A-2 provides 15 compounds A-2.001 to A-2.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0198] Table A-3 provides 15 compounds A-3.001 to A-3.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0199] Table A-4 provides 15 compounds A-4.001 to A-4.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0200] Table A-5 provides 15 compounds A-5.001 to A-5.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0201] Table A-6 provides 15 compounds A-6.001 to A-6.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0202] Table A-7 provides 15 compounds A-7.001 to A-7.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0203] Table A-8 provides 15 compounds A-8.001 to A-8.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0204] Table A-9 provides 15 compounds A-9.001 to A-9.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. 82994 FF [0205] Table A-10 provides 15 compounds A-10.001 to A-10.015 of formula I-A-1 wherein R2a is CF3, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0206] Table A-11 provides 15 compounds A-11.001 to A-11.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0207] Table A-12 provides 15 compounds A-12.001 to A-12.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0208] Table A-13 provides 15 compounds A-13.001 to A-13.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0209] Table A-14 provides 15 compounds A-14.001 to A-14.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0210] Table A-15 provides 15 compounds A-15.001 to A-15.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0211] Table A-16 provides 15 compounds A-16.001 to A-16.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0212] Table A-17 provides 15 compounds A-17.001 to A-17.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0213] Table A-18 provides 15 compounds A-18.001 to A-18.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0214] Table A-19 provides 15 compounds A-19.001 to A-19.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0215] Table A-20 provides 15 compounds A-20.001 to A-20.015 of formula I-A-1 wherein R2a is CHF2, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0216] Table A-21 provides 15 compounds A-21.001 to A-21.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0217] Table A-22 provides 15 compounds A-22.001 to A-22.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0218] Table A-23 provides 15 compounds A-23.001 to A-23.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0219] Table A-24 provides 15 compounds A-24.001 to A-24.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0220] Table A-25 provides 15 compounds A-25.001 to A-25.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0221] Table A-26 provides 15 compounds A-26.001 to A-26.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0222] Table A-27 provides 15 compounds A-27.001 to A-27.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0223] Table A-28 provides 15 compounds A-28.001 to A-28.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. 82994 FF [0224] Table A-29 provides 15 compounds A-29.001 to A-29.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0225] Table A-30 provides 15 compounds A-30.001 to A-30.015 of formula I-A-1 wherein R2a is Br, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0226] Table A-31 provides 15 compounds A-31.001 to A-31.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0227] Table A-32 provides 15 compounds A-32.001 to A-32.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0228] Table A-33 provides 15 compounds A-33.001 to A-33.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0229] Table A-34 provides 15 compounds A-34.001 to A-34.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0230] Table A-35 provides 15 compounds A-35.001 to A-35.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0231] Table A-36 provides 15 compounds A-36.001 to A-36.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0232] Table A-37 provides 15 compounds A-37.001 to A-37.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0233] Table A-38 provides 15 compounds A-38.001 to A-38.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0234] Table A-39 provides 15 compounds A-39.001 to A-39.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0235] Table A-40 provides 15 compounds A-40.001 to A-40.015 of formula I-A-1 wherein R2a is I, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0236] Table A-41 provides 15 compounds A-41.001 to A-41.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0237] Table A-42 provides 15 compounds A-42.001 to A-42.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0238] Table A-43 provides 15 compounds A-43.001 to A-43.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0239] Table A-44 provides 15 compounds A-44.001 to A-44.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0240] Table A-45 provides 15 compounds A-45.001 to A-45.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0241] Table A-46 provides 15 compounds A-46.001 to A-46.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0242] Table A-47 provides 15 compounds A-47.001 to A-47.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. 82994 FF [0243] Table A-48 provides 15 compounds A-48.001 to A-48.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0244] Table A-49 provides 15 compounds A-49.001 to A-49.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0245] Table A-50 provides 15 compounds A-50.001 to A-50.015 of formula I-A-1 wherein R2a is Cyp, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0246] Table A-51 provides 15 compounds A-51.001 to A-51.015 of formula I-A-1 wherein R2a is isopropoxy, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0247] Table A-52 provides 15 compounds A-52.001 to A-52.015 of formula I-A-1 wherein R2a is isopropoxy, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. Tables B-1 to B-52 (formula I-B-1) [0248] Table B-1 provides 15 compounds B-1.001 to B-1.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. For example, compound B-29.006 is
Figure imgf000053_0001
(B-29.006) [0249] Table B-2 provides 15 compounds B-2.001 to B-2.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0250] Table B-3 provides 15 compounds B-3.001 to B-3.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0251] Table B-4 provides 15 compounds B-4.001 to B-4.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0252] Table B-5 provides 15 compounds B-5.001 to B-5.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0253] Table B-6 provides 15 compounds B-6.001 to B-6.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0254] Table B-7 provides 15 compounds B-7.001 to B-7.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0255] Table B-8 provides 15 compounds B-8.001 to B-8.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. 82994 FF [0256] Table B-9 provides 15 compounds B-9.001 to B-9.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0257] Table B-10 provides 15 compounds B-10.001 to B-10.015 of formula I-B-1 wherein R2a is CF3, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0258] Table B-11 provides 15 compounds B-11.001 to B-11.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0259] Table B-12 provides 15 compounds B-12.001 to B-12.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0260] Table B-13 provides 15 compounds B-13.001 to B-13.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0261] Table B-14 provides 15 compounds B-14.001 to B-14.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0262] Table B-15 provides 15 compounds B-15.001 to B-15.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0263] Table B-16 provides 15 compounds B-16.001 to B-16.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0264] Table B-17 provides 15 compounds B-17.001 to B-17.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0265] Table B-18 provides 15 compounds B-18.001 to B-18.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0266] Table B-19 provides 15 compounds B-19.001 to B-19.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0267] Table B-20 provides 15 compounds B-20.001 to B-20.015 of formula I-B-1 wherein R2a is CHF2, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0268] Table B-21 provides 15 compounds B-21.001 to B-21.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0269] Table B-22 provides 15 compounds B-22.001 to B-22.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0270] Table B-23 provides 15 compounds B-23.001 to B-23.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0271] Table B-24 provides 15 compounds B-24.001 to B-24.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0272] Table B-25 provides 15 compounds B-25.001 to B-25.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0273] Table B-26 provides 15 compounds B-26.001 to B-26.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0274] Table B-27 provides 15 compounds B-27.001 to B-27.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. 82994 FF [0275] Table B-28 provides 15 compounds B-28.001 to B-28.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0276] Table B-29 provides 15 compounds B-29.001 to B-29.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0277] Table B-30 provides 15 compounds B-30.001 to B-30.015 of formula I-B-1 wherein R2a is Br, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0278] Table B-31 provides 15 compounds B-31.001 to B-31.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0279] Table B-32 provides 15 compounds B-32.001 to B-32.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0280] Table B-33 provides 15 compounds B-33.001 to B-33.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0281] Table B-34 provides 15 compounds B-34.001 to B-34.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0282] Table B-35 provides 15 compounds B-35.001 to B-35.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0283] Table B-36 provides 15 compounds B-36.001 to B-36.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. [0284] Table B-37 provides 15 compounds B-37.001 to B-37.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0285] Table B-38 provides 15 compounds B-38.001 to B-38.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0286] Table B-39 provides 15 compounds B-39.001 to B-39.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0287] Table B-40 provides 15 compounds B-40.001 to B-40.015 of formula I-B-1 wherein R2a is I, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0288] Table B-41 provides 15 compounds B-41.001 to B-41.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is Cl, R1 is H and Q are as defined in table Z. [0289] Table B-42 provides 15 compounds B-42.001 to B-42.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z. [0290] Table B-43 provides 15 compounds B-43.001 to B-43.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is Br, R1 is H and Q are as defined in table Z. [0291] Table B-44 provides 15 compounds B-44.001 to B-44.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z. [0292] Table B-45 provides 15 compounds B-45.001 to B-45.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0293] Table B-46 provides 15 compounds B-46.001 to B-46.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. 82994 FF [0294] Table B-47 provides 15 compounds B-47.001 to B-47.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is CHF2, R1 is H and Q are as defined in table Z. [0295] Table B-48 provides 15 compounds B-48.001 to B-48.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is CHF2, R1 is CH3 and Q are as defined in table Z. [0296] Table B-49 provides 15 compounds B-49.001 to B-49.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is Cyp, R1 is H and Q are as defined in table Z. [0297] Table B-50 provides 15 compounds B-50.001 to B-50.015 of formula I-B-1 wherein R2a is Cyp, A is CH, R2b is Cyp, R1 is CH3 and Q are as defined in table Z. [0298] Table B-51 provides 15 compounds B-51.001 to B-51.015 of formula I-B-1 wherein R2a is isopropoxy, A is CH, R2b is CF3, R1 is H and Q are as defined in table Z. [0299] Table B-52 provides 15 compounds B-52.001 to B-52.015 of formula I-B-1 wherein R2a is isopropoxy, A is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z. Table Z: Substituent definitions of Q
Figure imgf000056_0001
82994 FF
Figure imgf000057_0001
[0300] In Tables A-1 to A-52 and Tables B-1 to B-52, Cyp represents cyclopropyl. [0301] Also made available are certain intermediate compounds as shown in Schemes 1 to 22, some of which are novel. For example: ^ A compound of formula IIa-1, as shown below, where A, R2a, and R2b are as defined for compounds of formula (I); for instance where A, R2a, and R2b are as described in Tables A-1 to A-52; in particular where A is CH, R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl and R2b is bromo, cyclopropyl, or trifluoromethyl; preferably A is CH, R2a is cyclopropyl and R2b is trifluoromethyl ^ A compound of formula IIa-2, as shown below, where A, R2a, and R2b are as defined for compounds of formula (I), Ra is C1-C6alkyl or benzyl, preferably Ra is methyl or ethyl; for instance where A, R2a, and R2b are as described in Tables A-1 to A-52, in particular where A is CH, R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl, and R2b is bromo, cyclopropyl, or trifluoromethyl; preferably A is CH, R2a is cyclopropyl and R2b is trifluoromethyl 82994 FF
Figure imgf000058_0001
^ A compound of formula IIb-1, as shown below, where A, R2a, and R2b are as defined for compounds of formula (I); for instance where A, R2a, and R2b are as described in Tables B-1 to B-52; in particular where A is CH, R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl, and R2b is bromo, cyclopropyl, or trifluoromethyl; preferably A is CH, R2a is cyclopropyl and R2b is trifluoromethyl ^ A compound of formula IIb-2, as shown below, where A, R2a, and R2b are as defined for compounds of formula (I), Ra is C1-C6alkyl or benzyl, preferably Ra is methyl or ethyl; for instance where A, R2a, and R2b are as described in Tables B-1 to B-52, in particular where A is CH, R2a is hydrogen, bromo, iodo, trifluoromethyl, isopropoxy, or cyclopropyl, and R2b is bromo, cyclopropyl, or trifluoromethyl; preferably A is CH, R2a is cyclopropyl and R2b is trifluoromethyl
Figure imgf000058_0002
