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WO2025132754A1 - Pesticidally active quinazoline compounds - Google Patents

Pesticidally active quinazoline compounds Download PDF

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Publication number
WO2025132754A1
WO2025132754A1 PCT/EP2024/087352 EP2024087352W WO2025132754A1 WO 2025132754 A1 WO2025132754 A1 WO 2025132754A1 EP 2024087352 W EP2024087352 W EP 2024087352W WO 2025132754 A1 WO2025132754 A1 WO 2025132754A1
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spp
methyl
formula
compounds
hydrogen
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French (fr)
Inventor
Andre Jeanguenat
Jagadeesh Prathap KILARU
Michel Muehlebach
Christopher Charles SCARBOROUGH
André Stoller
Rushil FERNANDES
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • 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
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to pesticidally active quinazoline compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active quinazoline compounds.
  • the invention also relates to the preparation of these quinazoline compounds, to intermediates useful in the preparation of these quinazoline compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these quinazoline compounds, to preparation of these compositions and to the use of these quinazoline compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina.
  • WO 2021/083936 A1, WO 2021/148639 A1, WO 2021/177160 A1, WO 2022/268648 A1, WO 2023/104714 A1, and WO 2023/247360 A1 describe certain quinazoline, quinazolinone and quinoline compounds.
  • Publication WO 2023/025682 A1 describes pyrazinyl-triazole compounds for use in the control of animal pests, as well as intermediate compounds useful in the preparation of such pyrazinyl-triazole compounds.
  • the present invention accordingly relates, in a first aspect, to a compound of the formula (I): wherein R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C3-C6alkenyl, C3- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R 2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, or C1-C4alkylsulfonyl; R 4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thi
  • 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 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 83101 / 109864 FFT 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
  • 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-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
  • 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-difluoroe
  • C1-C2fluoroalkyl refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, 83101 / 109864 FFT 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.
  • C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms
  • C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms
  • C3-C4cycloalkyl substituted with 1 halo atom
  • C3-C4cycloalkyl substituted with 2 halo atoms means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3-C4cycloalkyl 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 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: w here R1, R2a, R4 and R5 are as defined in the first aspect.
  • the present invention contemplates both racemates and individual enantiomers.
  • Particularly preferred compounds of the present invention are compounds of formula (I’a), where R1, R2a, R4 and R5 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.
  • Embodiments according to the invention are provided as set out below.
  • R1 is as follows: A.
  • R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C3-C6alkenyl, C3- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B .
  • R1 is hydrogen, methyl, ethyl, or cyclopropylmethyl; or C.
  • R1 is hydrogen, methyl, or cyclopropylmethyl; or D.
  • R1 is hydrogen or methyl; or E.
  • R1 is hydrogen.
  • R1 is hydrogen, methyl, or cyclopropylmethyl; or R1 is hydrogen or methyl. Most preferably, R1 is hydrogen.
  • R2a is as follows: A. R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, or C1-C4alkylsulfonyl; or B .
  • R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, or 1- chlorocyclopropyl; or C .
  • R2a is halogen, C1-C2fluoroalkyl, or cyclopropyl; or D.
  • R2a is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, or cyclopropyl; or E.
  • R2a is chloro, bromo, iodo, trifluoromethyl, or cyclopropyl; or F.
  • R2a is chloro, bromo, trifluoromethyl, or cyclopropyl; or 83101 / 109864 FFT G .
  • R2a is chloro, bromo, or cyclopropyl; or H.
  • R2a is chloro.
  • R2a is chloro, bromo, trifluoromethyl, or cyclopropyl.
  • R 2a is chloro, bromo, or cyclopropyl.
  • R 2a is chloro.
  • R5 is as follows: A.
  • R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; or B. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, or cyclobutyl or C. R5 is hydrogen, chloro, bromo, methyl, or cyclopropyl; or D. R5 is hydrogen, bromo, methyl, ethyl, methoxy, or cyclopropyl; or E. R5 is hydrogen, bromo, methyl, or cyclopropyl; or F. R5 is hydrogen, methyl, or ethyl; or G.
  • R5 is hydrogen or methyl; or H. R5 is hydrogen. [0043] [0044] [0045] In preferred embodiments, R5 is as follows: A. R5 is hydrogen, methyl, or ethyl; or B. R5 is hydrogen or methyl; or C. R5 is hydrogen. [0046]
  • Q as defined above, is selected from Qa-1 to Qa-6, in which R4 has the same meaning as given for compounds of formula (I): [0047] As an example, Q is Qa-1, Qa-2, Qa-3, or Qa-4; or Q is Qa-1, Qa-2, Qa-3, or Qa-5. Preferably, Q is Q a -1 or Q a -2.
  • R4 is as follows: 83101 / 109864 FFT A .
  • R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; or R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; or B.
  • R4 is R4-1, R4-2, R4-3, R4-4, R4-5, R4-6, or R4-7: R 4-1 R4-2 R4-3 R4-4 R4-5 R4-6 R4-7 where the staggered line represents the connection of R4 to the remainder of the compound of Formula (I); or C .
  • R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R 4a ; or D .
  • R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; or E. R4 is pyrimidin-4-yl or pyrimidin-2-yl, each of which, independently of each other, is substituted with a single substituent R 4a ; or F .
  • R4 is R4-1, R4-2, R4-3, R4-4, R4-5, or R4-7; or G.
  • R4 is R4-1 or R4-5; or H.
  • R4 is R4-2 or R4-7; or I.
  • R4 is R4-3; or J. R4 is R4-4; or K. R4 is R4-6; or L.
  • R4 is 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5- carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6-cyanopyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, or 5-bromopyrazin-2-yl; or M .
  • R4 is 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5- carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6-cyanopyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- fluoropyrimidin-2-yl, or 5-bromopyrazin-2-y.; [0049] In preferred embodiments of each aspect of the invention, R4 is 1-methyl-6-oxo-pyridazin-3- yl, 6-methoxypyridazin-3-yl,
  • 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 has the same meaning as given above for compounds of the formula (I), and wherein Q has the meaning given above.
  • 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 hydrobromid
  • 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 at a temperature ranging from ambient temperature to 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, diisopropylethylamine or pyridine.
  • 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, diisopropylethylamine or pyridine.
  • This reaction is done in the presence of a reducing agent, such as 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 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 or titanium(IV) isopropoxide
  • a solvent or without a solvent such as, for instance, methanol.
  • the reaction can be conducted in a temperature ranging from -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • 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 Q has the same meaning as given above in Scheme 1, 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.
  • 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 Q has the same meaning as given above in Scheme 1, 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 Q has the same meaning as given above in Scheme 1, can be reacted with a compound of the formula (VI), wherein R1 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, dimethylsulfoxide (DMSO), N,N- dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature 83101 / 109864 FFT 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, dimethylsulfoxide (DMSO), N,N- dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature 83101 / 109864 FFT range 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 hexafluoro- phosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium), PyBOP (benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate) 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 hexafluoro- phosphate
  • 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) or for instance a metal catalyst such as a palladium complex, and with or without the addition of a base, such as an inorganic 83101 / 109864 FFT 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, t
  • 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, diisopropylethyl
  • 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
  • a compound of the formula (IX), or a salt thereof is either known, or it 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 R 4 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.
  • Compounds of the formula (I’a) can be prepared by the reaction of an amine of the formula (IIIa), or a salt thereof, 83101 / 109864 FFT wherein R1, R4 and R5 are as described in formula (I), with a compound of the formula (IIa) wherein R2a is 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.
  • Scheme 7 Compounds of the formula (IIa-2), wherein R2a is as described in formula (I) and X1 is Cl, can be prepared (Scheme 7) by treating compounds of the formula (IIa-1), wherein R 2a is as described in formula (I), with oxalyl chloride or thionyl chloride (alternatively phosphorus oxychloride), optionally 83101 / 109864 FFT in the presence of catalytic N,N-dimethylformamide (DMF), in an inert solvent, analogous to descriptions found in Scheme 1 or, for example, in WO2015/54572, p.263.
  • DMF catalytic N,N-dimethylformamide
  • Compounds of the formula (IIa-1), wherein R2a is as described in formula (I), may exist in different tautomeric forms, for example as represented by the formula (IIa-1’). This invention covers all such tautomers and mixtures thereof in all proportions.
  • Compounds of the formula (IIa-1), wherein R2a is as described in formula (I) can be prepared by treating compounds of the formula (XIX), wherein R 2a is as described in formula (I), with formic acid and sulfuric acid, at temperatures between 80 and 100 °C, following procedures analogous to descriptions found, for example, in WO2018/206539, p.80.
  • Compounds of the formula (XIX), wherein R2a is as described in formula (I), can be prepared by cyanation of compounds of the formula (XVIII), wherein R 2a is as described in formula (I), and in which X3 is a halogen leaving group, preferably iodo or bromo, with for example copper(I) cyanide (CuCN), in a solvent such as N,N-dimethylformamide (DMF), at temperatures between 80 and 150 °C, under analogous conditions found, for example, in WO2005/100298, p.44.
  • CuCN copper(I) cyanide
  • DMF N,N-dimethylformamide
  • Compounds of formula (XVII), wherein R2a is as described in formula (I), can be prepared by reduction of compounds of the formula (XVI), wherein R 2a is as described in formula (I), using reagents such as iron, ferrous salts, or iron catalyst in aqueous acid (generally referred to as Béchamp reduction), or zinc or iron in the presence of ammonium chloride in alcohols (such as ethanol or isopropanol) and water, and at temperature between 0°C to boiling point of the reaction mixture.
  • reagents such as iron, ferrous salts, or iron catalyst in aqueous acid (generally referred to as Béchamp reduction), or zinc or iron in the presence of ammonium chloride in alcohols (such as ethanol or isopropanol) and water, and at temperature between 0°C to boiling point of the reaction mixture.
  • compounds of the formula (XV) are reacted with a :CF2 carbene species, generated from difluoromethylating agents such a difluoroacetate XcCF2COONa or a difluoromethyl(phosphonate) XcCF2P(O)(OEt)2, wherein Xc can be chloro or bromo, in the presence of a base such as for example sodium or potassium carbonate, or sodium or potassium hydroxide, in an appropriate solvent like for example acetonitrile, ⁇ , ⁇ -dimethylformamide or N-methyl-2-pyrrolidone (NMP), optionally in a mixture with water, optionally in the presence of an additive (such as 2'-hydroxyaceto-phenone), and at temperature 83101 / 109864 FFT between -40°C to 80°C.
  • difluoromethylating agents such as for example sodium or potassium carbonate, or sodium or potassium hydroxide
  • a base such as for example sodium or potassium carbonate, or sodium or potassium hydrox
  • Difluoro- methylation agents of the formula XcCF2COONa for instance sodium 2-chloro-2,2-difluoroacetate
  • XcCF2P(O)(OEt)2 for instance diethyl (bromodifluoromethyl)phosphonate
  • Xc is chloro or bromo
  • Scheme 8 83101 / 109864 FFT [0097]
  • compounds of the formula (IIIc) wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl)
  • X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl)
  • X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin.
  • the anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid.
  • an acid such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like
  • an organic acid such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid.
  • a great number of such acids are known to a person skilled in the art.
  • Compounds of formula (IIIc-1), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, can be made from compounds of the formula (XX), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), by treatment with an acid, such as the acids listed above.
  • the reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • a solvent for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • the reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambient temperature.
  • Compounds of the formula (XX), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared by reaction of compounds of the formula (XXII), or a tautomer thereof, or a salt thereof, wherein X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), with a compound of the formula (XXI), wherein R1 and R5 are as defined for compounds of the formula (I).
  • the reaction can be done neat, or in a solvent, for instance an organic solvent, such as dioxane or acetic acid, or a mixture thereof.
  • the reaction can be performed in the presence or in the absence of a drying agent, such as for example in the presence of molecular sieves, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 80 °C.
  • a drying agent such as for example in the presence of molecular sieves
  • X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl)
  • X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl)
  • 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.
  • Table A-18 provides 22 compounds A-18.001 to A-18.022 of formula I-A wherein R2a is Cl, R 1 is CH3, R 5 is CH2CH3 and R 4x are as defined in table Z.
  • Table A-19 provides 22 compounds A-19.001 to A-19.022 of formula I-A wherein R2a is Cl, R 1 is H, R 5 is cyclopropyl and R 4x are as defined in table Z.
  • Table A-20 provides 22 compounds A-20.001 to A-20.022 of formula I-A wherein R2a is Cl, R 1 is CH3, R 5 is cyclopropyl and R 4x are as defined in table Z.
  • Table A-24 provides 22 compounds A-24.001 to A-24.022 of formula I-A wherein R2a is Cl, R 1 is CH3, R 5 is Br and R 4x are as defined in table Z.
  • Table Z Substituent definitions of R 4x 83101 / 109864 FFT [0149] Also made available are certain intermediate compounds as shown in Schemes 1 to 8, some of which are novel.
  • the compounds of formula (I) according to the invention are preventively and/or curatively valuable active 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.
  • 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
  • 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. 83101 / 109864 FFT ⁇ 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
  • 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.
  • 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.
  • 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 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 Thr
  • 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 83101 / 109864 FFT 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, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,
  • ⁇ -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.
  • 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-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, 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).
  • 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 Cry1FA 2 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
  • 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 83101 / 109864 FFT 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-0 392 225, WO 95/33818 and EP-A-0 353 191.
  • 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 defence (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
  • 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.
  • 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 Psoroptesovis; Cheyletiella; Dermanyssus; for example Dermanyssusgallinae; Ortnithonyssus; Demodex, for example Demodexcanis; 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, 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 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 83101 / 109864 FFT 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 83101 / 109864 FFT 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., Glossina spp., Chrysomyia spppp
  • 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 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.
  • a compound TX 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.
  • 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 83101 / 109864 FFT 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, Nilaparva
  • a compound selected from the compounds defined in Tables A-1 to A-24 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.
  • a compound selected from the compounds defined in Tables A-1 to A-24 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).
  • 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).
  • 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).
  • certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera.
  • TX means "one compound selected from the compounds defined in Tables A-1 to A-24 and Table P”
  • TX means "one compound selected from the compounds defined in Tables A-1 to A-24 and Table P”
  • Israelensis + TX Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thuringiensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec.
  • 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.
  • 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 83101 / 109864 FFT (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
  • 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, 83101 / 109864 FFT Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • 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,
  • 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, Chondrostereum purpureum (Chontrol Paste®)
  • 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 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 83101 / 109864 FFT 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
  • ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM 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 LifeGardTM 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.
  • 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 83101 / 109864 FFT (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No.
  • IMI 392151 e.g., BIO-TAMTM from Isagro USA, Inc. or BIODERMA® by Agrobio
  • CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (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.
  • 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.
  • 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.
  • 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.
  • 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
  • strain GL-21 e.g. SoilGard by Certis, US
  • 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, 83101 / 109864 FFT 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; 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, in particular strain H
  • 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
  • SD-5428 e.g. NOVODOR® FC from BioFa 83101 / 109864 FFT DE
  • Bacillus thuringiensis var. Colmeri e.g. TIANBAOBTC by Changzhou Jianghai
  • 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 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, Zoophtora radicans + TX; Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armiger
  • 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-24 and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-24 and Table P, 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,
  • 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-24 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 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.
