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WO2024022910A1 - Dérivés de 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]éthyl]-3-[2,4-dichloro-5-phényl]urée et composés similaires utilisés comme pesticides - Google Patents

Dérivés de 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]éthyl]-3-[2,4-dichloro-5-phényl]urée et composés similaires utilisés comme pesticides Download PDF

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Publication number
WO2024022910A1
WO2024022910A1 PCT/EP2023/070002 EP2023070002W WO2024022910A1 WO 2024022910 A1 WO2024022910 A1 WO 2024022910A1 EP 2023070002 W EP2023070002 W EP 2023070002W WO 2024022910 A1 WO2024022910 A1 WO 2024022910A1
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spp
compounds
hydrogen
alkyl
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PCT/EP2023/070002
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Inventor
Matthias Weiss
Andre Jeanguenat
Jagadeesh Prathap KILARU
Michel Muehlebach
Christopher Charles SCARBOROUGH
André Stoller
Lars SUESSE
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Syngenta Crop Protection Ag
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Publication of WO2024022910A1 publication Critical patent/WO2024022910A1/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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • 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 compounds which have pesticidal activity, in particular insecticidal activity, e.g. as active ingredients.
  • the invention also relates to preparation of these compounds, to intermediates useful in the preparation of these compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these compounds, to preparation of these compositions and to the use of these compounds or compositions in agriculture or horticulture for controlling controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.
  • the present invention therefore provides, in a first aspect, compounds of formula (I): or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of the compound of formula (I), wherein:
  • X is O or S
  • T is an aromatic ring selected from phenyl, pyridine, pyrimidine, pyrazine, pyridazine, and a 5- or 9-membered heteroaromatic ring comprising one to three heteroatoms independently selected from N, O and S, wherein said aromatic ring is optionally substituted with one to three substituents independently selected from R 2 ;
  • R 1a and R 1b are independently selected from hydrogen, C1-C6alkyl optionally with one substituent independently selected from CN, C 1 -C 3 alkoxy, C(O)NH2, C(O)OH, NO2, and -Si(CH3)3; C1- C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C4cycloalkyl-C1-C2alkyl optionally substituted with one or two halo atoms, oxetan-3-yl-CH2-, C1-C6alkylcarbonyl, C1- C6alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, and benzyl optionally substituted with one to three substituents independently selected from halogen, C1-C6alkoxy, and C1-C6haloalkyl;
  • R 1b and T together with the nitrogen atom they are connected to, form a nine or ten membered bicyclic heterocyclic ring, which is optionally substituted with one to three substituents independently selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C3-C4cycloalkyl, halogen, hydroxyl, cyano, and C 1 -C 3 haloakoxy;
  • R 2 is independently selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkylthio, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, halo, NO2, SF5, CN, C(O)NR7R8, C(O)OH, C(S)NH2, C1-C4alkylsulfonylamino, aminosulfonyl, C1-C4alkylaminosulfonyl, di(C1-C4alkyl)aminosulfonyl, C3-C6cycloalkylaminosulfonyl, C3-C6cycloalkyl optionally substituted with one to three substituents independently selected from R x , C3- C6cycloalkylcarbonyl, phenyl optionally substituted with one to three substituents independently selected from R x , heteroaryl optionally substituted with one to three
  • R 3 is C 1 -C 3 alkyl or C 1 -C 3 haloalkyl
  • R 4 is pyrimidinyl, pyrazinyl, or pyridazinyl, each of which, independently of each other, is substituted with a single -CN or -C(O)NR 10 R 11 ;
  • R 4a is pyrimidinyl, pyrazinyl, pyridazinyl, N-linked pyrazolyl, or N-linked triazolyl, each of which, independently of each other, is substituted with a single -CN or -C(O)NR 10 R 11 ;
  • R 5 is hydrogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C3-C4cycloalkyl, C 1 -C 3 alkoxy, C3-C4alkoxyC(C)-, (C1-C3alkoxy)2CH-, halogen, CN, NH2C(O), amino (i.e.
  • R 5 is phenyl substituted with one to three substituents selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C3-C4cycloalkyl, halogen, CN, and hydroxyl; or R 5 is a 5-membered heteroaromatic ring substituted with one to three substituents selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C3-C4cycloalkyl, halogen, CN, and hydroxyl;
  • R 5a and R 5b are, independently of each other, selected from hydrogen, halogen, CN, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C3-C4cycloalkyl, C 1 -C 3 alkoxy and C 1 -C 3 haloalkoxy;
  • R 6 is phenyl, benzyl, heteroaryl, C3-C6 cycloalkyl, or C3-C6cycloalkylC 1 -C 3 alkyl, each of which, independently of each other, is optionally substituted with one to three substituents independently selected from R x ;
  • R 7 and R 8 are, independently of each other, hydrogen, C 1 -C 3 alkyl, or C3-C6cycloalkyl; or
  • R 7 and R 8 are, independently of each other, C 1 -C 3 alkyl or C3-C6cycloalkyl, each of which is substituted with one to three substituents independently selected from R z ;or
  • R 7 and R 8 together are -(CH2)2-O-(CH2) 2- and form a 6-membered ring together with the nitrogen atom they are connected to;
  • R 10 is hydrogen, C 1 -C 3 alkyl, C 1 -C 3 cyanoalkyl, C 1 -C 3 haloalkyl, C3-C4cycloalkyl, C3- C4halocycloalkyl, or cyanoC3-C4cycloalkyl;
  • R 11 is hydrogen, C 1 -C 3 alkyl, or C 1 -C 3 haloalkyl
  • R x is independently selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, NO2, SFs, CN, C(O)NH2, C(S)NH2, C3-C6cycloalkyl, C1-C4haloalkylsulfanyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl and C1-C4alkylsulfonyl;
  • R Y is C1-C4 alkyl, C3-C5 alkenyl, C3-C4 cycloalkyl, C2-C5 alkynyl, or benzyl;
  • R z is selected from oxo, halogen, C1-C3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy and CN.
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as 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.
  • the compounds of formula I according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g., an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • C 1 -C n alkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2- dimethylpropyl, 1 -ethylpropyl, n-hexyl, n-pentyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl,
  • C 1 -C n haloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2- fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroeth
  • 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,
  • C 1 -C n alkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1 -methylethoxy, n-butoxy, 1- methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • haloC 1 -C n alkoxy refers to a C 1 -C n alkoxy 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,
  • C 1 -C n cyanoalkyl refers to a straight chain or branched saturated C 1 -C n alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is be replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
  • C3-Cncycloalkyl refers to 3-n membered cycloalkyl groups such as cyclopropane, cyclobutane, cyclopentane and cyclohexane.
  • cyanoC3-C4cycloalkyl refers to 1-cyanocyclopropanyl, 2- cyanocyclopropanyl, or 1-cyanocyclobutanyl, 2-cyanocyclobutanyl, or 3-cyanocyclobutanyl.
  • C3-C4cycloalkyl-C1-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.
  • 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 cycloalkyl group connected to a 1 to 4 membered haloalkoxy, which haloalkoxy group is connected to the rest of the molecule.
  • aminocarbonylC 1 -C n alkyl“ as used herein refers to an alkyl radical where one of the hydrogen atoms in the radical is replaced by CONH2 group.
  • hydroxycarbonylC 1 -C n alkyl“ as used herein refers to an alkyl radical where one of the hydrogen atoms in the radical is replaced by COOH group.
  • C 1 -C n alkylsulfanyl“ as used herein refers to a C 1 -C n alkyl moiety linked through a sulfur atom.
  • C 1 -C n haloalkylthio“ or “C 1 -C n haloalkylsulfanyl“ 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.
  • trimethylsilaneC 1 -C n alkyl“ as used herein refers to an C 1 -C n alkyl radical where one of the hydrogen atoms in the radical is replaced by a -Si(CH3)3 group.
  • C1-C4alkylsulfonylamino“ as used herein refers to C 1 -C n alkylsulfonyl moiety linked through an amino (or NH) group; examples are methylsulfonyl amino (MeS(O)2NH-).
  • aminosulfonyl refers to an amino moiety linked through a sulfonyl group, i.e. NH2S(O)2-.
  • C1-C4alkylaminosulfonyl“ as used herein refers to a C 1 -C n alkylamino moiety linked through a sulfonyl group; examples are, i.e. MeNHS(O)2-, EtNHS(O)2.
  • di(C1-C4alkyl)aminosulfonyl“ as used herein refers to a di(C1-C4alkyl)amino moiety linked through a sulfonyl group; examples are, i.e. Me2NS(O)2-, Et(Me)NS(O)2.
  • C3-C6cycloalkylaminosulfonyl refers to a C3-C6cycloalkylamino moiety linked through a sulfonyl group; examples are, i.e. cyclopropylNHS(0)2-.
  • -0-C1-C2haloalkanediyl-0- refers to a straight-chain saturated halogenated divalent group attached via each of the oxygen atoms and having 1 or 2 carbon atoms between the oxygen atoms.
  • the -0-C1-C2haloalkanediyl-0- group is connected to adjacent ring members of the T ring (i.e.
  • oxygen atoms being linked by 1 to 2 carbon atoms substituted with one or more halogen atoms.
  • Examples include -OCF2O- and -OCF2CF2O-. Together with the two adjacent ring members of the T ring to which it is attached, the -0-C1-C2haloalkanediyl-0- group thus forms a 5- or 6-membered ring.
  • C2-C n alkenyl 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-C n haloalkenyl refers to a C2-C n alkenyl moiety substituted with one or more halo atoms which may be the same or different.
  • C2-C n alkynyl 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-C n haloalkynyl refers to a C2-C n alkynyl moiety substituted with one 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- 41 shown in Scheme A below. Preferred heteroaryl is pyridyl, pyrimidinyl and pyrazolyl.
  • heteroaromatic rings for T are heteroaromatics made up of two rings, having 1 to 3 carbon atoms replaced independently by nitrogen, sulfur, or oxygen (the heteroatoms can be in one ring or distributed amongst the two).
  • heteroaromatics made up of two rings, having 1 to 3 carbon atoms replaced independently by nitrogen, sulfur, or oxygen (the heteroatoms can be in one ring or distributed amongst the two).
  • Examples are purinyl, thieno[2,3- d]pyrimidinyl, [1 ,2,4]triazolo[1 ,5-a]pyrimidinyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.
  • heterocyclic heterocyclic ring as used herein in context of the ring formed by T and R1b with the N atom refers to a partially or fully saturated ring; having in addition to the N atom, optionally 1 or 2 more heteroatoms selected from N and O.
  • An example of a 9-membered heterocyclic ring formed by Rit and T together is indolinyl.
  • spiroheterocyclic ring refers to an 8- to 12-membered spiro ring, preferably a ten membered spiro ring, having 3 to 4 heteroatoms selected from N and O, which ring is partially or fully saturated. If substituted, the subsituent can be on a carbon atom or a heteroatom.
  • An example of spiroheterocyclic ring is oxa-2,8-diazaspiro[4.5]dec-2-en-3-yl.
  • the pyridine, pyrimidine, pyrazine and pyridazine groups (unsubstituted or substituted) for R4 and R4a are each connected via a carbon atom on the respective ring 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 reduced.
  • the staggered line as used herein, for example, in Q a and Y1 , and the arrow used, for example, in scheme A, represent the point of connection or attachment to the rest of the compound.
  • pest refers to insects and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain, and timber); and those pests associated with the damage of man-made structures.
  • the term pest encompasses all stages in the life cycle of the pest.
  • the term "effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
  • an effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount, a number of factors are considered including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
  • compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in the structure below: where T, X, R 1a , R 1b , R 3 , and Q are as defined in the first aspect.
  • the present invention contemplates both racemates and individual enantiomers.
