WO2024133551A1 - Composés de pyridazine à activité pesticide - Google Patents

Composés de pyridazine à activité pesticide Download PDF

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WO2024133551A1
WO2024133551A1 PCT/EP2023/087084 EP2023087084W WO2024133551A1 WO 2024133551 A1 WO2024133551 A1 WO 2024133551A1 EP 2023087084 W EP2023087084 W EP 2023087084W WO 2024133551 A1 WO2024133551 A1 WO 2024133551A1
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spp
compounds
formula
methyl
independently selected
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PCT/EP2023/087084
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Matthias Weiss
Andre Jeanguenat
Jagadeesh Prathap KILARU
Michel Muehlebach
André Stoller
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Syngenta Crop Protection Ag
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Publication of WO2024133551A1 publication Critical patent/WO2024133551A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • A01P7/02—Acaricides
    • 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
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings

Definitions

  • the present invention relates to pesticidally active pyridazine compounds, e.g. as active ingredients, which have pesticidal activity.
  • the invention also relates to preparation of these pyridazine compounds, to intermediates useful in the preparation of these pyridazine compounds, to the 5 preparation of these intermediates, to agrochemical compositions which comprise at least one of these pyridazine compounds, to preparation of these compositions and to the use of these pyridazine compounds or compositions in agriculture or horticulture for controlling animal pests, including arthropods and in particular insects, or representatives of the order Acarina.
  • pesticidally active 3-oxy pyridazine compounds are disclosed herein. 10 WO2021069575, WO2021068179, WO2020208036, WO2020201079, WO2020201398 and WO2020070049 describe pesticidally active pyrazine-amide compounds. It has now surprisingly been found that certain novel pyridazine compounds have pesticidal activity.
  • the present invention therefore provides, in a first aspect, compounds of formula (I) 15 wherein: A is N or CR Y ; R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, aminocarbonylC1-C6alkyl, hydroxycarbonylC1- C6alkyl, C1-C6nitroalkyl, trimethylsilaneC1-C6alkyl, C1-C3alkoxy-C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, 20 C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C4cycloalkyl-C1-C2alkyl, C3-C4cycloalkyl-C1- C2alkyl wherein the C3-C4cycloalkyl group is substituted with 1 or 2 halogen atoms, oxetan-3
  • 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), 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 insects, acarines, nematodes or molluscs, which method 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 of formula (I) or a composition comprising such a compound.
  • the present invention makes available a method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which method comprises treating the propagation material, or the site where the propagation material is planted, with an effective amount of a compound of formula (I) or a composition comprising such a compound.
  • the present invention makes available a plant propagation material, such as a 20 seed, comprising, or treated with or adhered thereto, a compound of formula (I) or a composition comprising such a compound.
  • 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 the first aspect.
  • the present invention further provides a method of controlling ectoparasites on an animal in need 25 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 30 addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as 35 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
  • 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, 82852 FF potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, 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, 82852 FF potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine,
  • 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. 10
  • 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- 15 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-trifluoride radicals methyl
  • C1-Cnhaloalkyl refers to a straight-chain or branched saturated alkyl 20 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- 25 fluoroethyl, 2-chloro-2,2-difluoroethy
  • C1-C2fluoroalkyl would refer to a C1-C2alkyl radical which carries 1, 2, 3, 4 or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.
  • C1-Cnalkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for 35 example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1- methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.
  • C1-Cnhaloalkoxy 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-CnalkoxyC1-Cmalkyl refers to an alkoxy radical having 1 to n carbon atoms (as mentioned above) which is attached via the oxygen atom to an alkyl radical having 1 to m carbon atoms (as mentioned above), which alkyl radical is connected to the rest of the molecule.
  • C1-Cncyanoalkyl refers to a straight chain or branched saturated C1- 5 Cnalkyl 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 -CN: for example, cyanomethyl, 2-cyanoethyl, 2- cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
  • C1-Cnnitroalkyl refers to a straight chain or branched saturated C1- 10 Cnalkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is replaced by a nitro group -NO2: for example, nitromethyl, 2-nitroethyl, 2-nitropropyl, 3- nitropropyl, 1-(nitromethyl)-2-ethyl, 1-(methyl)-2-nitroethyl, 4-nitrobutyl, and the like.
  • C3-Cncycloalkyl refers to 3-n membered cycloalkyl groups such as cyclopropane, cyclobutane, cyclopentane and cyclohexane.
  • C3-C4cycloalkylC1-C2alkyl “ as used herein refers to 3 or 4 membered cycloalkyl group with either a methylene or ethylene group, which methylene or ethylene group is connected to the rest of the molecule.
  • C3-C4cycloalkyl-C1-C2alkyl group is substituted, the substituent(s) can be on the cycloalkyl group and/or on the alkyl group.
  • C3-C6cycloalkylC1-C4haloalkoxy refers to a 3 to 6 membered 25 cycloalkyl group connected to a 1 to 4 membered haloalkoxy group, which haloalkoxy group is connected to the rest of the molecule.
  • aminocarbonylC1-Cnalkyl refers to an alkyl radical where one of the hydrogen atoms in the radical is replaced by CONH2 group.
  • hydroxycarbonylC1-Cnalkyl refers to an alkyl radical where one of the 30 hydrogen atoms in the radical is replaced by COOH group.
  • 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.
  • trimethylsilaneC1-Cnalkyl refers to an alkyl radical where one of the hydrogen atoms in the radical is replaced by a -Si(CH3)3 group.
  • 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-Cnhaloalkenyl refers to a C2-Cnalkenyl moiety substituted with one or more halo atoms which may be the same or different.
  • 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.
  • C2-Cnhaloalkynyl refers to a C2-Cnalkynyl moiety substituted with one 15 or more halo atoms which may be the same or different.
  • Halogen or “halo” is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl.
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O and S. Examples are heteroaryls J-1 to J- 20 39 shown in Scheme A below. Preferred heteroaryl is pyridyl, pyrimidyl, and pyrazolyl.
  • heteroaryl-methyl refers to a heteoaryl connected to a methyl group, which methyl group is connected to the rest of the molecule. Examples of heteroaryl are shown in Table J below. As used herein, the term “substituted heteroaryl-methyl” refers to a heteroaryl-methyl wherein the heteraryl group is substituted by a designated substituent. Preferred heteroaryls include J-3 (4- 25 pyridyl) and J-5 (pyrimidin-2-yl).
  • C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms
  • C3-C4cycloalkyl means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom 5 and C3-C4cycloalkyl substituted with 2 halo atoms.
  • the staggered line as used herein, for example, in table J above, or in group T, represent the point of connection / attachment to the rest of the compound.
  • 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 10 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. 82852 FF 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; 5 the type of application; and other relevant circumstances.
  • compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in the formula (I*) below: where A, R 1 , R 2a , R 2b , R 3 , R 4c , R 5a , R 5b and X are as defined in the first aspect. 10
  • the present invention contemplates both racemates and individual enantiomers.