  • 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.
  • 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, di
  • 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 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
  • 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 83101 / 109864 FFT 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. Whereas commercial products may preferably be formulated as concentrates, 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.
  • 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 % ⁇ 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-
  • 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 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 tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • 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 83101 / 109864 FFT 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.
  • 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 .
  • 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 % [0244] 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 % 83101 / 109864 FFT xylene mixture 50 % [0245] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • 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 % [0249]
  • 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.
  • 83101 / 109864 FFT 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 % Water 45.3 % [0250] 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: [0253] 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 83101 / 109864 FFT 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.
  • Method 3 [0255] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 5000°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range: 110 to 800 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector.
  • an electrospray source Polyity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 5000°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/
  • Method 4 [0256] 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.
  • Step 2 Preparation of 4-chloro-2-(difluoromethoxy)aniline (I-2) [0260] To a solution of 4-chloro-2-(difluoromethoxy)-1-nitro-benzene (I-1) (17.2 g, 90%, 69.3 mmol) in ethanol (231 mL) and water (38.5 mL) were added zinc (9.06 g, 138 mmol) and ammonium chloride (7.4 g, 138 mmol). The reaction mixture was stirred at room temperature for 16 h, then filtered and concentrated under vacuum.
  • Step 3 Preparation of 4-chloro-2-(difluoromethoxy)-6-iodo-aniline (I-3)
  • I-3 4-chloro-2-(difluoromethoxy)-6-iodo-aniline
  • Step 4 Preparation of 2-amino-5-chloro-3-(difluoromethoxy)benzonitrile (I-4) [0264] To a solution of 4-chloro-2-(difluoromethoxy)-6-iodo-aniline (I-3) (9.66 g, 80%, 24.18 mmol) in DMF (40.3 mL) was added copper cyanide (3.25 g, 36.2 mmol). The reaction mixture was purged with argon and stirred at 120°C for 7 h, then cooled to room temperature.
  • Step 5 Preparation of 6-chloro-8-(difluoromethoxy)-3H-quinazolin-4-one (I-5) 83101 / 109864 FFT [0266] To a solution of 2-amino-5-chloro-3-(difluoromethoxy)benzonitrile (I-4) (6.76 g, 80%, 24.7 mmol) in formic acid (67.6 mL) was added sulfuric acid (37.1 mmol). The reaction mixture was stirred at 50°C for 3 h, cooled to room temperature and poured into ice-water. The formed solid was filtered, rinsed with pentane and dried under vacuum.
  • Step 6 Preparation of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) [0268] A mixture of 6-chloro-8-(difluoromethoxy)-3H-quinazolin-4-one (I-5) (320 mg, 1.29 mmol), N,N-dimethylformamide (0.064 mmol) and thionyl chloride (3.2 mL, 43.87 mmol) was stirred at 90°C for 1 h. The reaction mixture was allowed to cool to room temperature and concentrated in vacuo to afford 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6, 370 mg) as a yellow solid.
  • Step 7 Preparation of 6-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]-2-methyl-pyridazin-3-one (P1) [0270] A solution of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) (0.42 mmol) and triethylamine (1.26 mmol) in DMF (2 mL) was added to [(1S)-1-[2-(1-methyl-6-oxo-pyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]ammonium;chloride (prepared as described in WO 23/104714) (109 mg, 0.42 83101 / 109864 FFT mmol).
  • Example E2 Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]thiazole-5-carboxamide (compound P4) P reparation of methyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]thiazole-5-carboxylate (I-7) [0272] To a solution of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (CAS 2641011-39-2, prepared as described for example in WO21/083936) (5.2 g, 21 mmol) in 1,4-dioxane (31 mL) and acetic acid
  • Step 4 Preparation of tert-butyl N-[(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-9) [0277] To a mixture of 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]thiazole-5- carboxylic acid (I-8) (400mg, 1.18 mmol), silica gel-supported ammonium chloride (NH4Cl/SiO2 prepared as described above, 700 mg) and tosyl chloride (227 mg, 1.18 mmol) was added triethylamine (479 mg, 4.71 mmol).
  • Step 5 Preparation of [(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-10) [0279] To a solution of tert-butyl N-[(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-9) (180 mg, 0.53 mmol) in 1,4-dioxane (1.4 mL) was added a hydrochloric acid solution (4.0 mol/L in 1,4-dioxane, 1.4 mL, 5.6 mmol).
  • Step 6 Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]thiazole-5-carboxamide (P4) [0281] To a solution of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) (200 mg, 95%, 0.72 mmol) in ACN (10.0 mL) were added potassium carbonate (297 mg, 2.15 mmol) and [(1S)-1-[2-(5- carbamoylthiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-10) (0.236 g, 0.86 mmol) at room temperature and the reaction mixture was heated to 80°C for 12 h.
  • 6-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]-methyl-amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidine-4-carboxamide (compound P27) can be prepared from 4,6-dichloro-8- (difluoromethoxy)quinazoline (I-6) (1 equiv.) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol- 3-yl]ethyl]-methyl-ammonium chloride (CAS 3024825-36-0, prepared as described in WO 23/247360) (1.05 equiv.) by following above protocol in analogy.
  • Example E3 Preparation of N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (difluoromethoxy)quinazolin-4-amine (compound P11) [0284] To a mixture of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) (223.0 mg, 0.84 mmol) and [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23, prepared as described below) (296.0 mg, 0.97 mmol, 1.15 equiv.) in DMF (6.7 mL) was added triethylamine (369 ⁇ L, 2.52 mmol, 3 equiv.).
  • reaction mixture was stirred at 90°C for 1 hour, cooled to room temperature, then diluted with water and EtOAc. The phases were separated, the aqueous layer extracted with EtOAc (3x), the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (difluoromethoxy)quinazolin-4-amine (compound P15) can be prepared from 4,6-dichloro-8- (difluoromethoxy)quinazoline (I-6) and [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-24, prepared as described below) by following above protocol in analogy.
  • Step 2 Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium;2,2,2- trifluoroacetate (I-11) [0291] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-12) (2.0 g, 5.52 mmol) in trifluoromethylbenzene (40 mL) was added 2,2,2- trifluoroacetic acid (10mL) dropwise at RT and the reaction mixture was stirred for 2.5 h.
  • Example PI-2 Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23) 83101 / 109864 FFT Step 1: Preparation of (5-bromopyrimidin-2-yl)hydrazine (I-16) [0293] To a solution of 5-bromo-2-chloro-pyrimidine (15.0 g, 77.55 mmol) in methanol (150 mL) was added hydrazine hydrate (10.1 mL, 155.1 mmol, 2.0 equiv.) at 0°C.
  • Step 2 Preparation of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17) (I-17) [0295] tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (CAS 85642-13-3) (70.0 g, 353 mmol, 1 equiv.) was mixed with 2-methyltetrahydrofuran (1.12 L) and N,N-dimethylformamide- dimethylacetal (DMF-DMA, 70 mL, 530 mmol, 1.5 equiv.), and the mixture heated to 40°C for 2 hours.
  • DMF-DMA N,N-dimethylformamide- dimethylacetal
  • tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) can be prepared from tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo- ethyl]carbamate (CAS 85642-13-3) and N,N-dimethylacetamide-dimethyl acetal (CAS 18871-66-4) by following above protocol in analogy.
  • the reaction mixture was stirred at 75°C for 3 hours, then concentrated under reduced pressure.
  • the solid residue was diluted with EtOAc and water, the layers separated, the aqueous phase extracted with EtOAc, the combined organic layers washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo.
  • the residue was purified with flash column chromatography over silica gel (tert-butyl methyl ether in dichloromethane) to provide the desired product (I-19) as a solid.
  • tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-20) can be prepared from tert-butyl N-[(1S)-2-[(E)-1- (dimethylamino)ethylideneamino]-1-methyl-2-oxo-ethyl]carbamate (I-18) and (5-bromopyrimidin-2- yl)hydrazine (I-16) by applying above protocol in analogy.
  • tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-21) can be prepared from tert-butyl N-[(1S)-2-[(E)-1- (dimethylamino)ethylideneamino]-1-methyl-2-oxo-ethyl]carbamate (I-18) and (5-fluoropyrimidin-2- yl)hydrazine (CAS 104408-28-8) by applying above protocol in analogy.
  • tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-22) can be prepared from tert-butyl N-[(1S)-2-[(E)-1- (dimethylamino)ethylideneamino]-1-methyl-2-oxo-ethyl]carbamate (I-18) and (5-chloropyrimidin-2- yl)hydrazine (CAS 823-90-5) by applying above protocol in analogy.
  • Step 4 Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23) [0307] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-19) (5.4 g, 14.6 mmol) in 1,4-dioxane (73 mL) was added a 4.0 M solution of hydrochloric acid in 1,4-dioxane (39 mL, 156 mmol) dropwise at 0°C.
  • [(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-25) can be prepared from tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4- triazol-3-yl]ethyl]carbamate (I-21) by applying above protocol in analogy.
  • [(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-26) can be prepared from tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4- triazol-3-yl]ethyl]carbamate (I-22) by applying above protocol in analogy.
  • tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I-28) can be prepared from (2S)-2-(tert-butoxycarbonylamino)propanoic acid and propanimidoyl- ammonium chloride by applying above protocol in analogy.
  • reaction mixture was heated at 45°C for 90 minutes, then at 60°C for 1 hour. After cooling to room temperature, the mixture was diluted with a saturated aqueous solution of sodium carbonate, and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure.
  • tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-30) can be prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1- methyl-2-oxo-ethyl]carbamate (I-28) and (5-bromopyrimidin-2-yl)hydrazine (I-16) by applying above protocol in analogy.
  • Step 3 Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-31) (I-31) [0321] tert-Butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-29) (3.2 g, 7.8 mmol) was added to a 4.0 M solution of HCl in ethyl acetate (64.0 mL, 33 equiv.) stirred at 0°C.
  • Step 2 Preparation of (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I- 34) [0327] To a solution of 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3- yl]ethyl]isoindoline-1,3-dione (I-33) (3.0 g, 6.29 mmol) in ethanol (60 mL) was added hydrazine hydrate (0.794 g, 15.7 mmol, 2.5 equiv.) dropwise.
  • Step 3 Preparation of tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-37) (I-37) 83101 / 109864 FFT [0333] To a solution of tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-36) (4.0 g, 10.9 mmol) in acetonitrile (40 mL) at 20°C was added triethylamine (4.7 mL, 33.6 mmol).
  • Step 4 Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) (I-38) [0335] [(1S)-1-[2-(5-Cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) was prepared from tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-37) by applying above protocol ‘Example PI-3, step 3’ in analogy.
  • Example B1 Activity against Chilo suppressalis (Striped rice stemborer) [0339] 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: P1, P2, P3, P4, P5, P6, P7, P8, P9, P11, P13, P14, P15, P16, P17, P18, P19, P21, P22, P23, P24, P25.
  • Example B2 Activity against Diabrotica balteata (Corn root worm) [0341] 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 Plutella xylostella (Diamond back moth) [0349] 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 B8 Activity against Frankliniella occidentalis (Western flower thrips). Feeding/Contact activity
  • 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 83101 / 109864 FFT with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation.
  • the following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P2, P7, P8, P24.
  • Example B9 Comparison of the insecticidal activity of compounds P11 and P6 according to the invention with a structurally most closely comparable compounds from the state of the art: [0355] Activity of compounds P11 and P6 according to the preparatory examples and compounds from WO 21/083936 against Spodoptera littoralis (Example B7 above) and Diabrotica balteata (Example B2 above) is summarized in Table B9.
  • Example B10 Comparison of the insecticidal activity of compound P5 according to the invention with a structurally most closely comparable compounds from the state of the art: [0357] Activity of compounds P5 according to the preparatory examples and of a compound from WO 22/268648 against Chilo suppressalis (Example B1 above) is summarized in Table B10.
  • Table B10 Concentration Mortality Compound Insect (ppm) (%) Compound P5 1 2.5 Chilo suppressalis 80 Present invention Described in WO 2022/268648 as compound P.10 (page 158) 1 2.5 Chilo suppressalis 0 State of the art 83101 / 109864 FFT [0358] Table B10 shows that compounds P5 according to the invention exerts a substantially better insecticidal action on Chilo suppressalis than the compound from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.
  • Example B11 Comparison of the insecticidal activity of compounds P21 and P6 according to the invention with a structurally most closely comparable compounds from the state of the art: [0359] Activity of compounds P21 and P6 according to the preparatory examples and of compounds from WO 23/247360 against Chilo suppressalis (Example B1 above), Diabrotica balteata (Example B2 above), Plutella xylostella (Example B6 above) and Euschistus heros (Example B3 above), is summarized in Table B11.
  • Table B11 Concentration Mortality Compound Insect (ppm) (%) Compound P21 3.12 Chilo suppressalis 80 12.5 Diabrotica balteata 100 Present invention Described in WO 2023/247360 as compound P21 (page 131) 3.12 Chilo suppressalis 0 12.5 Diabrotica balteata 50 State of the art 83101 / 109864 FFT 110 Concentration Mortality Compound Insect (ppm) (%) Described in WO 2023/247360 as compound P68 (page 140) 3.12 Chilo suppressalis 0 12.5 Diabrotica balteata 0 State of the art Described in WO 2023/247360 as compound P20 (page 130) 3.12 Chilo suppressalis 0 12.5 Diabrotica balteata 0 State of the art Compound P6 Plutella 0.8 xylostellaError!
  • Example B12 Comparison of the insecticidal activity of compounds P11 according to the invention with a structurally most closely comparable compounds from the state of the art: Activity of compound P11 according to the preparatory examples and of a compound from WO 21/177160 and WO 23/247360 against Spodoptera littoralis (Example B7 above), Plutella xylostella (Example B6 above) and Chilo suppressalis (Example B1 above) is summarized in Table B12.
  • Table B12 Concentration Mortality Compound Insect (ppm) (%) Compound P11 0.8 Spodoptera littoralis 50 12.5 Plutella xylostella 100 12.5 Chilo suppressalis 50 Present invention 83101 / 109864 FFT 112 Concentration Mortality Compound Insect (ppm) (%) Described in WO 2021/177160 as compound A-42 (page 66) and in WO 2023/247360 (preparation of compound P68, step 1 p.124) 0.8 Spodoptera littoralis 0 12.5 Plutella xylostella 50 12.5 Chilo suppressalis 0 State of the art Table B12 shows that compound P11 according to the invention exert a substantially better insecticidal action on Spodoptera littoralis, Plutella xylostella and Chilo suppressalis than the compound from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.