  • Compounds having preferred stereochemistry are set out below.
  • Particularly preferred compounds of the present invention are compounds of formula (I’a) where T, X, R 1a , R 1b , R 3 , and Q are as defined in the first aspect, and stereoisomers, enantiomers, tautomers, and N-oxides of the compounds of formula (I’a), and agrochemically acceptable salts thereof.
  • C3-C4cycloalkyl optionally substituted with 1 or 2 halo atoms means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3-C4cycloalkyl substituted with 2 halo atoms.
  • Embodiments according to the invention are provided as set out below.
  • A. X is oxygen
  • X is oxygen
  • R 1a is
  • B hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, aminocarbonylC1-C6alkyl, hydroxycarbonylC1-C6alkyl, C1-C6nitroalkyl, trimethylsilaneC1-C6alkyl, C 1 -C 3 alkoxy-C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C4cycloalkylC1-C2alkyl-, benzyloxycarbonyl, or benzyl; or
  • D hydrogen, C1-C4alkyl, C1-C4cyanoalkyl, C1-C2alkoxy-C1-C2alkyl, C1-C4haloalkyl, C2-C3alkenyl, C2-C3haloalkenyl, C2-C3alkynyl, C2-C3haloalkynyl, C3-C4cycloalkylC1-C2alkyl-, benzyloxycarbonyl, or benzyl; or E.
  • F hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl; or
  • G hydrogen, methyl, ethyl, allyl, propargyl, or cyclopropyl-methyl; or
  • H hydrogen, methyl, propargyl, or cyclopropyl-methyl
  • R 1b is
  • B hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, aminocarbonylC1-C6alkyl, hydroxycarbonylC1-C6alkyl, C1-C6nitroalkyl, trimethylsilaneC1-C6alkyl, C 1 -C 3 alkoxy-C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C4cycloalkylC1-C2alkyl-, benzyloxycarbonyl, or benzyl; or
  • F hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl; or
  • G hydrogen, methyl, ethyl, allyl, propargyl, or cyclopropyl-methyl; or
  • R 1a and R 1b are, independently of each other, hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl. More preferably, R 1a is hydrogen and R 1b is hydrogen, or methyl. In an embodiment of each aspect of the invention, T is
  • K phenyl, or pyrid-3-yl, each of which, independently of each other, is substituted with one to three substituents independently selected from chlorine, bromine, iodine, trifluoromethyl, chlorodifluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, and 1 , 1 ,2,2- tetrafluoroethoxy; or
  • B a nine membered bicyclic heterocyclic ring, which can be substituted with one to three substituents independently selected from trifluoromethyl, methoxy, trifluoromethoxy, cyclopropyl, chloro, fluoro, and bromo; or
  • an indoline ring which can be substituted with one to three substituents independently selected from trifluoromethyl, methoxy, trifluoromethoxy, cyclopropyl, chloro, fluoro, and bromo; or
  • an indoline ring which can be substituted with one to three substituents independently selected from trifluoromethyl, chloro, fluoro, and bromo; or
  • E an indoline ring, substituted with one to three substituents independently selected from trifluoromethyl, chloro, fluoro, and bromo.
  • T is phenyl, or pyridine, such as 3-pyridyl, substituted with one to three R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, and C1- C 3 haloalkoxy. More preferably, T is phenyl, or pyridine, such as 3-pyridyl, substituted with two or three R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, and C1- C 3 haloalkoxy.
  • T is phenyl substituted with two or three R 2 substituents, preferably three R 2 substituents, independently selected from halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, and C1- C 3 haloalkoxy.
  • T is pyridine, preferably 3-pyridyl, substituted with two R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, and C 1 -C 3 haloalkoxy.
  • T is wherein T c is C-R 2c ,
  • R 2a and R 2b are chloro; and R 2c is trifluoromethyl, 1 ,1 ,2,2-tetrafluoroethoxy, chloro(difluoro)methoxy, 2,2- difluoroethoxy, or difluoromethoxy; or wherein T c is N, R 2a is chloro, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy; and R 2b is difluoromethyl, or trifluoromethyl.
  • R 2 is, independently of each other, selected from
  • halogen C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, C3-C4cycloalkyl, C3- C6cycloalkylcarbonyl, phenyl, heteroaryl selected from J-1 , J-13 and J-25.
  • pyrazolyl each of C3- C4cycloalkyl, phenyl, heteroaryl and pyrazolyl, independently of each other, is substituted with one to three substituents R x OR 6 , piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl optionally substituted with R x , pyrrolidin-1 -yl, C3-C6cycloalkylC1-C4alkyl optionally substituted with one or two substituents R z , C3-C6cycloalkylC 1 -C 3 alkoxy optionally substituted with R x , C 1 -C 3 cyanoalkyl, C1- C5cyanoalkoxy, C1-C4alkylsulfanyl optionally substituted by one to three substituents R x , C1- C4alkylsulfonyl optionally substituted by one to three substituents R x and
  • halogen C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, C3-C4cycloalkyl, C3- C4cycloalkyl substituted with one to two substituents independently selected from halogen, C1- C 3 alkyl and C 1 -C 3 haloalkyl, C3-C4cycloalkylcarbonyl, OR 6 , C3-C4cycloalkylmethyl, C3- C4cycloalkylmethyl substituted with one to two substituents independently selected from oxo, halogen, C 1 -C 3 alkyl and C 1 -C 3 haloalkyl, C1-C2alkylsulfanyl substituted with one to three halogens, C1-C2alkylsulfonyl substituted with one to three halogens, C(O)NH(C
  • halogen C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, cyclopropyl, cyclopropyl substituted with one to two substituents independently selected from halogen, methyl and trifluoromethyl, cyclopropylcarbonyl, OR 6 , cyclopropylmethyl substituted with one to two substituents independently selected from oxo, halogen and trifluoromethyl, C1-C2alkylsulfanyl substituted with one to three halogens, C1-C2alkylsulfonyl substituted with one to three halogens, C(O)NH(C1-C4alkyl), C1-C4alkylsulfonylamino, C1-C4alkylaminosulfonyl, C3- C6cycloalkylaminosulfonyl
  • halogen C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkylsulfanyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, C3- C6cycloalkyl, C3-C6cycloalkyl substituted with one to three substituents independently selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and halogen, cyclopropylcarbonyl, OR 6 , C3-C6cycloalkylC1- C4alkyl, C3-C6cycloalkylC1-C4alkyl substituted with one to five substituents independently selected from oxo, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and halogen, C 1 -C 3 cyanoalkyl, C1-C4alkyl
  • halogen C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkylsulfanyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, C3- C6cycloalkyl, C3-C6cycloalkyl substituted with one or two substituents independently selected from C 1 -C 3 haloalkyl, cyano and halogen, C3-C4cycloalkylcarbonyl, OR 6 , C3-C6cycloalkylC1-C4alkyl, C3- C6cycloalkylC1-C4alkyl substituted with one to three substituents independently selected from oxo, C 1 -C 3 haloalkyl, cyano and halogen, C 1 -C 3 cyanoalkyl, C1-C4alkylsulfonyl, C1-C4halo
  • halogen C 1 -C 3 haloalkyl, C 1 -C 3 haloalkylsulfanyl, C 1 -C 3 haloalkoxy, CN, C3-C6cycloalkyl, C3- C6cycloalkyl substituted with one or two substituents independently selected from C 1 -C 3 haloalkyl, cyano and halogen, C3-C4cycloalkylcarbonyl, OR 6 , C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1- C4alkyl substituted with one to three substituents independently selected from oxo, C 1 -C 3 haloalkyl, cyano and halogen, C 1 -C 3 cyanoalkyl, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, C1-C4alkylsulfany
  • K halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, OR 6 (where R 6 is phenyl, J-1 or J-17, each of which can be substituted by one to three substituents independently selected from R x ), C 1 -C 3 haloalkylsulfanyl, C 1 -C 3 haloalkysulfonyl, -O-CF2-O-; -OCF2CF2O-, and C 1 -C 3 haloalkoxy; or
  • M chlorine, fluorine, bromine, iodine, cyclopropyl, difluoromethyl, trifluoromethyl, trifluoromethylsulfanyl, trifluoromethylsulfonyl, difluoromethoxy, trifluoromethoxy, 1 , 1 ,2,2- tetrafluoroethoxy, 1 ,1 ,1 ,2,2-pentafluoroethoxy, -O-CF2CF2-O-, and -O-CF2-O-; or
  • N fluorine, chlorine, bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 1 ,1 ,1 ,2,2-pentafluoroethoxy, -O-CF2CF2-O-, and -O-CF2-O-; or
  • R 2 is chloro, difluoromethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, chloro(difluoro)methoxy, 2,2,2-trifluoroethoxy, or 1 , 1 ,2,2- tetrafluoroethoxy.
  • T carries only one such divalent group as R 2 and said divalent group is connected to T via two adjacent ring members of T.
  • divalent groups include -0-C1-C 2 haloalkanediyl-0-, -CH 2 -C(CH3) 2 -O-, -CH 2 -C(CH3) 2 -S-, -CH 2 -C(CH3)2-SO 2 .
  • Examples of-O-C1- C 2 haloalkanediyl-0- include -O-CF2-CF2-O-, -O-CFH-CF2-O-, -O-CFH-CFH-O-, -OCH2-CHF-O-, -OCH2-CF2-O-, -O-CF2-O-, and -O-CFH-O-; preferably -O-CF2CF2-O-, and -O-CF2-O-.
  • T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a five or nine membered heteroaromatic ring, substituted via two adjacent ring members of the phenyl, pyridine, pyrimidine, pyrazine, pyridazine or five or nine membered heteroaromatic ring, with a divalent groups selected from -0-C1-C2haloalkanediyl-0-, -CH2-C(CH3)2-O-, -CH2-C(CH3)2-S-, -CH2-C(CH3)2-SC>2, preferably selected from -O-CF2CF2-O-, and -O-CF2-O-.
  • R 3 is
  • Q is Q a -1 ; or Preferably, Q is Q a -1 : , i.e. R 5 is hydrogen.
  • R 4 is:
  • R 11 is hydrogen, C 1 -C 3 alkyl, or C 1 -C 3 haloalkyl; or
  • R 4 -1 , or R 4 -6 wherein R 10 is hydrogen, methyl, ethyl or cyclopropyl; and R 11 is hydrogen, methyl or ethyl; or
  • R 4 -1 or R 4 -6; wherein R 10 is hydrogen, methyl, or ethyl; and R 11 is hydrogen, or methyl; or
  • R 4 -1 or R 4 -6; wherein R 10 is hydrogen, or methyl; and R 11 is hydrogen; or
  • R 4 -1 wherein R 10 and R 11 are hydrogen.
  • R 4a is:
  • R 10 is hydrogen, methyl, ethyl, cyclopropyl or 1 -cyanocyclopropyl
  • R 11 is hydrogen, methyl or ethyl
  • R 4 -1 , R 4 -6, or R 4 -11 wherein R 10 is hydrogen, methyl, or ethyl; and R 11 is hydrogen, or methyl; or
  • R 4 -1 , R 4 -6, or R 4 -11 wherein R 10 is hydrogen, or methyl; and R 11 is hydrogen; or
  • R 4 -1 or R 4 -11 , wherein R 10 and R 11 are hydrogen; or
  • R 5 is
  • F hydrogen, methyl, trifluoromethoxy, methoxy, cyclopropyl, 2,2-difluroroethoxy, 2,2,2- trifluroroethoxy, difluoromethoxy, 2,2,2-trifluroroethyl, chloro, bromo, methoxyethoxy, methylcarbonyl, or methoxycarbonyl; or
  • R 5a is
  • R 5b is
  • R 6 is
  • phenyl, J-1 , J-17, or cyclopropylmethyl each of which, independently of each other, is optionally substituted with one to three substituents independently selected from halogen, C 1 -C 3 alkyl, C1- C3haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy and C3-C6cycloalkyl; or
  • R 7 is
  • R 8 is
  • R x is independently selected from
  • halogen C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C3-C6cycloalkyl, C 1 -C 3 haloalkoxy and CN; or
  • R Y is independently selected from
  • R z is independently selected from
  • the present invention accordingly, makes available a compound of formula I having the substituents T, X, R 1a , R 1b , R 3 and Q as defined above in all combinations I each permutation. Accordingly, made available, for example, is a compound of formula I with X as oxygen; T being an embodiment B (i.e.