  • Particularly preferred compounds of the present invention are compounds of formula (I’) where A, R 1 , R 2a , R 2b , R 3 , R 4c , R 5a , R 5b and X are as defined in the first aspect, and stereoisomers, enantiomers, 15 tautomers and N-oxides of the compounds of formula (I’a), and agrochemically acceptable salts thereof.
  • Preferred compounds of formula (I*) include compounds of formula (I*a) as shown below, where X is oxygen, and A, R 1 , R 2a , R 2b , R 3 , R 4c , R 5a , and R 5b 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.
  • Particularly preferred compounds of formula (I’) include compounds of formula (I’a) as shown below, where X is oxygen, and A, R 1 , R 2a , R 2b , R 3 , R 4c , R 5a , and R 5b 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. 5
  • A is: 10 A. N; or B. CR Y ; or C. CH.
  • A is CH.
  • X is: A. S; or B. O. In preferred embodiments of each aspect of the invention, X is oxygen. 20
  • R 1 is A. hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, aminocarbonylC1-C6alkyl, hydroxycarbonylC1-C6alkyl, C1-C6nitroalkyl, trimethylsilaneC1-C6alkyl, C1-C3alkoxy-C1-C6alkyl, C1–C6haloalkyl, C2- C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C4cycloalkylC1-C2alkyl-, C3- C4cycloalkylC1-C2alkyl- wherein the C3-C4cycloalkyl group is substitute
  • R 1 is hydrogen, methyl, or cyclopropyl-methyl. More preferably, R 1 is hydrogen or methyl. Even more preferably, R 1 is hydrogen. In an embodiment of each aspect of the invention, R 2a is A.
  • halogen C1-C3haloalkyl, C1-C3haloalkylsulfanyl, C1-C3haloalkysulfonyl, or C1-C3haloalkoxy; or 20 L. halogen, C1-C2fluoroalkyl, C1-C2fluoroalkylsulfanyl, C1-C2fluoroalkysulfonyl, or C1- C2fluoroalkoxy; or M. chlorine, fluorine, bromine, iodine, difluoromethyl, trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; or N.
  • R 2a is chlorine, bromine, trifluoromethyl, or difluoromethoxy.
  • R 2a is chlorine, bromine, or difluoromethoxy.
  • R 2b is : 35 A.
  • halogen C1-C3haloalkyl, C1-C3haloalkylsulfanyl, C1-C3haloalkysulfonyl, or C1-C3haloalkoxy
  • D halogen, C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkysulfonyl, or C1-C2haloalkoxy
  • E fluorine, chlorine, bromine, iodine, difluoromethyl, trifluoromethyl, trifluoromethylsulfanyl, trifluoromethylsulfonyl; or F.
  • R 2b is bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylsulfonyl, 1-cyano-1-methyl-ethyl, or 1- cyanocyclopropyl.
  • R 2b is bromine, iodine, trifluoromethyl, trifluoromethoxy, or 1- 20 cyanocyclopropyl.
  • A is bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylsulfonyl, 1-cyano-1-methyl-ethyl, or 1- cyanocyclopropyl.
  • R 2a and R 2b are independently selected from halogen, C1-C3haloalkyl, C1-C3haloalkysulfanyl, C1-C3haloalkysulfonyl, and C1-C3haloalkoxy; or 25 B.
  • R 2a and R 2b are independently selected from halogen, C1-C3fluoroalkyl, C1-C3fluoroalkysulfanyl, C1-C3fluoroalkysulfonyl, and C1-C3fluoroalkoxy; or C.
  • R 2a and R 2b are independently selected from chlorine, bromine, iodine, C1-C3fluoroalkyl, C1- C3fluoroalkysulfonyl, and C1-C3fluoroalkoxy; or D. R 2a and R 2b are independently selected from fluorine, chlorine, bromine, iodine, 30 trifluoromethylsulfanyl, trifluoromethylsulfonyl, and trifluoromethyl; or E. R 2a and R 2b are independently selected from chlorine, bromine, iodine, trifluoromethylsulfonyl, and trifluoromethyl; or F.
  • R 2a and R 2b are independently selected from chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy, trifluoromethoxy, and 1-cyanocyclopropyl; or 35 G.
  • R 2a and R 2b are differently selected from chlorine, bromine, iodine, trifluoromethylsulfonyl, and trifluoromethyl; or H.
  • R 2a and R 2b are differently selected from chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy, trifluoromethoxy, and 1-cyanocyclopropyl; or 82852 FF I.
  • R 2a and R 2b are differently selected from chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy, and trifluoromethoxy.
  • R 2a is chlorine, bromine, trifluoromethyl, or difluoromethoxy
  • R 2b is bromine, iodine, difluoromethyl, trifluoromethyl, 5 difluoromethoxy, trifluoromethoxy, trifluoromethylsulfonyl, 1-cyano-1-methyl-ethyl, or 1- cyanocyclopropyl.
  • R 2a is chlorine, bromine, trifluoromethyl, or difluoromethoxy
  • R 2b is bromine, iodine, trifluoromethyl, trifluoromethoxy, or 1-cyanocyclopropyl.
  • R 2a is chlorine, bromine, or difluoromethoxy
  • R 2b is bromine, iodine, trifluoromethyl, trifluoromethoxy, or 1- cyanocyclopropyl.
  • R 2a is chlorine, bromine, or difluoromethoxy
  • R 2b is 10 bromine, iodine, or trifluoromethyl, such as trifluoromethyl.
  • R 2a is chlorine, or difluoromethoxy, such as chlorine, and R 2b is bromine, iodine, or trifluoromethyl, such as trifluoromethyl.
  • R 3 is A. C1-C3alkyl or C1-C3haloalkyl; or 15 B. methyl or trifluoromethyl; or C. methyl.
  • R 3 is methyl.
  • R 4c is: 20 A.
  • C1-C3alkyl optionally substituted with a single substituent selected from cyano, -SCH3, -S(O)CH3, -SO2CH3 and -C(O)NR 4d R 4e ; C1-C3haloalkyl, allyl, propargyl, C3- C6cycloalkylC1-C4alkyl, C1-C2alkoxyC1-C3alkyl, -C(O)NR 4d R 4e ; isopropylideneamino, 1- methylpropylideneamino, 1-ethylpropylideneamino, cyclobutylideneamino, cyclopentylideneamino, cyclohexylideneamino, oxetan-3-ylideneamino, tetrahydrofuran-3- 82852 FF ylideneamino, tetrahydropyran-4-ylid
  • C1-C3alkyl optionally substituted with a single substituent selected from cyano, -SCH3, -S(O)CH3, -SO2CH3 and -C(O)NR 4d R 4e ; C1-C3haloalkyl, allyl, propargyl, C3- C6cycloalkylC1-C4alkyl, C1-C2alkoxyC1-C3alkyl, -C(O)NR 4d R 4e ; isopropylideneamino, 1- methylpropylideneamino, 1-ethylpropylideneamino, cyclobutylideneamino, 15 cyclopentylideneamino, cyclohexylideneamino, oxetan-3-ylideneamino, tetrahydrofuran-3- ylideneamino, tetrahydropyran-4-ylideneamino
  • C3-C4cycloalkylC1-C4alkyl isopropylideneamino, 1-methylpropylideneamino, 15 cyclobutylideneamino, cyclopentylideneamino, oxetan-3-ylideneamino, tetrahydrofuran-3- ylideneamino, pyrimidin-2-yl-methyl, 4-pyridinyl-methyl; or H. hydrogen, methyl, ethyl, cyclopropylmethyl, oxetan-3-ylideneamino, isopropylideneamino, or pyrimidin-2-ylmethyl; or I.