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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

83101 / 109864 FFT PESTICIDALLY ACTIVE QUINAZOLINE COMPOUNDS TECHNICAL FIELD [0001] The present invention relates to pesticidally active quinazoline compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active quinazoline compounds. The invention also relates to the preparation of these quinazoline compounds, to intermediates useful in the preparation of these quinazoline compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these quinazoline compounds, to preparation of these compositions and to the use of these quinazoline 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 2021/083936 A1, WO 2021/148639 A1, WO 2021/177160 A1, WO 2022/268648 A1, WO 2023/104714 A1, and WO 2023/247360 A1 describe certain quinazoline, quinazolinone and quinoline compounds. Publication WO 2023/025682 A1, describes pyrazinyl-triazole compounds for use in the control of animal pests, as well as intermediate compounds useful in the preparation of such pyrazinyl-triazole compounds. BRIEF SUMMARY [0003] It has now surprisingly been found that certain novel quinazoline compounds have pesticidal activity. Hence, the present invention accordingly relates, in a first aspect, to a compound of the formula (I):
Figure imgf000002_0001
wherein R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C3-C6alkenyl, C3- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, or C1-C4alkylsulfonyl; R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; or R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; R4a is halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; 83101 / 109864 FFT R4b is C1-C3alkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R10 is hydrogen, C1-C3alkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, or C1-C3alkoxyC1-C3alkyl; R11 is hydrogen or C1-C3alkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of the compound of formula (I). [0004] 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). [0005] 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. [0006] 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. [0007] 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 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. [0008] 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. [0009] 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 [0010] 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 83101 / 109864 FFT 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. [0011] 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. [0012] 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. [0013] The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation. [0014] 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-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. [0015] 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, 83101 / 109864 FFT trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2- tetrafluoroethyl or pentafluoroethyl. [0016] 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. [0017] 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. [0018] 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. [0019] 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. [0020] 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. [0021] 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 radical is substituted, the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge. [0022] 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. [0023] 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. [0024] 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- 83101 / 109864 FFT 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. [0025] 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. [0026] 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. [0027] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl. [0028] 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. [0029] 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. [0030] 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. [0031] 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. [0032] 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 be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances. [0033] 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 imgf000006_0001
where R1, R2a, R4 and R5 are as defined in the first aspect. [0034] The present invention contemplates both racemates and individual enantiomers. Compounds of formula (I'a) having a preferred stereochemistry are set out below: 83101 / 109864 FFT
Figure imgf000007_0001
[0035] Particularly preferred compounds of the present invention are compounds of formula (I’a), where R1, R2a, R4 and R5 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. [0036] Embodiments according to the invention are provided as set out below. [0037] The formula of compounds of formula (I) and (I'a) may be simplified as T-N(R1)-CH(CH3)-Q, where T and Q represent:
Figure imgf000007_0002
in which R1, R2a, R4 and R5 have the same meaning as given for compounds of formula (I), and the staggered lines represent the connection of the moieties T and Q to the remainder of the compound. [0038] In an embodiment of each aspect of the invention, R1 is as follows: A. R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C3-C6alkenyl, C3- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B. R1 is hydrogen, methyl, ethyl, or cyclopropylmethyl; or C. R1 is hydrogen, methyl, or cyclopropylmethyl; or D. R1 is hydrogen or methyl; or E. R1 is hydrogen. [0039] 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. [0040] In an embodiment of each aspect of the invention, R2a is as follows: A. R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, or C1-C4alkylsulfonyl; or B. R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, or 1- chlorocyclopropyl; or C. R2a is halogen, C1-C2fluoroalkyl, or cyclopropyl; or D. R2a is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, or cyclopropyl; or E. R2a is chloro, bromo, iodo, trifluoromethyl, or cyclopropyl; or F. R2a is chloro, bromo, trifluoromethyl, or cyclopropyl; or 83101 / 109864 FFT G. R2a is chloro, bromo, or cyclopropyl; or H. R2a is chloro. [0041] In preferred embodiments of each aspect of the invention, R2a is chloro, bromo, trifluoromethyl, or cyclopropyl. For instance, R2a is chloro, bromo, or cyclopropyl. In more preferred embodiments of each aspect of the invention, R2a is chloro. [0042] In an embodiment of each aspect of the invention, R5 is as follows: A. R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; or B. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, or cyclobutyl or C. R5 is hydrogen, chloro, bromo, methyl, or cyclopropyl; or D. R5 is hydrogen, bromo, methyl, ethyl, methoxy, or cyclopropyl; or E. R5 is hydrogen, bromo, methyl, or cyclopropyl; or F. R5 is hydrogen, methyl, or ethyl; or G. R5 is hydrogen or methyl; or H. R5 is hydrogen. [0043] [0044] [0045] In preferred embodiments, R5 is as follows: A. R5 is hydrogen, methyl, or ethyl; or B. R5 is hydrogen or methyl; or C. R5 is hydrogen. [0046] For instance, Q, as defined above, is selected from Qa-1 to Qa-6, in which R4 has the same meaning as given for compounds of formula (I):
Figure imgf000008_0001
[0047] As an example, Q is Qa-1, Qa-2, Qa-3, or Qa-4; or Q is Qa-1, Qa-2, Qa-3, or Qa-5. Preferably, Q is Qa-1 or Qa-2. Most preferably, Q is Qa-1. [0048] In an embodiment of each aspect of the invention, R4 is as follows: 83101 / 109864 FFT A. R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; or R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; or B. R4 is R4-1, R4-2, R4-3, R4-4, R4-5, R4-6, or R4-7:
Figure imgf000009_0001
R4-1 R4-2 R4-3 R4-4 R4-5 R4-6 R4-7 where the staggered line represents the connection of R4 to the remainder of the compound of Formula (I); or C. R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; or D. R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; or E. R4 is pyrimidin-4-yl or pyrimidin-2-yl, each of which, independently of each other, is substituted with a single substituent R4a; or F. R4 is R4-1, R4-2, R4-3, R4-4, R4-5, or R4-7; or G. R4 is R4-1 or R4-5; or H. R4 is R4-2 or R4-7; or I. R4 is R4-3; or J. R4 is R4-4; or K. R4 is R4-6; or L. R4 is 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5- carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6-cyanopyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, or 5-bromopyrazin-2-yl; or M. R4 is 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5- carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6-cyanopyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- fluoropyrimidin-2-yl, or 5-bromopyrazin-2-y.; [0049] In preferred embodiments of each aspect of the invention, R4 is 1-methyl-6-oxo-pyridazin-3- yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5-carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-cyanopyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, 5- chloropyrimidin-2-yl, 5-fluoropyrimidin-2-yl, or 5-bromopyrazin-2-yl. Preferably, R4 is 1-methyl-6-oxo- 83101 / 109864 FFT pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5-carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-cyanopyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, or 5- bromopyrazin-2-yl. [0050] In preferred embodiments of each aspect of the invention, the pyrimidinyl, pyrazinyl, pyridazinyl, oxo-pyridazinyl, and thiazolyl rings of R4 are each connected to the remainder of the compound via a carbon atom. In other words, a carbon atom of the pyrimidinyl, pyrazinyl, pyridazinyl, oxo-pyridazinyl, and thiazolyl rings of R4 is linked to the triazole moiety of the compound of Formula (I). [0051] Preferably, R4 is not a pyridinyl ring (substituted or non-substituted). Also preferably, R4 is not a non-substituted pyrimidin-2-yl ring. [0052] In an embodiment of each aspect of the invention, R4a is as follows: A. R4a is 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. R4a is halogen, cyano, C1-C3haloalkyl, C1-C3alkoxy, -C(O)NR10R11, or -N(R11)C(O)OR10; or C. R4a is chloro, bromo, iodo, cyano, -C(O)NR10R11, or -N(R11)C(O)OR10; or D. R4a is bromo, iodo, cyano, -C(O)NR10R11, or -N(R11)C(O)OR10; or E. R4a is bromo, cyano, -C(O)NR10R11, or -N(R11)C(O)OR10; or F. R4a is bromo, cyano, C1-C3alkoxy, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or - NHC(O)OCH3; or G. R4a is fluoro, chloro, bromo, cyano, C1-C3alkoxy, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or -NHC(O)OCH3; or H. R4a is fluoro, chloro, bromo, cyano, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or - NHC(O)OCH3. [0053] In preferred embodiments of each aspect of the invention, R4a is fluoro, chloro, bromo, cyano, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or -NHC(O)OCH3; such as, R4a is bromo, cyano, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or -NHC(O)OCH3. More preferably, R4a is bromo, cyano, or -C(O)NH2. [0054] In an embodiment of each aspect of the invention, R4b is as follows: A. R4b is C1-C3alkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; or B. R4b is C1-C3alkyl, allyl, or propargyl; or C. R4b is C1-C3alkyl or C3-C6cycloalkylC1-C4alkyl; or D. R4b is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; or E. R4b is C1-C3alkyl; or F. R4b is methyl or ethyl; or G. R4b is methyl. [0055] In preferred embodiments of each aspect of the invention, R4b is methyl. [0056] In an embodiment of each aspect of the invention, R10 is as follows: 83101 / 109864 FFT A. R10 is hydrogen, C1-C3alkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, or C1-C3alkoxyC1-C3alkyl; or B. R10 is hydrogen, methyl, ethyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, or cyanomethyl: or C. R10 is hydrogen, C1-C3alkyl, or C1-C3cyanoalkyl; or D. R10 is hydrogen, methyl, ethyl, cyclopropyl, 1-cyanocyclopropyl, or cyanomethyl; or E. R10 is hydrogen, methyl, ethyl, or cyanomethyl; or F. R10 is hydrogen, methyl, or cyanomethyl; or G. R10 is hydrogen, methyl, or ethyl; or H. R10 is methyl or ethyl; or I. R10 is hydrogen. [0057] In preferred embodiments of each aspect of the invention, R10 is hydrogen, methyl, ethyl, or cyanomethyl, such as R10 is hydrogen, methyl, or cyanomethyl. For instance, R10 is hydrogen. [0058] In an embodiment of each aspect of the invention, R11 is as follows: A. R11 is hydrogen or C1-C3alkyl; or B. R11 is hydrogen, methyl or ethyl; or C. R11 is hydrogen or methyl; or D. R11 is hydrogen. [0059] In preferred embodiments of each aspect of the invention, R4a is -C(O)NR10R11 or - N(R11)C(O)R10, and A. R10 is hydrogen, C1-C3alkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, or C1-C3alkoxyC1-C3alkyl; and R11 is hydrogen; or B. R10 is hydrogen, methyl, ethyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, or cyanomethyl; and R11 is hydrogen; or C. R10 is hydrogen, C1-C3alkyl, or C1-C3cyanoalkyl; and R11 is hydrogen; or D. R10 is hydrogen, methyl, or cyanomethyl; and R11 is hydrogen. [0060] In embodiments of each aspect of the invention, R4a is -C(O)NR10R11, R10 is hydrogen, methyl, ethyl, or cyanomethyl, and R11 is hydrogen, methyl or ethyl, preferably R11 is hydrogen or methyl, such as R11 is hydrogen. [0061] In embodiments of each aspect of the invention, R4a is -N(R11)C(O)R10, R10 is methyl or ethyl, and R11 is hydrogen or methyl, preferably R11 is hydrogen. [0062] Accordingly, the present invention makes available a compound of formula (I) having the substituents R1, R2a, R4, R4a, R4b, R5, R10, and R11 as defined above, in all combinations and each permutation. [0063] For instance, compounds of formula (I) are made available, where R1 is hydrogen, methyl, ethyl, or cyclopropylmethyl; R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1- fluorocyclopropyl, or 1-chlorocyclopropyl; R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each 83101 / 109864 FFT of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; or R4 is oxo-pyridazinyl which is N- substituted with a single substituent R4b; R4a is bromo, cyano, -C(O)NR10R11, or -N(R11)C(O)OR10; R4b is methyl or ethyl; R5 is hydrogen, chloro, bromo, methyl, or cyclopropyl; and R10 is hydrogen, C1- C3alkyl, or C1-C3cyanoalkyl; R11 is hydrogen, methyl or ethyl. [0064] Compounds of formula (I) are made available, where R1 is hydrogen, methyl, or cyclopropylmethyl; R2a is chloro, bromo, or cyclopropyl; R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; R4a is halogen, cyano, C1-C3haloalkyl, -C(O)NR10R11, or -N(R11)C(O)OR10; and R5 is hydrogen, methyl, or ethyl; R10 is hydrogen, methyl, ethyl, or cyanomethyl; R11 is hydrogen, methyl or ethyl. [0065] Compounds of formula (I) are made available, where R1 is hydrogen or methyl; R2a is chloro, bromo, or cyclopropyl; R4 is 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5- carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin- 4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, or 5-bromopyrazin-2-yl; and R5 is hydrogen or methyl. [0066] Compounds of formula (I) are made available, where R1 is hydrogen or methyl; R2a is chloro, bromo, or cyclopropyl; R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin- 2-yl which is substituted with a single substituent R4a; or R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; R4a is bromo, cyano, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or - NHC(O)OCH3; R4b is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; and R5 is hydrogen or methyl. [0067] Compounds of formula (I) are made available, where R1 is hydrogen; R2a is chloro; R4 is R4- 1, R4-2, R4-3, R4-4, R4-5, R4-6, or R4-7; R4a is Br, -CN, -C(O)NH2, -C(O)NHCH3, -C(O)NHCH2CN, or - NHC(O)OCH3; R4b is methyl or ethyl; R5 is hydrogen or methyl; for instance, R4 is 1-methyl-6-oxo- pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5-carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-cyanopyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, or 5- bromopyrazin-2-yl. Synthesis [0068] 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. 83101 / 109864 FFT
Figure imgf000013_0001
Scheme 1 [0069] Compounds of formula (I) can be made, for example, as outlined in Scheme 1 above, wherein R1 is as defined for compounds of formula (I), and where T and Q represent:
Figure imgf000013_0002
where R2a, R4 and R5 have the same meaning as given for compounds of formula (I), and the staggered lines represent the connection to the remainder of the compound of formula (I), or to the other compounds shown in Schemes 1 to 6, such as compounds of formulae (Ia), (Ia-1), (Ib), (II), (III), (IV), (IVa), (V), (VII), (VIII), (X), (XI). [0070] 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 has the same meaning as given above for compounds of the formula (I), and wherein Q has the meaning given above. 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), PyBOP (benzotriazol- 1-yloxytripyrrolidinophosphonium hexafluorophosphate) 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) or 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 sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0071] 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) 83101 / 109864 FFT wherein X1 is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), in an inert solvent, such as, for instance, dichloromethane (DCM) or tetrahydrofuran (THF), in a temperature range of 0°C to 100°C, preferably about 25°C. Such methods are known to those skilled in the art and described for example in Tetrahedron 2005, 61 (46), 10827-10852.