  • phenyl pyridine, pyrimidine, pyrazine, pyridazine or a heteroaromatic ring selected from J-13, J-16, J-22, J-25, J-26, J-27, J-28, J-31 , J-36, J-37, J-38, J-39, J-40, J-41 , thieno[2,3- d]pyrimidinyl, [1 ,2,4]triazolo[1 ,5-a]pyrimidinyl, and indazolyl, each of which, independently of each other, is substituted with one to three substituents independently selected from R 2 ), where R 2 is of embodiment A (i.e.
  • R 2 independently ofthe ring and the number of substituents, is selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, C3-C4cycloalkyl, C3-C6cycloalkylcarbonyl, phenyl, heteroaryl selected from J-1 and J-41 , each of C3-C4cycloalkyl, phenyl or heteroaryl, independently of each other, is substituted with one to three substituents R x OR 6 , piperidin-2-one-1-yl, pyridin-2-one-1- yl, azetidin-1-yl optionally substituted with R x , pyrrolidin-1 -yl, C3-C6cycloalkylC1-C4alkyl substituted with one or two substituents R z , C3-C6cycloal
  • R 1b being embodiment G (i.e. R 1b is hydrogen, methyl, propargyl, or cyclopropyl-methyl); R 3 being embodiment B (i.e.
  • R 3 is methyl or trifluoromethyl
  • Q is embodiment F (i.e. Q is Q a -1 , or Q b -1)
  • R 4 is embodiment B (i.e. R 4 is R 4 -1 , R 4 -2, R 4 -3, R 4 -4, R 4 -5, R 4 -6, R 4 -7, R 4 -8, R 4 -9, or R 4 -10, wherein R 10 is hydrogen, methyl, ethyl, cyclopropyl or 1 -cyanocyclopropyl; and R 11 is hydrogen, methyl or ethyl );
  • R 4a is embodiment C (i.e.
  • R 4a is R 4 -1 , R 4 -2, R 4 -3, R 4 -4, R 4 -5, R 4 -6, R 4 -7, R 4 -8, R 4 -9, R 4 -10, R 4 -11 , R 4 -12, R 4 -13, or R 4 -14; wherein R 10 is hydrogen, methyl, ethyl or cyclopropyl; and R 11 is hydrogen, methyl or ethyl); R 6 is of embodiment E (i.e.
  • R 6 is phenyl, J-1 , J-17, or cyclopropylmethyl, each of which, independently of each other, is optionally substituted with one to three substituents independently selected F, Cl, Br, and cyclopropyl);
  • R 7 is of embodiment D (i.e. R 7 is hydrogen);
  • R 8 is of embodiment D (i.e. R 8 is cyclopentyl);
  • R x is of embodiment B (i.e. R x is independently selected from F, Cl, Br, OCF2H, CF3, cyclopropyl, OCH3 and CN); and
  • R z is of embodiment B (i.e. R z is independently selected from oxo, F, Cl, Br, OCF2H, OCH3 and CN).
  • the compound of formula I is formula laa and lab (with asterisk indicating a stereogenic centre), wherein T, R 1a , R 1b , R 3 are as defined in the first aspect and Q1 corresponds to Q as defined in the first aspect, each with the corresponding embodiments as described above.
  • the preferred stereochemistry of compounds of formula laa lab is that depicted in formula I’a above.
  • the present invention makes available a compound of formulae laa and lab having the substituents T, R 1a , R 1b , R 3 and Q1 as defined in all combinations I each permutation.
  • the compound of formula I has as X oxygen; as T phenyl, or pyridine, each of which, independently of each other, is substituted with one to three substituents independently selected from R 2 , where R 2 , independently of the ring and of the number of substituents, is selected from trifluoromethyl, iodine, bromine chlorine, difluoromethoxy, and 1 , 1 ,2,2- tettrafluoroethoxy; as R 1a and R 1b are each hydrogen; R3 is methyl; Q is either Q a -1 or Q b -1 ; R 4 is R 4 -1 , R 4 -2, R 4 -3, R 4 -4, R 4 -5, R 4 -6, R 4 -7, R 4 -8, R 4 -9, or R 4 -10; R 4a is R 4 -1 , R 4 -6, R 4 -11 , or R 4 -13; and R 10 is hydrogen, methyl, or ethyl, or pyridine, each of
  • the compound of formula I is represented by formula I’a and has as X oxygen; as T phenyl, or pyridine, each of which, independently of each other, is substituted with one to three substituents independently selected from R 2 , where R 2 , independently of the ring and of the number of substituents, is selected from trifluoromethyl, bromine chlorine, difluoromethoxy, and 1 ,1 ,2,2-tetrafluoroethoxy; R 1a and R 1b are each hydrogen; R 3 is methyl; Q is either Q a -1 ; and R 4 is R 4 -1 , R 4 -2, R 4 -3, R 4 -4, R 4 -5, R 4 -6, R 4 -7, R 4 -8, R 4 -9, or R 4 -10; R 10 is hydrogen, methyl, ethyl or cyclopropyl; and R 11 is hydrogen, methyl or ethyl.
  • the compound of formula I is represented by formula I’a and has as X oxygen; as T phenyl, or pyridine, each of which, independently of each other, is substituted with one to three substituents independently selected from R 2 , where R 2 , independently of the ring and of the number of substituents, is selected from trifluoromethyl, bromine chlorine, difluoromethoxy, and 1 ,1 ,2,2-tetrafluoroethoxy; R 1a and R 1b are each hydrogen; R 3 is methyl; Q is either Q b -1 ; and R 4a is R 4 -1 , R 4 -6, or R 4 -11 ; R 10 is hydrogen, methyl, or ethyl; and R 11 is hydrogen, or methyl.
  • embodiment 1 provides compounds of formula (I), as defined above.
  • Embodiment 2 provides compounds as defined for embodiment 1 , wherein X is O or S.
  • Embodiment 3 provides compounds as defined for embodiment 1 or 2, wherein X is O.
  • Embodiment 4 provides compounds as defined for embodiment 1 or 2, wherein X is S.
  • Embodiment 5 provides compounds as defined for any one of embodiments 1 , 2, 3 or 4, wherein
  • R 1a and R 1b are, independently of each other, hydrogen, methyl, ethyl, allyl, propargyl, or cyclopropylmethyl.
  • Embodiment 6 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, or 5, wherein R 1a and R 1b are, independently of each other, hydrogen, methyl, or ethyl.
  • Embodiment 7 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, or 6, wherein R 1a and R 1b are, independently of each other, hydrogen, or methyl.
  • Embodiment 8 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, or 7, wherein R 1a and R 1b are both hydrogen.
  • Embodiment 9 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, or 8, wherein R 3 is methyl or trifluoromethyl.
  • Embodiment 10 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, or 9, wherein R 3 is methyl.
  • Embodiment 11 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein T is 2,4-bis(trifluoromethyl)phenyl, 2,4-chloro-5-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl, 2- bromo-4-chloro-5-(trifluoromethyl)phenyl, 2-bromo-4-(difluoromethoxy)phenyl, 2-iodo-4- (trifluoromethyl)phenyl, 3,5-bis(trifluoromethyl)phenyl, 2-chloro-4-(trifluoromethyl)phenyl, 4-chloro-2- (trifluoromethyl)phenyl, 2,4-dibromophenyl, 5-chloro-2-(trifluoromethyl)phenyl, 2-chloro-5- (trifluoromethyl)phenyl, 4-chloro-3-(trifluoromethyl)phenyl, 3-chloro-4-
  • Embodiment 12 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 , wherein T is 2,4-dichloro-5-(trifluoromethyl)phenyl, 2,4-dichloro-5-(2,2- difluoroethoxy)phenyl, 2,4-dichloro-5-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl, 2,4-dichloro-5-(chloro-difluoro- methoxy)-phenyl, 4-(difluoromethoxy)-6-(trifluoromethyl)-3-pyridyl, and 4-(difluoromethoxy)-6- (difluoromethyl)-3-pyridyl.
  • Embodiment 13 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein Q is Q a -1 or Q b -1.
  • Embodiment 14 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12 or 13, wherein R 4 is pyrimidin-4-yl, pyrimidin-2-yl, pyrazin-2-yl, or pyridazin-3-yl, each of which, independently of each other, is substituted with a single -CN or -C(O)NR 10 R 11 ; or R 4a is pyrimidin-4-yl, pyrimidin-2-yl, pyrazin-2-yl, pyridazin-3-yl, N-linked pyrazol-1-yl, or N-linked-triazol-1 -yl, each of which, independently of each other, is substituted with a single -CN or -C(O)NR 10 R 11 ; and wherein R 10 is hydrogen, C 1 -C 3 alkyl, C 1 -C 3 cyanoalkyl, C 1 -C 3 haloalkyl
  • Embodiment 15 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13 or 14, Q is Q a -1 ; R 4 is R 4 -1 , R 4 -2, R 4 -3, R 4 -4, R 4 -5, R 4 -6, R 4 -7, R 4 -8, R 4 -9, or R 4 -10; R 10 is hydrogen, methyl, ethyl or cyclopropyl; and R 11 is hydrogen, methyl or ethyl.
  • Embodiment 16 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14 or 15, wherein Q is Q a -1 ; R 4 is R 4 -1 , or R 4 -6; R 10 is hydrogen, or methyl; and R 11 is hydrogen.
  • Embodiment 17 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, or 14, wherein Q is Q b -1 ;
  • R 4a is R 4 -1 , R 4 -2, R 4 -3, R 4 -4, R 4 -5, R 4 -6, R 4 -7, R 4 -8, R 4 -9, R 4 -10, R 4 -1 1 , R 4 -12, R 4 -13, or R 4 -14; wherein R 10 is hydrogen, methyl, ethyl or cyclopropyl; and R 11 is hydrogen, methyl or ethyl.
  • Embodiment 18 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, or 17, wherein Q is Q b -1 ; R 4a is R 4 -1 , R 4 -6, or R 4 -11 ; wherein R 10 is hydrogen, or methyl; and R 11 is hydrogen.