  • R 4f and R 4g are independently selected from methyl, ethyl, propyl, and isopropyl, or R 4f and R 4g form, together with the carbon atom they are attached to, a cyclopropyl, cyclobutyl or cyclohexyl group, or a 4- to 6-membered saturated heterocycle containing one oxygen atom; or 30 B.
  • R 4f and R 4g are independently selected from methyl, ethyl, and propyl, or R 4f and R 4g form, together with the carbon atom they are attached to, a cyclopropyl, cyclobutyl, cyclohexyl, oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl group; C.
  • R 4f and R 4g are independently selected from methyl and ethyl, or R 4f and R 4g form, together with the carbon atom they are attached to, a cyclopropyl, cyclobutyl, cyclohexyl, oxetan-3-yl, 35 tetrahydrofuran-3-yl, tetrahydropyran-4-yl group; or D.
  • R 4f and R 4g are independently selected from methyl and ethyl; or E.
  • R 4f and R 4g form, together with the carbon atom they are attached to, a cyclopropyl, cyclobutyl, cyclohexyl, oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-4-yl group; or 82852 FF F.
  • R 4f and R 4g are independently selected from methyl and ethyl; or R 4f and R 4g form, together with the carbon atom they are attached to, a cyclopropyl, cyclobutyl, or cyclohexyl group; or G.
  • R 4f and R 4g are independently selected from methyl and ethyl; or R 4f and R 4g form, together with the carbon atom they are attached to, an oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-4- 5 yl group; or H. R 4f and R 4g form, together with the carbon atom they are attached to, a cyclopropyl, cyclobutyl, or cyclohexyl group; or I.
  • R 4f and R 4g form, together with the carbon atom they are attached to, an oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-4-yl group; or 10 J.
  • R 4f and R 4g are methyl; or R 4f and R 4g form, together with the carbon atom they are attached to, an oxetan-3-yl group.
  • R 4c is hydrogen, methyl, ethyl, 2,2- difluoroethyl, cyclopropylmethyl, propargyl, or pyrimidin-2-ylmethyl.
  • R 4c is hydrogen, methyl, 15 ethyl, or cyclopropylmethyl. More preferably, R 4c is hydrogen, methyl, or ethyl; such as R 4c is methyl or ethyl.
  • R 5a is A. hydrogen, halogen, CN, C1-C3alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, C1-C3alkoxy or C1- 20 C3haloalkoxy; or B.
  • R 5b is A.
  • R 5a and R 5b are hydrogen.
  • R 6 is A. phenyl, benzyl, heteroaryl, or C3-C6 cycloalkyl, each of which, independently of each other, is optionally substituted with one substituent selected from R x ; or 35 B.
  • R x is independently selected from A. halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy or CN; or B. F, Cl, Br, OCF2H, OCH3 or CN. 82852 FF
  • R Z is independently selected from A. oxo, halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy or CN; or B.
  • R Y is independently selected from A. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, CN and cyclopropyl; or B. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, and cyclopropyl; or 10 C.
  • the present invention accordingly, makes available a compound of formula (I) having the 15 substituents A, R 1 , R 2a , R 2b , R 3 , R 4c , R 5a , R 5b and X as defined above in all combinations and each permutation.
  • compounds of formula (I) are made available, where, for instance, A is CH or nitrogen, preferably A is CH; X is oxygen or sulfur, preferably X is oxygen; R 1 is hydrogen, methyl, ethyl, allyl, propargyl or cyclopropyl-methyl, such as R 1 is hydrogen or methyl; R 2a is halogen, C1-C2fluoroalkyl, 20 C1-C2fluoroalkylsulfanyl, C1-C2fluoroalkysulfonyl, or C1-C2fluoroalkoxy; R 2b is fluorine, chlorine, bromine, iodine, difluoromethyl, trifluoromethyl, trifluoromethylsulfanyl, trifluoromethylsulfonyl; R 3 is C1-C3alkyl or C1-C3haloalkyl, such as R 3 is methyl or trifluoromethyl; R 4c is hydrogen, C1-C1-
  • A is CH or nitrogen, 35 preferably A is CH;
  • X is oxygen or sulfur, preferably X is oxygen;
  • R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, aminocarbonylC1-C6alkyl, hydroxycarbonylC1-C6alkyl, C1-C6nitroalkyl, trimethylsilaneC1-C6alkyl, C1-C3alkoxy-C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2- C6alkynyl, C2-C6haloalkynyl, C3-C4cycloalkyl-C1-C2alkyl, C3-C4cycloalkyl-C1-C2alkyl wherein the C3- C4cycloalkyl group is substituted with 1 or 2 halogen atom
  • A is CH or nitrogen, for instance A is CH;
  • X is oxygen;
  • R 1 is hydrogen, C1-C3alkyl, C1-C3cyanoalkyl, C1-C3alkoxy-C1-C3alkyl, C1–C3haloalkyl, C2- C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3-C4cycloalkylC1-C2alkyl-, benzyloxycarbonyl, or benzyl; such as R 1 is hydrogen, methyl, ethyl, allyl, propargyl or cyclopropyl- 15 methyl;
  • R 2a is chlorine, bromine, trifluoromethyl, or difluoromethoxy;
  • R 2b is bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, triflu
  • A is CH or nitrogen, preferably A is CH; X is oxygen or sulfur, preferably X is oxygen; R 1 is hydrogen, methyl, or cyclopropyl-methyl; R 2a is chlorine, bromine, trifluoromethyl, or difluoromethoxy; R 2b is bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylsulfonyl, 1-cyano-1-methyl-ethyl, or 1- 25 cyanocyclopropyl; R 3 is methyl; R 4c is hydrogen, methyl, ethyl, 2,2-difluoroethyl, cyclopropylmethyl, propargyl, or pyrimidin-2-ylmethyl; and R 5a and R 5b are hydrogen.