Figure imgf000014_0001
Scheme 2 [0072] Compounds of formula (III), or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), and wherein Q has the same meaning as given above in Scheme 1, can be made, for example, as shown in Scheme 2. Treatment of a compound of the formula (V), wherein Q has the same meaning as given above in Scheme 1 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 R1 has the same meaning as given above for compounds of the formula (I), and Q has the same meaning as given above in Scheme 1. 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 at a temperature ranging from ambient temperature to 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, diisopropylethylamine or pyridine. [0073] Alternatively, treatment of a compound of the formula (VII), wherein Q has the same meaning as given above in Scheme 1, 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 R1 has the same meaning as given above for compounds of the formula (I), and Q has the same meaning as given above in Scheme 1. This reaction is done in the presence of a reducing agent, such as 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 ranging from -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 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 83101 / 109864 FFT 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 imgf000015_0001
Scheme 3 [0074] 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 Q has the same meaning as given above in Scheme 1, 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. [0075] 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 Q has the same meaning as given above in Scheme 1. This reaction is done in the presence of a reducing agent, such as 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 imgf000015_0002
VIII V VII Scheme 4 [0076] Compounds of formula (V), wherein Q has the same meaning as given above in Scheme 1, 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 Q has the same meaning as given above in Scheme 1, with a halogenating agent, such as chlorine, bromine, N-chlorosuccinimide or N-bromosuccinimide, for example, gives compound of the formula 83101 / 109864 FFT (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. [0077] Alternatively, a compound of the formula (VII), wherein Q has the same meaning as given above in Scheme 1, 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 Q has the same meaning as given above in Scheme 1, are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000016_0001
Ia VI Ia-1 Scheme 5 [0078] Alternatively, compounds of formula (Ia-1), wherein T has the same meaning as given above in Scheme 1, Q 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), 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 Q has the same meaning as given above in Scheme 1, can be reacted 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, 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, dimethylsulfoxide (DMSO), N,N- dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature 83101 / 109864 FFT 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 imgf000017_0001
Scheme 6 [0079] Compounds of formula (Ib), wherein T has the same meaning as given above in Scheme 1, and 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, gives a compound of the formula (X), wherein T has the same meaning as given above in Scheme 1. 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 hexafluoro- phosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium), PyBOP (benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate) or propanephosphonic acid cyclic anhydride (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) or for instance a metal catalyst such as a palladium complex, and with or without the addition of a base, such as an inorganic 83101 / 109864 FFT base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine, or pyridine. [0080] Subsequent treatment of compound of the formula (X), wherein T has the same meaning as given above in Scheme 1, with compounds of the formula (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 in which 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. [0081] Further reaction of compound of the formula (XI), wherein T has the same meaning as given above in Scheme 1, and in which 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, R4 has the same meaning as given above for compounds of the formula (I), and in which 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. [0082] A compound of the formula (IX), or a salt thereof, is either known, or it 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. [0083] Compounds of the formula (I’a)
Figure imgf000018_0001
can be prepared by the reaction of an amine of the formula (IIIa), or a salt thereof, 83101 / 109864 FFT
Figure imgf000019_0001
wherein R1, R4 and R5 are as described in formula (I), with a compound of the formula (IIa)
Figure imgf000019_0002
wherein R2a is 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. [0084] Compounds of formula (IIa), wherein R2a is as described in formula (I) and X1 is hydroxy or a leaving group, such as a halogen or a sulfonate, for instance chloride, can be prepared by following descriptions found in, for example, WO 2021/083936, WO 2021/148639 and WO 2021/177160. [0085] In particular, compounds of the formula (IIa-2), wherein R2a is as described in formula (I) and X1 is Cl, can be prepared according to reactions outlined in Scheme 7.
Figure imgf000019_0003
Scheme 7 [0086] Compounds of the formula (IIa-2), wherein R2a is as described in formula (I) and X1 is Cl, can be prepared (Scheme 7) by treating compounds of the formula (IIa-1), wherein R2a is as described in formula (I), with oxalyl chloride or thionyl chloride (alternatively phosphorus oxychloride), optionally 83101 / 109864 FFT in the presence of catalytic N,N-dimethylformamide (DMF), in an inert solvent, analogous to descriptions found in Scheme 1 or, for example, in WO2015/54572, p.263. [0087] Compounds of the formula (IIa-1), wherein R2a is as described in formula (I), may exist in different tautomeric forms, for example as represented by the formula (IIa-1’). This invention covers all such tautomers and mixtures thereof in all proportions. [0088] Compounds of the formula (IIa-1), wherein R2a is as described in formula (I), can be prepared by treating compounds of the formula (XIX), wherein R2a is as described in formula (I), with formic acid and sulfuric acid, at temperatures between 80 and 100 °C, following procedures analogous to descriptions found, for example, in WO2018/206539, p.80. [0089] Compounds of the formula (XIX), wherein R2a is as described in formula (I), can be prepared by cyanation of compounds of the formula (XVIII), wherein R2a is as described in formula (I), and in which X3 is a halogen leaving group, preferably iodo or bromo, with for example copper(I) cyanide (CuCN), in a solvent such as N,N-dimethylformamide (DMF), at temperatures between 80 and 150 °C, under analogous conditions found, for example, in WO2005/100298, p.44. [0090] Compounds of the formula (XVIII), wherein R2a is as described in formula (I), and in which X3 is a halogen leaving group, preferably iodo or bromo, can be prepared by reacting compounds of formula (XVII), wherein R2a is as described in formula (I), with an electrophilic halogenating reagent, such as N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), in an inert solvent, such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, ethers, acetonitrile, N,N- dimethylformamide or hexafluoroisopropanol (as described for example in J. Org. Chem. 2018, 83, 930), and at temperatures between 20-200 °C, preferably between room temperature to 100 °C. [0091] Compounds of formula (XVII), wherein R2a is as described in formula (I), can be prepared by reduction of compounds of the formula (XVI), wherein R2a is as described in formula (I), using reagents such as iron, ferrous salts, or iron catalyst in aqueous acid (generally referred to as Béchamp reduction), or zinc or iron in the presence of ammonium chloride in alcohols (such as ethanol or isopropanol) and water, and at temperature between 0°C to boiling point of the reaction mixture. Alternatively, such a reduction may also be achieved under conditions known to a person skilled in the art, for example by involving molecular hydrogen (H2), optionally under pressure, in the presence of a catalyst such as for example palladium on charcoal, in alcohols (such as methanol, ethanol or isopropanol), and at temperature between 0°C to boiling point of the reaction mixture. [0092] Compounds of formula (XVI), wherein R2a is as described in formula (I), can be prepared by difluoromethylation of compounds of the formula (XV), wherein R2a is as described in formula (I), under conditions known to a person skilled in the art. Typically, compounds of the formula (XV) are reacted with a :CF2 carbene species, generated from difluoromethylating agents such a difluoroacetate XcCF2COONa or a difluoromethyl(phosphonate) XcCF2P(O)(OEt)2, wherein Xc can be chloro or bromo, in the presence of a base such as for example sodium or potassium carbonate, or sodium or potassium hydroxide, in an appropriate solvent like for example acetonitrile, Ν,Ν-dimethylformamide or N-methyl-2-pyrrolidone (NMP), optionally in a mixture with water, optionally in the presence of an additive (such as 2'-hydroxyaceto-phenone), and at temperature 83101 / 109864 FFT between -40°C to 80°C. Such methods have been described in the literature, for example in Org. Lett. 15(19), 5036-5039; 2013, Tetrahedron 65(27), 5278-5283; 2009 or Chem. Commun. 53, 5706; 2017. [0093] Compounds of the formula (XV), wherein R2a is as described in formula (I), are either known, commercial, or they can be prepared by methods known to a person skilled in the art. Difluoro- methylation agents of the formula XcCF2COONa (for instance sodium 2-chloro-2,2-difluoroacetate) or XcCF2P(O)(OEt)2 (for instance diethyl (bromodifluoromethyl)phosphonate), wherein Xc is chloro or bromo, are either known, commercial, or they can be prepared by methods known to a person skilled in the art. [0094] 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 has the same meaning as given above for compounds of the formula (I) and Q has the same meaning as given above in Scheme 1, are known in the literature.
Figure imgf000021_0001
[0095] For example, compounds of the formula (IIIa) or (IIIb), or a salt thereof as defined above, wherein R1, R4 and R5 are as described in formula (I), 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 and WO 2023/247360. [0096] In particular, compounds of the formula (IIIc), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared according to reactions outlined in Scheme 8.
Figure imgf000021_0002
Scheme 8 83101 / 109864 FFT [0097] As shown in Scheme 8, compounds of the formula (IIIc), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared from compounds of formula (IIIc-1), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin. Such procedures are well known to a person skilled in the art and known from the literature and textbooks. The anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid. A great number of such acids are known to a person skilled in the art. [0098] Compounds of formula (IIIc-1), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, can be made from compounds of the formula (XX), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), by treatment with an acid, such as the acids listed above. The reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents. The reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambient temperature. [0099] Compounds of the formula (XX), wherein R1 and R5 are as described in formula (I) and X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared by reaction of compounds of the formula (XXII), or a tautomer thereof, or a salt thereof, wherein X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), with a compound of the formula (XXI), wherein R1 and R5 are as defined for compounds of the formula (I). The reaction can be done neat, or in a solvent, for instance an organic solvent, such as dioxane or acetic acid, or a mixture thereof. The reaction can be performed in the presence or in the absence of a drying agent, such as for example in the presence of molecular sieves, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 80 °C. [0100] Compounds of the formula (XXII), or a tautomer thereof, or a salt thereof, wherein X4 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), are known or even commercially available, or they can be made by known methods. Compound of the formula (XXI), wherein R1 and R5 are as defined for compounds of the formula (I), are known, for instance from WO2021/083936 or WO2021/165195, or they can be made in analogy to descriptions found therein. [0101] Alternatively, compounds of the formula (IIIa), wherein R1, R4 and R5 are as defined for compounds of the formula (I), or a salt thereof (IIIa-1), in which X- is an anion as defined above in Scheme 8, can be made (Scheme 9) from compounds of the formula (IIIa-2), wherein R1, R4 and R5 are as defined for compounds of the formula (I), following the chemistry and conditions described above in Scheme 8 (transformation XX into IIIc via IIIc-1). 83101 / 109864 FFT
Figure imgf000023_0001
Scheme 9 [0102] Compounds of the formula (IIIa-2), wherein R1 and R4 are as defined for compounds of the formula (I), and in which R5 is hydrogen or C1-C3alkyl, can be prepared by reacting compounds of the formula (XXI), wherein R1 is as defined for compounds of the formula (I) and R5 is hydrogen or C1-C3alkyl, with hydrazine compounds of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 is as defined for compounds of the formula (I), under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib). [0103] Alternatively, compounds of the formula (IIIa-2), wherein R1 and R4 are as defined for compounds of the formula (I), and in which R5 is C1-C3alkyl or C3-C4cycloalkyl, can be prepared by reacting compounds of the formula (IIIa-3), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, with hydrazine compounds of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4 is as defined for compounds of the formula (I), under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib) or detailed in J Org Chem, 2011, 76, 1177-1179. [0104] Compounds of the formula (IIIa-3), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, can be prepared by reacting compounds of the formula (IIIa-4), wherein R1 is as defined for compounds of the formula (I), with compounds of the formula (IIIa-5) or a tautomer thereof, 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 R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, in the presence of a coupling reagent, such as, for example, HATU (1- [bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium), PyBOP (benzotriazol- 1-yloxytripyrrolidinophosphonium hexafluorophosphate) 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, 83101 / 109864 FFT preferably between ambient temperature and 200 °C, 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. Such conditions are described for example in J Org Chem, 2011, 76, 1177-1179. [0105] Compounds of the formula (IIIa-4), wherein R1 is as defined for compounds of the formula (I), are known or even commercially available, or they can be made by known methods. [0106] Compounds of the formula (IIIa-5) or a tautomer thereof, or a salt thereof, wherein R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 (compound IIIa-5 is an alkyl or cycloalkyl amidine, for example cyclopropanecarboxamidine) or -OC1-C4alkyl (compound IIIa-5 is an alkyl or cycloalkyl imidate, for example ethyl propanimidate), are known or even commercially available, or they can be made by known methods. [0107] 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 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). [0108] 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. [0109] 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. [0110] 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. [0111] 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 83101 / 109864 FFT 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. [0112] 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. [0113] 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. [0114] 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. [0115] 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 case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case. [0116] 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. [0117] 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, 83101 / 109864 FFT from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents. [0118] 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. [0119] 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. [0120] 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. [0121] 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. [0122] The compounds of formula (I) according to the following Tables A-1 to A-24, 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):
Figure imgf000026_0001
Tables A-1 to A-24 [0123] Table A-1 provides 22 compounds A-1.001 to A-1.022 of formula I-A wherein R2a is Cl, R1 is H, R5 is H and R4x are as defined in table Z. [0124] For example, compound A-8.010 is
Figure imgf000026_0002
83101 / 109864 FFT [0125] Table A-2 provides 22 compounds A-2.001 to A-2.022 of formula I-A wherein R2a is Cl, R1 is H, R5 is CH3 and R4x are as defined in table Z. [0126] Table A-3 provides 22 compounds A-3.001 to A-3.022 of formula I-A wherein R2a is Cl, R1 is CH3, R5 is H and R4x are as defined in table Z. [0127] Table A-4 provides 22 compounds A-4.001 to A-4.022 of formula I-A wherein R2a is Cl, R1 is CH3, R5 is CH3 and R4x are as defined in table Z. [0128] Table A-5 provides 22 compounds A-5.001 to A-5.022 of formula I-A wherein R2a is Br, R1 is H, R5 is H and R4x are as defined in table Z. [0129] Table A-6 provides 22 compounds A-6.001 to A-6.022 of formula I-A wherein R2a is Br, R1 is H, R5 is CH3 and R4x are as defined in table Z. [0130] Table A-7 provides 22 compounds A-7.001 to A-7.022 of formula I-A wherein R2a is Br, R1 is CH3, R5 is H and R4x are as defined in table Z. [0131] Table A-8 provides 22 compounds A-8.001 to A-8.022 of formula I-A wherein R2a is Br, R1 is CH3, R5 is CH3 and R4x are as defined in table Z. [0132] Table A-9 provides 22 compounds A-9.001 to A-9.022 of formula I-A wherein R2a is CF3, R1 is H, R5 is H and R4x are as defined in table Z. [0133] Table A-10 provides 22 compounds A-10.001 to A-10.022 of formula I-A wherein R2a is CF3, R1 is H, R5 is CH3 and R4x are as defined in table Z. [0134] Table A-11 provides 22 compounds A-11.001 to A-11.022 of formula I-A wherein R2a is CF3, R1 is CH3, R5 is H and R4x are as defined in table Z. [0135] Table A-12 provides 22 compounds A-12.001 to A-12.022 of formula I-A wherein R2a is CF3, R1 is CH3, R5 is CH3 and R4x are as defined in table Z. [0136] Table A-13 provides 22 compounds A-13.001 to A-13.022 of formula I-A wherein R2a is Cyp, R1 is H, R5 is H and R4x are as defined in table Z. [0137] Table A-14 provides 22 compounds A-14.001 to A-14.022 of formula I-A wherein R2a is Cyp, R1 is H, R5 is CH3 and R4x are as defined in table Z. [0138] Table A-15 provides 22 compounds A-15.001 to A-15.022 of formula I-A wherein R2a is Cyp, R1 is CH3, R5 is H and R4x are as defined in table Z. [0139] Table A-16 provides 22 compounds A-16.001 to A-16.022 of formula I-A wherein R2a is Cyp, R1 is CH3, R5 is CH3 and R4x are as defined in table Z. [0140] Table A-17 provides 22 compounds A-17.001 to A-17.022 of formula I-A wherein R2a is Cl, R1 is H, R5 is CH2CH3 and R4x are as defined in table Z. [0141] Table A-18 provides 22 compounds A-18.001 to A-18.022 of formula I-A wherein R2a is Cl, R1 is CH3, R5 is CH2CH3 and R4x are as defined in table Z. [0142] Table A-19 provides 22 compounds A-19.001 to A-19.022 of formula I-A wherein R2a is Cl, R1 is H, R5 is cyclopropyl and R4x are as defined in table Z. [0143] Table A-20 provides 22 compounds A-20.001 to A-20.022 of formula I-A wherein R2a is Cl, R1 is CH3, R5 is cyclopropyl and R4x are as defined in table Z. 83101 / 109864 FFT [0144] Table A-21 provides 22 compounds A-21.001 to A-21.022 of formula I-A wherein R2a is Cl, R1 is H, R5 is OCH3 and R4x are as defined in table Z. [0145] Table A-22 provides 22 compounds A-22.001 to A-22.022 of formula I-A wherein R2a is Cl, R1 is CH3, R5 is OCH3 and R4x are as defined in table Z. [0146] Table A-23 provides 22 compounds A-23.001 to A-23.022 of formula I-A wherein R2a is Cl, R1 is H, R5 is Br and R4x are as defined in table Z. [0147] Table A-24 provides 22 compounds A-24.001 to A-24.022 of formula I-A wherein R2a is Cl, R1 is CH3, R5 is Br and R4x are as defined in table Z. Table Z: Substituent definitions of R4x