  • Embodiment 19 provides compounds as defined for any one of embodiments 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 17, or 18 wherein Q is Q b -1 ; R 4a is R 4 -1 , R 4 -6, or R 4 -11 ; wherein R 10 is hydrogen, or methyl; and R 11 is hydrogen.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a and R 1b are, independently of each other, hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl; T is phenyl, or pyridine, substituted with one to three R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, and C 1 -C 3 haloalkoxy; R 3 is methyl or ethyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 - 6; R 10 is hydrogen, methyl, ethyl, cyclopropyl, or 1 -cyanocyclopropyl; and R 11 is hydrogen, methyl, or ethyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is phenyl, or pyridine, substituted with one to three R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C1- C3haloalkyl, and C 1 -C 3 haloalkoxy; R 3 is methyl or ethyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is phenyl, or 3-pyridyl, substituted with one to three R 2 substituents independently selected from chloro, difluoromethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, chloro(difluoro)methoxy, 2,2,2-trifluoroethoxy, or 1 ,1 ,2,2-tetrafluoroethoxy; R 3 is methyl or ethyl; Q is Q a - 1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is phenyl, or pyridine, such as 3-pyridyl, substituted with two or three R 2 substituents independently selected from halogen, C3- C4cycloalkyl, C 1 -C 3 haloalkyl, and C 1 -C 3 haloalkoxy; R 3 is methyl or ethyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is phenyl substituted with two or three, preferably three, R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C1- C3haloalkyl, and C 1 -C 3 haloalkoxy; R 3 is methyl or ethyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is 3-pyridyl substituted with two R 2 substituents independently selected from halogen, C3-C4cycloalkyl, C 1 -C 3 haloalkyl, and C1- C 3 haloalkoxy; R 3 is methyl or ethyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is phenyl substituted with two or three, preferably three, R 2 substituents independently selected from chloro, difluoromethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, chloro(difluoro)methoxy, 2,2,2-trifluoroethoxy, or 1 ,1 ,2,2-tetrafluoroethoxy; R 3 is methyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; T is 3-pyridyl substituted with two R 2 substituents independently selected from chloro, difluoromethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, chloro(difluoro)methoxy, 2,2,2-trifluoroethoxy, or 1 ,1 ,2,2-tetrafluoroethoxy; R 3 is methyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; wherein T c is C-R 2c , R 2a and R 2b are chloro; and R 2c is trifluoromethyl, 1 ,1 ,2,2- tetrafluoroethoxy, chloro(difluoro)methoxy, 2,2-difluoroethoxy, or difluoromethoxy; or wherein T c is N, R 2a is chloro, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy; and R 2b is difluoromethyl, or trifluoromethyl; R 3 is methyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • the present invention makes available a composition
  • a composition comprising a compound of formula I as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient.
  • the present invention makes available a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect.
  • the present invention makes available a method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.
  • the present invention makes available a plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.
  • the present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of the first aspect.
  • the present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula I as defined om 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.
  • the present invention makes available a process for preparing a compound of the formula (I), comprising reacting an amine of formula II, 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), with (i) a compound of formula III when R 1a is hydrogen (i.e. this corresponds to a compound of the formula l-a) or (ii) with a compound of formula IV, where X, R 3 , R 1a , R 1b , T and Q are as defined above for a compound of the formula (I).
  • 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
  • the present invention makes available a process for preparing a compound of the formula (I), comprising reacting an amine of formula VI, 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), with (i) a compound of formula VII, or (ii) with a compound of formula VIII when R 1b is hydrogen (i.e. this corresponds to a compound of the formula l-b) where X, R 3 , R 1a , R 1b , T and Q are as defined above for a compound of the formula (I).
  • 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
  • Reaction of a compound of the formula II, or a salt thereof, with a compound of formula III gives a compound of the formula l-a, where X, R3, R1, T and Q are as defined above for a compound of the formula (I).
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, ethyl acetate, toluene, chlorobenzene, N,N- dimethyl-acetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance aceton
  • phosgene or phosgene surrogates such as di- or triphosgene
  • a base such as triethylamine, diisopropylethylamine or pyridine
  • an inert solvent such as acetonitrile, tetrahydrofuran, ethyl acetate, toluene, chlorobenzene, N,N-dimethylacetamide or N,N-dimethyl- formamide, in a temperature range of -20 to +80 °C, preferably between 0°C and ambient temperature.
  • Such compounds of the formula III may be worked up and isolated, or alternatively may form in situ and can be used as such in a next step.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 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 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, ethyl acetate, N,N-dimethylacetamide or N,N- dimethylformamide
  • a base such as an inorganic base, for instance sodium, potassium or cesium carbonate
  • an organic base such as, for example, trie
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 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 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, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide
  • a base such as an inorganic base, for instance sodium, potassium or cesium carbonate
  • an organic base such as, for example,
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 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 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,
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 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 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, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide
  • a base such as an inorganic base, for instance sodium, potassium or cesium carbonate
  • an organic base such as, for example,
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, ethyl acetate, toluene, chlorobenzene, 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 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
  • phosgene or phosgene surrogates such as di- or triphosgene
  • a base such as triethylamine, diisopropylethylamine or pyridine
  • an inert solvent such as acetonitrile, tetrahydrofuran, ethyl acetate, toluene, chlorobenzene, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -20 to +80 °C, preferably between 0°C and ambient temperature.
  • Such compounds of the formula VIII may be worked up and isolated, or alternatively may form in situ and can be used as such in a next step.
  • compounds of the formula l-b can be prepared in a one-pot two steps process by (i) reacting compounds of the formula II (Rib is hydrogen) with phosgene (or a surrogate thereof) with in situ formation of compounds of the formula VIII which are not isolated; followed by (ii) addition of a compound of formula VI, or a salt thereof, to form the compounds of the formula l-b.
  • 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, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid, or a Lewis acid, such as zinc bromide
  • a solvent or without a solvent such as, for instance, methanol.
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • the reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula Vl-b 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 Vl-a, wherein the leaving group X2 is a sulfonate, for instance a mesylate.
  • This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a base such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • Such methods for the halogenation, the reduction of carbonyl compounds and the sulfonylation of alcohols, and the range of conditions to perform them, are well known to a person skilled in the art.
  • the compounds of formula Vl-b and the compounds of formula VI-c are either known, or they can be prepared by methods known to a person skilled in the art.
  • compounds of the formula l-d wherein T, X, R3 and Q are as defined for formula (I) can be made from compounds of formula l-c by treatment with a compound of formula IX, wherein X2a and X2b are leaving groups, such as halogen or sulfonate, for example bromide or iodide, or tosylate or mesylate.
  • X2a and X2b are leaving groups, such as halogen or sulfonate, for example bromide or iodide, or tosylate or mesylate.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • organic base such as, for example, triethylamine
  • compounds of the formula l-e wherein T, X, R3 and Q are as defined for formula (I) can be made from compounds of formula l-c by treatment with a compound of formula X 9 , wherein X2a and X2b are leaving groups, such as halogen or sulfonate, for example bromide or iodide, or tosylate or mesylate.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • organic base such as, for example, triethylamine
  • compounds of the formula l-f can be made from compounds of formula l-c by treatment with formaldehyde.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1 ,2-dichloroethane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of an acid, such as an inorganic acid, for instance hydrochloric acid, or an organic acid, such as, for example, acetic acid or trifluoroacetic acid.
  • an acid such as an inorganic acid, for instance hydrochloric acid
  • an organic acid such as, for example, acetic acid or trifluoroacetic acid.
  • compounds of the formula l-h wherein T, X, R3 and Q are as defined for formula (I) can be made from compounds of formula l-c by treatment with formaldehyde and an amine XI, wherein R y has the same meaning as defined for compounds of the formula (I).
  • the amine can be used as such or in the form of a salt, such as, for instance, in the form of a hydrochloride.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance ethanol, or in water, or in a mixture of solvents, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of an acid, such as an inorganic acid, for instance hydrochloric acid, or an organic acid, such as, for example, p-toluenesulfonic acid.
  • a solvent such as an organic solvent, for instance ethanol, or in water, or in a mixture of solvents, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C
  • an acid such as an inorganic acid, for instance hydrochloric acid
  • an organic acid such as, for example, p-toluenesulfonic acid.
  • compounds of the formula l-i can be made from compounds of formula l-g by treatment with an oxidizing agent, such as hydrogen peroxide or a peracid, for instance m-chloroperbenzoic acid.
  • an oxidizing agent such as hydrogen peroxide or a peracid, for instance m-chloroperbenzoic acid.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a catalyst, such as a metal catalyst, for instance 12- tungstophosphoric acid.
  • a catalyst such as a metal catalyst, for instance 12- tungstophosphoric acid.
  • compounds of the formula l-j can be made from compounds of formula l-g by treatment with an oxidizing agent, such as hydrogen peroxide or a peracid, for instance m-chloroperbenzoic acid.
  • an oxidizing agent such as hydrogen peroxide or a peracid, for instance m-chloroperbenzoic acid.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a catalyst, such as a metal catalyst, for instance 12- tungstophosphoric acid.
  • a catalyst such as a metal catalyst, for instance 12- tungstophosphoric acid.
  • compounds of the formula l-j can be made from compounds of formula l-i by treatment with an oxidizing agent, such as hydrogen peroxide or a peracid, for instance m-chloroperbenzoic acid.
  • an oxidizing agent such as hydrogen peroxide or a peracid, for instance m-chloroperbenzoic acid.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a catalyst, such as a metal catalyst, for instance 12-tungstophosphoric acid.
  • a catalyst such as a metal catalyst, for instance 12-tungstophosphoric acid.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile or N,N-dimethylformamide
  • a catalyst for instance a metal catalyst, such as a palladium complex
  • a base such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • reaction of compound XIII with hydrazine XIV gives the compound of formula l-k, wherein T, R3 and R4 have the same meaning as given above for compounds of the formula (I).
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1 ,4-dioxane, or acetic acid, or a mixture of 1 ,4-dioxane and acetic acid, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, or between ambient temperature and 80 °C.
  • the intermediate compounds of formula XVI and of formula XIII can be used as crude products for the subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid, or a Lewis acid, such as zinc bromide
  • a solvent or without a solvent such as, for instance, methanol.
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a catalyst for instance a metal catalyst, such as a palladium complex
  • a base such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • R4a-Mi is a metal, such as for instance lithium, or - MgCI, or -ZnBr, or -B(OH)2; or R4a-Mi represents a boronate, such as a pinacol ester of a boronic acid, or a stannane such as R4a-Sn(n-Bu)3.
  • Suzuki-, Kumada-, Negishi- or Stille-coupling reactions are known to a person skilled in the art as Suzuki-, Kumada-, Negishi- or Stille-coupling reactions, respectively.
  • Such reactions are carried out in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst, and a ligand, such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand.
  • a catalyst such as a metal catalyst, for instance a palladium catalyst
  • a ligand such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand.
  • a catalyst such as a metal catalyst, for instance a palladium catalyst
  • a ligand such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite
  • the reaction is done with or without a base, which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or an organic base, such as an amine base, for instance triethyl amine.
  • a base which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or an organic base, such as an amine base, for instance triethyl amine.
  • a base which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate
  • an organic base such as an amine base, for instance triethyl amine.
  • This reaction is done with or without a solvent, preferentially in a solvent.
  • the reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath.
  • compound XV can be reacted with a compound of the formula XX to give intermediate XXI, wherein R3 and R4a have the same meaning as given above for compounds of the formula (I).
  • This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate XVIII to the compound of formula l-m. Subsequently, the intermediate
  • XXI is reacted with amine XIX, or a salt thereof, to give intermediate XVIIa, or a salt thereof, wherein Ria, R3 and R4a have the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound XV to intermediate XVII.
  • the intermediate of the formula XVIIa is reacted with a compound of the formula VIII (where X is oxygen) to give the compound of the formula l-m, wherein T, Ria, R3 and R4a have the same meaning as given above for compounds of the formula (I).
  • This reaction is done essentially under the same conditions as described above for the transformation of intermediate XVII to intermediate XVIII.
  • the intermediate compounds of formulas XVII, XVIIa, XVIII and XXI can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.
  • Compounds of the formula XV are known, or they can be prepared by methods known to a person skilled in the art.
  • Amines of formula XVI Ic may be obtained by biocatalyzed deracemization of amines of formula XVIId, wherein R3, R4a, R5a, and R5b are as defined in 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.
  • Treatment of a compound of the formula XVIIc with a compound of the formula XXII gives compounds of the formula XVIIb.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • Such methods, and the range of conditions to perform them, for the alkylation of amines and for the reductive alkylation of amines are well known to a person skilled in the art.