Pest control [0302] The compounds of formula (I) according to the invention are preventively and/or curatively valuable ac-tive ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate. [0303] Examples of the above mentioned animal pests are: 82994 FF ^ from the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; ^ from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; ^ from the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae spp., Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.; ^ from the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; ^ from the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, 82994 FF Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae , Unaspis citri, Zygina flammigera, Zyginidia scutellaris ; ^ from the order Hymenoptera, for example, Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; ^ from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminata; ^ from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.; ^ from the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; 82994 FF ^ from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp., and Schistocerca spp.; ^ from the order Psocoptera, for example, Liposcelis spp.; ^ from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; ^ from the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; ^ from the order Thysanura, for example, Lepisma saccharina. [0304] In a further aspect, the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria 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; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, 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 primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.. [0305] The compounds of the invention may also have activity against the molluscs. Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. 82994 FF flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides. [0306] The active ingredients according to the invention can be used for controlling, i.e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests. [0307] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants. [0308] The compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens. [0309] For example the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants. [0310] For example the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. 82994 FF cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba. [0311] Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber. [0312] The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice). [0313] The compounds of formula (I) are particularly suitable for control of ^ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in sunflower, vegetables, soybeans, and sugarcane); ^ a pest of the order Lepidoptera, for example, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn); ^ a pest of the order Thysanoptera, such as the family Thripidae, for example, one or more of Thrips tabaci and Frankliniella occidentalis (preferably in sunflower and vegetables, such as beans); and ^ soil pests (such as of the order Coleoptera), for example, the species Diabrotica balteata, Agriotes spp. and Leptinotarsa decemlineata (preferably in vegetables and corn). [0314] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. [0315] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, 82994 FF such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. [0316] In the context of the present invention there are to be understood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). [0317] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073. [0318] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651. [0319] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera). [0320] Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1FA2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); Nature-Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®. [0321] Further examples of such transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to 82994 FF attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 × MON 810 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. [0322] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch). [0323] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. 82994 FF [0324] Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens. [0325] Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode. [0326] Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art. [0327] Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related proteins" (PRPs; see e.g. EP-A-0392225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03/000906). [0328] Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type. [0329] The present invention provides a compound of the first aspect for use in therapy. The present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal. The present invention further provides a compound of the first aspect, for use in preventing and/or treating diseases transmitted by ectoparasites. [0330] The present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and/or treating diseases transmitted by ectoparasites. [0331] The present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal. [0332] The term "controlling" when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation. [0333] The term "treating" when used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease. 82994 FF [0334] The term "preventing" when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal. [0335] The term "animal" when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses. Companion animals include, but are not limited to, dogs, cats and rabbits. [0336] A "parasite" is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense. An "endoparasite" is a parasite which lives in the host animal. An "ectoparasite" is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice). The Acari (or Acarina) sub-class comprises ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates. Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera. Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis. Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola ovis and Bovicola bovis. [0337] The term "effective amount" when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal. The effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances. [0338] The compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally' and subcutaneously. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, 82994 FF emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip. In the alternative, the compounds of the invention may be administered by means of an ear tag or collar. [0339] Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts. Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, S.M., et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977). One skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as a salt, such as a hydrochloride salt, using techniques and conditions well known to one of ordinary skill in the art. In addition, one skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as the corresponding free base from the corresponding salt. [0340] The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents. [0341] In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents. [0342] Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005/113886 or WO 2007/090739. [0343] Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees. 82994 FF [0344] In the field of tree injection/trunk treatment, the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A. Examples of exotic woodborers of economic importance. Family Species Host or Crop Infested Buprestidae Agrilus planipennis Ash Cerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandrus crassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperda Conifers Table B. Examples of native woodborers of economic importance. Family Species Host or Crop Infested Buprestidae Agrilus anxius Birch Agrilus politus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilus vittaticolllis Apple, Pear, Cranberry, Serviceberry, Hawthorn Chrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry, Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut, Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum, Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texania campestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplar Cerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak, Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytus acuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Eastern hophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust, 82994 FF Family Species Host or Crop Infested Honeylocust, Yellow-poplar, Chestnut, Osage- orange, Sassafras, Lilac, Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood, Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleaf hackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant, Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood, Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, Mulberry Oncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood, Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit trees Saperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory, Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak, Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, Elm Dendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wild cherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut, Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, Pine Phloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry, Mountain-ash Pseudopityophthorus Oak, American beech, Black cherry, Chickasaw pruinosus plum, Chestnut, Maple, Hickory, Hornbeam, Hophornbeam Sesiidae Paranthrene simulans Oak, American chestnut Sannina uroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine, Cherry, Apricot, Almond, Black cherry 82994 FF Family Species Host or Crop Infested Synanthedon pictipes Peach, Plum, Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedon scitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Black cherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark, Bayberry Vitacea polistiformis Grape [0345] The present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs, ticks, spittlebugs, southern chinch bugs and white grubs. The present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults. [0346] In particular, the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and Tomarus spp., ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.). [0347] The present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis). [0348] The present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two- lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs. [0349] The present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf. [0350] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. [0351] Examples of such parasites are: ^ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.. ^ Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.. 82994 FF ^ Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.. ^ Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. ^ Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. ^ Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.. ^ Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.. ^ Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.. [0352] The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings. [0353] The compositions according to the invention can be used, for example, against the following pests : beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina. [0354] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P”) controls one 82994 FF or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. [0355] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp. [0356] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P”) controls one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp. [0357] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis. [0358] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P”) controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilaparvata lugens + TX, Myzus persicae + TX, Chrysodeixis incIudens + TX, Aphis craccivora + TX, Diabrotica balteata + TX, Rhopalosiphum Padi + TX, and Chilo suppressalis + TX. [0359] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops. [0360] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice). [0361] Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been surprisingly found that certain compounds of formula (I) may show an advantageous safety profile with respect 82994 FF to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera. [0362] The following combinations of a compound of formula I with another active substance in a weight ratio of 1:1 are preferred (where the abbreviation “TX” means "one compound selected from the compounds defined in Tables A-1 to A-52, Tables B-1 to B-52, and Table P”): (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)- tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec- 5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en- 1-yl acetate + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn- 1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)- tetradec-9-en-1-yl acetate + TX, 1,2-dibromo-3-chloropropane + TX, 1,2-dichloropropane + TX, 1,2- dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 14-methyloctadec-1-ene + TX, 1- hydroxy-1H-pyridine-2-thione + TX, 2-(octylthio)ethanol + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4- (quinoxalin-2-ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5- methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, Adoxophyes orana GV + TX, afidopyropen + TX, afoxolaner + TX, Agrobacterium radiobacter + TX, AKD-3088 + TX, alanycarb + TX, aldicarb + TX, aldoxycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, alpha-multistriatin + TX, Amblyseius spp. + TX, amidoflumet + TX, amino acids + TX, aminocarb + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, Autographa californica NPV + TX, AZ 60541 + TX, azadirachtin + TX, azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No.55609) + TX, Bacillus sp. AQ178 (ATCC Accession No.53522) + TX, Bacillus sphaericus Neide + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus subtilis unspecified + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No B-21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. Aizawai + TX, Bacillus thuringiensis subsp. Israelensis + TX, Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thuringiensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, Beauveria brongniartii + TX, benclothiaz + TX, benomyl + TX, bensultap + TX, benzoximate + TX, benzpyrimoxan + TX, betacyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, bioresmethrin + TX, bis(tributyltin) oxide + TX, bisazir + TX, bistrifluron + TX, bisulflufen + TX, brevicomin 82994 FF + TX, broflanilide + TX, brofluthrinate + TX, bromoacetamide + TX, bromophos-ethyl + TX, bronopol + TX, busulfan + TX, butocarboxim + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butylpyridaben + TX, cadusafos + TX, calcium arsenate + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbosulfan + TX, cartap + TX, CAS number: 1594624-87-9 + TX, CAS number: 1922957-47-8 + TX, CAS number: 1255091-74-7 + TX, CAS number: 1365070-72-9 + TX, CAS number: 1445683-71-5 + TX, CAS number: 1445684-82-1 + TX, CAS number: 1594626-19-3 + TX, CAS number: 1594637-65-6 + TX, CAS number: 1632218-00-8 + TX, CAS number: 1808115-49-2 + TX, CAS number: 1922957-46-7 + TX, CAS number: 1922957-48-9 + TX, CAS number: 1956329-03-5 + TX, CAS number: 1990457-52-7 + TX, CAS number: 1990457-55-0 + TX, CAS number: 1990457-57-2 + TX, CAS number: 1990457-66-3 + TX, CAS number: 1990457-77-6 + TX, CAS number: 1990457-85-6 + TX, CAS number: 2032403-97-5 + TX, CAS number: 2044701-44-0 + TX, CAS number: 2095470-94-1 + TX, CAS Number: 2128706-04-5 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2133042-31-4 + TX, CAS number: 2133042-44-9 + TX, CAS number: 2171099-09-3 + TX, CAS number: 2220132-55-6 + TX, CAS number: 2396747-83-2 + TX, CAS number: 2408220-91-5 + TX, CAS number: 2408220-94-8 + TX, CAS number: 2415706-16-8 + TX, piperflanilide + TX, CAS number: 2719848-60-7 + TX, CAS number: RNA (Leptinotarsa decemlineata-specific recombinant double-stranded interfering GS2) + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloropicrin + TX, chloroprallethrin + TX, chlorpyrifos + TX, chromafenozide + TX, Chrysoperla carnea + TX, clenpirin + TX, cloethocarb + TX, clothianidin + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper dioctanoate + TX, copper hydroxide + TX, copper sulfate + TX, cresol + TX, crufomate + TX, Cryptolaemus montrouzieri + TX, cuelure + TX, cyanofenphos + TX, cyantraniliprole + TX, cybutryne + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxaprid + TX, Cydia pomonella GV + TX, cyenopyrafen + TX, cyetpyrafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cylohalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyproflanilide + TX, cyromazine + TX, cytokinins + TX, Dacnusa sibirica + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, diafenthiuron + TX, dialifos + TX, diamidafos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dichlofenthion + TX, dichlone + TX, dichlorophen + TX, dicliphos + TX, dicloromezotiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea + TX, dimatif + TX, dimethoate + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimpropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzofos + TX, dipyrithione + TX, disparlure + TX, D-limonene + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8,10- dien-1-yl acetate + TX, dodicin + TX, dominicalure + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, empenthrin + TX, Encarsia formosa + TX, endothal + TX, endrin + TX, eprinomectin + TX, epsilon - momfluorothrin + TX, epsilon-metofluthrin + TX, Eretmocerus eremicus + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, ethoprophos + TX, ethyl 4-methyloctanoate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, etofenprox + TX, etoxazole + TX, etpyrafen + TX, eugenol + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones, vitamins, EDTA-chelated copper, zinc, and iron + TX, famphur + TX, fenaminosulf + TX, fenamiphos + TX, fenazaquin + TX, fenfluthrin + TX, fenitrothion + TX, 82994 FF fenmezoditiaz + TX, fenobucarb + TX, fenothiocarb + TX, fenoxycarb + TX, fenpropathrin + TX, fenpyrad + TX, fenpyroximate + TX, fensulfothion + TX, fenthion + TX, fentin + TX, fentinacetate + TX, fenvalerate + TX, ferric phosphate + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, fluchlordiniliprole + TX, flucitrinate + TX, flucycloxuron + TX, flucythrinate + TX, fluensulfone [318290-98-1] + TX, fluensulfone + TX, flufenerim + TX, flufenprox + TX, flufiprole + TX, fluhexafon + TX, flumethrin + TX, fluopyram + TX, flupyradifurone + TX, flupyrimin + TX, flupyroxystrobin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, formaldehyde + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, furfural + TX, gamma-cyhalothrin + TX, Gossyplure® (1:1 mixture of the (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien-1-yl-acetate) + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, Granulovirus + TX, guadipyr + TX, GY-81 + TX, halfenprox + TX, halofenozide + TX, Harpin + TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, hemel + TX, hempa + TX, heptafluthrin + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexalure + TX, hexamide + TX, hexythiazox + TX, Hippodamia convergens + TX, hydramethylnon + TX, hydrargaphen + TX, hydrated lime + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, Indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, ipsdienol + TX, ipsenol + TX, isamidofos + TX, isazofos + TX, isocycloseram + TX, Isoflualanam (CAS number: 2892524-05-7) + TX, isothioate + TX, ivermectin + TX, japonilure + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, lambda- cyhalothrin + TX, ledprona + TX, lepimectin + TX, Leptomastix dactylopii + TX, lineatin + TX, litlure + TX, looplure + TX, lotilaner + TX, lufenuron + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, mecarphon + TX, medlure + TX, megatomoic acid + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Metarhizium spp. + TX, metepa + TX, methiocarb + TX, methiotepa + TX, methomyl + TX, methoquin-butyl + TX, methoxyfenozide + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methylneodecanamide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime + TX, momfluorothrin + TX, morzid + TX, moxidectin + TX, muscalure + TX, Muscodor albus 620 (NRRL Accession No. 30547) + TX, Muscodor roseus A3-5 (NRRL Accession No.30548) + TX, Myrothecium verrucaria composition + TX, nabam + TX, NC-184 + TX, Neem tree based products + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, ostramone + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, parathion-ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, penfluron + TX, pentachlorophenol + TX, permethrin + TX, phenothrin + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, Phytoseiulus persimilis + TX, picaridin + TX, pioxaniliprole + TX, piperazine + TX, 82994 FF piperonylbutoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, potassium and molybdenum and EDTA-chelated manganese + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, prallethrin + TX, probenazole + TX, profenofos + TX, profluthrin + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyrethrum + TX, pyridaben + TX, pyridalyl + TX, pyridin-4-amine + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, quinoclamine + TX, quinonamid + TX, resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663) + TX, sarolaner + TX, S-bioallethrin + TX, sebufos + TX, selamectin + TX, siglure + TX, silafluofen + TX, simazine + TX, sodium pentachlorophenoxide + TX, sordidin + TX, spidoxamat + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Spodoptera frugiperda Nucleopolyhedrovirus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Streptomyces galbus (NRRL Accession No.30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulfiflumin (CAS number: 2377084-09-6) + TX, sulfoxaflor + TX, tazimcarb + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tecloftalam + TX, tefluthrin + TX, temephos + TX, tepa + TX, terbam + TX, terbufos + TX, terpenoid blend + TX, tetrachlorantraniliprole + TX, tetrachlorothiophene + TX, tetradec-11-en-1-yl acetate + TX, tetradiphon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiosultap + TX, thiotepa + TX, tigolaner + TX, tiorantraniliprole + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, tretamine + TX, triazamate + TX, triazophos + TX, triazuron + TX, tributyltin oxide + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, Trichogramma spp. + TX, trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc- call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp. + TX, xylenols + TX, YI-5302 + TX, zeatin + TX, zeta-Cypermethrin + TX; N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1- benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-ethyl-N’-[5-methoxy-2-methyl- 4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019/110427) + TX, (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, (3- methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds may be prepared from the methods described in WO 2017/220485) + TX, (4-phenoxyphenyl)methyl 2-amino-6-methyl- pyridine-3-carboxylate (this compound may be prepared from the methods described in WO 2014/006945) + 82994 FF TX, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca- 7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)- tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate, + TX, (R)-3-(difluoromethyl)-1-methyl-N- [1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-en- 1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10- one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (Z,2E)- 5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3- yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, , [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1- yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, 1-(4,5- dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)- 4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3- dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO2017/025510) + TX, 1,1-bis(4-chlorophenyl)- 2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dibromo-3-chloropropane + TX, 1,2- dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 1,3-dimethoxy-1-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3- yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 10-dien-1-yl acetate + TX, 14-methyloctadec-1- ene + TX, 1-bromo-2-chloroethane + TX, 1-dichloro-1-nitroethane + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-methyl-4-[3- methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4-yl) pyridine- 3- carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2- (difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3R)-3- ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl- indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2- (octylthio)ethanol + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2- ethylsulfinylethyl methyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]acetamide + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3- c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound may be prepared from the methods described in WO 2011/138281) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4- bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]- 82994 FF 1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2- imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2018/065414) + TX, 2-thiocyanatoethyl laurate + TX, 3-(4,4- difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds may be prepared from the methods described in WO2016/156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3- dimethylisoquinolin-1-yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1- methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3- chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-chloro-6-methyl-5-phenyl- 4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid + TX, 3- ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-methyl-1- phenylpyrazol-5-yl dimethylcarbamate + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1, 3- dimethyl- 1H- pyrazol- 5- amine + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4- (quinoxalin-2-ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3- dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)- 1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4- difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, 4-chlorophenyl phenyl sulfone + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 4-methylnonan-5-ol with 4- methylnonan-5-one + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, 5,5-dimethyl-2-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-3-oxocyclohex-1- enyl dimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, 5-methyl-6-thioxo-1,3,5- thiadiazinan-3-ylacetic acid + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2- difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]- 5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4- methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-ethyl-5,7-dioxo- pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 6-isopentenylaminopurine + TX, 8-fluoro-N-[(1R)- 82994 FF 1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3- fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-hydroxyquinoline sulfate + TX, acethion + TX, acetoprole + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, acrylonitrile + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, aldoxycarb + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-chlorohydrin + TX, alpha-ecdysone + TX, alpha-multistriatin + TX, aluminium phosphide + TX, Amblyseius spp. + TX, amectotractin + TX, ametoctradin + TX, amidithion + TX, amidothioate + TX, aminocarb + TX, aminopyrifen + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasine + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancymidol + TX, anilazine + TX, anisiflupurin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, aramite + TX, arsenous oxide + TX, athidathion + TX, Autographa californica NPV + TX, azaconazole + TX, azamethiphos + TX, azobenzene + TX, azothoate + TX, azoxystrobin + TX, Bacillus sphaericus Neide + TX, Bacillus thuringiensis delta endotoxins + TX, barium carbonate + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, Beauveria brongniartii + TX, benalaxyl + TX, benclothiaz + TX, benomyl + TX, benoxafos + TX, benthiavalicarb + TX, benzothiostrobin + TX, benzovindiflupyr + TX, benzyl benzoate + TX, beta-cyfluthrin + TX, beta- cypermethrin + TX, bethoxazin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, bis(tributyltin) oxide + TX, bisazir + TX, bisthiosemi + TX, bitertanol + TX, bixafen + TX, blasticidin-S + TX, borax + TX, bordeaux mixture + TX, boscalid + TX, brevicomin + TX, brodifacoum + TX, brofenvalerate + TX, bromadiolone + TX, bromethalin + TX, bromfenvinfos + TX, bromoacetamide + TX, bromociclen + TX, bromo- DDT + TX, bromophos + TX, bromopropylate + TX, bromuconazole + TX, bronopol + TX, bufencarb + TX, bupirimate + TX, buprofezin + TX, busulfan + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, butacarb + TX, butathiofos + TX, butocarboxim + TX, butonate + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, camphechlor + TX, captafol + TX, captan + TX, carbanolate + TX, carbendazim + TX, carbon disulfide + TX, carbon tetrachloride + TX, carbophenothion + TX, carboxin + TX, cartap hydrochloride + TX, CAS Number: 2132414-04-9 + TX, CAS Number: 2344721-61-3 + TX, cevadine + TX, chinomethionat + TX, chloralose + TX, chlorbenside + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloroform + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron + TX, chloroneb + TX, chlorophacinone + TX, chloropicrin + TX, chloropropylate + TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorthiophos + TX, chlozolinate + TX, cholecalciferol + TX, Chrysoperla carnea + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, cismethrin + TX, cis-resmethrin + TX, clocythrin + TX, closantel + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX, coumachlor + TX, coumafuryl + TX, coumaphos + TX, coumatetralyl + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, coumithoate + TX, coumoxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, crotoxyphos + TX, crufomate + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, CS 708 + TX, cuelure + 82994 FF TX, cufraneb + TX, cyanofenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclethrin + TX, cyclobutrifluram + TX, Cydia pomonella GV + TX, cyflufenamid + TX, cymiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinins + TX, Dacnusa sibirica + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb + TX, decarbofuran + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, diamidafos + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofenthion + TX, dichlofluanid + TX, dichlone + TX, dichlorophen + TX, dichlorvos + TX, dichlozoline + TX, dicliphos + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicresyl + TX, dicyclanil + TX, dicyclopentadiene + TX, dieldrin + TX, dienochlor + TX, diethofencarb + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difethialone + TX, diflovidazin + TX, Diglyphus isaea + TX, dilor + TX, dimatif + TX, dimefluthrin + TX, dimefox + TX, dimetan + TX, dimethirimol + TX, dimetho- morph + TX, dimethrin + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimethylvinphos + TX, dimetilan + TX, dimoxystrobin + TX, dinex + TX, dinex-diclexine + TX, diniconazole + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, dinosulfon + TX, dinoterbon + TX, diofenolan + TX, dioxabenzofos + TX, dioxathion + TX, diphacinone + TX, diphenyl sulfone + TX, dipymetitrone + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, dithianon + TX, dithicrofos + TX, DNOC + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, DSP + TX, d-tetramethrin + TX, ecdysterone + TX, edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, endothal + TX, endothion + TX, enestroburin + TX, enoxastrobin + TX, EPBP + TX, epoxiconazole + TX, eprinomectin + TX, Eretmocerus eremicus + TX, ergocalciferol + TX, etaphos + TX, ethaboxam + TX, ethiofencarb + TX, ethirimol + TX, ethoate-methyl + TX, ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3- carboxylate (may be prepared from the methods described in WO 2020/056090) + TX, ethyl 1-[[4-[[2- (trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole-4-carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2- thienyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2018/158365) + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol with nerolidol + TX, fenamidone + TX, fenaminosulf + TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, fenethacarb + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrad + TX, fenpyrazamine + TX, fenpyroximate + TX, fenson + TX, fensulfothion + TX, fenthion + TX, fenthion-ethyl + TX, fentin + TX, fentrifanil + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, flocoumafen + TX, florylpicoxamid + TX, fluazinam + TX, flubeneteram + TX, flubenzimine + TX, flucofuron + TX, flucycloxuron + TX, fludioxonil + TX, fluenetil + TX, flufenoxadiazam + TX, flufenoxystrobin 82994 FF + TX, fluindapyr + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluorbenside + TX, fluoroacetamide + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin + TX, fluoxytioconazole + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, FMC 1137 + TX, folpet + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, fosetyl- aluminium + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, frontalin + TX, fuberidazole + TX, furalaxyl + TX, furametpyr + TX, furathiocarb + TX, furethrin + TX, furfural + TX, gamma-HCH + TX, glyodin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, guazatine + TX, guazatine acetates + TX, halfenprox + TX, HCH + TX, hemel + TX, hempa + TX, HEOD + TX, heptachlor + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecyl cyclopropanecarboxylate + TX, hexalure + TX, hexamide + TX, HHDN + TX, Hippodamia convergens + TX, hydrargaphen + TX, hydrated lime + TX, hydrogen cyanide + TX, hymexazol + TX, hyquincarb + TX, imanin + TX, imazalil + TX, imibenconazole + TX, iminoctadine + TX, inpyrfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidofos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrin + TX, isofenphos + TX, isofetamid + TX, isoflucypram + TX, isolane + TX, isoprothiolane + TX, isopyrazam + TX, isotianil + TX, isoxathion + TX, japonilure + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kadethrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kelevan + TX, kinetin + TX, kinoprene + TX, kresoxim-methyl + TX, lead arsenate + TX, Leptomastix dactylopii + TX, leptophos + TX, lindane + TX, lineatin + TX, lirimfos + TX, litlure + TX, looplure + TX, lvbenmixianan + TX, lythidathion + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, malonoben + TX, Mamestra brassicae NPV + TX, mancopper + TX, mancozeb + TX, mandestrobin + TX, mandipropamid + TX, maneb + TX, mazidox + TX, m-cumenyl methylcarbamate + TX, mecarbam + TX, mecarphon + TX, medlure + TX, mefentrifluconazole + TX, megatomoic acid + TX, menazon + TX, mepanipyrim + TX, meperfluthrin + TX, mephosfolan + TX, mepronil + TX, mercuric oxide + TX, mercurous chloride + TX, mesulfen + TX, mesulfenfos + TX, metalaxyl + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020/193387) + TX, methyl (Z)-2-[5- (3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2- methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(4- propyltriazol-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol- 1-yl]phenoxy]prop-2-enoate (these compounds may be prepared from the methods described in WO2020/079111) + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2- enoate + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, 82994 FF methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro- phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, methylchloroform + TX, methylene chloride + TX, methylneodecanamide + TX, metiram + TX, metolcarb + TX, metominostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, MGK 264 + TX, milbemycin oxime + TX, mipafox + TX, mirex + TX, monocrotophos + TX, morphothion + TX, morzid + TX, moxidectin + TX, muscalure + TX, myclobutanil + TX, myclozoline + TX, Myrothecium verrucaria composition + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017/153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl- but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017/153380) + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-(2- chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (THESE COMPOUNDS may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689) + TX, N- [(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl- butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro- quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3- trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole- 4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole- 4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016/202742) + TX, N'-[4-(4,5-dichlorothiazol- 2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2015/155075) + TX, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine (this compound may be prepared from the methods described in IPCOM000249876D) + TX, N'- [5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5- bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5- chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N-[N-methoxy- C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds may be prepared from the methods described in WO 2018/202428) + TX, N’-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy- ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared 82994 FF from the methods described in WO2018/228896) + TX, nabam + TX, naftalofos + TX, naled + TX, naphthalene + TX, NC-170 + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nerolidol + TX, N-ethyl-2-methyl-N-[[4- [5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N’-[5-methoxy-2-methyl-4- [(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nifluridide + TX, nikkomycins + TX, N-isopropyl- N’-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrilacarb 1:1 zinc chloride complex + TX, nitrothal-isopropyl + TX, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzenecarbothioamide + TX, norbormide + TX, nuarimol + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, ofurace + TX, oleic acid + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, orysastrobin + TX, ostramone + TX, oxadixyl + TX, oxamate + TX, oxathiapiprolin + TX, oxine-copper + TX, oxolinic acid + TX, oxycarboxin + TX, oxydeprofos + TX, oxydisulfoton + TX, oxytetracycline + TX, paclobutrazole + TX, Paecilomyces fumosoroseus + TX, para-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penflufen + TX, penfluron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, PH 60-38 + TX, phenamacril + TX, phenkapton + TX, phosacetim + TX, phosalone + TX, phosdiphen + TX, phosfolan + TX, phosglycin + TX, phosnichlor + TX, phosphamidon + TX, phosphine + TX, phosphorus + TX, phoxim- methyl + TX, phthalide + TX, Phytoseiulus persimilis + TX, picarbutrazox + TX, picaridin + TX, picoxystrobin + TX, pindone + TX, piperazine + TX, piperonyl butoxide + TX, piprotal + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, polychloroterpenes + TX, polynactins + TX, polyoxins + TX, potassium arsenite + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, potassium thiocyanate + TX, pp'-DDT + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, probenazole + TX, prochloraz + TX, proclonol + TX, procymidone + TX, profluthrin + TX, promacyl + TX, promecarb + TX, propamocarb + TX, propiconazole + TX, propineb + TX, propoxur + TX, propyl isomer + TX, proquinazid + TX, prothidathion + TX, prothioconazole + TX, prothiofos + TX, prothoate + TX, pydiflumetofen + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, pyrapropoyne + TX, pyraziflumid + TX, pyrazophos + TX, pyresmethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyribencarb + TX, pyridachlometyl + TX, pyridaphenthion + TX, pyridin-4-amine + TX, pyrifenox + TX, pyrimethanil + TX, pyrimitate + TX, pyrimorph + TX, pyrinuron + TX, pyriofenone + TX, pyrisoxazole + TX, pyroquilon + TX, quassia + TX, quinalphos + TX, quinalphos-methyl + TX, quinoclamine + TX, quinofumelin + TX, quinonamid + TX, quinothion + TX, quinoxyfen + TX, quintiofos + TX, quintozene + TX, R-1492 + TX, rafoxanide + TX, resmethrin + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, R-metalaxyl + TX, rotenone + TX, ryania + TX, ryanodine + TX, S421 + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sebufos + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesasmolin + TX, SI-0009 + TX, siglure + TX, simazine + TX, simeconazole + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium fluoro- acetate + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, 82994 FF sodium tetrathiocarbonate + TX, sodium thiocyanate + TX, sophamide + TX, sordidin + TX, spiroxamine + TX, SSI-121 + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfoxide + TX, sulfur + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tau-fluvalinate + TX, tazimcarb + TX, TDE + TX, tebuconazole + TX, tebufloquin + TX, tebupirimfos + TX, tecloftalam + TX, temephos + TX, tepa + TX, TEPP + TX, terallethrin + TX, terbam + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, tetrachloroethane + TX, tetrachlorothiophene + TX, tetraconazole + TX, tetradec-11-en-1-yl acetate + TX, tetradifon + TX, tetramethylfluthrin + TX, tetrasul + TX, thallium sulfate + TX, thiabendazole + TX, thiafenox + TX, thiapronil + TX, thicrofos + TX, thifluzamide + TX, thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodiazole copper + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap + TX, thiosultap-sodium + TX, thiotepa + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tolclofos-methyl + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tretamine + TX, triadimefon + TX, triadimenol + TX, triamiphos + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, triazuron + TX, tributyltin oxide + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma spp. + TX, triclopyricarb + TX, tricyclazole + TX, tridemorph + TX, trifenmorph + TX, trifenofos + TX, trifloxystrobin + TX, triflumizole + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, Typhlodromus occidentalis + TX, uredepa + TX, validamycin + TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenols + TX, zeatin + TX, zetamethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiazole + TX, zineb + TX, ziram + TX, zolaprofos + TX; Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®) in particular strain CNMC 1-1582 (e.g. VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis strain HB-2 (Biostart™ formerly Rhizoboost®) + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield 82994 FF Shield®) + TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus sphaericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis (Novodor®, BtBooster) + TX, Bacillus thuringiensis var. aizawai (XenTari®, DiPel®) + TX, bacteria spp. (GROWMEND®, GROWSWEET®, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES®, Mycotrol O®, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz®, Schweizer Beauveria®, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium chlorocephalum + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®, Madex®, Madex® Plus, Madex Max, Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, 82994 FF Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isaria fumosorosea (previously known as Paecilomyces fumosoroseus strain, PFR-97®, PreFeRal®) + TX, Isoflavone formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus in particular strain A3-5 (Accession No. NRRL 30548) + TX, Mycorrhizae spp. (AMykor®, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal®, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor (SARRITOR®) + TX, Sclerotinia minor + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, 82994 FF Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P®, PlantShield HC®, RootShield®, Trianum-G® + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp. + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus + TX; AGNIQUE® MMF + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X® e.g. AZATIN XL from Certis, US) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, essentials oils of Labiatae (Botania®) + TX, extract of neem oil (Trilogy®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, garlic + TX, Glycinebetaine (Greenstim®) + TX, kaolin (Screen®) + TX, lemongrass oil (GreenMatch®) + TX, Melaleuca alternifolia extract (also called tea tree oil) (Timorex Gold®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pine oil (Retenol®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia®, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, storage glucam of brown algae (Laminarin®) + TX, thyme oil + TX; (E,Z)-7,9-Dodecadien-1-yl acetate + TX, (E,Z,Z)-3,8,11 Tetradecatrienyl acetate + TX, (Z,Z,E)-7,11,13- Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, Biolure® + TX, blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Calcium acetate + TX, Check-Mate® + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Lavandulyl senecioate + TX, Leafroller pheromone (3M MEC – LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + TX, Scenturion® + TX, Starbar Premium Fly Bait®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX; Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius 82994 FF andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris (Thripex®, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii®, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline®, Aphiline®), + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Aphelinus-System®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®, Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus®, Digline®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max®, Encarline®, En-Strip®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Enermix®, Ercal®, Eretline e®, Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar®, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Feltiline®) + TX, Feltiella acarisuga (Spidend®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis bacteriophora (NemaShield HB®, Nemaseek®, Terranem-Nam®, Terranem®, Larvanem®, B-Green®, NemAttack ®, Nematop®) + TX, Heterorhabditis megidis (Nemasys H®, BioNem H®, Exhibitline hm®, Larvanem-M®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System®, Entomite-A®) + TX, Hypoaspis miles (Hypoline m®, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N®, Macroline c®, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Ophyra aenescens (Biofly®) + 82994 FF TX, Orius insidiosus (Thripor-I®, Oriline i®) + TX, Orius laevigatus (Thripor-L®, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex®, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®) + TX, Steinernema feltiae (NemaShield®, Nemasys F®, BioNem F®, Steinernema-System®, NemAttack®, Nemaplus®, Exhibitline sf®, Scia-rid®, Entonem®) + TX, Steinernema kraussei (Nemasys L®, BioNem L®, Exhibitline srb®) + TX, Steinernema riobrave (BioVector®, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, CAS Number: 2643947-26-4 + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta traps (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct®, Ni- HIBIT Gold CST®) + TX, fatty acids derived from a natural by-product of extra virgin olive oil (FLIPPER®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, Spider venom + TX, Sticky traps (Trapline YF®, Rebell Amarillo®) + TX, SuffOil-X® + TX, Traps (Takitrapline y + b®) + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX, Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No.71840-19) + TX, Bacillus subtilis CX-9060 from Certis USA LLC, Bacillus sp., in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S. Patent No.7,094,592 + TX, Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S. Patent No.6,060,051, available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US) + TX, Paenibacillus polymyxa, in particular strain 82994 FF AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX, Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX; Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX, Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014/028521) (STARGUS® from Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No. 7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX, Bacillus licheniformis, in particular strain SB3086, having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAF™ from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having Accession No. B-30890 (available as BMJ TGAI® or WG and LifeGard™ from Certis USA LLC) + TX, Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No. 6,245,551) + TX, Bacillus subtilis CX-9060 from Certis USA LLC + TX, Bacillus subtilis IAB/BS03 (AVIV™ from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) + TX, Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX, Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX, Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No. 5,061,495 + TX, Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE + TX, Paenibacillus sp. strain having 82994 FF Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX, Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017/019448 (e.g., HOWLER™ and ZIO® from AgBiome Innovations, US) + TX, Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescens strain A506 (e.g. BLIGHTBAN® A506 by NuFarm) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf. Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® from Novozymes) + TX; Trichoderma atroviride strain T11 (IMI352941/ CECT20498) + TX, Ampelomyces quisqualis strain AQ10, having Accession No. CNCM 1-807 (e.g., AQ 10® by IntrachemBio Italia) + TX, Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta/ChemChina) + TX, Aureobasidium pullulans, in particular blastospores of strain DSM 14941 + TX, Aureobasidium pullulans, in particular blastospores of strain DSM14940 + TX, Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH) + TX, Chaetomium cupreum (Accession No. CABI 353812) (e.g. BIOKUPRUM™ by AgriLife) + TX, Chaetomium globosum (available as RIVADIOM® by Rivale) + TX, Cladosporium cladosporioides, strain H39, having Accession No. CBS122244, US 2010/0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM9660, e.g. Contans ® from Bayer CropScience Biologics GmbH) + TX, Cryptococcus flavescens, strain 3C (NRRL Y-50378), + TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST FUNGUS®), Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection) + TX, Gliocladium catenulatum (Synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g. Prestop ® by Lallemand) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea) strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain ’IK726’, Australasian Plant Pathol. 