  • A is nitrogen; X is oxygen or sulfur, preferably X is oxygen;
  • R 1 is hydrogen, methyl, or cyclopropyl-methyl;
  • R 2a is chlorine, bromine, trifluoromethyl, or difluoromethoxy;
  • R 2b is bromine, iodine, difluoromethyl, trifluoromethyl, 30 difluoromethoxy, trifluoromethoxy, trifluoromethylsulfonyl, 1-cyano-1-methyl-ethyl, or 1- cyanocyclopropyl;
  • R 3 is methyl;
  • R 4c is hydrogen, methyl, ethyl, 2,2-difluoroethyl, cyclopropylmethyl, propargyl, or pyrimidin-2-ylmethyl; and
  • R 5a and R 5b are hydrogen.
  • 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 and R 3 have the same meaning as given above for 20 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
  • X 1 is hydroxy
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide or propanephosphonic acid 82852 FF 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 5 instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate
  • compounds of the formula (II) are either known, or they can be prepared by methods known to a person skilled in the art.
  • compounds of the formula (II) wherein X 1 is a leaving group, such as a halogen, for 10 instance chloride can be formed by treatment of compounds of formula (II) wherein X 1 is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N- dimethylformamide (DMF), in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C.
  • DMF N,N- dimethylformamide
  • DCM dichloromethane
  • THF tetrahydrofuran
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • an organic base such as, for example, triethylamine.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without 5 a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid
  • a Lewis acid such as zinc bromide or titanium(IV) isopropoxide
  • Scheme 3 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 R 1 has the same meaning as given above for compounds of the formula (I), with a compound of the formula (V), wherein 20 Q has the same meaning as given above in Scheme 1, and wherein R 3 has the same meaning as given above for compounds of the formula (I), and X 2 is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide.
  • 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 25 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 25 inorganic base, for instance potassium carbonate
  • an organic base such as, for example, triethylamine.
  • a compound of the formula (I) can be made by reaction of a compound of the formula (IVa), wherein T has the same meaning as given above in Scheme 1, with a compound of the 30 formula (VII), wherein Q has the same meaning as given above in Scheme 1, and wherein R 3 has the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without 82852 FF the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • 82852 FF the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • Scheme 4 Compounds of formula (V) can be made, for example, as shown in scheme 4.
  • a halogenating agent such as chlorine or bromine or N- bromosuccinimide, for example, gives compound of the formula (V), wherein the leaving group X 2 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, 15 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) 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 20 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 25 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 and Q have the same meaning as given above in Scheme 1, and R 3 has the same meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula (VI), wherein R 1 has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen, and wherein X 3 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula 10 (Ib).
  • a leaving group such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, 15 diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance tetrahydrofuran, dioxane, acetonitrile, N,N-dimethylformamide (DMF) or N,N- dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably 5 between ambient temperature and 200 °C, optionally under microwave conditions, with or without the addition of a base, such as an inorganic base, for instance alkali metal carbonates such as sodium, potassium or cesium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or sodium or potassium tert-butoxide, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance tetrahydrofuran,
  • the reaction can be done in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst, for example palladium acetate, and in the presence of a ligand, such as a phosphine ligand, for example 2-dicyclohexyl-phosphino-2′,4′,6′-triisopropylbiphenyl (XPhos).
  • a catalyst such as a metal catalyst, for instance a palladium catalyst, for example palladium acetate
  • a ligand such as a phosphine ligand, for example 2-dicyclohexyl-phosphino-2′,4′,6′-triisopropylbiphenyl (XPhos).
  • a base such as an alkoxide or a carboxylate base, for instance potassium acetate.
  • the reaction can be done neat or in a solvent, for instance in dioxane or toluene as a solvent, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 100 °C.
  • a solvent for instance in dioxane or toluene as a solvent, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 100 °C.
  • Scheme 8 Compounds of the formula (Ic), wherein T has the same meaning as given above in Scheme 1, 10 and wherein R 1 , R 3 , R 4c , R 5a and R 5b have the same meaning as given above for compounds of the formula (I), can be made (Scheme 8) from compounds of the formula (XVII), wherein T has the same meaning as given above in Scheme 1, and wherein R 1 , R 3 , R 5a and R 5b have the same meaning as given above for compounds of the formula (I), and in which X 5 is a leaving group such as for example chlorine, bromine or iodine, by reaction with compounds of the formula (XVI), in which R 4c has the same 15 meaning as defined above for compounds of the formula (I), and M 1 is a metal-containing substituent which has the same meaning as given above in Scheme 7.
  • the reaction can be done in the presence of a catalyst, such as a palladium catalyst, for instance 1,1'-bis(diphenylphosphino)- ferrocene]palladium(II) dichloride (PdCl2dppf), in the presence of a base, such as a carbonate base, for example cesium carbonate Cs2CO3, or such as a carboxylate base, for instance potassium acetate.
  • a catalyst such as a palladium catalyst, for instance 1,1'-bis(diphenylphosphino)- ferrocene]palladium(II) dichloride (PdCl2dppf)
  • a base such as a carbonate base, for example cesium carbonate Cs2CO3, or such as a carboxylate base, for instance potassium acetate.
  • the 20 reaction can be done neat or in a solvent, for instance in dioxane or toluene as a solvent, at a temperature between -100 °C
  • Scheme 9 Compounds of the formula (Id), a subset of compounds of formula (I) wherein R 4c is hydrogen, 10 and wherein T has the same meaning as given above in Scheme 1, and wherein R 1 , R 3 , R 5a and R 5b have the same meaning as given above for compounds of the formula (I), can be made (Scheme 9) by treatment of compounds of the formula (Ic), wherein T has the same meaning as given above in Scheme 1, and wherein R 1 , R 3 , R 4c , R 5a and R 5b have the same meaning as given above for compounds of the formula (I), preferably in this transformation R 4c is methyl or ethyl (even more preferably R 4c is methyl), 15 with an acid such hydrochloric acid, for example in form of a solution of gasous hydrochloric acid in an inert organic solvent (for instance dioxane), in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane, and
  • boron tribromide (BBr3) may be used as a reagent 20 for this ether cleavage (demethylation), under conditions known to a person skilled in the art.
  • Scheme 10 5 Compounds of the formula (IIIa), 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), a subset of compounds of formula (III) above in which R 1 is hydrogen, wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), may be made (Scheme 10) from 10 compounds of the formula (VII-1), a subset of compounds of formula (VII), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), by a reductive amination reaction under analogous conditions already described above in Scheme 2 (transformation VII into III).
  • a hydrohalide salt preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt
  • Scheme 10 5
  • compounds of the formula (VII-1), a subset of compounds of formula (VII), wherein 25 R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), may 82852 FF be made by oxidation of compounds of the formula (XXXI) described below (Scheme 11), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), for example using Dess-Martin periodinane (or similar hypervalent iodine reagents), commonly conducted in chlorinated solvents, such as dichloromethane or chloroform, at temperatures between 0 and 50 °C, 5 preferably around room temperature.