  • compounds of formula XVIIc, or a salt thereof can be obtained from compounds of the formula XVIId wherein R3, R4a, R5a, and R5b are as described in formula (I), following the synthesis described in Scheme 14:
  • Amines of formula XVIIc, or a salt thereof may be obtained from intermediates of formula XXV, wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NB0C2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green
  • Such intermediates of formula XXV wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NB0C2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula XXIII, wherein R3, R4a, R5a, and R5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula XXIII 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(te/Y- butoxycarbonyl)amine (HNB0C2).
  • a Mitsunobu reaction which involves treating alcohols
  • amines of formula XVIIc may be obtained by reduction of azides of formula XXIV, wherein R3, R4a, R5a, and R5b are as described in formula (I), by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen.
  • Azides of formula XXIV may be obtained by treatment of alcohols of formula XXIII, wherein R3, R4a, R5a, and R5b are as described in formula (I), with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • Alcohols of formula XXIII may be obtained by enantioselective reduction of ketones of formula XVa, wherein R3, R4a, R5a, and R5b are as described in formula (I).
  • reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCI[(R,R)- TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/EtsN or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/EtsN or HCO2NH4.
  • Amines of formula XVIIc, or a salt thereof can be prepared by deprotection of amines of formula XXXI, wherein R3, R4a, R5a, and R5b are as described in formula (I), for instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane.
  • Amines of formula XXXI can be obtained by condensation of diamines of formula XXX, wherein R5a, and R5b are as described in formula (I), on diketones of formula XXIX, wherein R3, and R4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ.
  • Diketones of formula XXIX may be formed by oxidation of hydroxyketones of formula XXVIII wherein R3, and R4a are as described in formula (I).
  • This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or N,N- diisopropylethylamine, or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/BU4NHSO4.
  • solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof
  • a base for instance triethylamine or N,N- diisopropylethylamine, or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/BU4NHSO4.
  • TEMPO/BU4NHSO4 TEMPO/BU4NHSO4
  • Hydroxyketones of formula XXVIII may be synthesized by cross-benzoin condensation between aldehydes of formula XXVII, wherein R4a is as described in formula (I), and aldehydes of formula XXVI, wherein R3 is as described in formula (I).
  • Aldehydes of formula XXVI are commercially available in chiral form, like for instance Boc-L-alaninal (CAS 79069-50-4) or tert-butyl N-[(1 S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36- 9).
  • Cross-benzoin condensations are done in the usual way by employing an org anocatalyst such as a triazolium salt or a thiazolium salt in the presence of a base such as potassium tert-butoxide or isopropyldiethylamine in a suitable solvent such as DCM or THF at a temperature between -20 °C and the boiling point of the solvent.
  • a base such as potassium tert-butoxide or isopropyldiethylamine
  • a suitable solvent such as DCM or THF
  • X 07 Cl, Br, I, OMs, OTs or OTf
  • X 07 Cl, Br, I, OMs, OTs or OTf
  • Amines of formula XVIIe may be obtained by biocatalyzed deracemization of amines of formula XVI If, wherein R3, R5a, and R5b are as defined in formula (I) and X07 is a leaving group such as bromine, chlorine or iodine. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • a lipase e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • Amines of formula XVIIe can be prepared from intermediates of formula XXXIII, wherein R3, R5a, and R5b are as in compounds of the formula (I), X07 is a leaving group such as bromine, chlorine or iodine, and X12* is a chiral auxiliary, by treatment with acids such as HCI or bases such as NaOH.
  • Chiral auxiliaries of formula XXXII are for instance mandelic acid or (I R)-menthylchloroformate.
  • Intermediates of formula XXXIII can be formed by coupling of a chiral auxiliary of formula XXXII, wherein Xo is a leaving group, such as chlorine, with amines of the formula XVIIf.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • amines of formula XVIIe, or a salt thereof can be formed as described in Scheme 18.
  • a hydrohalide salt preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt
  • amines of formula XVI le, or a salt thereof may be obtained from intermediates of formula XXVa, wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NB0C2 (N- bis(te/Y-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is - NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NB0C2), under deprotection conditions known to a person skilled in the art
  • Such intermediates of formula XXVa wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N- phthalimide group) or -NB0C2 (N-bis(te/Y-butyloxycarbonyl) group), can be obtained from alcohols of formula XXI I la, wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula XXIIIa 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 (HNPh
  • amines of formula XVIIe may be obtained by reduction of azides of formula XXIVa, wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen.
  • Azides of formula XXIVa may be obtained by treatment of alcohols of formula XXIIIa with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • Alcohols of formula XXI Ila may be obtained by enantioselective reduction of ketones of formula XVb, wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide.
  • Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCI[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/EtsN or HCO2NH4.
  • catalysts for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCI[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/EtsN or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/EtsN or HCO2NH4.
  • compounds of the formula XVIIa and XVIIb (each a particular subset of compounds of formula VI), or a salt thereof as defined above, wherein Ria, R3, R4a, R5a and R5b are as described in formula (I), particularly those compounds of the formula XVIIa and XVIIb, or a salt thereof as defined above, wherein R3 and R4a are as described in formula (I) and in which Ria, R5a and R5b are hydrogen, can be prepared in analogy to descriptions found for example in WO 2021/069575.
  • compounds of the formula XVIIg and XVIIh (each another particular subset of compounds of formula VI), or a salt thereof as defined above, wherein Ria, R3, R4 and R5 are as described in formula (I), particularly those compounds of the formula XVIIg and XVIIh, or a salt thereof as defined above, wherein R3 and R4 are as described in formula (I) and in which Ria is hydrogen and R5 is hydrogen, methyl or cyclopropyl, can be prepared in analogy to descriptions found for example in WO 2021/099303, WO 2021/105091 , WO 2021/165195 and WO 2021/224323.
  • Such compounds of formula 11-1 can be prepared as shown on scheme 19, from compounds of formula 11-1 a by reduction of the nitro group using reagents such as iron, ferrous salts, or iron catalyst in aqueous acid (generally referred to as Bechamp reduction), or iron in the presence of ammonium chloride in alcohols (such as ethanol or isopropanol) and water, and at temperature between 0°C to boiling point of the reaction mixture.
  • reagents such as iron, ferrous salts, or iron catalyst in aqueous acid (generally referred to as Bechamp reduction), or iron in the presence of ammonium chloride in alcohols (such as ethanol or isopropanol) and water, and at temperature between 0°C to boiling point of the reaction mixture.
  • such a reduction may also be achieved under conditions known to a person skilled in the art, for example by involving molecular hydrogen (H2), optionally under pressure, in the presence of a catalyst such as for example palladium on charcoal, in alcohols (such as methanol, ethanol or isopropanol), and at temperature between 0°C to boiling point of the reaction mixture.
  • H2 molecular hydrogen
  • a catalyst such as for example palladium on charcoal
  • alcohols such as methanol, ethanol or isopropanol
  • the alkylating reagent of formula R20-LG can be replaced by diethyl (bromodifluoromethyl)phosphonate as described for example in Tetrahedron 2009, 65, 5278-5283, (or sodium 2-chloro-2,2-difluoroacetate, and the like), as difluoromethylating agent when performing a difluoromethylation to generate compounds of formula 11-1 a, wherein R20 is - CHF2.
  • Usage of diethyl (bromodifluoromethyl)phosphonate as a difluorocarbene precursor proceeds in the presence of a base such as sodium or potassium carbonate, or sodium or potassium hydroxide, in the presence of a solvent such as acetonitrile, N,N-dimethylformamide or N-methyl-2-pyrrolidone (NMP), preferably in a mixture with water, optionally in the presence of an additive (such as 2'- hydroxyaceto-phenone), and at temperature between -40°C to 80°C.
  • a base such as sodium or potassium carbonate, or sodium or potassium hydroxide
  • a solvent such as acetonitrile, N,N-dimethylformamide or N-methyl-2-pyrrolidone (NMP)
  • NMP N-methyl-2-pyrrolidone
  • compounds of formula 11-1 can be prepared from compounds of formula 11-1 b by involving the same chemistry as described above (scheme 19), but by changing the order of the steps (i.e. by running the sequence 11-1 b to 11-1 c via nitro reduction, followed by alkylation or carbene addition on 11-1 c to form 11-1 , wherein all substituent definitions mentioned previously remain valid).
  • Scheme 20 Such compounds of formula II-2, can be prepared as shown on scheme 20 above, from compounds of formula I l-2a by reduction of the nitro group using conditions already described in scheme 19 (transformation of compounds of formula 11-1 a into compounds of formula 11-1).
  • Compounds of formula ll-2a wherein S 2 is halo or C 1 -C 3 haloalkyl, and R21 is C 1 -C 3 alkyl or C1- C3haloalkyl can be prepared from compounds of formula ll-2b, wherein S 2 is halo or C 1 -C 3 haloalkyl by means of an alkylation with a reagent of the formula R21-LG, wherein R21 is C 1 -C 3 alkyl or C1- C3haloalkyl and LG is a leaving group such as chloro, bromo or iodo (or a pseudo halogen leaving group such as trifluoromethanesulfonate), or alternatively by means of a carbene addition (difluoromethylation, R21 is -CHF2), under conditions already described in scheme 19 (transformation of compounds of formula 11-1 b into compounds of formula 11-1 a).
  • compounds of formula 11-2 may be prepared from compounds of formula ll-2b by involving the same chemistry as described above (scheme 20), but by changing the order of the steps (i.e. by running the sequence ll-2b to ll-2c via nitro reduction, followed by alkylation or carbene addition on ll-2c to form 11-2, wherein all substituent definitions mentioned previously remain valid).
  • compounds of the formula II-2 (or a salt thereof), wherein S 2 is halo or C 1 -C 3 haloalkyl, and R21 is C 1 -C 3 alkyl or C 1 -C 3 haloalkyl
  • R21 is C 1 -C 3 alkyl or C1- C3haloalkyl
  • PG is a protective group such as tert-butyloxycarbonyl (Boc) or acetyl, by means of cleavage of the group PG under conditions well known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W.
  • Tert-butyloxycarbonyl cleavage can be achieved, for instance by treatment of compounds of the formula ll-2d with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as methanol, ethanol, ispropanol, dichloromethane, tetrahydrofuran or dioxane, and at temperatures ranging from 0°C to the boiling point of the reaction mixture, preferably around room temperature.
  • an acid such as trifluoroacetic acid or hydrochloric acid
  • a suitable solvent such as methanol, ethanol, ispropanol, dichloromethane, tetrahydrofuran or dioxane
  • Such a cross-coupling reaction is achieved in the presence of a palladium based catalyst, for example tetrakis(triphenylphosphine)palladium(0), or palladium ⁇ I) acetate or tris(dibenzylideneacetone)dipalladium(0) in presence of a phosphine ligand, such as 2- dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl tricyclohexylphosphane XPhos, (1 ,1 'bis(diphenyl- phosphino)ferrocene)dichloropalladium-dichloromethane (1 :1 complex), chloro(2-dicyclohexyl- phosphino-2',4',6'-triisopropyl-1 ,1 '-biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium
  • compounds of the formula 11-2-1 may be prepared from compounds of the formula ll-2d by involving the same chemistry as described above in Scheme 21 , but by changing the order of the steps (i.e. by running the sequence ll-2d to ll-2d-1 via treatment with R 1b -Xb, followed by the PG cleavage step to form 11-2-1 , whereby all substituent definitions remain valid).
  • R 1b -Xb wherein R 1b has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen, and wherein Xb is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, are either known, or they can be prepared by methods known to a person skilled in the art.