Figure imgf000028_0001
83101 / 109864 FFT
Figure imgf000029_0001
[0149] Also made available are certain intermediate compounds as shown in Schemes 1 to 8, some of which are novel. For example: ^ A compound of formula (IIa-1), or its quinazolin-4-one tautomers (IIa-1’) and (IIa-1’’), where R2a is as defined for compounds of formula (I), preferably where R2a is as defined in Tables A-1 to A-24, such as R2a is chloro, bromo, trifluoromethyl, or cyclopropyl:
Figure imgf000029_0002
(IIa-1) with R2a = Cl (IIa-1’) with R2a = Cl (IIa-1’’) with R2a = Cl 83101 / 109864 FFT ^ A compound of formula (IIa-2), where R2a is as defined for compounds of formula (I), preferably where R2a is as defined in Tables A-1 to A-24, such as R2a is chloro, bromo, trifluoromethyl, or cyclopropyl;
Figure imgf000030_0001
more preferably, compound of formula (IIa-2) is 4,6-dichloro-8-(difluoromethoxy)quinazoline. ^ A compound of formula (IIIc) or of formula (IIIc-1), where R1 and R5 are as defined for compounds of formula (I), X- is an anion, such as a halide, sulfate, carboxylate, or sulfonate anion, and X4 is halogen, such as bromo, chloro, or iodo:
Figure imgf000030_0002
preferably, where R1 and R5 are as defined in Tables A-1 to A-24; X- is chloride, bromide, iodide, sulfate, 2,2,2-trifluoroacetate, mesylate, or triflate, and X4 is bromo, chloro, or iodo; such as R1 is hydrogen or methyl, R5 is hydrogen or methyl, X- is chloride, sulfate, or 2,2,2- trifluoroacetate, and X4 is bromo or chloro; more preferably, where R5 is as defined in Tables A-1 to A-24; X- is chloride or 2,2,2- trifluoroacetate; and X4 is bromo. [0150] The compounds of formula (I) according to the invention are preventively and/or curatively valuable active 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. [0151] Examples of the above mentioned animal pests are: ^ 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 83101 / 109864 FFT 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, 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, 83101 / 109864 FFT 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.; 83101 / 109864 FFT ^ 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. [0152] 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.. [0153] 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. 83101 / 109864 FFT aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides. [0154] 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. [0155] 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. [0156] 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. [0157] 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. [0158] 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. 83101 / 109864 FFT 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. 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. [0159] 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. [0160] 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). [0161] 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 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 vegetables); 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). [0162] 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. [0163] 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 83101 / 109864 FFT 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, 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. [0164] 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). [0165] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, EP-A-451 878 and WO 03/052073. [0166] 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. [0167] 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). [0168] 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); 83101 / 109864 FFT Nature-Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®. [0169] Further examples of such transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 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 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-31790 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. [0170] 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). [0171] 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 83101 / 109864 FFT 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-0 392 225, WO 95/33818 and EP-A-0 353 191. 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. [0172] 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. [0173] Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode. [0174] 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. [0175] 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 defence (so-called "plant disease resistance genes", as described in WO 03/000906). [0176] 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. [0177] 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. [0178] 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. [0179] 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. 83101 / 109864 FFT [0180] 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. [0181] 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. [0182] 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. [0183] 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. [0184] 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 Psoroptesovis; Cheyletiella; Dermanyssus; for example Dermanyssusgallinae; Ortnithonyssus; Demodex, for example Demodexcanis; 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. [0185] 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 83101 / 109864 FFT 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. [0186] 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, 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. [0187] 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. [0188] 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. [0189] 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. 83101 / 109864 FFT [0190] 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. [0191] 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. [0192] 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
83101 / 109864 FFT 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, 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 83101 / 109864 FFT
Figure imgf000043_0001
Host or Crop 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 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 [0193] 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. [0194] 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.). [0195] 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 83101 / 109864 FFT verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis). [0196] 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. [0197] 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. [0198] 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. [0199] 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.. ^ 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.. 83101 / 109864 FFT [0200] 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. [0201] 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. [0202] 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-24 and Table P”) controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. [0203] 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. [0204] 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-24 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. [0205] 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. [0206] 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-24 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 83101 / 109864 FFT 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. [0207] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-24 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. [0208] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-24 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). [0209] 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 to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera. [0210] 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-24 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-(4-chlorophenyl)- 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)benzene + 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-[5-(2-chloro-3,3,3-trifluoro-prop-1-enyl)-1-methyl-imidazol-2-yl]-5-cyclopropyl-3-ethylsulfonyl- pyridine + 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 83101 / 109864 FFT 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-21 618) + 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, bentioflumin (CAS Number: 2566451-67-8) + 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 + 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: 158062-71-6 + 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: 2128706-05-6 + 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- 83101 / 109864 FFT 16-8 + TX, CAS Number: 2583740-14-9 + TX, CAS Number: 2583751-98-6 + TX, CAS number: 2719848-60-7 + TX, CAS Number: 2898489-71-7 + TX, CAS Number: 2922115-20-4 + TX, CAS Number: 34763-86-5 + 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, cybenzoxasulfyl (CAS Number: 2128706-04-5) + 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, 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, flupentiofenox + TX, flupyradifurone + TX, flupyrimin + TX, flupyroxystrobin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, formaldehyde + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, furfural + TX, galquin (CAS Number: 2644770-30-7) + 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 83101 / 109864 FFT + 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, piperflanilide (CAS number: 2615135-05-0) + TX, 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 + 83101 / 109864 FFT 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 + 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, tiapyrachlor (CAS Number: 1255091-74-7) + 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- 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) + 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- 83101 / 109864 FFT 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]- 1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 83101 / 109864 FFT 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 (3',4',5'-trifluoro-biphenyl-2-yl)-amide + 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- 83101 / 109864 FFT 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)-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, bromocyclen + 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: 2049581-78-2 + TX, CAS Number: 2454319-63-0 + TX, CAS Number: 83-46-5 + 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, 83101 / 109864 FFT 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 + 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, dimethomorph + 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 + 83101 / 109864 FFT TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, feneptamidoquin (CAS Number: 2132414-04-9) + TX, fenethacarb + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenopyramid (CAS Number: 2344721-61-3) + 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 + 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 83101 / 109864 FFT + 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, 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- 83101 / 109864 FFT 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 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 + 83101 / 109864 FFT 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, Rmetalaxyl + 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 fluoroacetate + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, 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, 83101 / 109864 FFT 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, zoxamide + TX, α- (1, 1- dimethylethyl) - α- [4'- (trifluoromethoxy) [1, 1'- biphenyl] - 4- yl] -5- pyrimidinemethanol + 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 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 83101 / 109864 FFT (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, 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 83101 / 109864 FFT (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, 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, 83101 / 109864 FFT 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 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, 83101 / 109864 FFT 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 + 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®) + 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 83101 / 109864 FFT 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, 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, vadescana (CAS Number: 2643947-26-4) + TX, Zenox® + 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 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 83101 / 109864 FFT 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 Accession No. NRRL B-50972 or Accession No. NRRL 83101 / 109864 FFT 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 83101 / 109864 FFT (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. 1-3939 (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, 83101 / 109864 FFT 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; 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; 83101 / 109864 FFT 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 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 83101 / 109864 FFT 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 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, Zoophtora radicans + TX; Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX, Spodoptera littoralis (African cotton leafworm) NPV + 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 83101 / 109864 FFT (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, 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 fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thiram + TX, trimethacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX. [0211] 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 83101 / 109864 FFT "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html. [0212] 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. [0213] The active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-24 and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-24 and Table P, 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. [0214] 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. [0215] The mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-24 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. [0216] 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, 83101 / 109864 FFT 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. [0217] 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. [0218] 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 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. [0219] 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, 83101 / 109864 FFT 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. [0220] 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. [0221] 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 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). [0222] 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. [0223] 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 83101 / 109864 FFT 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. [0224] 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. [0225] 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. [0226] 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 % ^ 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 % [0227] 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 83101 / 109864 FFT (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. [0228] 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. [0229] 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. [0230] 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 tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides. [0231] 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. [0232] 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. [0233] 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 83101 / 109864 FFT 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. [0234] 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. [0235] 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. [0236] 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 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). [0237] 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. [0238] 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). 83101 / 109864 FFT [0239] 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. [0240] The disclosure in the present application makes available each and every combination of embodiments disclosed herein. [0241] 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-24. EXAMPLES Formulation Examples [0242] 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 % - [0243] 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. 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 % [0244] 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 % 83101 / 109864 FFT
Figure imgf000079_0001
xylene mixture 50 % [0245] 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 % [0246] 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 % Kaolin 82 % [0247] 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 % [0248] 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 % [0249] 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. 83101 / 109864 FFT 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 % Water 45.3 % [0250] 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 [0251] 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 [0252] 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: [0253] 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 83101 / 109864 FFT 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. Method 2: [0254] Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60°C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1% formic acid, B= Acetonitrile + 0.1% formic acid, gradient: 0-100% B in 3.0 min; Flow (ml/min) 0.75. Method 3: [0255] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 5000°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range: 110 to 800 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, Temp: 40 °C, PDA Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B = Acetonitrile + 0.05 % HCOOH, gradient: 10-100% B in 1.3 min; Flow (ml/min) 0.6. Method 4: [0256] 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. 83101 / 109864 FFT Method 5: [0257] Spectra were recorded on a Mass Spectrometer from Agilent, LCMS model 1260 infinity with MSD- Q1, MSD source Multimode ES+APCI. Example E1: Preparation of 6-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]-2-methyl-pyridazin-3-one (compound P1)
Figure imgf000082_0001
Step 1: Preparation of 4-chloro-2-(difluoromethoxy)-1-nitro-benzene (I-1)
Figure imgf000082_0002
[0258] To a solution of 5-chloro-2-nitro-phenol (15 g, 86.4 mmol) and sodium chlorodifluoroacetate (26.35 g, 173 mmol) in DMF (150 mL) was added potassium carbonate (35.84 g, 260 mmol) under inert atmosphere. The reaction mixture was stirred at 100°C for 2 h, then cooled to room temperature, poured into water (800 mL) and the product extracted with ethyl acetate. The combined organic layers were washed with NH4Cl, water, and brine, then dried over magnesium sulfate, filtered and concentrated under vacuum to afford 4-chloro-2-(difluoromethoxy)-1-nitro- benzene (I-1, 17.6 g) as a liquid. This material was used without further purification into the next step. [0259] 1H NMR (400 MHz, CDCl3) δ ppm 7.93 (d, 1H), 7.50-7.36 (m, 2H), 6.66 (t, 1H). Step 2: Preparation of 4-chloro-2-(difluoromethoxy)aniline (I-2)
Figure imgf000082_0003