2007,36(2):95-101) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue A.G. (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 2003, 83(3): 519-524) + TX, Metschnikowia fructicola, in particular strain NRRL Y-30752 + TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, WO 2015/067800) from BASF SE + TX, mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No. CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having Accession No. IMI 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938, CNCM No.1- 82994 FF 3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX, Saccharomyces cerevisiae, in particular strain LASO2 (from Agro-Levures et Dérivés) + TX, Simplicillium lanosoniveum + TX, strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro + TX, strain WRL-076 (NRRL Y-30842), U.S. Patent No.7,579,183 + TX, Talaromyces flavus, strain V117b + TX, Trichoderma asperelloides JM41R (Accession No. NRRL B-50759) (TRICHO PLUS® from BASF SE) + TX, Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. ECO-HOPE® from Kumiai Chemical Industry) + TX, Trichoderma asperellum, in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (T77 from Andermatt Biocontrol) + TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX, Trichoderma atroviride strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX, Trichoderma atroviride strain LU132 (e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08/002388 + TX, Trichoderma atroviride strain NMI no. V08/002389 + TX, Trichoderma atroviride strain NMI no. V08/002390 + TX, Trichoderma atroviride strain no. V08/002387 + TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009/116106 and U.S. Patent No. 8,431,120 (from Bi-PA)) + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma harmatum + TX, Trichoderma harmatum, having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro), + TX, Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g. Root-Pro by Mycontrol) + TX, Trichoderma polysporum strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX, Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX, Trichoderma virens (also known as Gliocladium virens) in particular strain GL-21 (e.g. SoilGard by Certis, US) + TX, Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No. NM 99/06216 (e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; 82994 FF a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IF™ from TerraMax, Inc.) + TX, Azotobacter chroococcum, in particular strain H23 + TX, Azotobacter vinelandii, in particular strain ATCC 12837 + TX, Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015) + TX, Bacillus amyloliquefaciens in particular strain FZB42 (e.g. RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens in particular strain IN937a + TX, Bacillus amyloliquefaciens pm414 (LOLI- PEPTA® from Biofilm Crop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC # PTA-7542, WO 2017/205258) + TX, Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus in particular strain BP01 (ATCC 55675, e.g. MEPICHLOR® from Arysta Lifescience, US) + TX, Bacillus mycoides BT155 (NRRL No. B-50921) + TX, Bacillus mycoides BT46-3 (NRRL No. B-50922) + TX, Bacillus mycoides EE118 (NRRL No. B-50918) + TX, Bacillus mycoides EE141 (NRRL No. B-50916) + TX, Bacillus pumilus in particular strain GB34 (e.g. YIELD SHIELD® from Bayer Crop Science, DE), + TX, Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B-50421 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No. 13/330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g. SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE) + TX, Bacillus tequilensis in particular strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7 + TX, Bradyrhizobium japonicum (e.g. OPTIMIZE® from Novozymes) + TX, Delftia acidovorans in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g. CROPAID® from Cropaid Ltd UK) + TX; Myrothecium verrucaria strain AARC-0255 (e.g. DiTera™ from Valent Biosciences) + TX, Penicillium bilaii strain ATCC 22348 (e.g. JumpStart® from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89/030550, e.g. BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472 e.g. Polyversum from Bioprepraty, CZ) + TX, Rhizopogon amylopogon (Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Rhizopogon 82994 FF fulvigleba (e.g. Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Talaromyces flavus strain V117b + TX, Trichoderma asperellum strain (Eco-T from Plant Health Products, ZA) + TX, Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride in particular strain no. V08/002387 + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain no. NMI No. V08/002388 + TX, Trichoderma atroviride strain no. NMI No. V08/002389 + TX, Trichoderma atroviride strain no. NMI No. V08/002390 + TX, Trichoderma atroviride strain SC1 (described in WO2009/116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g. SoilGard® from Certis, USA) + TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g. Dutch Trig from Tree Care Innovations) + TX; Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc.), + TX, Bacillus amyloliquefaciens in particular strain PTS-4838 (e.g. AVEO from Valent Biosciences, US), + TX, Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC), + TX, Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US), + TX, Bacillus thuringiensis israelensis strain BMP 144 (e.g. AQUABAC® by Becker Microbial Products IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensis strain Buibui + TX, Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global) + TX, Brevibacillus laterosporus + TX, Burkholderia spp. in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319, WO 2011/106491 and WO 2013/032693, e.g. MBI206 TGAI and ZELTO® from Marrone Bio Innovations), + TX, Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI-203, e.g. GRANDEVO® from Marrone Bio Innovations) + TX, Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX, Paenibacillus popilliae (formerly Bacillus 82994 FF popilliae, e.g. MILKY SPORE POWDER™ or MILKY SPORE GRANULAR™ from St. Gabriel Laboratories) + TX, Serratia entomophila (e.g. INVADE® by Wrightson Seeds) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708) + TX, Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX, Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX; Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (Accession No. DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (Accession No. ATCC74250, e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017/066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX; Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX; Burkholderia spp. in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp. + TX, Agrobacterium spp. + TX, Azorhizobium caulinodans + TX, Azospirillum spp. + TX, Azotobacter spp. + TX, Bradyrhizobium spp. + TX, Gigaspora monosporum + TX; Allium sativum (NEMGUARD from Eco-Spray, BRALIC from ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae extract in particular oilseed rape powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Chenopodium quinoa saponin extract from quinoa seeds (e.g. Heads Up® (Saponins of Quinoa) from Heads Up plant Protectants, CA) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from STK) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (FRACTURE® from FMC) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (PROBLAD® from Certis EU) + TX, Pyrethrins + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX from Marrone Bio) + TX, Requiem™ Insecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX, ryania/ryanodine + TX, Symphytum officinale + TX, Tanacetum vulgare + TX, Thymol + TX, Thymol mixed with Geraniol (CEDROZ from Eden Research) + TX, Thymol mixed with Geraniol and Eugenol (MEVALONE from Eden Research) + TX, Triact 70 + TX, TriCon + TX, Tropaeulum majus + TX, Urtica dioica + TX, Veratrin + TX, Viscum album + TX; mercuric oxide + TX, octhilinone + TX, thiophanate-methyl + TX; MGK 264 + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-isovalerylindan-1,3-dione + TX, 4- (quinoxalin-2-ylamino)benzenesulfonamide + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, 82994 FF acibenzolar + TX, acibenzolar-S-methyl + TX, alpha-bromadiolone + TX, alpha-chlorohydrin + TX, aluminium phosphide + TX, anthraquinone + TX, antu + TX, arsenous oxide + TX, barium carbonate + TX, benoxacor + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, calcium cyanide + TX, chloralose + TX, chlorophacinone + TX, cholecalciferol + TX, cloquintocet (including cloquintocet-mexyl) + TX, copper naphthenate + TX, copper oxychloride + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, cyprosulfamide + TX, diazinon + TX, dichlormid + TX, dicyclopentadiene + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, farnesol + TX, farnesol with nerolidol + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluxofenim + TX, furilazole + TX, gamma-HCH + TX, guazatine + TX, guazatine acetates + TX, HCH + TX, hydrogen cyanide + TX, imanin + TX, iodomethane + TX, isoxadifen (including isoxadifen-ethyl) + TX, lindane + TX, magnesium phosphide + TX, MB-599 + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX, methiocarb + TX, methyl bromide + TX, nerolidol + TX, norbormide + TX, petroleum oils + TX, phosacetim + TX, phosphine + TX, phosphorus + TX, pindone + TX, piperonyl butoxide + TX, piprotal + TX, potassium arsenite + TX, probenazole + TX, propyl isomer + TX, pyridin-4-amine + TX, pyrinuron + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, S421 + TX, scilliroside + TX, sesamex + TX, sesasmolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoro- acetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thiram + TX, trimethacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX. [0363] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html. [0364] Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number. [0365] The active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-52, Tables B-1 to B-52, and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-52, Tables B-1 to B-52, and Table P, 82994 FF and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight. [0366] The compounds and mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body. [0367] The mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-52, Tables B-1 to B-52, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention. [0368] The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, micro-emulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents. [0369] The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface- active substances or combinations thereof. [0370] The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The 82994 FF active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated. [0371] The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethyl-formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. [0372] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances. [0373] A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of 82994 FF sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981). [0374] Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers. [0375] The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010. [0376] The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula-tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations. [0377] The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha. [0378] Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: ^ active ingredient: 1 to 95 %, preferably 60 to 90 % ^ surface-active agent: 1 to 30 %, preferably 5 to 20 % ^ liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts: ^ active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % 82994 FF ^ solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: ^ active ingredient: 5 to 75 %, preferably 10 to 50 % ^ water: 94 to 24 %, preferably 88 to 30 % ^ surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: ^ active ingredient: 0.5 to 90 %, preferably 1 to 80 % ^ surface-active agent: 0.5 to 20 %, preferably 1 to 15 % ^ solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: ^ active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % ^ solid carrier: 99.5 to 70 %, preferably 97 to 85 % [0379] Formulation types include an emulsifiable concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. A short definition of formulation types may be found in the OECD Guidance for Industry Data Submissions on Plant Protection Products and their Active Substances (Revision 2 May 2005), Appendix 2. [0380] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use. [0381] Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations. [0382] The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or 82994 FF tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides. [0383] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention. [0384] The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha. [0385] A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredi-ent can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field. [0386] The compounds of formula (I) of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds. [0387] The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds. [0388] The present invention also comprises seeds coated or treated with or containing a compound of formula (I). The term "coated or treated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed 82994 FF product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I). [0389] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds. [0390] The compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m2. The greater efficacy can be observed by an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). [0391] In each aspect and embodiment of the invention, "consisting essentially" and inflections thereof are a preferred embodiment of "comprising" and its inflections, and "consisting of" and inflections thereof are a preferred embodiment of "consisting essentially of" and its inflections. [0392] The disclosure in the present application makes available each and every combination of embodiments disclosed herein. [0393] It should be noted that the disclosure herein in respect of a compound of formula (I) applies equally in respect of a compound of each of formulae (I*), (I’a), Tables A-1 to A-52 and Tables B-1 to B-52. EXAMPLES Formulation Examples [0394] The following Examples further illustrate, but do not limit, the invention. Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - [0395] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration. 82994 FF Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20 % [0396] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment. Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % [0397] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c) Active ingredients 5 % 6 % 4 % Talcum 95 % - - Kaolin - 94 % - mineral filler - - 96 % [0398] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruded granules Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % 82994 FF Kaolin 82 % [0399] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Coated granules Active ingredients 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % [0400] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % [0401] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % 82994 FF Water 45.3 % [0402] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Slow Release Capsule Suspension [0403] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose. Preparation Examples [0404] Free radicals represent methyl groups.1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion [M+H]+ or [M-H]-. Method 1: [0405] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector. Column: Acquity UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-50% B; 0.2-0.6 min 50-100% B; 0.6-1.3 min 100% B; 1.3-1.4 min 100-10% B; 1.4-1.6 min 10% B; Flow (mL/min) 0.6. Method 2: [0406] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from 82994 FF Waters: Quaternary solvent manager, heated column compartment , diode-array detector. Column: Acquity UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.0-0.5 min 10% B; 0.5-2 min 100% B; 2-3 min 100% B; 3-3.5 min 10% B; 3.5-4 min 10% B; Flow (mL/min) 0.6. Method 3: [0407] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 1.5 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 1.0 min, 100% B isocratic for 0.2min, 100-10% B in 0.05min, 10% B isocratic for 0.05 min. Example E1: Preparation of 5-bromo-N-[(1S)-1-[3-(5-cyano-2-pyridyl)pyrazin-2-yl]ethyl]-3-iodo-1H-indazole-7- carboxamide (compound P4)