  • a leaving group such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate
  • compounds of the formula 11-1-1 (or a salt thereof), wherein S 1 is halo or C 1 -C 3 haloalkyl, S 2 is halo or C 1 -C 3 haloalkyl, R20 is C 1 -C 3 haloalkyl, and R 1b has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen, may be made by reacting compounds of the formula 11-1 , wherein S 1 is halo or C 1 -C 3 haloalkyl, S 2 is halo or C 1 -C 3 haloalkyl, and R20 is C 1 -C 3 haloalkyl, with a compound of the formula R 1b -Xb, wherein R 1b has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen, and wherein Xb is a leaving group, such as a halogen or sulfonate, for
  • compounds of the formula (II lf-PYM-1 ), a subset of compounds of formula (XVI Ih) wherein R 1a and R 5 are hydrogen, R 3 is as defined for compounds of the formula (I), and in which R 4 is pyrimidinyl substituted with a single -C(O)NR 10 R 11 , wherein R 10 and R 11 are as defined for compounds of the formula (I), can be made from compounds of the formula (I I lf-PYM-2), wherein R 3 , R 10 and R 11 are as defined for compounds of the formula (I) and X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin.
  • a base such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion exchange resin.
  • the anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid.
  • an acid such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like
  • an organic acid such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid.
  • a great number of such acids are known to a person skilled in the art.
  • Compounds of the formula (I I lf-PYM-2), wherein R 3 , R 10 and R 11 are as defined for compounds of the formula (I) and X- is an anion can be made from compounds of the formula (XXXIXa), wherein R 3 , R 10 and R 11 are as defined for compounds of the formula (I), by treatment with an acid, such as the acids listed above.
  • the reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • the reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambient temperature.
  • acid compounds of the formula (XXXIXb) will be activated to their corresponding acid chlorides with oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N-dimethylformamide (DMF), in inert solvents such as for instance dichloromethane (DCM) or tetrahydrofuran (THF), at temperatures between 0°C to 100°C, preferably around 25°C.
  • DMF dichloromethane
  • THF tetrahydrofuran
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)- methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®).
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)- methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cycl
  • amidation reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetra hydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetra hydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N
  • ammonia surrogates such as ammonium salts (for instance ammonium hydroxide or ammonium chloride) or silica gel-supported ammonium salts (for instance silica gel-supported ammonium chloride NH4CI/SiC>2 as described in Tetrahedron Letters 2005, 46, 6879-6882).
  • Compounds of the formula (XXXIXb), wherein R 3 is as defined for compounds of the formula (I), can be prepared by saponification of the compounds of the formula (XXXIXc), wherein R 3 is as defined for compounds of the formula (I), and in which Ra is C1-C6alkyl, under conditions known to a person skilled in the art (using for example conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature, or up to refluxing conditions).
  • compounds of the formula (XXXIXa), wherein R 3 , R 10 and R 11 are as defined for compounds of the formula (I) can be made directly from compounds of the formula (XXXIXc), wherein R 3 is as defined for compounds of the formula (I), and in which Ra is C1-C6alkyl, by reaction with amine compounds of the formula HNR 10 R 11 , or a salt thereof, wherein R 10 and R 11 are as defined for compounds of the formula (I), optionally in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine, in a solvent, such as an organic solvent, for instance methanol, acetonitrile, tetra hydrofuran, 2-methyltetrahydrofuran, ethyl acetate, dimethyl sulfoxide, N,N- dimethylacetamide or N
  • the reaction can be performed in the presence or in the absence of a drying agent, such as for example in the presence of molecular sieves, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 80 °C.
  • a drying agent such as for example in the presence of molecular sieves
  • 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 metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • 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.
  • the reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • N-oxides can be prepared by reacting a compound of the formula I (when A2 and A3 are each N) with a suitable oxidizing agent, for example the H2C>2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2C>2/urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • acid anhydride e.g. trifluoroacetic anhydride
  • oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000/15615. It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • Table A-1 provides 10 compounds A-1 .001 to A-1.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is
  • Table A-2 provides 10 compounds A-2.001 to A-2.010 of formula ⁇ A wherein $ is C-O-CF2CF2H, S 1 is
  • Table A- provides 10 compounds A-3.001 to A-3.010 of formula ⁇ A wherein $ is C-O-CF2CF2H
  • Table A-4 provides 10 compounds A-4.001 to A-4.010 of formula ⁇ A wherein $ is C-O-CF2CF2H, S 1 is
  • Table A- 5 provides 10 compounds A-5.001 to A-5.010 of formula ⁇ A wherein $ is C-O-CF2CF2H, S 1 is
  • Table A-6 provides 10 compounds A-6.001 to A-6.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A- 7 provides 10 compounds A-7.001 to A-7.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-8 provides 10 compounds A-8.001 to A-8.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-9 provides 10 compounds A-9.001 to A-9.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-10 provides 10 compounds A-10.001 to A-10.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is CF3, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-11 provides 10 compounds A-11 .001 to A-11 .010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-12 provides 10 compounds A-12.001 to A-12.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Cl, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-13 provides 10 compounds A-13.001 to A-13.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Cl
  • R1b is H
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-14 provides 10 compounds A-14.001 to A-14.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Cl
  • R1b is H
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-15 provides 10 compounds A-15.001 to A-15.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Cl
  • R1b is CH3
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-16 provides 10 compounds A-16.001 to A-16.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Cl
  • R1b is CH3
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-17 provides 10 compounds A-17.001 to A-17.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Br
  • R1b is H
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-18 provides 10 compounds A-18.001 to A-18.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Br
  • R1b is H
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-19 provides 10 compounds A-19.001 to A-19.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Br
  • R1b is CH3
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-20 provides 10 compounds A-20.001 to A-20.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is Br
  • R1b is CH3
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-21 provides 10 compounds A-21.001 to A-21.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • S 2 is CF3
  • R1b is H
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-22 provides 10 compounds A-22.001 to A-22.010 of formula l-A wherein $ is C-O-CF2CF2H,
  • S 1 is Br
  • R1a is CH3
  • R3 is CH3 and Q are as defined in table Z.
  • Table A-23 provides 10 compounds A-23.001 to A-23.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Br, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-24 provides 10 compounds A-24.001 to A-24.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is Br, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-25 provides 10 compounds A-25.001 to A-25.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-26 provides 10 compounds A-26.001 to A-26.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-27 provides 10 compounds A-27.001 to A-27.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-28 provides 10 compounds A-28.001 to A-28.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-29 provides 10 compounds A-29.001 to A-29.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-30 provides 10 compounds A-30.001 to A-30.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-31 provides 10 compounds A-31 .001 to A-31 .010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-32 provides 10 compounds A-32.001 to A-32.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-33 provides 10 compounds A-33.001 to A-33.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-34 provides 10 compounds A-34.001 to A-34.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is CF3, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-35 provides 10 compounds A-35.001 to A-35.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-36 provides 10 compounds A-36.001 to A-36.010 of formula l-A wherein $ is C-O-CF2CF2H, S 1 is CF3, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-37 provides 10 compounds A-37.001 to A-37.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-38 provides 10 compounds A-38.001 to A-38.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-39 provides 10 compounds A-39.001 to A-39.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-40 provides 10 compounds A-40.001 to A-40.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-41 provides 10 compounds A-41 .001 to A-41 .010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-42 provides 10 compounds A-42.001 to A-42.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-43 provides 10 compounds A-43.001 to A-43.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-44 provides 10 compounds A-44.001 to A-44.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-45 provides 10 compounds A-45.001 to A-45.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-46 provides 10 compounds A-46.001 to A-46.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is CF3, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-47 provides 10 compounds A-47.001 to A-47.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-48 provides 10 compounds A-48.001 to A-48.010 of formula l-A wherein $ is C-CF3, S 1 is Cl, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-49 provides 10 compounds A-49.001 to A-49.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-50 provides 10 compounds A-50.001 to A-50.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-51 provides 10 compounds A-51 .001 to A-51 .010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-52 provides 10 compounds A-52.001 to A-52.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-53 provides 10 compounds A-53.001 to A-53.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-54 provides 10 compounds A-54.001 to A-54.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-55 provides 10 compounds A-55.001 to A-55.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-56 provides 10 compounds A-56.001 to A-56.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-57 provides 10 compounds A-57.001 to A-57.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-58 provides 10 compounds A-58.001 to A-58.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is CF3, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-59 provides 10 compounds A-59.001 to A-59.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-60 provides 10 compounds A-60.001 to A-60.010 of formula l-A wherein $ is C-CF3, S 1 is Br, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-61 provides 10 compounds A-61 .001 to A-61 .010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-62 provides 10 compounds A-62.001 to A-62.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-63 provides 10 compounds A-63.001 to A-63.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-64 provides 10 compounds A-64.001 to A-64.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-65 provides 10 compounds A-65.001 to A-65.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-66 provides 10 compounds A-66.001 to A-66.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-67 provides 10 compounds A-67.001 to A-67.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-68 provides 10 compounds A-68.001 to A-68.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-69 provides 10 compounds A-69.001 to A-69.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-70 provides 10 compounds A-70.001 to A-70.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is CF3, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-71 provides 10 compounds A-71 .001 to A-71 .010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-72 provides 10 compounds A-72.001 to A-72.010 of formula l-A wherein $ is C-CF3, S 1 is CF3, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-73 provides 10 compounds A-73.001 to A-73.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-74 provides 10 compounds A-74.001 to A-74.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-75 provides 10 compounds A-75.001 to A-75.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-76 provides 10 compounds A-76.001 to A-76.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-77 provides 10 compounds A-77.001 to A-77.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-78 provides 10 compounds A-78.001 to A-78.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-79 provides 10 compounds A-79.001 to A-79.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-80 provides 10 compounds A-80.001 to A-80.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-81 provides 10 compounds A-81 .001 to A-81 .010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is
  • R1b is H
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-82 provides 10 compounds A-82.001 to A-82.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is
  • R1b is H
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-83 provides 10 compounds A-83.001 to A-83.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is
  • R1b is CH3
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-84 provides 10 compounds A-84.001 to A-84.010 of formula l-A wherein $ is N, S 1 is Cl, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-85 provides 10 compounds A-85.001 to A-85.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-86 provides 10 compounds A-86.001 to A-86.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-87 provides 10 compounds A-87.001 to A-87.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-88 provides 10 compounds A-88.001 to A-88.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-89 provides 10 compounds A-89.001 to A-89.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-90 provides 10 compounds A-90.001 to A-90.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-91 provides 10 compounds A-91 .001 to A-91.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-92 provides 10 compounds A-92.001 to A-92.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-93 provides 10 compounds A-93.001 to A-93.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-94 provides 10 compounds A-94.001 to A-94.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is
  • R1b is H
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-95 provides 10 compounds A-95.001 to A-95.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is
  • R1b is CH3
  • R1a is H
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-96 provides 10 compounds A-96.001 to A-96.010 of formula l-A wherein $ is N, S 1 is Br, S 2 is
  • R1b is CH3
  • R1a is CH3
  • R3 is CH3
  • Q are as defined in table Z.
  • Table A-97 provides 10 compounds A-97.001 to A-97.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-98 provides 10 compounds A-98.001 to A-98.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Cl, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-99 provides 10 compounds A-99.001 to A-99.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Cl, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-100 provides 10 compounds A-100.001 to A-100.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Cl, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-101 provides 10 compounds A-101.001 to A-101.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-102 provides 10 compounds A-102.001 to A-102.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Br, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-103 provides 10 compounds A-103.001 to A-103.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Br, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-104 provides 10 compounds A-104.001 to A-104.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is Br, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-105 provides 10 compounds A-105.001 to A-105.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-106 provides 10 compounds A-106.001 to A-106.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is CF3, R1b is H, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-107 provides 10 compounds A-107.001 to A-107.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is CF3, R1b is CH3, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-108 provides 10 compounds A-108.001 to A-108.010 of formula l-A wherein $ is N, S 1 is CF3, S 2 is CF3, R1b is CH3, R1a is CH3, R3 is CH3 and Q are as defined in table Z.