[0260] To a solution of 4-chloro-2-(difluoromethoxy)-1-nitro-benzene (I-1) (17.2 g, 90%, 69.3 mmol) in ethanol (231 mL) and water (38.5 mL) were added zinc (9.06 g, 138 mmol) and ammonium chloride (7.4 g, 138 mmol). The reaction mixture was stirred at room temperature for 16 h, then filtered and concentrated under vacuum. The residue was dissolved in ethyl acetate, the organic phase washed with water and brine, dried over magnesium sulfate, filtered and concentrated in 83101 / 109864 FFT vacuo to afford 4-chloro-2-(difluoromethoxy)aniline (I-2, 13.7 g) as a liquid. This material was used without further purification into the next step. [0261] LCMS (method 1): retention time 0.9 min, m/z 194/196 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm δ = 7.12-6.97 (m, 2H), 6.75 (d, 1H), 6.46 (t, 1H), 3.48 (br s, 2H). Step 3: Preparation of 4-chloro-2-(difluoromethoxy)-6-iodo-aniline (I-3)
Figure imgf000083_0001
[0262] To a solution of 4-chloro-2-(difluoromethoxy)aniline (I-2) (13.7 g, 68.7 mmol) in ethanol (229 mL) were added silver sulfate (32.1 g, 103 mmol) and iodine (20.9 g, 82.4 mmol). The reaction mixture was stirred at room temperature for 16 h, filtered and quenched with an aqueous sodium thiosulfate solution. The product was extracted with ethyl acetate, the combined organic layers washed with water and brine, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 4-chloro-2- (difluoromethoxy)-6-iodo-aniline (I-3, 11.4 g, 80 mass%) as an oil. [0263] LCMS (method 1): retention time 1.07 min, m/z 320/322 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 7.52 (m, 1H), 7.08 (m, 1H), 6.48 (t, 1H). Step 4: Preparation of 2-amino-5-chloro-3-(difluoromethoxy)benzonitrile (I-4)
Figure imgf000083_0002
[0264] To a solution of 4-chloro-2-(difluoromethoxy)-6-iodo-aniline (I-3) (9.66 g, 80%, 24.18 mmol) in DMF (40.3 mL) was added copper cyanide (3.25 g, 36.2 mmol). The reaction mixture was purged with argon and stirred at 120°C for 7 h, then cooled to room temperature. The mixture was filtered, then diluted with ethyl acetate, the solution washed with water, brine, and concentrated in vacuo to afford 2-amino-5-chloro-3-(difluoromethoxy)benzonitrile (I-4, 6.76 g, 80 mass%) as an oil. This material was used without further purification into the next step. [0265] LCMS (method 1): retention time 0.91 min, m/z 219/221 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.50 (m, 1H), 7.37 (m, 1H), 7.18 (t, 1H), 6.25 (s, 2H). Step 5: Preparation of 6-chloro-8-(difluoromethoxy)-3H-quinazolin-4-one (I-5) 83101 / 109864 FFT
Figure imgf000084_0001
[0266] To a solution of 2-amino-5-chloro-3-(difluoromethoxy)benzonitrile (I-4) (6.76 g, 80%, 24.7 mmol) in formic acid (67.6 mL) was added sulfuric acid (37.1 mmol). The reaction mixture was stirred at 50°C for 3 h, cooled to room temperature and poured into ice-water. The formed solid was filtered, rinsed with pentane and dried under vacuum. Recrystallization from cyclopentylmethylether afforded 6-chloro-8-(difluoromethoxy)-3H-quinazolin-4-one (I-5, 5.5 g) as a solid. [0267] LCMS (method 1): retention time 0.77 min, m/z 247/249 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 12.65 (br s, 1H), 8.21 (s, 1H), 7.96 (d, 1H), 7.77 (d, 1H), 7.40 (t, 1H). Step 6: Preparation of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6)
Figure imgf000084_0002
[0268] A mixture of 6-chloro-8-(difluoromethoxy)-3H-quinazolin-4-one (I-5) (320 mg, 1.29 mmol), N,N-dimethylformamide (0.064 mmol) and thionyl chloride (3.2 mL, 43.87 mmol) was stirred at 90°C for 1 h. The reaction mixture was allowed to cool to room temperature and concentrated in vacuo to afford 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6, 370 mg) as a yellow solid. This material was used without further purification into the next step. [0269] LCMS (method 1): retention time 1.00 min, m/z 261/263 [M+H]+ (methanol quench, compliant with 6-chloro-8-(difluoromethoxy)-4-methoxy-quinazoline C10H7ClF2N2O2, molecular weight 260.62). Step 7: Preparation of 6-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]-2-methyl-pyridazin-3-one (P1)
Figure imgf000084_0003
[0270] A solution of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) (0.42 mmol) and triethylamine (1.26 mmol) in DMF (2 mL) was added to [(1S)-1-[2-(1-methyl-6-oxo-pyridazin-3-yl)- 1,2,4-triazol-3-yl]ethyl]ammonium;chloride (prepared as described in WO 23/104714) (109 mg, 0.42 83101 / 109864 FFT mmol). The reaction mixture was stirred at 100°C for 2 h, then diluted with methanol (1 mL) and the solution purified via reverse phase preparative HPLC to afford 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1-yl]-2-methyl-pyridazin-3-one (P1) as a solid (117 mg). [0271] LCMS (method 2): retention time 1.06 min, m/z 449/451 [M+H]+. Example E2: Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]thiazole-5-carboxamide (compound P4)
Figure imgf000085_0001
Preparation of methyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]thiazole-5-carboxylate (I-7)
Figure imgf000085_0002
[0272] To a solution of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (CAS 2641011-39-2, prepared as described for example in WO21/083936) (5.2 g, 21 mmol) in 1,4-dioxane (31 mL) and acetic acid (31 mL) was added methyl 2-hydrazinothiazole-5- carboxylate (CAS 2648006-04-4) (3.7 g, 21 mmol). The reaction mixture was heated at 50°C for 16 hours, then cooled to RT and diluted with EtOAc and water. The phases were separated, the aqueous layer extracted with EtOAc, the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (gradient ethyl acetate in cyclohexane) to afford methyl 2-[5-[(1S)-1-(tert- butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]thiazole-5-carboxylate (I-7). [0273] LCMS (method 3): retention time 1.11 min, m/z 298 [M+H-tBu]+. Step 2: Preparation of 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]thiazole-5- carboxylic acid (I-8) 83101 / 109864 FFT
Figure imgf000086_0001
[0274] A mixture of methyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]thiazole-5-carboxylate (I-7) (3.7 g, 10 mmol) and lithium hydroxide (0.78 g, 31 mmol) in tetrahydrofuran (37 mL) and water (3.7 mL) was stirred at room temperature for 16 hours, then diluted with EtOAc, water and a 5% aqueous monosodium phosphate (NaH2PO4) solution. The phases were separated, and the aqueous layer washed with EtOAc, cooled by addition of crushed ice, then acidified using a 10% aqueous HCl solution. The formed precipitate was filtered, the solid washed with water and dried. The solid was further washed with pentane and dried in vacuo to afford 2-[5-[(1S)-1-(tert-butoxycarbonyl-amino)ethyl]-1,2,4-triazol-1-yl]thiazole-5-carboxylic acid (I-8) as an off-white solid. This material was used without further purification for the next step. [0275] LCMS (method 3): retention time 1.03 min, m/z 284 [M+H-tBu]+. Step 3: Preparation of silica gel-supported ammonium chloride (NH4Cl/SiO2) [0276] According to Tetrahedron Letters 2005, 46, 6879-6882: Silica gel (5.0 g, Merck Kieselgel 60, particle size 0.063-0.200 mm, 70-230 mesh) was mixed with a solution of ammonium chloride (20 mmol) in water (5.0 mL). Evaporation of water in vacuo gave a white powder which was further dried under reduced pressure. This material was used as an ammonia source in the next step. Step 4: Preparation of tert-butyl N-[(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-9)
Figure imgf000086_0002
[0277] To a mixture of 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]thiazole-5- carboxylic acid (I-8) (400mg, 1.18 mmol), silica gel-supported ammonium chloride (NH4Cl/SiO2 prepared as described above, 700 mg) and tosyl chloride (227 mg, 1.18 mmol) was added triethylamine (479 mg, 4.71 mmol). The reaction mixture was thoroughly mixed with a spatula. After 2 min the mixture was directly purified by column chromatography without any work up (50% EtOAc in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-9) as a white solid. [0278] LCMS (method 4): retention time 0.44 min, m/z 283 [M+H-tBu]+. 1H NMR (400 MHz, 83101 / 109864 FFT MeOH-d4) δ ppm 8.21 (s, 1H), 8.05 (s, 1H), 5.77 (m, 1H), 1.54 (d, 1H), 1.40 (br s, 9H). Step 5: Preparation of [(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-10)
Figure imgf000087_0001
[0279] To a solution of tert-butyl N-[(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-9) (180 mg, 0.53 mmol) in 1,4-dioxane (1.4 mL) was added a hydrochloric acid solution (4.0 mol/L in 1,4-dioxane, 1.4 mL, 5.6 mmol). The reaction mixture was stirred at RT for 5 h, then concentrated to dryness under reduced pressure. The residue was triturated with TBME, the solid filtered and dried in vacuo to afford [(1S)-1-[2-(5-carbamoylthiazol-2-yl)-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-10) as a white solid. [0280] LCMS (method 4): retention time 0.16 min, m/z 239 [M+H]+ of the corresponding free base. Step 6: Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]thiazole-5-carboxamide (P4)
Figure imgf000087_0002
[0281] To a solution of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) (200 mg, 95%, 0.72 mmol) in ACN (10.0 mL) were added potassium carbonate (297 mg, 2.15 mmol) and [(1S)-1-[2-(5- carbamoylthiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-10) (0.236 g, 0.86 mmol) at room temperature and the reaction mixture was heated to 80°C for 12 h. The mixture was cooled to room temperature, poured in ice cold water and the product extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate in hexane) to afford 2-[5-[(1S)-1-[[6- chloro-8-(difluoro-methoxy)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1-yl]thiazole-5-carboxamide (P4) as an off-white solid (195 mg). [0282] MS (method 5): m/z 467/469 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ ppm 9.03 (d, 1H), 8.6 (d, 1H), 8.38 (s, 1H), 8.30 (br s, 2H), 8.20 (s, 1H), 7.81 (br s, 1H), 7.70 (d, 1H), 7.43 (t, 1H), 6.31 (quint, 1H), 1.75 (d, 3H). 83101 / 109864 FFT [0283] Similarly, 6-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]-methyl-amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidine-4-carboxamide (compound P27) can be prepared from 4,6-dichloro-8- (difluoromethoxy)quinazoline (I-6) (1 equiv.) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol- 3-yl]ethyl]-methyl-ammonium chloride (CAS 3024825-36-0, prepared as described in WO 23/247360) (1.05 equiv.) by following above protocol in analogy. In this instance, triethylamine (2 equiv.) and potassium carbonate (0.1 equiv.) were used as the base and the reaction mixture stirred at 80°C for 6 hours. LCMS (method 4): retention time 1.09 min, m/z 476/478 [M+H]+. Example E3: Preparation of N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (difluoromethoxy)quinazolin-4-amine (compound P11)
Figure imgf000088_0001
[0284] To a mixture of 4,6-dichloro-8-(difluoromethoxy)quinazoline (I-6) (223.0 mg, 0.84 mmol) and [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23, prepared as described below) (296.0 mg, 0.97 mmol, 1.15 equiv.) in DMF (6.7 mL) was added triethylamine (369 ^L, 2.52 mmol, 3 equiv.). The reaction mixture was stirred at 90°C for 1 hour, cooled to room temperature, then diluted with water and EtOAc. The phases were separated, the aqueous layer extracted with EtOAc (3x), the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate in hexane) and preparative reversed phase HPLC (C18 column, water/acetonitrile eluent) to afford N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]-6- chloro-8-(difluoromethoxy)quinazolin-4-amine (P11) as an off-white solid. [0285] LCMS (method 1): retention time 0.91 min, m/z 497/499/501 [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 9.01 (s, 2H), 8.55 (s, 1H), 8.13 (s, 1H), 7.69 (s, 1H), 7.49 (s, 1H), 7.44 (br s, 1H), 7.08 (t, 1H), 6.59 (quint, 1H), 1.82 (d, 3H). [0286] Similarly, N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (difluoromethoxy)quinazolin-4-amine (compound P15) can be prepared from 4,6-dichloro-8- (difluoromethoxy)quinazoline (I-6) and [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-24, prepared as described below) by following above protocol in analogy. LCMS (method 2): retention time 1.31 min, m/z 511/513/515 [M+H]+. [0287] Similarly, 6-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]-3- cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide (compound P20) can be prepared from 4,6- dichloro-8-(difluoromethoxy)quinazoline (I-6) and [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5- cyclopropyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (CAS 2694010-05-2, prepared in analogy to 83101 / 109864 FFT descriptions found for example in WO21/224323) by following above protocol in analogy. LCMS (method 2): retention time 1.33 min, m/z 502/504 [M+H]+. [0288] Similarly, 5-[5-[(1S)-1-[[6-chloro-8-(difluoromethoxy)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]pyrazine-2-carboxamide (compound P21) can be prepared from 4,6-dichloro-8- (difluoromethoxy)quinazoline (I-6) and [(1S)-1-[2-(5-carbamoylpyrazin-2-yl)-1,2,4-triazol-3- yl]ethyl]ammonium chloride (CAS 3024825-20-2, prepared as described in WO23/247360) by following above protocol in analogy. LCMS (method 2): retention time 1.02 min, m/z 462/464 [M+H]+. Table P: Prepared compounds Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-1,2,4- P1 triazol-1-yl]-2-methyl- 1.06 449/451 2 pyridazin-3-one 6-chloro-8-(difluoromethoxy)- N-[(1S)-1-[2-(6- methoxypyridazin-3-yl)-1,2,4- P2 triazol-3-yl]ethyl]quinazolin-4- 1.23 449/451 2 amine 6-chloro-8-(difluoromethoxy)- N-[(1S)-1-(2-pyrazin-2-yl- 1,2,4-triazol-3- P3 1.15 419/421 2 yl)ethyl]quinazolin-4-amine 2-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-1,2,4- P4 triazol-1-yl]thiazole-5- - 467/469 5 carboxamide 2-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-1,2,4- P5 triazol-1-yl]thiazole-5- - 449/451 5 carbonitrile 83101 / 109864 FFT 89 Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-1,2,4- P6 - 462/464 5 triazol-1-yl]pyrimidine-4- carboxamide 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- P7 4-yl]amino]ethyl]-1,2,4- 1.16 476/478 2 triazol-1-yl]-N-methyl- pyrimidine-4-carboxamide 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-1,2,4- P8 1.16 501/503 2 triazol-1-yl]-N- (cyanomethyl)pyrimidine-4- carboxamide 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- P9 4-yl]amino]ethyl]-1,2,4- 1.32 444/446 2 triazol-1-yl]pyrimidine-4- carbonitrile methyl N-[6-[5-[(1S)-1-[[6- chloro-8- (difluoromethoxy)quinazolin- P10 4-yl]amino]ethyl]-1,2,4- triazol-1-yl]pyrimidin-4- yl]carbamate N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-1,2,4- triazol-3-yl]ethyl]-6-chloro-8- P11 (difluoromethoxy)quinazolin- 0.91 497/499/501 1 4-amine 83101 / 109864 FFT 90 Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- bromopyrazin-2-yl)-1,2,4- triazol-3-yl]ethyl]-6-chloro-8- P12 (difluoromethoxy)quinazolin- 1.01 497/499/501 1 4-amine 2-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-3-methyl- P13 1,2,4-triazol-1-yl]thiazole-5- 1.49 463/465 2 carbonitrile 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-3-methyl- P14 1.12 476/478 2 1,2,4-triazol-1-yl]pyrimidine- 4-carboxamide N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P15 yl]ethyl]-6-chloro-8- 1.31 511/513/515 2 (difluoromethoxy)quinazolin- 4-amine N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5-ethyl- 1,2,4-triazol-3-yl]ethyl]-6- P16 chloro-8- 1.44 526/528/530 2 (difluoromethoxy)quinazolin- 4-amine 5-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-3-methyl- P17 1,2,4-triazol-1-yl]pyrazine-2- 1.09 476/478 2 carboxamide 83101 / 109864 FFT 91 Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- cyclopropyl-1,2,4-triazol-3- P18 yl]ethyl]-6-chloro-8- 1.50 537/539/541 2 (difluoromethoxy)quinazolin- 4-amine N-[(1S)-1-[2-(5- bromopyrimidin-2-yl)-5- methoxy-1,2,4-triazol-3- P19 yl]ethyl]-6-chloro-8- 1.38 527/529/531 2 (difluoromethoxy)quinazolin- 4-amine 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-3- P20 cyclopropyl-1,2,4-triazol-1- 1.33 502/504 2 yl]pyrimidine-4-carboxamide 5-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-1,2,4- P21 triazol-1-yl]pyrazine-2- 1.02 462/464 2 carboxamide 2-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-3-ethyl- P22 1,2,4-triazol-1-yl]thiazole-5- 1.63 477/479 2 carbonitrile 2-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]amino]ethyl]-3- P23 cyclopropyl-1,2,4-triazol-1- 1.69 489/491 2 yl]thiazole-5-carbonitrile 83101 / 109864 FFT 92 Rt [M+H]+ Entry IUPAC name STRUCTURE Method (min) (measured) 6-chloro-8-(difluoromethoxy)- N-[(1S)-1-[2-(5- fluoropyrimidin-2-yl)-5- P24 methyl-1,2,4-triazol-3- 1.15 451/453 2 yl]ethyl]quinazolin-4-amine 6-chloro-N-[(1S)-1-[2-(5- chloropyrimidin-2-yl)-5- methyl-1,2,4-triazol-3- P25 yl]ethyl]-8- 1.27 467/469/471 2 (difluoromethoxy)quinazolin- 4-amine 2-[3-bromo-5-[(1S)-1-[[6- chloro-8- (difluoromethoxy)quinazolin- P26 4-yl]amino]ethyl]-1,2,4- 1.08 527/529/531 1 triazol-1-yl]thiazole-5- carbonitrile 6-[5-[(1S)-1-[[6-chloro-8- (difluoromethoxy)quinazolin- 4-yl]-methyl-amino]ethyl]- P27 1.09 476/478 4 1,2,4-triazol-1-yl]pyrimidine- 4-carboxamide Preparation of intermediates Example PI-1: Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3- yl]ethyl]ammonium;2,2,2-trifluoroacetate (I-11)
Figure imgf000093_0001
Step 1: Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-12) 83101 / 109864 FFT
Figure imgf000094_0001
[0289] To a solution of tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (1.8 g, 9.56 mmol) in 2-methyltetrahydrofuran (29 mL) was added N,N-dimethylformamide dimethyl acetal (14.35 mmol) at room temperature. The resulting reaction mixture was stirred at 40°C for 1.5 hour, then concentrated in vacuo to get the crude intermediate tert-butyl N-[(1S)-2-[(E)- dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]carbamate (I-17). [0290] 1,4-Dioxane (9.6 mL), acetic acid (9.6 mL) and 2-bromo-5-hydrazinylpyrazine (CAS 1001050-24-3) (1.6 g, 95%, 8.04 mmol) were added to this intermediate and the mixture was stirred at 80°C for 2 hours, then cooled to room temperature and poured over water and EtOAc. The phases were separated, the aqueous layer extracted with EtOAc, the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by combiflash (ethyl acetate in cyclohexane) to afford tert-butyl N-[(1S)- 1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-12) as a gum. LCMS (method 1): retention time 0.95 min, m/z 369/371 [M+H]+. Step 2: Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium;2,2,2- trifluoroacetate (I-11)
Figure imgf000094_0002
[0291] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-12) (2.0 g, 5.52 mmol) in trifluoromethylbenzene (40 mL) was added 2,2,2- trifluoroacetic acid (10mL) dropwise at RT and the reaction mixture was stirred for 2.5 h. The mixture was evaporated to dryness under reduced pressure, the oily residue triturated with TBME, and the resulting solid filtered and dried in vacuo to afford [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4- triazol-3-yl]ethyl]ammonium;2,2,2-trifluoroacetate (I-11) as an off-white solid. [0292] LCMS (method 4): retention time 0.3 min, m/z 269/271 [M+H]+ of the corresponding free base.1H NMR (400 MHz, DMSO-d6) δ ppm 9.08 (s, 1H) 8.93 (s, 1H), 8.61 (br s, 3H), 8.50 (s, 1H), 5.27 (q, 1H), 1.60 (d, 3H). Example PI-2: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23) 83101 / 109864 FFT
Figure imgf000095_0001
Step 1: Preparation of (5-bromopyrimidin-2-yl)hydrazine (I-16)
Figure imgf000095_0002
[0293] To a solution of 5-bromo-2-chloro-pyrimidine (15.0 g, 77.55 mmol) in methanol (150 mL) was added hydrazine hydrate (10.1 mL, 155.1 mmol, 2.0 equiv.) at 0°C. After addition, the reaction mixture was stirred at room temperature, then at 60°C for 6 hours. Upon cooling to room temperature, the formed solid was filtered and dried in vacuo to afford (5-bromopyrimidin-2-yl)hydrazine (I-16) as an off-white solid (11.0 g). This material was used without further purification in the next step. [0294] 1H NMR (400 MHz, DMSO-d6) δ ppm 8.48 (s, 1H), 8.40 (s, 2H), 4.20 (s, 2H). Step 2: Preparation of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17)
Figure imgf000095_0003
(I-17) [0295] tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (CAS 85642-13-3) (70.0 g, 353 mmol, 1 equiv.) was mixed with 2-methyltetrahydrofuran (1.12 L) and N,N-dimethylformamide- dimethylacetal (DMF-DMA, 70 mL, 530 mmol, 1.5 equiv.), and the mixture heated to 40°C for 2 hours. The reaction mixture was concentrated under reduced pressure to yield the title compound (I-17) (105g, 97% yield, 80% purity). [0296] 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.39 (s, 1H), 6.69 (br d, 1H), 3.97 (quint, 1H), 3.13 (s, 3H), 3.00 (s, 3H), 1.38 (s, 9H), 1.22 (d, 3H). [0297] Similarly, tert-butyl N-[(1S)-2-[(E)-1-(dimethylamino)ethylideneamino]-1-methyl-2-oxo- ethyl]carbamate (I-18) can be prepared from tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo- ethyl]carbamate (CAS 85642-13-3) and N,N-dimethylacetamide-dimethyl acetal (CAS 18871-66-4) by following above protocol in analogy. [0298] 1H NMR (400 MHz, CDCl3) δ ppm: 5.50-5.40 (m, 1H), 4.30-4.20 (m, 1H), 3.08 (s, 6H), 2.24 (s, 3H), 1.45 (s, 9H), 1.38 (d, 3H).