  • chlorinated solvents such as dichloromethane or chloroform
  • Such a reaction involves treating compounds of the formula (XXXI) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide (HNPhth) or bis(tert- butoxycarbonyl)amine (HNBoc2), in an inert solvent, such as for example tetrahydrofuran, and in a temperature range of -10°C to 60°C, for instance between 0°C and 30°C.
  • an azodicarboxylate such as diethyl azodicarboxylate or diisopropyl azodicarboxylate
  • a phosphine such as triphenylphosphine or tributylphosphine
  • an amine such as phthalimide (HNPhth
  • the reaction can be done in a temperature range of -10°C to 80°C, for instance between 0°C and 30°C.
  • deprotection reactions are known to a person skilled in the art, and described in the literature, for instance in: Protective Groups in Organic Synthesis, 3rd Edition Theodora 20 W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company). John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9.
  • compounds of the formula (XXXI), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I) may be made by reduction of compounds of the formula (VII-1) described above (Scheme 10), a subset of compounds of formula (VII), wherein 25 R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), for example with sodium borohydride NaBH4, under conditions known known to a person skilled in the art (see for example WO2012/082997, p.141), preferably in MeOH as solvent.
  • the lithium- or magnesium species thus generated can be transmetalated, for instance with a zinc halide, for example zinc chloride, and subsequently coupled with compounds of the formula (XV), wherein R 4c has the same meaning as defined above for 82852 FF compounds of the formula (I), except that R 4c is different from hydrogen, and X 4 is a leaving group, such as a halogen, for example a bromide or iodide, in the presence of a catalyst, for instance a palladium catalyst, for example tris(dibenzylideneacetone)dipalladium(0), and of a ligand, for instance a phosphine ligand, such as for example tri(2-furyl)phosphine, in an inert solvent, such as for example 5 tetrahydrofuran, optionally in the presence of a co-solvent such as toluene.
  • a catalyst for instance a palladium catalyst, for example tris(dibenzylideneace
  • (2- dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) [2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate (SPhos Pd G3, a stable phosphine-ligated palladium precatalyst), and related palladacycle precatalysts, can also be used as a catalyst.
  • the reaction can be done in a temperature range of -100°C to 100°C, for instance between -78°C and 80°C.
  • the reaction can be done in a temperature range of 0°C to 100°C, for instance between 10°C and 80°C.
  • Such silylation reactions are known to a person skilled in the art, and described in the literature, such 25 as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company). John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9.
  • This reaction can be done neat or in a solvent, for instance in an organic solvent, such as for example in tetrahydrofuran as a solvent.
  • the reaction can be done in a temperature range of -100°C to 100°C, for instance between -80°C and 0°C, for example at 0°C or at -78°C.
  • Scheme 12 15 82852 FF Compounds of formula (IIIb), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R 1 , R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), may be made (Scheme 12) by treatment of compounds of formula (IIIa-1), or a salt thereof, wherein R 3 , 5 R 4c , R 5a and R 5b have same meaning as defined above for compounds of the formula (I), with compounds of formula (XXXVII), wherein R 1 is as defined in formula I, by a reductive amination reaction under analogous conditions already described above in Scheme 2 (transformation VII into III).
  • a hydrohalide salt preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt
  • Compounds of formula (IIIa-1), or a salt thereof, wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), may be obtained by biocatalyzed 10 deracemization of compounds of formula (IIIa), or a salt thereof, wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I). This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • a lipase e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase
  • Scheme 13 In an alternative process (Scheme 13), compounds of formula (IIIa-1), or a salt thereof, wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), may 25 be obtained from compounds of the formula (XXX-1), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I) and Z3 is -NPhth (N-phthalimide group) or - 82852 FF NBoc2 (N-bis(tert-butyloxycarbonyl) group), under deprotection conditions already described above in Scheme 11 (transformation XXX into IIIa).
  • Such reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)- 15 TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • compounds of formula (IIIa-1), or a salt thereof, wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I) may be obtained by reduction of azide compounds of formula (XXXVIII), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined 20 above for compounds of the formula (I), by treatment with for instance triphenylphosphine (or tributylphosphine) and water (2 steps Staudinger reduction), or by hydrogenation using for example a palladium catalyst in the presence of hydrogen. Procedures and conditions for such azide reductions are well known to a person skilled in the art, and known from the literature and text books.
  • Compounds of formula (XXXVIII), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as 25 defined above for compounds of the formula (I), may be obtained by treatment of alcohol compounds of the formula (XXXI-1), wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of the formula (I), with an azidation reagent such as diphenyl phosphoryl azide (amongst others like sodium azide, trimethylsilyl azide or tetrabutylammonium azide), in a solvent such as toluene, tetrahydrofuran or 2-methyltetrahydrofuran, in the presence of a base such as for example 1,8- 30 diazabicyclo(5.4.0)undec-7-ene DBU, and at temperatures preferably around room temperature.
  • an azidation reagent such as diphenyl phosphoryl azide (amongst others like sodium azide, tri
  • the reactants can be reacted in the presence of a base.
  • 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 5 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, 10 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).
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.
  • bases which are employed in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.
  • the reactions are advantageously carried out in a temperature range from approximately -80°C 20 to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • Salts of compounds of formula (I) can be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds of formula (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts 35 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. 82852 FF 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.
  • 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 5 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 10 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.
  • 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 15 physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid 20 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 25 separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give
  • N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2O2/urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • Tables A-1 to A-21 10 Table A-1 provides 25 compounds A-1.001 to A-1.025 of formula I-A wherein R1 is H, R 3 is CH3, R 4c is H and T are as defined in table Z.
  • compound A-20.007 is (A-20.007).
  • Table A-2 provides 25 compounds A-2.001 to A-2.025 of formula I-A wherein R1 is H, R 3 is CH3, R 4c is CH3 and T are as defined in table Z.
  • Table A-3 provides 25 compounds A-3.001 to A-3.025 of formula I-A wherein R1 is H, R 3 is CH3, R 4c is CH2CH3 and T are as defined in table Z.
  • Table A-4 provides 25 compounds A-4.001 to A-4.025 of formula I-A wherein R1 is H, R 3 is CH3, R 4c is CH2CHF2 and T are as defined in table Z.
  • Table A-5 provides 25 compounds A-5.001 to A-5.025 of formula I-A wherein R 1 is H, R 3 is CH 3 , R 4c is 20 CH2-cyclopropyl and T are as defined in table Z.
  • Table A-6 provides 25 compounds A-6.001 to A-6.025 of formula I-A wherein R1 is H, R 3 is CH3, R 4c is pyrimidin-2-ylmethyl and T are as defined in table Z. 82852 FF
  • Table A-7 provides 25 compounds A-7.001 to A-7.025 of formula I-A wherein R1 is H, R 3 is CH3, R 4c is propargyl and T are as defined in table Z.