  • Table A-109 provides 10 compounds A-109.001 to A-109.010 of formula l-A wherein $ is C-O-CHF2, S 1 is Cl, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-110 provides 10 compounds A-110.001 to A-110.010 of formula l-A wherein $ is C-O-CHF2, S 1 is Cl, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-111 provides 10 compounds A-111 .001 to A-111 .010 of formula l-A wherein $ is C-O-CHF2, S 1 is Cl, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-112 provides 10 compounds A-112.001 to A-112.010 of formula l-A wherein $ is C-O-CHF2, S 1 is Br, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-113 provides 10 compounds A-113.001 to A-113.010 of formula l-A wherein $ is C-O-CHF2, S 1 is Br, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-114 provides 10 compounds A-114.001 to A-114.010 of formula l-A wherein $ is C-O-CHF2, S 1 is Br, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-115 provides 10 compounds A-115.001 to A-115.010 of formula l-A wherein $ is C-O-CHF2, S 1 is CF3, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-116 provides 10 compounds A-116.001 to A-116.010 of formula l-A wherein $ is C-O-CHF2, S 1 is CF3, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-117 provides 10 compounds A-117.001 to A-117.010 of formula l-A wherein $ is C-O-CHF2, S 1 is CF3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-118 provides 10 compounds A-118.001 to A-118.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is Cl, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-119 provides 10 compounds A-119.001 to A-119.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is Cl, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-120 provides 10 compounds A-120.001 to A-120.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is Cl, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-121 provides 10 compounds A-121 .001 to A-121 .010 of formula l-A wherein $ is C-O-CCIF2, S 1 is Br, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-122 provides 10 compounds A-122.001 to A-122.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is Br, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-123 provides 10 compounds A-123.001 to A-123.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is Br, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-124 provides 10 compounds A-124.001 to A-124.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is CF3, S 2 is Cl, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-125 provides 10 compounds A-125.001 to A-125.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is CF3, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-126 provides 10 compounds A-126.001 to A-126.010 of formula l-A wherein $ is C-O-CCIF2, S 1 is CF3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-127 provides 10 compounds A-127.001 to A-127.010 of formula l-A wherein $ is C-O-
  • Table A-128 provides 10 compounds A-128.001 to A-128.010 of formula l-A wherein $ is C-O-
  • Table A-129 provides 10 compounds A-129.001 to A-129.010 of formula l-A wherein $ is C-O-
  • Table A-130 provides 10 compounds A-130.001 to A-130.010 of formula l-A wherein $ is C-O-
  • Table A-131 provides 10 compounds A-131 .001 to A-131 .010 of formula l-A wherein $ is C-O- CH2CF2H, S 1 is Br, S 2 is Br, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-132 provides 10 compounds A-132.001 to A-132.010 of formula l-A wherein $ is C-O-
  • Table A-133 provides 10 compounds A-133.001 to A-133.010 of formula l-A wherein $ is C-O-
  • Table A-134 provides 10 compounds A-134.001 to A-134.010 of formula l-A wherein $ is C-O-
  • Table A-135 provides 10 compounds A-135.001 to A-135.010 of formula l-A wherein $ is C-O-
  • Table A-136 provides 10 compounds A-136.001 to A-136.010 of formula l-A wherein $ is N, S 1 is OCHF2, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-137 provides 10 compounds A-137.001 to A-137.010 of formula l-A wherein $ is N, S 1 is OCHF2, S 2 is CHF2, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-138 provides 10 compounds A-138.001 to A-138.010 of formula l-A wherein $ is N, S 1 is OCH2CHF2, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-139 provides 10 compounds A-139.001 to A-139.010 of formula l-A wherein $ is N, S 1 is OCH2CHF2, S 2 is CHF2, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-140 provides 10 compounds A-140.001 to A-140.010 of formula l-A wherein $ is N, S 1 is OCH2CF3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-141 provides 10 compounds A-141 .001 to A-141 .010 of formula l-A wherein $ is N, S 1 is OCH2CF3, S 2 is CHF2, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-142 provides 10 compounds A-142.001 to A-142.010 of formula l-A wherein $ is N, S 1 is OCH3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-143 provides 10 compounds A-143.001 to A-143.010 of formula l-A wherein $ is N, S 1 is OCH3, S 2 is CHF2, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-144 provides 10 compounds A-144.001 to A-144.010 of formula l-A wherein $ is N, S 1 is OCH2CH3, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-145 provides 10 compounds A-145.001 to A-145.010 of formula l-A wherein $ is N, S 1 is OCH2CH3, S 2 is CHF2, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-146 provides 10 compounds A-146.001 to A-146.010 of formula l-A wherein $ is N, S 1 is OCH(CH3)2, S 2 is CF3, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • Table A-147 provides 10 compounds A-147.001 to A-147.010 of formula l-A wherein $ is N, S 1 is OCH(CH3)2, S 2 is CHF2, R1b is H, R1a is H, R3 is CH3 and Q are as defined in table Z.
  • the compound of formula (I) is defined as follows: X is oxygen; R 1a is hydrogen and R 1b is hydrogen, or methyl; wherein T c is C-R 2c , R 2a and R 2b are chloro; and R 2c is trifluoromethyl, 1 ,1 ,2,2- tetrafluoroethoxy, chloro(difluoro)methoxy, 2,2-difluoroethoxy, or difluoromethoxy; or wherein T c is N, R 2a is chloro, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy; and R 2b is difluoromethyl, or trifluoromethyl; R 3 is methyl; Q is Q a -1 ; R4 is R 4 -1 , or R 4 -6; R 10 is hydrogen; and R 11 is hydrogen, or methyl.
  • X is oxygen
  • R 1a is
  • a compound of formula III wherein Q is selected from Q-1 to Q-10, such as from Q-1 to Q-4 and Q-9, R3 is methyl and X is sulfur;
  • a compound of formula IV wherein Q is selected from Q-1 to Q-10, such as from Q-1 to Q-4 and Q-9, R3 is methyl, Ria is hydrogen and X is sulfur;
  • T is wherein T c is C-R 2c , R 2a and R 2b are chloro; and R 2c is trifluoromethyl, 1 ,1 ,2,2-tetrafluoroethoxy, chloro(difluoro)methoxy, 2,2- difluoroethoxy, or difluoromethoxy; or wherein T c is N, R 2a is chloro, methoxy, ethoxy, isopropoxy, difluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy; and R 2b is difluoromethyl, or trifluoromethyl;
  • R1 b is hydrogen or methyl; and X is oxygen;
  • T is selected from 2,4-bis(trifluoromethyl)phenyl, 2,4- chloro-5-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl, 2-bromo-4-chloro-5-(trifluoromethyl)phenyl, 4-bromo-2- (difluoromethoxy)-5-fluoro-phenyl, 2-bromo-4-(difluoromethoxy)phenyl, 2-iodo-4-
  • T is selected from 2,4-bis(trifluoromethyl)phenyl, 2,4- chloro-5-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl, 2-bromo-4-chloro-5-(trifluoromethyl)phenyl, 4-bromo-2- (difluoromethoxy)-5-fluoro-phenyl, 2-bromo-4-(difluoromethoxy)phenyl, 2-iodo-4-
  • the present invention accordingly makes available compounds of formulae III, IV, VII, XIII, and XVI, wherein in each case, as applicable, X is sulfur or oxygen, Ria, Rit, R3, Q and T are as defined for formula I in the first aspect. Furthermore, the corresponding embodiments illustrated for formula I also apply to the compounds of formulae III, IV, VII, XIII, and XVI.
  • the compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate.
  • Examples of the above-mentioned animal pests are: from the order Acarina, for example,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megas
  • Acyrthosium pisum Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spec
  • Coptotermes spp Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example,
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.; from the order Psocoptera, for example, Liposcelis spp.; from the order Siphonaptera, for example,
  • Calliothrips phaseoli Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; from the order Thysanura, for example, Lepisma saccharina.
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (endoparasitic, semiendoparasitic and ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H.
  • H. aperta Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, 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 spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Ageratum spp. Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp.
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (/.
  • 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. (Xt. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the compounds of formula I are particularly suitable for control of
  • a pest of the order Hemiptera for example, one or more of the species Bemisia tabaci , Aphis craccivora, Myzus persicae, Rhopalosiphum Padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans, and sugarcane);
  • a pest of the order Lepidoptera for example, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn);
  • Thysanoptera such as the family Thripidae, for example, one or more of Thrips tabaci and Frankliniella occidentalis (preferably in vegetables);
  • soil pests such as of the order Coleoptera
  • the species Diabrotica balteata, Agriotes spp. and Leptinotarsa decemlineata preferably in vegetables and corn.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popilliae
  • Bacillus thuringiensis such as 8-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab,
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ec
  • 8-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • 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.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x 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 CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis- related proteins" (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis- related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191 .
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • fungal for example Fusarium, Anthracnose, or Phytophthora
  • bacterial for example Pseudomonas
  • viral for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus
  • 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, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called
  • compositions according to the invention are the protection of stored goods and storerooms 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 use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal.
  • the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and/or treating diseases transmitted by ectoparasites.
  • the present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal.
  • the present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal.
  • controlling when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation.
  • treating when used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease.
  • preventing when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal.
  • animal when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal.
  • Non-human mammals include, but are not limited to, livestock animals and companion animals.
  • Livestock animals include, but are not limited to, cattle, camellids, pigs, sheep, goats and horses.
  • Companion animals include, but are not limited to, dogs, cats and rabbits.
  • a “parasite” is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense.
  • An “endoparasite” is a parasite which lives in the host animal.
  • An “ectoparasite” is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice).
  • the Acari (or Acarina) sub-class comprises ticks and mites.
  • Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor, Haemaphysalis; Hyalomma; Ixodes; Rhipicentor, Margaropus; Argas; Otobius; and Omithodoros.
  • Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates.
  • Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera.
  • Members of the Siphonaptera order include, but are not limited to, Ctenocephalides fells and Ctenocephatides canis.
  • Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes.
  • Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola Ovis and Bovicola Bovis.
  • an effective amount when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal.
  • the effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of or 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 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. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, S.M., et al., “Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977).
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • 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.
  • 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:
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs, ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A.
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls
  • mole crickets tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, B/issus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • chinch bugs such as southern chinch bugs, B/issus insularis
  • Bermudagrass mite Eriophyes cynodoniensis
  • rhodesgrass mealybug Antonina graminis
  • two-lined spittlebug Propsapia bicincta
  • 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.
  • red imported fire ants Solenopsis invicta
  • 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.
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp., Call
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
  • Blattarida for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taign
  • the compounds of formulae I, and I’a, orsalts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • a compound TX controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • the compounds of formulae I, and I’a, orsalts thereof, are especially suitable for controlling one or more of pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp. .
  • a compound TX controls one or more of pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
  • pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
  • the compounds of formulae I, and I’a, orsalts 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 includens, 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 includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilaparvata lugens + TX, Myzus pers
  • one compound from Tables A-1 to A-147, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.
  • one compound from Tables A-1 to A-147, and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
  • advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
  • certain compounds of formula I may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees.
  • Apis mellifera is particularly, for example, Apis mellifera.
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, /V,/V-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane,
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, 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 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • 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.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • the following Examples further illustrate, but do not limit, the invention.
  • 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.
  • 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.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • 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.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 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.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • 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 (EG), 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 formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo-emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • EG
  • Mp melting point in °C. Free radicals represent methyl groups. 1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) + or (M-H)-.
  • Method 1 Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 500 °C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range: 110 to 800 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector.