Figure imgf000107_0001
Step 1: Preparation of 5-bromo-3-iodo-1H-indazole-7-carboxylic acid (I-16)
Figure imgf000107_0002
(I-16) [0408] To a solution of 5-bromo-1H-indazole-7-carboxylic acid (CAS 953409-99-9) (1.00 g, 4.15 mmol) in N,N-dimethylformamide (12.4 mL) at 0°C were added potassium hydroxide (0.419 g, 7.47 mmol), followed after 5 min by iodine (1.16 g, 4.56 mmol). The reaction mixture was stirred at RT for 2 hours, then quenched with an aqueous solution of sodium thiosulfate and diluted with water and EtOAc. The layers were separated, the 82994 FF aqueous phase neutralized and extracted with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was triturated in diisopropylether to afford 5-bromo-3-iodo-1H-indazole-7-carboxylic acid (I-16) as a white solid. [0409] LCMS (method 3): retention time 0.91 min, m/z 365/367 [M-H]-. Step 2: Preparation of 5-bromo-N-[(1S)-1-[3-(5-cyano-2-pyridyl)pyrazin-2-yl]ethyl]-3-iodo-1H-indazole-7- carboxamide (P4)
Figure imgf000108_0001
[0410] To a solution of 6-[3-[(1S)-1-aminoethyl]pyrazin-2-yl]pyridine-3-carbonitrile (CAS 2497659-69-3) (1.2 g, 4.6 mmol) in ethyl acetate (15 mL) were added propanephosphonic acid cyclic anhydride (T3P®, 50 wt.% in ethyl acetate, 4.2 mmol), 5-bromo-3-iodo-1H-indazole-7-carboxylic acid (I-16) (1.4 g, 3.8 mmol) and N,N- diisopropylethylamine (2.6 mL, 15 mmol) at room temperature. The reaction mixture was stirred at 50°C for 1.5 h, then diluted with water and the product extracted twice with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 5-bromo-N-[(1S)-1-[3-(5-cyano-2-pyridyl)pyrazin-2-yl]ethyl]- 3-iodo-1H-indazole-7-carboxamide (P4) as a white solid. [0411] LCMS (method 3): retention time 1.06 min, m/z 574/576 [M+H]+. Example E2: Preparation of 3-cyclopropyl-N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5- (trifluoromethyl)-1H-indazole-7-carboxamide (compound P8)
Figure imgf000108_0002
Step 1: Preparation of 7-bromo-5-(trifluoromethyl)-1H-indazole (I-1) 82994 FF
Figure imgf000109_0001
[0412] To a solution of 2-bromo-6-methyl-4-(trifluoromethyl)aniline (CAS 1100212-65-4) (20 g, 78.72 mmol) in ACN (200 mL) was added concentrated hydrochloric acid (17.9 g, 157.45 mmol) at 0-5°C, followed by a solution of sodium nitrite (70.85 mmol) in water (40 mL) dropwise. After addition the reaction mixture was stirred at 0-5°C for 30 minutes, then potassium acetate (19.7 g, 196.8 mmol) was further added and stirring continued at room temperature for 1 hour. The mixture was poured into ice cold water (1500 mL), stirred for 10 minutes and the precipitated solid was filtered, washed with water and dried in vacuo to afford 7-bromo-5- (trifluoromethyl)-1H-indazole (I-1) as a brown solid. [0413] LCMS (method 1): retention time 1.26 min, m/z 265/267 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 13.99 (br s, 1H), 8.42 (d, 1H), 8.30 (s, 1H), 7.90-7.94 (m, 1H). Step 2: Preparation of methyl 5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-2)
Figure imgf000109_0002
(I-2) [0414] A pressure vessel was charged with 7-bromo-5-(trifluoromethyl)-1H-indazole (I-1) (5.7 g, 21.5 mmol), 1,1’-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (Pd(dppf)Cl2·CH2Cl2; 1.79 g, 2.15 mmol), triethylamine (4.39 g, 43 mmol) and methanol (57 mL). The vessel was flushed with nitrogen, then with carbon monoxide. The reaction mixture was heated to 100°C under a 20 bar carbon monoxide pressure for 5 hours. After cooling to room temperature, the pressure was carefully released and the vessel flushed with nitrogen. The mixture was filtered through a celite bed, the filter cake washed with EtOAc and the filtrate concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford methyl 5-(trifluoromethyl)-1H-indazole-7-carboxylate (I- 2) as a pale brown solid. [0415] LCMS (method 1): retention time 1.07 min, m/z 245 [M+H]+.1H NMR (400 MHz, CDCl3) δ: ~11.5 (br s, 1H), 8.33 (d, 2H), 8.30 (s, 1H), 4.10 (s, 3H). Step 3: Preparation of methyl 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-3) 82994 FF
Figure imgf000110_0001
(I-3) [0416] To a solution of methyl 5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-2) (4.3 g, 17.6 mmol) in acetic acid (43 mL) was added N-iodosuccinimide (5.94 g, 26.41 mmol) at room temperature. The reaction mixture was heated at 80°C for 20 h, then cooled and diluted with water (500 mL). Sodium metabisulfite (1 g) was added to the mixture, stirring continued shortly, then the precipitated solid was filtered, washed with water and dried in vacuo. The solid was adsorbed on silica and purified by combiflash (ethyl acetate in cyclohexane) to afford methyl 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-3) as a white solid. [0417] LCMS (method 1): retention time 1.17 min, m/z 369 [M-H]-.1H NMR (400 MHz, DMSO-d6) δ: 11.66 (br s, 1H), 8.36 (d, 1H), 8.05 (s, 1H), 7.27 (s, 1H), 4.09 (s, 3H). Step 4: Preparation of methyl 3-iodo-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-4)
Figure imgf000110_0002
(I-4) [0418] To a suspension of sodium hydride (0.51 g, 12.97 mmol, 60 mass%) in tetrahydrofuran (32 mL) cooled to 0-5°C under nitrogen was added a solution of methyl 3-iodo-5-(trifluoromethyl)-1H-indazole-7- carboxylate (I-3) (3.2 g, 8.64 mmol) in tetrahydrofuran (32 mL) dropwise at 0-5°C (effervescence observed). The mixture was stirred for 5 minutes, then a solution of chloromethyl methyl ether (1.31 mL, 17.29 mmol) in tetrahydrofuran (5 mL) was added dropwise at 0-5°C over 10 minutes. The reaction mixture was stirred at 0- 5°C for 30 minutes, then quenched with an aqueous saturated ammonium chloride solution and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford methyl 3-iodo-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-4) as a white solid. [0419] LCMS (method 1): retention time 1.13 min, m/z 415 [M+H]+. 1H NMR (400 MHz, CDCl3) δ: 8.32 (d, 1H), 8.06 (s, 1H), 5.94 (s, 2H), 4.06 (s, 3H), 3.47 (s, 3H). Step 5: Preparation of methyl 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-5) and 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) 82994 FF
Figure imgf000111_0001
[0420] A solution of methyl 3-iodo-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-4) (3 g, 7.24 mmol) and cyclopropylboronic acid (3.11 g, 36.2 mmol) in acetonitrile (90 mL) was flushed with nitrogen for 5 minutes, then 1,1’-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloro-methane complex (Pd(dppf)Cl2·CH2Cl2; 0.622740 g, 0.72 mmol) was added. The reaction mixture was heated to 85°C and a solution of tribasic potassium phosphate (3.23 g, 14.4 mmol) in degassed water (28 mL) was added dropwise at 80°C. The mixture was heated at 85°C for 5 h, cooled to room temperature, diluted with water and the product extracted with EtOAc. The layers were separated and the aqueous phase kept aside. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford methyl 3-cyclopropyl-2-(methoxymethyl)-5- (trifluoromethyl)indazole-7-carboxylate (I-5) as a gum. [0421] LCMS (method 1): retention time 1.12 min, m/z 329 [M+H]+.1H NMR (400 MHz, CDCl3) δ: 8.39 (m, 2H), 6.08 (s, 2H), 4.18 (s, 3H), 3.60 (s, 3H), 2.34-2.41 (m, 1H), 1.36-1.50 (m, 2H), 1.18-1.23 (m, 2H). [0422] Above kept aside aqueous layer was passed though celite, the filtrate acidified with concentrated hydrochloric acid and the mixture stirred at room temperature for 15 hours. The precipitated solid was filtered, washed with water and dried under vacuum to afford 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) as a white solid. [0423] LCMS (method 1): retention time 1.06 min, m/z 269 [M-H]-.1H NMR (400 MHz, DMSO-d6) δ: 13.70- 13.89 (br s, 1H), 13.11 (s, 1H), 8.58 (s, 1H), 8.12 (d, 1H), 2.50 (m, 1H), 0.95-1.09 (m, 4H). Step 6: Preparation of 3-cyclopropyl-N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-(trifluoromethyl)-1H- indazole-7-carboxamide (P8)
Figure imgf000111_0002
82994 FF [0424] To a solution of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) (0.3 g, 1.11 mmol) and N,N-diisopropylethylamine (0.432 g, 3.33 mmol) in acetonitrile (6 mL) was added propane- phosphonic acid cyclic anhydride (T3P®, 50 wt.% in ethyl acetate, 2.22 mmol) and the mixture stirred at room temperature for 10 minutes, then cooled to 0-5°C. [(1S)-1-(2-Pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]ammonium 2,2,2-trifluoroacetate (CAS 2641011-44-9) (0.405 g, 1.33 mmol) was added, the reaction mixture warmed to room temperature and stirred for 40 minutes. The mixture was diluted with water and the product extracted with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 3- cyclopropyl-N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-(trifluoromethyl)-1H-indazole-7-carboxamide (P8) as a solid. [0425] LCMS (method 2): retention time 1.86 min, m/z 443 [M+H]+.1H NMR (400 MHz, CDCl3) δ: 8.93 (d, 2H), 8.33 (br d, 1H), 8.14(s, 1H), 8.09 (s, 1H), 7.94 (s, 1H), 7.42 (T, 1H), 6.56 (quint, 1H), 2.18-2.26 (m, 1H), 1.74 (d, 3H), 0.99-1.16 (m, 4H). [0426] Similarly, 3-iodo-N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-(trifluoromethyl)-1H-indazole- 7-carboxamide (P7) can be obtained from 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-15) and [(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]ammonium 2,2,2-trifluoroacetate (CAS 2641011-44-9) with above protocol in analogy. [0427] LCMS (method 1): retention time 1.07 min, m/z 529 [M+H]+. Example E3: Preparation of N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-N-methyl-5-(trifluoromethyl)indazole-7-carboxamide (compound P20)
Figure imgf000112_0001
Step 1: Preparation of 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7)
Figure imgf000112_0002
[0428] To a solution of methyl 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 5) (2.7 g, 4.93 mmol, 60 mass%) in methanol (54 mL) and water (54 mL) was added NaOH (0.296 g, 7.4 mmol) 82994 FF at room temperature. The reaction mixture was stirred at 60°C for 6 h, cooled to room temperature and concentrated under reduced pressure. The residue was diluted with ice cold water (100mL) and acidified carefully under cooling with concentrated hydrochloric acid (0.71 mL, 7.89 mmol). The precipitated solid was immediately filtered, washed with water and dried in vacuo to afford 3-cyclopropyl-2-(methoxymethyl)-5- (trifluoromethyl)indazole-7-carboxylic acid (I-7) as a white solid. [0429] LCMS (method 1): retention time 1.09 min, m/z 315 [M+H]+. 1H NMR (CH3CN-d3) δ: 8.32 (s, 1H), 8.09-8.13 (m, 1H), 5.87 (s, 2H), 3.38 (s, 3H), 2.12-2.36 (m, 1H), 1.17-1.30 (m, 2H), 1.01-1.14 (m, 2H). Step 2: Preparation of N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-N-methyl-5-(trifluoromethyl)indazole-7-carboxamide (P20)
Figure imgf000113_0001
[0430] To a mixture of 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7) (0.08 g, 0.25 mmol) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-methyl-ammonium chloride (0.108 g, 0.38 mmol), prepared as described in WO 2023/247360, in acetonitrile (1.6 mL) was added propane-phosphonic acid cyclic anhydride (T3P®, 50 wt.% in ethyl acetate, 0.509 mmol), followed by N,N-diisopropylethylamine (0.099 g, 0.131 mL, 0.763 mmol) at room temperature. After addition the reaction mixture was stirred at room temperature for 2 h, then diluted with aqueous saturated sodium bicarbonate and the product extracted with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-N-methyl-5-(trifluoromethyl)indazole-7-carboxamide (P20) as a white solid. [0431] LCMS (method 1): retention time 1.03 min, m/z 544 [M+H]+.1H NMR (400 MHz, DMSO-d6, 100°C) δ: 8.16-8.26 (m, 2H), 7.70-8.12 (m, 3H), 7.11 (br s, 1H), 6.19-6.81 (m, 2H), 5.74 (d, 1H), 5.57 (d, 1H), 3.34 (s, 3H), 2.90 (s, 3H), 2.20 (m, 1H),1.70 (d, 3H), 1.20 (m, 2H), 0.98 (m, 2H). [0432] Similarly, 3-cyclopropyl-2-(methoxymethyl)-N-[(1S)-1-[2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2,4- triazol-3-yl]ethyl]-5-(trifluoromethyl)indazole-7-carboxamide (P17) can be obtained from 3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7) and [(1S)-1-[2-[6-(methyl- carbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]ammonium chloride (prepared in analogy to CAS 2694010-27- 8 as described for example in WO 2021/224323) with the above protocol in analogy. [0433] LCMS (method 1): retention time 1.15 min, m/z 544 [M+H]+. [0434] Similarly, N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P25) can be obtained from 3-cyclopropyl-5-(trifluoromethyl)-1H- 82994 FF indazole-7-carboxylic acid (I-6) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2694010-27-8) with above protocol in analogy. [0435] LCMS (method 1): retention time 1.05 min, m/z 486 [M+H]+. Example E4: Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole-7-carboxamide (compound P10)
Figure imgf000114_0001
Step 1: Preparation of N-[4-(trifluoromethyl)phenyl]cyclopropanecarboxamide (I-8)
Figure imgf000114_0002
[0436] To a solution of 4-(trifluoromethyl)aniline (21 g, 130.3 mmol) in ethyl acetate (260 mL) was added pyridine (10.5 mL, 129 mmol) at 0°C. The reaction mixture was stirred for 10 minutes, then a solution of cyclopropanecarbonyl chloride (14.3 mL, 149.8 mmol) in ethyl acetate (26 mL) was added over 15 minutes at 0°C. The mixture was stirred at room temperature for 15 hours, diluted with water and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford N-[4- (trifluoromethyl)phenyl]cyclopropanecarboxamide (I-8) as a white solid. [0437] LCMS (method 1): retention time 1.10 min, m/z 230 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 10.56 (s, 1H), 7.79 (m, 2H), 7.65 (m, 2H), 1.80 (m, 1H), 0.83 (m, 4H). Step 2: Preparation of [2-amino-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-9)
Figure imgf000114_0003
[0438] A solution of N-[4-(trifluoromethyl)phenyl]cyclopropanecarboxamide (I-8) (16 g, 69.81 mmol) in acetonitrile (4600 mL) was passed through a 55 mL-photo flow reactor (254 nm; flow: 1ml/minute; residence 82994 FF time: 55 min) at room temperature. The collected solution was evaporated under reduced pressure and the obtained residue purified by combiflash (ethyl acetate in cyclohexane) to afford [2-amino-5- (trifluoromethyl)phenyl]-cyclopropyl-methanone (I-9) as a solid. [0439] 1H NMR (400 MHz, CDCl3) δ ppm 8.22 (s, 1H), 7.47 (d, 1H), 6.71 (d, 1H), 2.64 (m, 1H), 1.17-1.26 (m, 2H), 1.02-1.08 (m, 2H). Step 3: Preparation of [2-amino-3-bromo-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-10)
Figure imgf000115_0001
[0440] To a solution of [2-amino-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-9) (5.8 g, 25 mmol) in acetonitrile (120 mL) was added N-bromosuccinimide (5.6 g, 30 mmol) and reaction mixture was stirred at RT for 15 h. The mixture was diluted with an aqueous saturated sodium bicarbonate solution and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford [2-amino-3-bromo-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-10). [0441] 1H NMR (400 MHz, DMSO-d6) δ ppm 8.37 (s, 1H), 8.00 (d, 1H), 7.72 (br s, 2H), 2.95 (m, 1H), 1.01- 1.06 (m, 4H). Step 4: Preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11)
Figure imgf000115_0002