  • Table A-8 provides 25 compounds A-8.001 to A-8.025 of formula I-A wherein R1 is CH3, R 3 is CH3, R4c is H and T are as defined in table Z.
  • Table A-9 provides 25 compounds A-9.001 to A-9.025 of formula I-A wherein R1 is CH3, R 3 is CH3, R 4c is CH3 and T are as defined in table Z.
  • Table A-10 provides 25 compounds A-10.001 to A-10.025 of formula I-A wherein R1 is CH3, R 3 is CH3, R 4c is CH2CH3 and T are as defined in table Z.
  • Table A-11 provides 25 compounds A-11.001 to A-11.025 of formula I-A wherein R1 is CH3, R 3 is CH3, 10 R 4c is CH2CHF2 and T are as defined in table Z.
  • Table A-12 provides 25 compounds A-12.001 to A-12.025 of formula I-A wherein R1 is CH3, R 3 is CH3, R 4c is CH2-cyclopropyl and T are as defined in table Z.
  • Table A-13 provides 25 compounds A-13.001 to A-13.025 of formula I-A wherein R1 is CH3, R 3 is CH3, R 4c is pyrimidin-2-ylmethyl and T are as defined in table Z.
  • Table A-14 provides 25 compounds A-14.001 to A-14.025 of formula I-A wherein R1 is CH3, R 3 is CH3, R 4c is propargyl and T are as defined in table Z.
  • Table A-15 provides 25 compounds A-15.001 to A-15.025 of formula I-A wherein R1 is CH2-cyclopropyl, R 3 is CH3, R 4c is H and T are as defined in table Z.
  • Table A-16 provides 25 compounds A-16.001 to A-16.025 of formula I-A wherein R1 is CH2-cyclopropyl, 20 R 3 is CH3, R 4c is CH3 and T are as defined in table Z.
  • Table A-17 provides 25 compounds A-17.001 to A-17.025 of formula I-A wherein R1 is CH2-cyclopropyl, R 3 is CH3, R 4c is CH2CH3 and T are as defined in table Z.
  • Table A-18 provides 25 compounds A-18.001 to A-18.025 of formula I-A wherein R1 is CH2-cyclopropyl, R 3 is CH3, R 4c is CH2CHF2 and T are as defined in table Z.
  • 25 Table A-19 provides 25 compounds A-19.001 to A-19.025 of formula I-A wherein R1 is CH2-cyclopropyl, R 3 is CH3, R 4c is CH2-cyclopropyl and T are as defined in table Z.
  • Table A-20 provides 25 compounds A-20.001 to A-20.025 of formula I-A wherein R1 is CH2-cyclopropyl, R 3 is CH3, R 4c is pyrimidin-2-ylmethyl and T are as defined in table Z.
  • Table A-21 provides 25 compounds A-21.001 to A-21.025 of formula I-A wherein R1 is CH2-cyclopropyl, 30 R 3 is CH3, R 4c is propargyl and T are as defined in table Z. 82852 FF 82852 FF Index T Index T Index T 8 17 9 18 Also made available are certain intermediate compounds of formulae III-1(i), III-2(i), III’-1(i), and III’-2(i), which are novel, and are shown in Table T-III below: Table T-III: Intermediate compounds of formulae III-1(i), III-2(i), III’-1(i), and III’-2(i) X- X- III’-1(i) III-1(i) III-2(i) III’-2(i) 5 wherein R 4c are as defined in any one of the Tables A-1 to A-21, and wherein X- is an anion, i.e.
  • 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.
  • R 4c is hydrogen, methyl or ethyl. 15 82852 FF
  • 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 5 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.
  • 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 spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., Ixodes spp., Olygonychus spp, Orni
  • Tetranychus spp. from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; 20 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
  • Trogoderma spp. 30 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
  • 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 82852 FF 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,
  • Vespa spp. from the order Isoptera, for example, Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis 30 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, C
  • Trichodectes spp. from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea 10 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.
  • 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 20 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 25 nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belono
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which 5 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 15 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 20 oilseed rape, mustard, poppies, olives, sunflowers, coconut, 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
  • 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 30 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, 35 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 20 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, 30 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
  • 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 82852 FF more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • 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 5 proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vip1, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • 10 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, e
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, 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- 25 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-451878 and WO 03/052073.
  • transgenic plants are generally known to the person 30 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-0367 474, 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 35 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 82852 FF 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);
  • transgenic crops are: 10 1.
  • 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.
  • 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. 25 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.
  • 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 82852 FF from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Bioschreib und Nachhaltmaschine, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 5 2003, (https://bats.ch).
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis- related proteins” (PRPs, see e.g. EP-A-0392225).
  • PRPs pathogenesis- related proteins
  • Examples of such antipathogenic substances and 10 transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353191.
  • 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, 15 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 tolerance to abiotic stress include those that have enhanced tolerance to drought, 20 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 25 “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, for example the viral KP1, KP4 or KP6 toxins
  • stilbene synthases such as the viral KP1, KP4 or KP6 toxins
  • bibenzyl synthases such as
  • compositions according to the invention are the protection of stored 30 goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention provides a compound of the first aspect for use in therapy.
  • the present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal.
  • the present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal.
  • the present invention further provides a compound of the first aspect, for use in preventing and/or treating diseases transmitted by ectoparasites.
  • the present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal.
  • the present invention further provides the 82852 FF 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 5 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 15 and a non-mammal, such as a bird or fish.
  • 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 20 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; 25 Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros.
  • Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates.
  • Insects include, but are not limited to, members of the orders: Siphonaptera, 30 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 35 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 82852 FF 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.
  • 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 5 the degree of infestation; the specific disease or disorder involved; the degree of involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances.
  • the compounds of the invention may be administered to the animal by any route which has the 10 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 https://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, 30 to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS indoor residual spraying
  • a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor 82852 FF surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO2006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • 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: 15 Table A. Examples of exotic woodborers of economic importance.
  • the 5 present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. 10 (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g.
  • Ataenius spp. e.g. Black turfgrass ataenius, A. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls
  • Margarodes spp. mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch 15 dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the 20 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.
  • parasites are: Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp.
  • Phtirus spp. Solenopotes spp.; 30 Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes 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., 82852 FF Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp
  • Siphonapta 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, Blattelagermanica 10 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., Hyalo
  • 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 25 rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.
  • hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as 30 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.
  • the compounds of formulae (I), and (I’), or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, 35 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, 82852 FF Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • the compounds of formulae (I), and (I’), or salts thereof, are especially suitable for controlling one or more of pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips 5 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, 10 Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
  • pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, 10 Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
  • the compounds of formulae (I), and (I’), or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.
  • a compound TX controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, 20 Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilaparvata lugens + TX, My
  • one compound from Tables A-1 to A-21, and Table P is 25 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 padi, and Chilo suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.