  • an electrospray source Polyity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 500 °C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range
  • Method 5 Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector.
  • an electrospray source Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/h
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • Example E1 Preparation of 1-[(1 S)-1-[2-(6-cvanopyrimidin-4-yl)-1 ,2,4-triazol-3-yl1ethyl1-3-[2,4-dichloro- 5-(trifluoromethyl)phenyl1urea (compound P1) and 6-[5-[(1 S)-1-[[2,4-dichloro-5-(trifluoromethyl)phenyl1- carbamoylaminolethyll-1 ,2,4-triazol-1-yllpyrimidine-4-carboxamide (compound P2)
  • Example E2 Preparation of 1-[(1 S)-1-[2-(6-cyanopyrimidin-4-yl)-1 ,2,4-triazol-3-yl1ethyl1-3-[2,4-dichloro- 5-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl1urea (compound P3) and 6-[5-[(1 S)-1-[[2,4-dichloro-5-(1 ,1 ,2,2- tetrafluoroethoxy)phenyl1carbamoyl-amino1ethyl1-1 ,2,4-triazol-1-yllpyrimidine-4-carboxamide (compound P4)
  • Example E3 Preparation of 6-[5-[(1 S)-1 -[[4-chloro-6-(trifluoromethyl)-3-pyridyl1carbamoylamino1ethyl1-
  • 6-[5-[(1 S)-1 -[[4-(difluoromethoxy)-6-(difluoromethyl)-3-pyridyl]carbamoylamino]ethyl]-1 ,2,4- triazol-1-yl]-N-methyl-pyrimidine-4-carboxamide (P13) can be obtained from 4-(difluoromethoxy)-6- (difluoromethyl)pyridine-3-amine (1-10) and [(1 S)-1-[2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1 ,2,4-triazol- 3-yl]ethyl]ammonium chloride (1-14) following above protocol in analogy.
  • 6-[5-[(1 S)-1 -[[4-ethoxy-6-(trifluoromethyl)-3-pyridyl]carbamoylamino]ethyl]-1 , 2 ,4-triazol- 1 - yl]pyrimidine-4-carboxamide can be obtained from 4-ethoxy-6-(trifluoromethyl)pyridin-3-amine (I- 21) and 6-[5-[(1 S)-1-aminoethyl]-1 ,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (I-6; CAS 2694010-27-8) following above protocol in analogy.
  • Example E4 Preparation of 6-[5-[(1 S)-1 -[[[4-(difluoromethoxy)-6-(trifluoromethyl)-3-pyridyl1-methyl- carbamoyllaminolethyll-1 ,2,4-triazol-1-yllpyrimidine-4-carboxamide (compound P34)
  • 6-[5-[(1S)-1-[[[4-(difluoromethoxy)-6-(trifluoromethyl)-3-pyridyl]-methyl-carbamoyl]amino]ethyl]-1 ,2,4- triazol-1-yl]pyrimidine-4-carboxamide (P34) can be obtained in analogy following above protocol Example E3 from 4-(difluoromethoxy)-N-methyl-6-(trifluoromethyl)pyridin-3-amine (1-19) and 6-[5- [(1 S)-1 -aminoethyl]-1 ,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (I-6; CAS 2694010-27-
  • Step 2 Preparation of [(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1 ,2,4-triazol-3-yl]ethyl]-methyl- ammonium chloride (1-16)
  • Potassium hydroxide (4.5 g, 80.17 mmol) was diluted in water (32 mL), then acetonitrile (32 mL) and 5-bromo-2-(trifluoromethyl)pyridin-4-ol (CAS 1196156-74-7) (2.0 g, 8.02 mmol) were added.
  • the colorless biphasic mixture was cooled with brine ice (-10°C) before diethyl (bromodifluoro- methyl)phosphonate (3.56 mL, 20.04 mmol) was added dropwise during 1 h to the solution. The temperature was slowly allowed to return to RT and the mixture stirred for 2 h, then diluted with water and the product extracted twice with ethyl acetate.
  • Step 2 Preparation of tert-butyl N-[4-(difluoromethoxy)-6-(trifluoromethyl)-3-pyridyl]carbamate
  • Example 110 Preparation of 4-(difluoromethoxy)-N-methyl-6-(trifluoromethyl)pyridin-3-amine (1-19) Sodium hydride (60 mass% in oil, 54.6 mg, 1.42 mmol) was added to a solution of 4- (difluoromethoxy)-6-(trifluoromethyl)pyridine-3-amine (1-11) (250 mg, 1.10 mmol) in tetrahydrofuran (3.65 mL) at 0°C. The mixture was stirred for 15 min until gas formation stopped before iodomethane (0.072 mL, 1.10 mmol) was added in one portion. The mixture was allowed to reach RT and stirred for 30 min.
  • Step 1 Preparation of 5-bromo-4-ethoxy-2-(trifluoromethyl)pyridine lodoethane (0.44 mL, 5.41 mmol) was added to a suspension of 5-bromo-2-(trifluoromethyl)pyridin-4- ol (CAS 1196156-74-7) (900 mg, 3.61 mmol) and potassium carbonate (599 mg, 4.33 mmol) in DMF (3.6 mL). The mixture was stirred at 50°C overnight, then quenched with water and the product extracted with EtOAc.
  • 5-bromo-4-isopropoxy-2-(trifluoromethyl)pyridine can be prepared from 5-bromo-2- (trifluoromethyl)pyridin-4-ol (1.2 g, 4.81 mmol), 2-iodopropane (0.984 mL, 9.62 mmol) and potassium carbonate (1.33 g, 9.62 mmol) in DMF (9.6 mL).
  • Step 2 Preparation of tert-butyl N-[4-ethoxy-6-(trifluoromethyl)-3-pyridyl]carbamate
  • tert-butyl N-[4-isopropoxy-6-(trifluoromethyl)-3-pyridyl]carbamate can be prepared from 5- bromo-4-isopropoxy-2-(trifluoromethyl)pyridine (745 mg, 2.62 mmol), tert-butyl carbamate (470.2 mg, 3.93 mmol), cesium carbonate (1.22 g, 3.67 mmol) and XantPhos Pd G3 (28 mg, 0.01 equiv.) in 2- methyltetrahydrofuran (8.7 mL).
  • 4-isopropoxy-6-(trifluoromethyl)pyridin-3-amine (I-22) can be prepared from tert-butyl N-[4- isopropoxy-6-(trifluoromethyl)-3-pyridyl]carbamate (1.18 g, 3.68 mmol) in hydrochloric acid (5-6N solution in iPrOH, 11 mL).
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl-methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means “one compound selected from the compounds defined in Tables A-1 to A-147, and Table P”
  • an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX; abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, afidopyropen + TX, afoxolaner + TX, alanycarb + TX, allethrin + TX, alpha- cypermethrin + TX, alphamethrin + TX, amidoflumet + TX, aminocarb + TX, azocyclotin + TX, bensultap + TX, benzoximate + TX
  • TX Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococc
  • TX Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp.
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • the compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1- yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in
  • TX Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (e.g, BiostartTM, formerly Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®, VOTiVO®) + TX,
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1 Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF I 3P®) + TX, Bac
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Ps
  • Rhodosporidium diobovatum + TX Rhodosporidium toruloides + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plantmate®
  • Trichoderma harzianum rifai My costar® + TX
  • Trichoderma harzianum -22 Trianum-P®, Plantshield HC®, Rootshield®, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + 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, Trichosporon spp. + TX, Trichothecium spp.
  • TX Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal®, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, and Xenorhabdus
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, Nepeta cataria (Catn
  • Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris (Thripex®, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii®, Swir
  • TX Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline®, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus Chamaeleon + TX, Closterocerus spp.
  • TX Coccidoxenoides perminutus (Pianopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeospori
  • antibacterial agents selected from the group of:
  • Bacillus mojavensis strain R3B accesion No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX
  • Bacillus pumilus in particular strain BU F-33, having NRRL Accession No. 50185 (CARTISSA® from BASF, EPA Reg. No. 71840-19) + TX
  • Bacillus subtilis in particular strain QST713/AQ713 (SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 , U.S. Patent No.
  • Bacillus subtilis strain BU1814 (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX
  • Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) + TX
  • Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No.
  • Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX; Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX; Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX; Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; and
  • fungi examples of which are Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (as disclosed in WO 2010/086790 from Lesaffre et Compagnie, FR) + TX;
  • Aureobasidium pullulans in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or
  • bacteria examples of which are Agrobacterium radiobacter strain K84 (e.g. GALLTROL- A® from AgBioChem, CA) + TX; Agrobacterium radiobacter strain K1026 (e.g. NOGALLTM from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.
  • Agrobacterium radiobacter strain K84 e.g. GALLTROL- A® from AgBioChem, CA
  • Agrobacterium radiobacter strain K1026 e.g. NOGALLTM 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.
  • 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 amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B- 50768, WO 2014/028521) (STARGUS® from Marrone Bio Innovations) + TX; Bacillus amyloliquefaciens strain FZB42, Accession No.
  • DSM 23117 available as RHIZOVITAL® from ABiTEP, DE
  • TX Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREENTM from University of Pretoria) + TX
  • Bacillus lichen! formis in particular strain SB3086, having Accession No.
  • ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM from Novozymes) + TX; Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX; Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX; Bacillus mycoides, isolate, having Accession No.
  • Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No. 6,245,551) + TX; Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX; Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No. 50185 (available as part of the CARTISSA product from BASF, EPA Reg. No.
  • Bacillus subtilis in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051) + TX; Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277) + TX; Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No.
  • Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX; Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX; Bacillus subtilis CX-9060 from Certis USA LLC + TX; Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX; Bacillus subtilis IAB/BS03 (AVIVTM from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) + TX; Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.
  • NRRL B-50897, WO 2017/019448 e.g., HOWLERTM and ZIO® from AgBiome Innovations, US
  • TX Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX
  • Pseudomonas fluorescens strain A506 e.g. BLIGHTBAN® A506 by NuFarm
  • Pseudomonas proradix e.g.
  • Streptomyces griseoviridis strain K61 also known as Streptomyces galbus strain K61
  • DSM 7206 MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf. Crop Protection 2006, 25, 468-475
  • Streptomyces lydicus strain WYEC108 also known as Streptomyces lydicus strain WYCD108US
  • (2.2) fungi examples of which are Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX; Ampelomyces quisqualis strain AQ10, having Accession No.
  • CNCM 1-807 e.g., AQ 10® by IntrachemBio Italia
  • TX Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta/ChemChina) + TX
  • Aureobasidium pullulans in particular blastospores of strain DSM14940 + TX
  • Aureobasidium pullulans in particular blastospores of strain DSM 14941 + TX
  • Aureobasidium pullulans in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH) + TX
  • Chaetomium cupreum accesion No.

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Abstract

La présente invention concerne des composés de formule (I) dans laquelle : X est O ou S ; Q est Qa ou Qb en tant que pesticides et insecticides. Les composés préférés sont par exemple des dérivés de 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl] éthyl]-3-[2,4-dichloro-5-phényl]urée et des composés similaires. Un composé donné à titre d'exemple est, par exemple, la 1-[(1S)-1-[2- (6-cyanopyrimidin-4-yl)-1,2,4-triazol-3-ylléthyll-3-[2,4-dichloro-5-(trifluorométhyl)phényllurée (exemple E1 ; composé P1). La présente invention concerne la synthèse et la caractérisation de composés donnés à titre d'exemple ainsi que des données biologiques associées.
PCT/EP2023/070002 2022-07-26 2023-07-19 Dérivés de 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]éthyl]-3-[2,4-dichloro-5-phényl]urée et composés similaires utilisés comme pesticides WO2024022910A1 (fr)

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IN202211042800 2022-07-26
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EP22195162.7 2022-09-12

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