Figure imgf000095_0004
83101 / 109864 FFT
Figure imgf000096_0001
2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-19)
Figure imgf000096_0002
[0299] To a mixture of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo- ethyl]carbamate (I-17, prepared as described above) (7.73 g, 30.5 mmol, 1.2 equiv.) in 1,4-dioxane (32 mL) were added (5-bromopyrimidin-2-yl)hydrazine (I-16) (5.0 g, 25.4 mmol, 1.0 equiv.) and acetic acid (32 mL). The reaction mixture was stirred at 75°C for 3 hours, then concentrated under reduced pressure. The solid residue was diluted with EtOAc and water, the layers separated, the aqueous phase extracted with EtOAc, the combined organic layers washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified with flash column chromatography over silica gel (tert-butyl methyl ether in dichloromethane) to provide the desired product (I-19) as a solid. [0300] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.21 (s, 2H), 8.18 (s, 1H), 7.53 (br d, 1H), 5.50 (quint, 1H), 1.45 (d, 3H), 1.31 (s, 9H). [0301] Similarly, tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-20) can be prepared from tert-butyl N-[(1S)-2-[(E)-1- (dimethylamino)ethylideneamino]-1-methyl-2-oxo-ethyl]carbamate (I-18) and (5-bromopyrimidin-2- yl)hydrazine (I-16) by applying above protocol in analogy. [0302] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.14 (s, 2H), 7.45 (br d, 1H), 5.47 (quint, 1H), 2.33 (s, 3H), 1.42 (d, 3H), 1.29 (s, 9H).
Figure imgf000096_0003
(I-20) [0303] Similarly, tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-21) can be prepared from tert-butyl N-[(1S)-2-[(E)-1- (dimethylamino)ethylideneamino]-1-methyl-2-oxo-ethyl]carbamate (I-18) and (5-fluoropyrimidin-2- yl)hydrazine (CAS 104408-28-8) by applying above protocol in analogy. [0304] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.06 (s, 2H), 7.41 (br d, 1H), 5.40 (quint, 1H), 2.31 (s, 3H), 1.43 (d, 3 H), 1.28 (s, 9H). 83101 / 109864 FFT
Figure imgf000097_0001
[0305] Similarly, tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-22) can be prepared from tert-butyl N-[(1S)-2-[(E)-1- (dimethylamino)ethylideneamino]-1-methyl-2-oxo-ethyl]carbamate (I-18) and (5-chloropyrimidin-2- yl)hydrazine (CAS 823-90-5) by applying above protocol in analogy. [0306] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.09 (s, 2H), 7.44 (d, 1H), 5.45 (quint, 1H), 2.33 (s, 3H), 1.42 (d, 3H), 1.30 (s, 9H).
Figure imgf000097_0002
Step 4: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23)
Figure imgf000097_0003
[0307] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-19) (5.4 g, 14.6 mmol) in 1,4-dioxane (73 mL) was added a 4.0 M solution of hydrochloric acid in 1,4-dioxane (39 mL, 156 mmol) dropwise at 0°C. The reaction mixture was stirred at room temperature for 5 hours, then concentrated under reduced pressure. The residue was triturated with EtOAc, filtered and the solid dried in vacuo to provide [(1S)-1-[2-(5-bromopyrimidin-2- yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-23). [0308] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.22 (s, 2H), 8.84 (br s, 3H), 8.39 (s, 1H), 5.29 (br m, 1H), 1.64 (d, 3H). LCMS (method 4): retention time 0.17 min, m/z 269/271 [M+H]+ for the corresponding free base. 83101 / 109864 FFT [0309] Similarly, [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-24) can be prepared from tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methyl-1,2,4- triazol-3-yl]ethyl]carbamate (I-20) by applying above protocol in analogy. [0310] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.18 (s, 2H), 8.74 (br s, 3H), 5.25 (m, 1H), 2.41 (s, 3H), 1.61 (d, 3H).
Figure imgf000098_0001
(I-24) [0311] Similarly, [(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-25) can be prepared from tert-butyl N-[(1S)-1-[2-(5-fluoropyrimidin-2-yl)-5-methyl-1,2,4- triazol-3-yl]ethyl]carbamate (I-21) by applying above protocol in analogy. [0312] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.11 (s, 2H), 8.72 (br s, 3H), 5.22 (m, 1H), 2.41 (s, 3H), 1.61 (d, 3H).
Figure imgf000098_0002
(I-25) [0313] Similarly, [(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-26) can be prepared from tert-butyl N-[(1S)-1-[2-(5-chloropyrimidin-2-yl)-5-methyl-1,2,4- triazol-3-yl]ethyl]carbamate (I-22) by applying above protocol in analogy. [0314] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.12 (s, 2H), 8.78 (br s, 3H), 5.25 (m, 1H), 2.40 (s, 3H), 1.61 (d, 3H).
Figure imgf000098_0003
(I-26) Example PI-3: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-31) 83101 / 109864 FFT
Figure imgf000099_0001
Step 1: Preparation of tert-butyl N-[(1S)-2-[[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo- ethyl]carbamate (I-27)
Figure imgf000099_0002
[0315] To a solution of (2S)-2-(tert-butoxycarbonylamino)propanoic acid (5.00 g, 26.4 mmol, 1.0 equiv.) and cyclopropanecarboximidoylammonium chloride (5.74 g, 47.6 mmol, 1.8 equiv.) in N,N- dimethylformamide (130 mL) at room temperature was added 1-[bis(dimethylamino)methylene]-1H- 1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU, CAS 148893-10-1) (20.1 g, 2.0 equiv.), followed by N,N-diisopropylethylamine (12.2 g, 3.5 equiv.). The reaction mixture was stirred at room temperature for 5 hours to afford tert-butyl N-[(1S)-2-[[amino(cyclopropyl)methylene]amino]- 1-methyl-2-oxo-ethyl]carbamate (I-27), which was not isolated. TLC (70% EtOAc in cyclohexane): Rf = 0.21. [0316] Similarly, tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2-oxo-ethyl]carbamate (I-28) can be prepared from (2S)-2-(tert-butoxycarbonylamino)propanoic acid and propanimidoyl- ammonium chloride by applying above protocol in analogy. TLC (50% EtOAc in cyclohexane): Rf = 0.12.
Figure imgf000099_0003
Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-29)
Figure imgf000099_0004
(I-29) 83101 / 109864 FFT [0317] To above solution in N,N-dimethylformamide of tert-butyl N-[(1S)-2- [[amino(cyclopropyl)methylene]amino]-1-methyl-2-oxo-ethyl]carbamate (I-27) were added (5- bromopyrimidin-2-yl)hydrazine (I-16, prepared as described above) (7.99 g, 1.6 equiv.) and acetic acid (16.70 g, 10.0 equiv.). The reaction mixture was heated at 45°C for 90 minutes, then at 60°C for 1 hour. After cooling to room temperature, the mixture was diluted with a saturated aqueous solution of sodium carbonate, and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient ethyl acetate in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-29) as a colorless solid. [0318] 1H NMR (400 MHz, CDCl3) δ ppm: 8.85 (s, 2H), 5.85 (quint, 1H), 5.59 (d, 1H), 2.15 (m, 1H), 1.49 (d, 3H), 1.43 (s, 9 H), 1.10-0.97 (m, 4H). [0319] Similarly, tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-30) can be prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1- methyl-2-oxo-ethyl]carbamate (I-28) and (5-bromopyrimidin-2-yl)hydrazine (I-16) by applying above protocol in analogy. [0320] 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.15 (s, 2H), 7.46 (d, 1H), 5.46 (quint, 1H), 2.69 (q, 2H), 1.41 (d, 3H), 1.30 (s, 9 H), 1.25 (t, 3H).
Figure imgf000100_0001
Step 3: Preparation of [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-31)
Figure imgf000100_0002
(I-31) [0321] tert-Butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-29) (3.2 g, 7.8 mmol) was added to a 4.0 M solution of HCl in ethyl acetate (64.0 mL, 33 equiv.) stirred at 0°C. The reaction mixture was stirred at room temperature for two hours, then evaporated under reduced pressure. The obtained solid material was washed with ethyl acetate 83101 / 109864 FFT and dried in vacuo to afford [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-cyclopropyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-31) as a light yellow solid. [0322] LCMS (method 4): retention time 0.55 min, m/z 309/311 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm: 9.15 (s, 2H), 8.76 (br s, 3H), 5.21 (m, 1H), 2.15-2.05 (m, 1H), 1.59 (d, 3H), 1.08-1.02 (m, 2H), 0.95-0.83 (m, 2H). [0323] Similarly, [(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-32) can be prepared from tert-butyl N-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-ethyl-1,2,4- triazol-3-yl]ethyl]carbamate (I-30) by applying above protocol in analogy. [0324] LCMS (method 4): retention time 0.57 min, m/z 297/299 [M+H]+ of the corresponding free base.1H NMR (400 MHz, DMSO-d6) δ ppm: 9.18 (s, 2H), 8.71 (br s, 3H), 5.26 (m, 1H), 2.77 (q, 2H), 1.61 (d, 3H), 1.30 (t, 3H).