[0442] A suspension of [2-amino-3-bromo-5-(trifluoromethyl)phenyl]-cyclopropyl-methanone (I-10) (0.05 g, 0.162 mmol) in acetonitrile (1.25 mL) was stirred for 15 minutes (until the solution becomes clear), then aqueous hydrobromic acid (48 mass%, 0.27 mL, 2.43 mmol) was added and the mixture cooled to 0-5°C. A solution of sodium nitrite (0.013 g, 0.194 mmol) in water (0.075 mL) was added to the reaction mixture at 0-5°C over 1-2 minutes and stirring continued for 20 minutes. A mixture of tin(II)chloride dihydrate (0.109 g, 0.486 mmol) in concentrated hydrochloric acid (0.175 mL, 5.8 mmol) was then added to the reaction mixture at 0-5°C and stirring continued at the same temperature for 1 hour. The mixture was diluted with ethyl acetate, the layers separated, the organic phase washed with brine till pH is ~ 6.5, then dried over sodium sulfate, filtered and 82994 FF concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 7- bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11)as an off-white solid. [0443] LCMS (method 1): retention time 1.22 min, m/z 305/307 [M+H]+.1H NMR (400 MHz, CDCl3) δ ppm 9.97 (br s, 1H), 8.04 (s, 1H), 7.76 (s, 1H), 2.23 (m, 1H), 1.09-1.13 (m, 4H). Step 5: Preparation of methyl 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-12)
Figure imgf000116_0001
(I-12) [0444] A pressure vessel was charged with 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11) (0.10 g, 0.327 mmol), 1,1’-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (Pd(dppf)Cl2·CH2Cl2; 0.027 g, 0.0328 mmol), triethylamine (0.0335 g, 0.327 mmol) and methanol (3 mL). The vessel was flushed with nitrogen, then with carbon monoxide. The reaction mixture was heated to 80°C under a 10 bar carbon monoxide pressure for 5 hours. After cooling to room temperature, the pressure was carefully released and the vessel flushed with nitrogen. The mixture was filtered through a celite bed, the filter cake washed with ethyl acetate and the filtrate concentrated under reduced pressure to afford crude methyl 3- cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-12) as a solid. This material was used without further purification into the next step. [0445] LCMS (method 2): retention time 2.13 min, m/z 285 [M+H]+. Step 6: Preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6)
Figure imgf000116_0002
[0446] To a solution of methyl 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylate (I-12) (0.1 g, 0.352 mmol) in methanol (1.00 mL) and water (1.00 mL) was added lithium hydroxide (0.01 g, 0.422 mmol). The reaction mixture was stirred at room temperature for 12 hours, then concentrated under reduced pressure. The residue was diluted with ice cold water and acidified with concentrated hydrochloric acid. The precipitated solid was filtered, washed with water and dried in vacuo to afford 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole- 7-carboxylic acid (I-6) as a white solid. 82994 FF [0447] 1H NMR (400 MHz, DMSO-d6) δ ppm 13.75 (br s, 1H), 13.11 (s, 1H), 8.58 (s, 1H), 8.11 (d, 1H), 2.48 (m, 1H), 0.95-1.07 (m, 4H). Step 7: Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P10)
Figure imgf000117_0001
[0448] To a mixture 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6) (0.06 g, 0.222 mmol), and [(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2378554-38-0) (0.066 g, 0.266 mmol) in acetonitrile (1.2 mL) was added N,N-diisopropylethylamine (0.114 mL, 0.666 mmol), followed by propanephosphonic acid cyclic anhydride (T3P®, 50 wt.% in ethyl acetate, 0.444 mmol) at room temperature. The reaction mixture was stirred at room temperature for 15 h, then diluted with water and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P10) as a solid. [0449] LCMS (method 1): retention time 1.15 min, m/z 467 [M+H]+.1H NMR (400 MHz, CDCl3) δ ppm 11.69 (br s, 1H), 8.89 (d, 1H), 8.22 (m, 2H), 8.16 (s, 1H), 8.04 (s, 1H), 7.79-7.89 (m, 2H) 6.47 (quint, 1H), 2.21 (m, 1H), 1.77 (d, 3H), 1.03-1.16 (m, 4H). [0450] Similarly, N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-iodo-5-(trifluoromethyl)-1H- indazole-7-carboxamide (P9) can be obtained from 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I- 15) and [(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2378554-38-0) with above protocol in analogy. [0451] LCMS (method 1): retention time 1.18 min, m/z 553 [M+H]+. [0452] Similarly, N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5-(trifluoromethyl)- 1H-indazole-7-carboxamide (P12) can be obtained from 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7- carboxylic acid (I-6) and [(1S)-1-[2-(5-cyanothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2648588-59-2) with above protocol in analogy. [0453] LCMS (method 1): retention time 1.16 min, m/z 473 [M+H]+. 82994 FF [0454] Similarly, 3-cyclopropyl-N-[(1S)-1-[2-(6-methoxypyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P28) can be obtained from 3-cyclopropyl-5-(trifluoromethyl)-1H- indazole-7-carboxylic acid (I-6) and [(1S)-1-[2-(6-methoxypyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 3039973-80-0) with above protocol in analogy. [0455] LCMS (method 1): retention time 1.11 min, m/z 473 [M+H]+. [0456] Similarly, N-[(1S)-1-[2-(6-chloropyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxamide (P22) can be obtained from 3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylic acid (I-7) and [(1S)-1-[2-(6-chloropyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 3039973-68-4) with above protocol in analogy. [0457] LCMS (method 1): retention time 1.19 min, m/z 521/523 [M+H]+. Example E5: Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-isopropoxy-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxamide (compound P24)
Figure imgf000118_0001
Step 1: Preparation of methyl 3-hydroxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-19)
Figure imgf000118_0002
(I-19) [0458] To a solution of methyl 3-iodo-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-4) (0.15 g, 0.362 mmol) in N,N-dimethylformamide (1.5 mL) was added cesium carbonate (0.236 g, 0.72 mmol) and (E)-benzaldehyde oxime (0.073 g, 0.543 mmol). The reaction mixture was stirred at room temperature for 15 hours, then diluted with water and the product extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford methyl 3-hydroxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7- carboxylate (I-19). 82994 FF [0459] LCMS (method 1): retention time 0.99 min, m/z 305 [M+H]+. Step 2: Preparation of methyl 3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 20)
Figure imgf000119_0001
(I-20) [0460] To a solution of methyl 3-hydroxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I-19) (0.05 g, 0.164 mmol) in toluene (1.25 mL) was added silver carbonate (0.328 mmol). The reaction mixture was heated to 100°C, then 2-iodopropane (0.493 mmol) was slowly added and stirring continued at 100°C for 5 hours. The mixture was diluted with water and the product extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by reversed phase column chromatography (H2O and ACN) to afford methyl 3-isopropoxy-2-(methoxymethyl)-5- (trifluoromethyl)indazole-7-carboxylate (I-20). [0461] LCMS (method 1): retention time 1.15 min, m/z 347 [M+H]+.1H NMR (400 MHz, CDCl3) δ ppm 8.20 (s, 1H), 8.12 (s, 1H), 5.66 (s, 2H), 5.04 (m, 1H), 4.02 (s, 3H), 3.48 (s, 3H), 1.50 (d, 6H). Step 3: Preparation of sodium 3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 21)
Figure imgf000119_0002
(I-21) [0462] To a solution of methyl 3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 20) (0.047 g, 0.14 mmol) in methanol (0.94 mL) and water (0.94 mL) was added sodium hydroxide (8.1 mg, 0.20 mmol) at room temperature. The reaction mixture was stirred at 60°C for 1 hour, then concentrated in vacuo to get crude sodium-3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)-indazole-7-carboxylate (I-21), which was taken as such for the next step. 82994 FF [0463] LCMS (method 1): retention time 1.07 min, m/z 333 [M+H]+for the corresponding carboxylic acid.1H NMR (400 MHz, D2O) δ ppm 8.18 (s, 1H), 7.74 (s, 1H), 5.56 (s, 2H), 5.15-5.22 (m, 1H), 3.32 (s, 3H), 1.39 (d, 6H). Step 4: Preparation of N-[(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-isopropoxy-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxamide(P24)
Figure imgf000120_0001
[0464] To a solution of sodium-3-isopropoxy-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 21) (0.05 g, 0.14 mmol) and 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (CAS 2378554- 37-9) (0.036 g, 0.17 mmol) in acetonitrile (1.0 mL) was added N,N-diisopropylethylamine (0.055 g, 0.42 mmol) and propanephosphonic acid cyclic anhydride (T3P®, 50 wt.% in ethyl acetate, 0.28 mmol) at room temperature. The reaction mixture was stirred at room temperature for 16 hours, then diluted with water and the product extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford N- [(1S)-1-[2-(5-cyano-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3-isopropoxy-2-(methoxymethyl)-5- (trifluoromethyl)indazole-7-carboxamide (P24). [0465] LCMS (method 1): retention time 1.20 min, m/z 529 [M+H]+.1H NMR (400 MHz, CDCl3) δ ppm 10.03 (d, 1H), 8.89 (d, 1H), 8.32 (d, 1H), 8.11-8.18 (m, 2H), 8.05 (s, 1H), 7.99 (s, 1H), 6.48 (quint, 1H), 5.66 (s, 2H), 5.09 (sept, 1H), 3.58 (s, 3H), 1.81 (d, 3H), 1.52 (d, 6H). Example E6: Preparation of 3-cyclopropyl-2-(methoxymethyl)-N-[(1S)-1-[2-(6-methoxypyridazin-3-yl)-1,2,4- triazol-3-yl]ethyl]-5-(trifluoromethyl)indazole-7-carboxamide (compound P21)
Figure imgf000120_0002
[0466] To a mixture of N-[(1S)-1-[2-(6-chloropyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-2- (methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxamide (P22) (280 mg, 0.54 mmol) in methanol (5 mL) was 82994 FF added potassium carbonate (187.6 mg, 1.34 mmol). The reaction mixture was heated at 60°C for 16 h, then concentrated in vacuo. Water was added to the residue and the product extracted with EtOAc. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 3- cyclopropyl-2-(methoxymethyl)-N-[(1S)-1-[2-(6-methoxypyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-5- (trifluoromethyl)indazole-7-carboxamide (P21) as an off-white solid. [0467] LCMS (method 1): retention time 1.19 min, m/z 517 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 9.95 (d, 1H), 8.27-8.32 (m, 2H), 8.10 (d, 1H), 8.04 (s, 1H), 7.56 (d, 1H), 6.05 (quint, 1H), 5.96 (m, 2H), 4.12 (s, 3H), 3.50 (s, 3H), 2.25 (m, 1H), 1.71 (d, 3H), 1.24 (m, 2H), 1.14 (m, 2H). [0468] Similarly, 3-cyclopropyl-N-[(1S)-1-[2-(6-ethoxypyridazin-3-yl)-1,2,4-triazol-3-yl]ethyl]-5- (trifluoromethyl)-1H-indazole-7-carboxamide (P30) can be obtained from N-[(1S)-1-[2-(6-chloropyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxamide (P29) and ethanol with above protocol in analogy. [0469] LCMS (method 1): retention time 1.15 min, m/z 487 [M+H]+. Preparation of intermediates Example PI-1: Preparation of 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-15)
Figure imgf000121_0001
Step 1: Preparation of 5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-14)
Figure imgf000121_0002
[0470] To a solution of 2-amino-3-methyl-5-(trifluoromethyl)benzoic acid (CAS 1450644-75-3) (5.5 g, 25.1 mmol) in acetic acid (63 mL) at 0-5°C was added sodium nitrite (3.64 g, 52.7 mmol) portionwise. After addition the reaction mixture was warmed to room temperature and stirred for 3 h. The mixture was diluted with water (500 mL) and the precipitated solid isolated by filtration. The solid was washed with water, dried in vacuo and 82994 FF purified by combiflash (EtOAc in cyclohexane) to afford still crude 5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-14) as a solid. This material was not further purified and used directly into the next step. [0471] LCMS (method 1): retention time 1.03 min, m/z 229 [M-H]-. Step 2: Preparation of 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-15)
Figure imgf000122_0001
[0472] To a solution of 5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-14) (0.8 g, 3.48 mmol) in acetic acid (8 mL) was added N-iodosuccinimide (0.82 g, 3.65 mmol) at room temperature. After addition the reaction mixture was heated at 60°C for 16 h. The mixture was diluted with an aqueous solution of sodium metabisulfite (100 mL) and the precipitated solid isolated by filtration. The solid was washed with water and dried in vacuo to afford crude 3-iodo-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-15) as a solid. This material was not further purified and used directly into the next step. [0473] LCMS (method 1): retention time 1.11 min, m/z 355 [M-H]-. Example PI-2: Alternative preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6)
Figure imgf000122_0002
[0474] To a solution of methyl 3-cyclopropyl-2-(methoxymethyl)-5-(trifluoromethyl)indazole-7-carboxylate (I- 5) (1.8 g, 5.48 mmol) in methanol (36 mL) and water (36 mL) was added NaOH (0.329 g, 8.22 mmol) at room temperature. After addition the reaction mixture was stirred at room temperature for 15 h, then concentrated under reduced pressure and the residue diluted with water. The resulting aqueous phase was extracted with TBME (2x 50 mL) and the organic layers discarded. The aqueous layer was acidified with concentrated hydrochloric acid (5 mL) and stirred at room temperature for 15 h. The precipitated solid was isolated by filtration, washed with water and dried in vacuo to afford crude 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7- carboxylic acid (I-6) as a solid. This material was used without further purification into the next step. [0475] LCMS (method 1): retention time 1.06 min, m/z 269 [M-H]-. 82994 FF Example PI-3: Alternative preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11)
Figure imgf000123_0001
Step 1: Preparation of 7-bromo-3-iodo-5-(trifluoromethyl)-1H-indazole (I-13)
Figure imgf000123_0002
[0476] To a solution of 7-bromo-5-(trifluoromethyl)-1H-indazole (I-1) (1.0 g, 3.8 mmol) and NaOH (0.45 g, 11 mmol) in methanol (11 mL) and water (11 mL) was added iodine (1.0 g, 4.0 mmol) portionwise keeping the internal temperature around room temperature. After addition the reaction mixture was stirred at room temperature for 1 h, then diluted with an aqueous solution of sodium metabisulfite. The precipitated solid was isolated by filtration, washed with water and dried in vacuo. The crude material was purified by combiflash (ethyl acetate in cyclohexane) to afford 7-bromo-3-iodo-5-(trifluoromethyl)-1H-indazole (I-13) as a solid. [0477] LCMS (method 1): retention time 1.29 min, m/z 391/393 [M+H]+. Step 2: Preparation of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11)
Figure imgf000123_0003
[0478] A solution of 7-bromo-3-iodo-5-(trifluoromethyl)-1H-indazole (I-13) (5.5 g, 14.07 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.83 g, 0.70 mmol) in tetrahydrofuran (28 mL) was flushed with argon and cooled to 0°C. A 0.5M solution of cyclopropylzinc bromide in tetrahydrofuran (58 ml, 29 mmol) was added and the dark solution was stirred at 0°C for 3 h, then at room temperature for 60 h. The reaction mixture was 82994 FF quenched with an aqueous solution of ammonium chloride, the product extracted with EtOAc, the combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 7-bromo-3-cyclopropyl-5- (trifluoromethyl)-1H-indazole (I-11). [0479] LCMS (method 1): retention time 1.22 min, m/z 305/307 [M+H]+. Example PI-4: Alternative preparation of 3-cyclopropyl-5-(trifluoromethyl)-1H-indazole-7-carboxylic acid (I-6)
Figure imgf000124_0001
[0480] A solution of 7-bromo-3-cyclopropyl-5-(trifluoromethyl)-1H-indazole (I-11) (0.212 g, 0.69 mmol) in tetrahydrofuran (4.6 mL) under argon was cooled to -78°C. A 1.6M solution of n-butyllithium in hexanes (0.96 mL, 1.53 mmol) was added slowly dropwise and the mixture was stirred at -78°C for 30 min. Carbon dioxide (produced from dry ice and dried by passing through sulfuric acid) was bubbled into above solution at -78°C during 15 min. The cooling bath was removed and the mixture allowed to warm to room temperature while stirring for 1 h. The reaction was quenched with an aqueous solution of ammonium chloride and the mixture poured into aqueous saturated sodium hydrogen carbonate. The resulting aqueous phase was extracted twice with EtOAc and the organic layers discarded. The aqueous layer was acidified with concentrated hydrochloric acid and the product extracted twice with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to afford crude 3-cyclopropyl-5-(trifluoromethyl)-1H- indazole-7-carboxylic acid (I-6). This material was used without further purification into the next step. [0481] LCMS (method 1): retention time 1.06 min, m/z 269 [M-H]-.