  • one compound from Tables A-1 to A-21, and Table P is suitable for 30 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, 35 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 82852 FF 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.
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, 5 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.
  • 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 15 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 20 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 25 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.
  • the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum 35 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-dimethylformamide, dimethyl sulfoxide, 1,4- 82852 FF dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenz
  • 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 25 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
  • 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, 35 corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, 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 82852 FF 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 5 an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a 20 suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible 25 formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo-emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • 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 % 30 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 % 35 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 % 82852 FF Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % 5 solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.1 to 30 %,
  • 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.
  • 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 15 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 + 15 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 30 AQ178 + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, 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® + TX, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, 35 Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Bari
  • aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage® + TX, Bakflor®) + TX, Beauveria bassiana 5 (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp.
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, 10 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® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX TX
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum 20 acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® + TX, Biofox C®) + TX, Fusarium proliferatum + TX, 30 Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, 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® 82852 FF 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 5 pulcherrima + TX, Microdochium dimerum (
  • TX Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina) + TX; + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans 15 + 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 20 aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX,
  • Rhizobia Distal® + TX, Vault®
  • Rhizoctonia + TX Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula 30 graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp.
  • TX Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + 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® + TX, Spexit®) + TX, Spodoptera 35 littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces hygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, TX
  • 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® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G® + TX, Trichoderma harzianum T- 5 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 + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, 10 Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp.
  • TX Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • Poae 15 (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus + TX; azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® e.g.
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa® + TX, DacDigline® + TX, Minex®) + TX, Delphastus catalinae (Delphastus®) + 25 TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea
  • 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, 30 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 + TX
  • Bacillus sp. in particular strain D747 (available as DOUBLE 10 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
  • 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 15 QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S. Patent No.
  • NRRL B-21856 (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940 + TX, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and 25 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 from Lesaffre et Compagnie (e..g CNCM No.1-393, CNCM No.1-3937, CNCM No
  • DSM 23117 35 (available as RHIZOVITAL® from ABiTEP, DE) + TX
  • Bacillus amyloliquefaciens in particular strain D747 (available as Double NickelTM 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.
  • Patent No.6,245,551 + TX, Bacillus subtilis CX-9060 from Certis USA LLC + TX, Bacillus subtilis IAB/BS03 (AVIVTM from STK Bio-Ag Technologies + TX, PORTENTO® from Idai Nature) + TX, 10 Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX, Bacillus subtilis strain BU1814 + TX, (available as VELONDIS® PLUS + TX, 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) + TX, having Accession Number NRRL B-50595 + TX, U.S.
  • Patent No.5,061,495 + TX Bacillus subtilis strain 15 Y1336 (available as BIOBAC® WP from Bion-Tech + TX, Taiwan + TX, registered as a biological fungicide in Taiwan under Registration Nos.4764 + TX, 5454 + TX, 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 + TX, Taiwan + TX, 20 registered as a biological fungicide in Taiwan under Registration Nos.4764 + TX, 5454 + TX, 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.
  • CABI 353812 e.g. BIOKUPRUMTM by AgriLife
  • TX Chaetomium globosum (available as RIVADIOM® by Rivale) + TX
  • Cladosporium cladosporioides strain H39, having Accession No. 5 CBS122244, US 2010/0291039 (by Stichting Moowgrass Onderzoek) + TX
  • Coniothyrium minitans in particular strain CON/M/91-8 (Accession No. DSM9660, e.g.
  • 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
  • Gliocladium roseum also known as 15 Clonostachys rosea f rosea
  • strain 321U from Adjuvants Plus strain ACM941 as disclosed in Xue A.G.
  • IMI 392151 e.g., BIO-TAMTM from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A.
  • CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938, or CNCM No.1- 3939 (WO 2010/086790)) + TX, Saccharomyces cerevisiae, in particular strain LASO2 (from 30 Agro-Levures et Dérivés) + TX, Simplicillium lanosoniveum strain T34 ((e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro, or 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. 35 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
  • 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
  • 82852 FF Trichoderma atroviride strain NMI no. V08/002388 + TX, Trichoderma atroviride strain NMI no.
  • Trichodex® from Makhteshim, US + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro) + TX, + 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 20 harzianum strain TH35 (e.g.
  • Trichoderma polysporum strain IMI 206039 e.g. Binab TF WP by BINAB Bio-Innovation AB + TX, Sweden
  • Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX
  • Trichoderma virens also known as Gliocladium virens
  • strain GL-21 e.g. SoilGard by Certis, US
  • Trichoderma virens strain G-41 + TX formerly known as Gliocladium virens (Accession 25 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. + TX, 1993 + TX, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1 (e.g. Trianum- P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No.
  • NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
  • TX 30 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; bacteria including a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 35 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation), 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 H23
  • 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 + TX, WO 2017/205258
  • Bacillus 5 amyloliquefaciens TJ1000 available as QUIKROOTS® from Novozymes
  • Bacillus cereus family member EE128 NRRL No.
  • 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, 25 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, + TX, Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from 30 Bayer CropScience) + TX, Thiobacillus sp. (e.g.
  • the designation is not a “common name”, the nature of the designation used instead is given 82852 FF 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-21, and Table P with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-21, 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 10 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 1:1
  • 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 20 Tables A-1 to A-21, 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 composed 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 sequential 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 25 (I) and the active ingredients as described above is not essential for working the present invention.
  • 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, 30 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, 30 for example bactericides, fungicides, nemato
  • 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.
  • 82852 FF 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 5 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 ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application).
  • granules can 10 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 15 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 20 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).
  • 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.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I).
  • a composition comprising a plant propagation material treated with 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 35 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 82852 FF example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m 2 .
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - 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 % 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 82852 FF active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % 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 % Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in 5 a suitable mill. Such powders can also be used for dry dressings for seed.
  • 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 % 82852 FF silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 %
  • 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.
  • 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 %
  • 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 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 20 suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil 25 dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo- emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • Method 1 Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and 20 an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • Method 2 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 30 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.
  • an electrospray source Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation 30 Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L
  • the reaction mixture was stirred at room temperature for 1 hour, then diluted with water and ethyl acetate. The layers were separated, the aqueous phase extracted with ethyl acetate, the combined organic layers washed with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified 10 by flash chromatography (ethyl acetate in cyclohexane) to afford the title compound which was further triturated with diethyl ether.
  • Example 2 Preparation of 3-chloro-N-[1-[3-(6-hydroxypyridazin-3-yl)pyrazin-2-yl]ethyl]-5- (trifluoromethyl)benzamide (compound P13) 20 To a solution of 3-chloro-N-[1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethyl]-5- (trifluoromethyl)benzamide (compound P12, prepared from 3-chloro-5-(trifluoromethyl)benzoic acid and intermediate I-9 by following in analogy preparation Example 1 above) (31.0 mg, 0.071 mmol) in 1,4-dioxane (0.24 mL) was added hydrochloric acid (4.0M solution in 1,4-dioxane, 0.0195 mL, 0.078 mmol).