Figure imgf000101_0001
(I-32) Example PI-4: Preparation of (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3- yl]ethanamine (I-34)
Figure imgf000101_0002
(I-34) Step 1: Preparation of 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3- yl]ethyl]isoindoline-1,3-dione (I-33)
Figure imgf000101_0003
(I-33) [0325] To a solution of O-methyl N-[(2S)-2-(1,3-dioxoisoindolin-2-yl)propanoyl]carbamothioate (CAS 2592405-42-8, prepared as described in WO21/165195) (8.4 g, 90 mass%, 26 mmol) in ethanol (170 mL) was added (5-bromopyrimidin-2-yl)hydrazine (I-16) (5.7 g, 1.1 equiv.) at room temperature. 83101 / 109864 FFT The reaction mixture was stirred at 90°C for 5 hours, then cooled to room temperature and diluted with water. The product was extracted with ethyl acetate, the combined organic layers washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by chromatography on silica gel (gradient ethyl acetate in cyclohexane) to afford 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethyl]isoindoline-1,3-dione (I-33) as a colorless solid. [0326] LCMS (method 4): retention time 1.10 min, m/z 429/431 [M+H]+. 1H NMR (400 MHz, DMSO- d6) δ ppm: 8.94 (s, 2H), 7.84 (s, 4H), 6.05 (q, 1H), 3.95 (s, 3H), 1.78 (d, 3H). Step 2: Preparation of (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I- 34)
Figure imgf000102_0001
[0327] To a solution of 2-[(1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3- yl]ethyl]isoindoline-1,3-dione (I-33) (3.0 g, 6.29 mmol) in ethanol (60 mL) was added hydrazine hydrate (0.794 g, 15.7 mmol, 2.5 equiv.) dropwise. The reaction mixture was stirred for 16 hours at room temperature, then the suspension was filtered, and the residue washed with ethanol. The combined filtrates were concentrated under reduced pressure and the obtained solid dried in vacuo to afford (1S)-1-[2-(5-bromopyrimidin-2-yl)-5-methoxy-1,2,4-triazol-3-yl]ethanamine (I-34) as an off- white solid. [0328] LCMS (method 4): retention time 0.44 min, m/z 299/301 [M+H]+. 1H NMR (400 MHz, DMSO- d6) δ ppm: 9.10 (s, 2H), 4.64 (q, 1H), 3.93 (s, 3H), 3.04-3.26 (br s, 2H), 1.37 (d, 3H). Example PI-5: Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-38)
Figure imgf000102_0002
Step 1: Preparation of ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1- yl]thiazole-5-carboxylate (I-35) 83101 / 109864 FFT
Figure imgf000103_0001
[0329] Ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1-yl]thiazole-5- carboxylate (I-35) was prepared from tert-butyl N-[(1S)-2-(1-aminopropylideneamino)-1-methyl-2- oxo-ethyl]carbamate (I-28) and ethyl 2-hydrazinothiazole-5-carboxylate (CAS 859485-62-4) by applying above protocol ‘Example PI-3, step 2’ in analogy. [0330] LCMS (method 4): retention time 1.25 min, m/z 396 [M+H]+. Step 2: Preparation of tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-36)
Figure imgf000103_0002
(I-36) [0331] A mixture of ethyl 2-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-ethyl-1,2,4-triazol-1- yl]thiazole-5-carboxylate (I-35) (5.4 g, 14.2 mmol) and a 2.0 M solution of ammonia in EtOH (540 mL) was stirred at 20°C for 18 hours. The reaction mixture was evaporated under reduced pressure, the solid residue triturated twice with tert-butyl methyl ether (300 mL, then 100 mL), filtered and dried in vacuo to afford tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-36) as a solid. [0332] 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.25 (s, 2H), 7.77 (s, 1H), 7.61 (d, 1H), 5.55 (quint, 1H), 2.68 (q, 2H), 1.40 (d, 3H), 1.34 (s, 9 H), 1.23 (t, 3H). Step 3: Preparation of tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-37)
Figure imgf000103_0003
(I-37) 83101 / 109864 FFT [0333] To a solution of tert-butyl N-[1-[2-(5-carbamoylthiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-36) (4.0 g, 10.9 mmol) in acetonitrile (40 mL) at 20°C was added triethylamine (4.7 mL, 33.6 mmol). The mixture was cooled to 0°C and trifluoroacetic anhydride (3.1 mL, 22.0 mmol) was added dropwise within 10 minutes. After addition, stirring was continued for 30 minutes, then water (100 mL) was carefully added, and the product extracted with EtOAc (total 160 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography over silica gel (gradient EtOAc in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]carbamate (I-37). [0334] 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.62 (s, 1H), 7.64 (d, 1H), 5.52 (quint, 1H), 2.69 (q, 2H), 1.39 (d, 3H), 1.33 (s, 9 H), 1.22 (t, 3H). Step 4: Preparation of [(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38)
Figure imgf000104_0001
(I-38) [0335] [(1S)-1-[2-(5-Cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-38) was prepared from tert-butyl N-[(1S)-1-[2-(5-cyanothiazol-2-yl)-5-ethyl-1,2,4-triazol-3- yl]ethyl]carbamate (I-37) by applying above protocol ‘Example PI-3, step 3’ in analogy. [0336] LCMS (method 4): retention time 0.98 min, m/z 249 [M+H]+ of the corresponding free base. 1H NMR (400 MHz, DMSO-d6) δ ppm: 8.78 (br s, 3H), 8.69 (s, 1H), 5.30 (m, 1H), 2.79 (q, 2H), 1.62 (d, 3H), 1.30 (t, 3H). [0337] Abbreviations used in synthesis schemes and preparatory examples ACN acetonitrile CPME cyclopentyl methyl ether (or methoxy cyclopentane) 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 DMSO dimethyl sulfoxide DMSO-d6 deuterated dimethylsulfoxide DPEN diphenylethylenediamine Et3N triethylamine EtOAc ethyl acetate 83101 / 109864 FFT EtOH ethanol HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) HCl hydrochloric acid MeOH methanol Ms methanesulfonyl (mesyl) NaHCO3 sodium hydrogencarbonate NaOH sodium hydroxide nBu, tBu n-butyl, t-butyl NH4Cl ammonium chloride NPhth phthalimide-1-yl OMs mesylate group OTf triflate group OTs tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride PyBOP benzotriazol-1-yloxy)tripyrrolidino-phosphonium hexafluorophosphate 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 Biological Examples 83101 / 109864 FFT [0338] 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) [0339] 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. [0340] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P11, P13, P14, P15, P16, P17, P18, P19, P21, P22, P23, P24, P25. Example B2: Activity against Diabrotica balteata (Corn root worm) [0341] 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. [0342] 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, P2, P3, P4, P5, P6, P7, P8, P9, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25. Example B3: Activity against Euschistus heros (Neotropical Brown Stink Bug) [0343] 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. [0344] 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, P6, P7, P8, P9, P14, P19, P20, P24, P25. Example B4: Activity against Myzus persicae (Green peach aphid). Intrinsic activity [0345] Test compounds prepared from 10'000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution or a nutrient 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 83101 / 109864 FFT gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation. [0346] The following compounds resulted in at least 80% mortality at a test rate of 12.5 ppm: P2, P4, P5, P6, P7, P8, P9, P11 (sucrose solution) and P4, P6, P11, P14, P15, P17, P18, P19, P20, P21, P24, P25 (nutrient solution). Example B5: Activity against Myzus persicae (Green peach aphid). Feeding/Contact activity [0347] 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. [0348] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P4, P6, P7, P13, P14, P19. Example B6: Activity against Plutella xylostella (Diamond back moth) [0349] 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. [0350] 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, P2, P3, P4, P5, P6, P7, P8, P9, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25. Example B7: Activity against Spodoptera littoralis (Egyptian cotton leaf worm) [0351] 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. [0352] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P11, P12, P13, P14, P15, P16, P18, P19, P20, P21, P22, P23, P24, P25. Example B8: Activity against Frankliniella occidentalis (Western flower thrips). Feeding/Contact activity [0353] 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 83101 / 109864 FFT with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation. [0354] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P2, P7, P8, P24. Example B9: Comparison of the insecticidal activity of compounds P11 and P6 according to the invention with a structurally most closely comparable compounds from the state of the art: [0355] Activity of compounds P11 and P6 according to the preparatory examples and compounds from WO 21/083936 against Spodoptera littoralis (Example B7 above) and Diabrotica balteata (Example B2 above) is summarized in Table B9. Table B9: (NT = not tested) Concentration Mortality Compound Insect (ppm) (%) Compound P11 3.12 Spodoptera littoralis 100 12.5 Diabrotica balteata 100 Present invention Compound P6 3.12 Spodoptera littoralis 100 12.5 Diabrotica balteata 85 Present invention Described in WO 2021/083936 as compound P.93 (page 145) 3.12 Spodoptera littoralis 50 12.5 Diabrotica balteata 20 State of the art 83101 / 109864 FFT 108 Concentration Mortality Compound Insect (ppm) (%) Described in WO 2021/083936 as compound P.94 (page 145) 3.12 Spodoptera littoralis 0 12.5 Diabrotica balteata NT State of the art [0356] Table B9 shows that compounds P11 and P6 according to the invention exert a substantially better insecticidal action on Spodoptera littoralis, and Diabrotica balteata than the compounds from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds. Example B10: Comparison of the insecticidal activity of compound P5 according to the invention with a structurally most closely comparable compounds from the state of the art: [0357] Activity of compounds P5 according to the preparatory examples and of a compound from WO 22/268648 against Chilo suppressalis (Example B1 above) is summarized in Table B10. Table B10: Concentration Mortality Compound Insect (ppm) (%) Compound P5 12.5 Chilo suppressalis 80 Present invention Described in WO 2022/268648 as compound P.10 (page 158) 12.5 Chilo suppressalis 0 State of the art 83101 / 109864 FFT [0358] Table B10 shows that compounds P5 according to the invention exerts a substantially better insecticidal action on Chilo suppressalis than the compound from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds. Example B11: Comparison of the insecticidal activity of compounds P21 and P6 according to the invention with a structurally most closely comparable compounds from the state of the art: [0359] Activity of compounds P21 and P6 according to the preparatory examples and of compounds from WO 23/247360 against Chilo suppressalis (Example B1 above), Diabrotica balteata (Example B2 above), Plutella xylostella (Example B6 above) and Euschistus heros (Example B3 above), is summarized in Table B11. Table B11: Concentration Mortality Compound Insect (ppm) (%) Compound P21 3.12 Chilo suppressalis 80 12.5 Diabrotica balteata 100 Present invention Described in WO 2023/247360 as compound P21 (page 131) 3.12 Chilo suppressalis 0 12.5 Diabrotica balteata 50 State of the art 83101 / 109864 FFT 110 Concentration Mortality Compound Insect (ppm) (%) Described in WO 2023/247360 as compound P68 (page 140) 3.12 Chilo suppressalis 0 12.5 Diabrotica balteata 0 State of the art Described in WO 2023/247360 as compound P20 (page 130) 3.12 Chilo suppressalis 0 12.5 Diabrotica balteata 0 State of the art Compound P6 Plutella 0.8 xylostellaError! Bookmark not 50 12.5 defined. 50 Euschistus heros Present invention Described in WO 2023/247360 as compound P5 (page 127) 0.8 Plutella xylostella 0 12.5 Euschistus heros 0 State of the art 83101 / 109864 FFT 111 Concentration Mortality Compound Insect (ppm) (%) Described in WO 2023/247360 as compound P56 (page 138) 0.8 Plutella xylostella 0 12.5 Euschistus heros 0 State of the art [0360] Table B11 shows that compounds P21 and P6 according to the invention exert a substantially better insecticidal action on Chilo suppressalis, Diabrotica balteata, Plutella xylostella, and Euschistus heros than the compounds from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds. Example B12: Comparison of the insecticidal activity of compounds P11 according to the invention with a structurally most closely comparable compounds from the state of the art: Activity of compound P11 according to the preparatory examples and of a compound from WO 21/177160 and WO 23/247360 against Spodoptera littoralis (Example B7 above), Plutella xylostella (Example B6 above) and Chilo suppressalis (Example B1 above) is summarized in Table B12. Table B12: Concentration Mortality Compound Insect (ppm) (%) Compound P11 0.8 Spodoptera littoralis 50 12.5 Plutella xylostella 100 12.5 Chilo suppressalis 50 Present invention 83101 / 109864 FFT 112 Concentration Mortality Compound Insect (ppm) (%) Described in WO 2021/177160 as compound A-42 (page 66) and in WO 2023/247360 (preparation of compound P68, step 1 p.124) 0.8 Spodoptera littoralis 0 12.5 Plutella xylostella 50 12.5 Chilo suppressalis 0 State of the art Table B12 shows that compound P11 according to the invention exert a substantially better insecticidal action on Spodoptera littoralis, Plutella xylostella and Chilo suppressalis than the compound from the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.

Claims

83101 / 109864 FFT Claims 1. A compound of the formula (I)
Figure imgf000114_0001
wherein R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C3-C6alkenyl, C3- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a is halogen, C1-C2fluoroalkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, or C1-C4alkylsulfonyl; R4 is pyrimidin-4-yl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4a; or R4 is pyrimidin-2-yl which is substituted with a single substituent R4a; or R4 is oxo-pyridazinyl which is N-substituted with a single substituent R4b; R4a is halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; R4b is C1-C3alkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R10 is hydrogen, C1-C3alkyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, or C1-C3alkoxyC1-C3alkyl; and R11 is hydrogen or C1-C3alkyl; 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 R1 is hydrogen, methyl, or cyclopropylmethyl; or wherein R1 is hydrogen or methyl; or wherein R1 is hydrogen. 3. The compound according to claim 1 or 2, wherein R2a is chloro, bromo, iodo, trifluoromethyl, or cyclopropyl; or wherein R2a is chloro, bromo, or cyclopropyl; or wherein R2a is chloro. 83101 / 109864 FFT 4. The compound according to any one of claims 1 to 3, wherein R4 is R4-1, R4-2, R4-3, R4-4, R4-5, R4-6, or R4-7:
Figure imgf000115_0001
where the staggered line represents de connection of R4 to the remainder of the compound of Formula (I). 5. The compound according to claim 4, wherein R4 is R4-1, R4-2, R4-3, R4-4, R4-5, or R4-7; R4a is halogen, cyano, C1-C3haloalkyl, C1-C3alkoxy, -C(O)NR10R11, or -N(R11)C(O)OR10; R10 is hydrogen, methyl, ethyl, cyclopropyl, 1-cyanocyclopropyl, 1-fluorocyclopropyl, 1- chlorocyclopropyl, or cyanomethyl; and R11 is hydrogen or methyl; or wherein R4 is R4-6; and R4b is C1-C3alkyl. 6. The compound according to any one of claims 1 to 5, wherein R10 is hydrogen, methyl, or cyanomethyl; and R11 is hydrogen. 7. The compound according to any one of claims 1 to 6, wherein R4a is fluoro, chloro, bromo, cyano, methoxy, -C(O)NH2, -C(O)NHCH3, -(CO)NHCH2CN, or -NHC(O)OCH3; or wherein R4a is bromo, cyano, methoxy, -C(O)NH2, -C(O)NHCH3, -(CO)NHCH2CN, or -NHC(O)OCH3; or wherein R4a is bromo, cyano, or -C(O)NH2. 8. The compound according to any one of claims 1 to 7, wherein R4 is 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, pyrazin-2-yl, 5-carbamoylthiazol-2-yl, 5-cyanothiazol-2-yl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(cyanomethylcarbamoyl)pyrimidin-4- yl, 6-cyanopyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 5-bromopyrimidin-2-yl, 5- chloropyrimidin-2-yl, 5-fluoropyrimidin-2-yl, or 5-bromopyrazin-2-yl. 9. The compound according to any one of claims 1 to 8, wherein R5 is hydrogen, bromo, methyl, ethyl, methoxy, or cyclopropyl; or wherein R5 is hydrogen, chloro, bromo, methyl, or cyclopropyl; or wherein R5 is hydrogen, methyl, ethyl, or cyclopropyl; or wherein R5 is hydrogen. 10. A composition comprising a compound as defined in any one of claims 1 to 9, one or more auxiliaries and diluent, and optionally one or more other active ingredient. 11. A method 83101 / 109864 FFT (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 9, or of a composition as defined in claim 10; 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 9, or of a composition as defined in claim 10; 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 9, or of a composition as defined in claim 10. 12. 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 9, or a composition as defined in claim 10. 13. A compound of the formula (IIa-1), (IIa-1’), (IIa-1’’), or (IIa-2)
Figure imgf000116_0001
(IIa-1) (IIa-1’) (IIa-1’’) (IIa-2) where R2a is as defined in claim 1 or 3. 14. A compound of formula (IIIc) or of formula (IIIc-1),
Figure imgf000116_0002
X- is a halide, sulfate, carboxylate, or sulfonate anion; preferably X- is a chloride, sulfate, or 2,2,2-trifluoroacetate anion; and X4 is halogen; preferably, X4 is bromo, chloro, or iodo.
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