82994 FF Table P: Prepared compounds Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) 5-bromo-N-[1-[2-(5-cyano-2- pyridyl)-1,2,4-triazol-3-yl]ethyl]-1H- indazole-7-carboxamide P1 0.89 437/439 3
Figure imgf000125_0001
Figure imgf000125_0003
Figure imgf000125_0004
5-bromo-N-[(1S)-1-[3-(5-cyano-2- pyridyl)pyrazin-2-yl]ethyl]-3-iodo- 1H-indazole-7-carboxamide P4 1.06 574/576 3
Figure imgf000125_0002
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000126_0005
Figure imgf000126_0006
3-iodo-N-[(1S)-1-(2-pyrimidin-2-yl- 1,2,4-triazol-3-yl)ethyl]-5- (trifluoromethyl)-1H-indazole-7- 1.07 529
Figure imgf000126_0002
carboxamide
Figure imgf000126_0001
Figure imgf000126_0007
N-[(1S)-1-[2-(5-cyano-2-pyridyl)- 1,2,4-triazol-3-yl]ethyl]-3-iodo-5- (trifluoromethyl)-1H-indazole-7- P9 carboxamide 1.18 553
Figure imgf000126_0003
Figure imgf000126_0004
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000127_0001
Figure imgf000127_0003
Figure imgf000127_0004
Figure imgf000127_0005
Figure imgf000127_0002
Figure imgf000127_0006
Figure imgf000127_0007
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000128_0005
N-[(1S)-1-[2-(5-cyanothiazol-2-yl)- 1,2,4-triazol-3-yl]ethyl]-3- cyclopropyl-2-(methoxymethyl)-5- P16 1.23 517 1 (trifluoromethyl)indazole-7- carboxamide
Figure imgf000128_0001
3-cyclopropyl-2-(methoxymethyl)- N-[(1S)-1-[2-[6- (methylcarbamoyl)pyrimidin-4-yl]- 1.15 544
Figure imgf000128_0003
1,2,4-triazol-3-yl]ethyl]-5- (trifluoromethyl)indazole-7-
Figure imgf000128_0002
carboxamide
Figure imgf000128_0004
Figure imgf000128_0006
Figure imgf000128_0007
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000129_0004
3-cyclopropyl-2-(methoxymethyl)- N-[(1S)-1-[2-(6-methoxypyridazin- 3-yl)-1,2,4-triazol-3-yl]ethyl]-5- P21 (trifluoromethyl)indazole-7- 1.19 517 1 carboxamide
Figure imgf000129_0001
Figure imgf000129_0005
Figure imgf000129_0002
Figure imgf000129_0006
N-[(1S)-1-[2-(5-cyano-2-pyridyl)- 1,2,4-triazol-3-yl]ethyl]-3- isopropoxy-2-(methoxymethyl)-5- P24 (trifluoromethyl)indazole-7- 1.20 529 1 carboxamide
Figure imgf000129_0003
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000130_0001
Figure imgf000130_0006
Figure imgf000130_0002
Figure imgf000130_0007
3-cyclopropyl-2-(methoxymethyl)- N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4- P27 triazol-3-yl)ethyl]-5- 1.11 487 1 (trifluoromethyl)indazole-7- carboxamide
Figure imgf000130_0003
3-cyclopropyl-N-[(1S)-1-[2-(6- methoxypyridazin-3-yl)-1,2,4- triazol-3-yl]ethyl]-5-(trifluoromethyl)- 1.11 473 1 1H-indazole-7-carboxamide
Figure imgf000130_0004
Figure imgf000130_0008
Figure imgf000130_0005
Figure imgf000130_0009
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000131_0001
Figure imgf000131_0005
Table PI: Intermediate compounds Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured)
Figure imgf000131_0002
methyl 3-iodo-5- (trifluoromethyl)-1H- indazole-7-carboxylate 369 I-3 1.17
Figure imgf000131_0003
[M-H]-
Figure imgf000131_0004
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) methyl 3-iodo-2- (methoxymethyl)-5- (trifluoromethyl)indazole- 7-carboxylate I-4 1.13 415 1
Figure imgf000132_0001
methyl 3-cyclopropyl-2- (methoxymethyl)-5- (trifluoromethyl)indazole- 7-carboxylate I-5 1.12 329 1
Figure imgf000132_0002
3-cyclopropyl-5- (trifluoromethyl)-1H- indazole-7-carboxylic acid 269 I-6 1.06
Figure imgf000132_0003
[M-H]-
Figure imgf000132_0004
3-cyclopropyl-2- (methoxymethyl)-5- (trifluoromethyl)indazole- 7-carboxylic acid I-7 1.09 315
Figure imgf000132_0005
Figure imgf000132_0006
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) 7-bromo-3-cyclopropyl-5- (trifluoromethyl)-1H- indazole I-11 1.22 305/307
Figure imgf000133_0001
Figure imgf000133_0002
methyl 3-cyclopropyl-5- (trifluoromethyl)-1H- indazole-7-carboxylate I-12 2.13 285 2
Figure imgf000133_0003
Figure imgf000133_0004
3-iodo-5-(trifluoromethyl)- 1H-indazole-7-carboxylic acid 355 I-15 1.11
Figure imgf000133_0005
[M-H]-
Figure imgf000133_0006
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) 1H-
Figure imgf000134_0005
methyl 5-bromo-3-iodo- 1H-indazole-7-carboxylate I-17 1.06 381/383 3
Figure imgf000134_0001
5-bromo-3-cyclopropyl- 1H-indazole-7-carboxylic acid I-18 0.90 281/283 3
Figure imgf000134_0002
methyl 3-hydroxy-2- (methoxymethyl)-5- (trifluoromethyl)indazole- 7-carboxylate I-19 0.99 305 1
Figure imgf000134_0003
methyl 3-isopropoxy-2- (methoxymethyl)-5- (trifluoromethyl)indazole- 7-carboxylate I-20 1.15 347 1
Figure imgf000134_0004
82994 FF Entry IUPAC name Structure Rt [M+H]+ Method (min) (measured) sodium 3-isopropoxy-2- (methoxymethyl)-5- (trifluoromethyl)indazole- 333 7-carboxylate I-21 1.07 for the 1 corresponding acid
Figure imgf000135_0001
[0482] Abbreviations used in synthesis schemes and preparatory examples ACN acetonitrile CPME cyclopentyl methyl ether (or methoxy cyclopentane) BINAP [1-(2-diphenylphosphanyl-1-naphthyl)-2-naphthyl]-diphenyl-phosphane Boc t-butoxycarbonyl DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCM dichloromethane DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DMA N,N-dimethylacetamide DMF N,N-dimethylformamide DMF-DMA N,N-dimethylformamide dimethyl acetal DMSO dimethyl sulfoxide DMSO-d6 deuterated dimethylsulfoxide DPEN diphenylethylenediamine Et3N triethylamine EtOAc ethyl acetate Ms methanesulfonyl (mesyl) NaHCO3 sodium hydrogencarbonate NaOH sodium hydroxide nBu, tBu n-butyl, t-butyl 82994 FF NPhth phthalimide-1-yl OMs mesylate group OTf triflate group OTs tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride TBME tert-butyl methyl ether TEA triethylamine TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl Tf trifluoromethanesulfonyl (triflyl) TFA trifluoroacetic acid THF tetrahydrofuran Ts p-toluenesulfonyl (tosyl) XPhos 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl aq. aqueous °C degrees Celsius equiv. equivalent h hour(s) LC/MS or LCMS liquid chromatography mass spectrometry M molar MHz megahertz min minutes mp or M.P. melting point NMR nuclear magnetic resonance ppm parts per million RT room temperature Rt retention time 82994 FF Biological Examples [0483] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm. Example B1: Activity against Chilo suppressalis (Striped rice stemborer) [0484] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0485] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P2, P6, P7, P8, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P23, P25, P26, P27, P28, P31. Example B2: Activity against Diabrotica balteata (Corn root worm) [0486] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation. [0487] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P4, P6, P7, P8, P9, P11, P12, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P30, P31. Example B3: Activity against Euschistus heros(Neotropical Brown Stink Bug) [0488] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. [0489] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P7, P8, P11, P13, P15, P17, P18, P19, P20, P23, P26, P27, P30, P31. Example B4: Activity against Frankliniella occidentalis (Western flower thrips). Feeding/contact activity [0490] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation. [0491] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P8. 82994 FF Example B5: Activity against Frankliniella occidentalis (Western flower thrips). Feeding/Contact activity [0492] Bean leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation. [0493] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P7, P12, P14, P15, P17, P23, P26, P27, P30, P31. Example B6: Activity against Myzus persicae (Green peach aphid). Feeding/Contact activity [0494] Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. [0495] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P8. Example B7: Activity against Myzus persicae (Green peach aphid). Intrinsic activity [0496] Test compounds prepared from 10'000 ppm DMSO stock solutions were applied by pipette into 24- well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation. [0497] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: P7, P8, P11, P13, P15, P17, P18, P19, P20, P23, P26, P27, P28, P30, P31. Example B8: Activity against Myzus persicae (Green peach aphid). Feeding/Contact activity [0498] Eggplant leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. [0499] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P11, P13, P17, P18, P19, P20, P23, P26, P27. Example B9: Activity against Plutella xylostella (Diamond back moth) [0500] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation. [0501] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P4, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P30, P31. Example B10: Activity against Spodoptera littoralis (Egyptian cotton leaf worm) 82994 FF [0502] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0503] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P6, P8, P11, P12, P16, P17, P20, P25, P26, P27, P31.

Claims

82994 FF CLAIMS 1. A compound of the formula (I)
Figure imgf000140_0001
wherein A is CH or N; X is an oxygen atom or a sulfur atom;
Figure imgf000140_0002
of Q to the rest of compound of the formula (I); R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a is hydrogen, halogen, -CN, C1-C4alkyl, C1-C3haloalkyl, C1-C4alkoxy, C1-C3haloalkoxy, C3- C4cycloalkyl, or cyclopropyl substituted with a single halogen or cyano; R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1- C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1- C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3- C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, -CN, C1-C3alkyl, and C1-C3haloalkyl; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo- pyridazinyl optionally N-substituted with a single substituent R4c; R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, - C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10 ; R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; 82994 FF R6 is connected to a nitrogen atom, and R6 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1- C3alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl or C1-C6alkoxycarbonyl; R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3- C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1- C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of the compound of formula (I). 2. The compound according to claim 1, wherein A is CH. 3. The compound according to claim 1 or 2, wherein X is oxygen. 4. The compound according to any one of claims 1 to 3, wherein R1 is hydrogen, methyl, or cyclopropylmethyl. 5. The compound according to any one of claims 1 to 4, R2a is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethyl, cyclopropyl, 1-fluorocyclopropyl, 1-cyanocyclopropyl, or isopropoxy. 6. The compound according to any one of claims 1 to 5, wherein R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl, or cyclopropyl. 7. The compound according to any one of claims 1 to 6, wherein R3 is methyl. 8. The compound according to any one of claims 1 to 7, wherein - Q is Qa and R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9; or - Q is Qb and R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11:
Figure imgf000141_0001
82994 FF R4b is hydrogen, chloro, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, - NHC(O)R10 or -N(CH3)C(O)R10; and R4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl. 9. The compound according to any one of claims 1 to 8, wherein R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl, preferably, R10 is hydrogen, methyl, or cyanomethyl; and R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy, preferably, R11 is hydrogen or methyl. 10. The compound according to any one of claims 1 to 9, wherein R4 is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 6-ethoxypyridazin-3-yl, 6-chloropyridazin-3-yl, 5- cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5-carbamoyl-thiazol-2-yl, or 5- cyanothiazol-2-yl; and R4a is 5-cyano-2-pyridyl or pyrimidin-2-yl. 11. The compound according to any one of claims 1 to 10, wherein - Q is Qa and R5 is hydrogen, cyclopropyl, or methoxy; or - Q is Qb, R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy and R5b is hydrogen, fluoro, or methoxy. 12. The compound according to any one of claims 1 to 11, wherein R5, R5a and R5b are hydrogen. 13. The compound according to any one of claims 1 to 12, wherein R6 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, 2-methoxyethyl, allyl, propargyl, cyclopropylmethyl, methoxycarbonyl, or ethoxycarbonyl. 14. A composition comprising a compound as defined in any one of claims 1 to 13, one or more auxiliaries and diluent, and optionally one or more other active ingredient. 15. A method (i) of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in any one of claims 1 to 13, or of a composition as defined in claim 14; or (ii) for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the plant propagation material or the site where the propagation material is planted, with an effective amount of a compound as defined in any one of claims 1 to 13, or of a composition as defined in claim 14; or (iii) of controlling parasites in or on an animal in need thereof, comprising administering an effective amount of a compound as defined in any one of claims 1 to 13, or of a composition as defined in claim 14. 82994 FF 16. A plant propagation material, such as a seed, comprising, or coated with, or treated with, or adhered thereto, a compound as defined in any one of claims 1 to 13, or a composition as defined in claim 14. 17. A compound of the formula IIa-1, IIa-2, IIb-1, or IIb-2:
Figure imgf000143_0001
wherein A, R2a and R2b are as defined in any one of claims 1, 2, 5 and 6; and Ra is C1-C6alkyl or benzyl, preferably Ra is methyl or ethyl.
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