  • Example PI-2 Preparation of 1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethanamine (compound I-9) 82852 FF Step A: Preparation of 1-(3-iodopyrazin-2-yl)ethanol (Int-A) Under an argon atmosphere THF (35 mL) was cooled to 0°C. Then 2,2,6,6-tetramethylpiperidine (5.4 5 mL, 30.9 mmol, 1.34 equiv.) was added at 0°C followed by a dropwise addition of 2.5M n-BuLi (12 mL, 29.98 mmol, 1.3 equiv.).
  • reaction mixture was cooled to -78°C, then a solution of 2-iodopyrazine (5.0 g, 23.06 mmol, 1.0 equiv.) in THF (5 mL) was added dropwise. After stirring for 1 hour, acetaldehyde (12 mL, 210 mmol, 9.2 equiv.) was added dropwise at -78°C. After addition, the reaction mixture was allowed to warm up to room temperature before it was quenched with saturated aqueous ammonium 10 chloride solution. The reaction mixture was diluted with water and a mixture of TBME and ethyl acetate. The aqueous layer was acidified with 1M HCl to pH 1-2.
  • Step B Preparation of tert-butyl-[1-(3-iodopyrazin-2-yl)ethoxy]-dimethyl-silane (Int-B) (Int-B) 20
  • Int-A 1-(3-iodopyrazin-2-yl)ethanol
  • Int-A tert-butyldimethylchlorosilane
  • Step C Preparation of tert-butyl-[1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethoxy]-dimethyl-silane 5 (compound I-6) (I-6)
  • I-B tert-butyl-[1-(3-iodopyrazin-2-yl)ethoxy]-dimethyl-silane
  • Step D Preparation of 1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethanol (compound I-7) 82852 FF
  • a solution under argon of tert-butyl-[1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethoxy]-dimethyl- silane (I-6) (548 mg, 1.58 mmol) in THF (15.8 mL) at 0°C was added tetrabutylammonium fluoride (1M solution in THF, 2.4 mL, 2.4 mmol).
  • Step E Preparation of 2-[1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (compound I-8) (I-8) 20
  • I-7 1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethanol (I-7) (330 mg, 1.42 mmol), phthalimide (232 mg, 1.56 mmol) and triphenylphosphine (452 mg, 1.71 mmol) in THF (4.3 mL) at 0°C was added diisopropyl azodicarboxylate (0.376 mL, 383 mg, 1.71 mmol).
  • the reaction mixture was stirred at 0°C for 20 minutes, then at room temperature for 1.7 hours.
  • the mixture was diluted with water and ethyl acetate, the layers were separated and the aqueous phase extracted once with ethyl 25 acetate.
  • the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
  • the residue was purified by flash column chromatography (gradient ethyl acetate in cyclohexane) 82852 FF to afford 2-[1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (I-8), as a white solid.
  • Step F Preparation of 1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethanamine (compound I-9) 10
  • 2-[1-[3-(6-methoxypyridazin-3-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (I-8) 420 mg, 1.16 mmol
  • EtOH aqueous sulfonitrile
  • hydrazine monohydrate 0.068 mL, 1.40 mmol
  • 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, 20 1.5 ppm, 0.8 ppm or 0.2 ppm.
  • Example B1 Activity against Chilo suppressalis (Striped rice stemborer) 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- 25 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 in at least one of the three categories 30 (mortality, anti-feedant effect, or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15.
  • Example B2 Activity against Diabrotica balteata (Corn root worm) Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test 35 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. 82852 FF The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15.
  • Example B3 Activity against Frankliniella occidentalis (Western flower thrips). Feeding/contact activity Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P13. 10
  • Example B4 Activity against Myzus persicae (Green peach aphid).
  • Feeding/Contact activity Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after 15 infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P6, P8, P9, P13, P14, P15.
  • Example B5 Activity against Myzus persicae (Green peach aphid). Intrinsic activity 20 Test compounds prepared from 10’000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution.
  • Example B6 Activity against Plutella xylostella (Diamond back moth) 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 30 10'000 ppm DMSO stock solutions by pipetting.
  • Example B7 Activity against Spodoptera littoralis (Egyptian cotton leaf worm) 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 82852 FF 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.
  • Example B8 Activity against Pseudoplusia includens (Soybean looper). Larvicide, feeding/contact 10 Soybean plants were treated in a spray chamber, cut off and placed into petri dishes containing wet filter paper.1d after application leaves were infested with 5 L2 larvae and covered with a fabric filter and plastic lids.5 days after infestation the samples were assessed for mortality and growth inhibition.
  • Example B9 Comparison of the insecticidal activity of compound P10 with structurally comparable compounds from the state of the art Table B9 shows the activity of compound P10 (Table P) according to the preparatory examples, and of structurally similar compounds from WO2020/070049 and WO2023/072849, against Spodoptera 20 littoralis (Example B7 above), Plutella xylostella (Example B6 above) and Chilo suppressalis (Example B1 above). The tests were performed as described in Examples B7, B6 and B1 above.
  • Table B9 Compound Concentration (ppm) Insect Mortality (%) Compound P10 (present application) Comparative 82852 FF Compound Concentration (ppm) Insect Mortality (%) Compound P11 in WO23/072849 Comparative This shows that compound P10 has a substantially better insecticidal action against Spodoptera littoralis, Plutella xylostella and Chilo suppressalis, than some compounds from the state of the art. This enhanced effect could not be expected in view of the structural similarity of these compounds.
  • Example B10 Comparison of the insecticidal activity of compound P13 according to the invention with structurally most closely comparable compounds from the state of the art: Table B10 shows the activity of compound P13 (Table P) according to the preparatory examples, and of structurally similar compounds from WO2020/070049 and WO2023/072849, against Spodoptera 10 littoralis (Example B7 above), Plutella xylostella (Example B6 above) and Chilo suppressalis (Example B1 above). The tests were performed as described in Examples B7, B6 and B1 above.
  • Table B10 Compound Concentration (ppm) Insect Mortality (%) Compound P13 (present application) Comparative 82852 FF Compound Concentration (ppm) Insect Mortality (%) Compound P7 in WO23/072849 Comparative Table B10 shows that compound P13 has a moderately to substantially better insecticidal action against Spodoptera littoralis, Plutella xylostella and Chilo suppressalis, than some compounds from the state of the art. This enhanced effect could not to be expected in view of the structural similarity of these 5 compounds.

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Abstract

Les composés de formule (I), les substituants étant tels que définis dans la revendication 1, et les stéréoisomères, énantiomères, tautomères, N-oxydes et sels agrochimiquement acceptables de ces composés, peuvent être utilisés en tant qu'insecticides.
PCT/EP2023/087084 2022-12-21 2023-12-20 Composés de pyridazine à activité pesticide WO2024133551A1 (fr)

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