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WO2025022007A1 - Pesticidally active quinazoline compounds - Google Patents

Pesticidally active quinazoline compounds Download PDF

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Publication number
WO2025022007A1
WO2025022007A1 PCT/EP2024/071370 EP2024071370W WO2025022007A1 WO 2025022007 A1 WO2025022007 A1 WO 2025022007A1 EP 2024071370 W EP2024071370 W EP 2024071370W WO 2025022007 A1 WO2025022007 A1 WO 2025022007A1
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Prior art keywords
formula
compounds
spp
methyl
hydrogen
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PCT/EP2024/071370
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French (fr)
Inventor
André Stoller
Jagadeesh Prathap KILARU
Andre Jeanguenat
Michel Muehlebach
Christopher Charles SCARBOROUGH
Ouidad LAHTIGUI
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Publication of WO2025022007A1 publication Critical patent/WO2025022007A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings

Definitions

  • the present invention relates to pesticidally active quinazoline compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active quinazoline compounds.
  • the invention also relates to the preparation of these quinazoline compounds, to intermediates useful in the preparation of these quinazoline compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these quinazoline compounds, to preparation of these compositions and to the use of these quinazoline compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina.
  • WO 2021/083936, WO 2021/148639, WO 2021/177160, WO 2022/268648, WO 2023/104714, WO 2023/247360, and WO 2024/110554 describe certain quinazoline, quinazolinone and quinoline compounds.
  • the present invention accordingly relates, in a first aspect, to a compound of the formula (I): wherein: A 1 , A 2 , and A 3 are, independently from each other, N or C-R Y ; A 4 and A 5 are, independently from each other, N or C-R Y ; the staggered line represents the connection of Q to the rest of compound of the formula (I); 82949 FF 2 R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R 2a and R 2b are independently hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3
  • the present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I).
  • the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient.
  • the present invention makes available a method of combating and controlling pests, such as insects, acarines, nematodes, or molluscs, which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally, such as insecticidally, acaricidally, nematicidally, or molluscicidally, effective amount of a compound as defined in the first aspect or of a composition as defined in the second aspect.
  • pests such as insects, acarines, nematodes, or molluscs
  • the present invention makes available a method for the protection of plant propagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which comprises treating the propagation material or the site where the propagation material is planted, with an effective amount of a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect.
  • a pest such as insects, acarines, nematodes, or molluscs
  • the present invention makes available a plant propagation material, such as a seed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect.
  • the present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect.
  • the present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect.
  • the present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof.
  • Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or 82949 FF 4 dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example e
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • C1-Cnalkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2- dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,
  • C1-Cnhaloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2- fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroe
  • C1-C2fluoroalkyl refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.
  • C1-Cnalkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1- methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.
  • haloC1-Cnalkoxy refers to a C1-Cnalkoxy radical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different halo atom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy.
  • C1-Cncyanoalkyl refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in 82949 FF 5 these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3- cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
  • C3-Cncycloalkyl refers to a saturated monocyclic hydrocarbon radical attached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cyanoC3-C4cycloalkyl refers to a cyclopropyl or cyclobutyl radical where one of the hydrogen atoms in these radicals is replaced by a cyano group.
  • C3-C4cycloalkylC1-C2alkyl refers to a cyclopropyl or cyclobutyl radical bonded via a methylene or ethylene bridge to the rest of the molecule.
  • the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge.
  • C1-Cnalkylsulfanyl refers to a C1-Cnalkyl moiety linked through a sulfur atom.
  • C1-Cnhaloalkylthio or “C1-Cnhaloalkylsulfanyl” as used herein refers to a C1-Cnhaloalkyl moiety linked through a sulfur atom.
  • C3-Cncycloalkylsulfanyl refers to 3-n membered cycloalkyl moiety linked through a sulfur atom.
  • C2-Cnalkenyl refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl.
  • C2-Cnalkynyl refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.
  • Halogen or "halo" is generally fluorine, chlorine, bromine or iodine.
  • 2-oxo-3-oxazolidinyl and 2,4-dioxo-3-oxazolidinyl refer to the following two radicals, where the staggered line represents the point of attachment of the radical to the rest of the compound: 82949 FF 6 2-oxo-3-oxazolidinyl 2,4-dioxo-3-oxazolidinyl
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring having 1, 2 or 3 heteroatoms independently selected from N, O and S.
  • heteroaryls are linked to the remainder of the compound via a carbon atom of the aromatic monocyclic ring.
  • heteroaryls J-1 to J-40 shown in Table J below, where the staggered line represents the connection of the heteroaryl to the remainder of the compound.
  • Preferred heteroaryl include pyridyl, pyrimidyl, and pyrazolyl.
  • controlling refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
  • pest refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest.
  • the term “effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
  • an effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
  • compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in formula (I*) below: where R 1 , R 2a , R 2b , R 3 , Q, A 1 , A 2 , A 3 , A 4 , and A 5 are as defined in the first aspect.
  • the present invention contemplates both racemates and individual enantiomers.
  • Compounds of formula (I'a) having a preferred stereochemistry are set out below: 82949 FF 8
  • Particularly preferred compounds of the present invention are compounds of formula (I’a) where R 1 , R 2a , R 2b , R 3 , Q, A 1 , A 2 , A 3 , A 4 , and A 5 are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I’a), and agrochemically acceptable salts thereof.
  • Embodiments according to the invention are provided as set out below.
  • A. A 1 , A 2 and A 3 are, independently from each other, N or C-R Y , with the proviso that at least one of A 1 , A 2 , and A 3 , is C-R Y ; or B. A 1 and A 3 are N and A 2 is CR Y ; or C. A 1 , A 2 and A 3 are, independently from each other, N or CH; or D. A 1 , A 2 and A 3 are, independently from each other, N or CH, with the proviso that at least one of A 1 , A 2 , and A 3 is CH; or E. A 1 is N, and A 2 and A 3 are CH; or F.
  • a 1 and A 2 CH, and A 3 is N; or G.
  • a 1 and A 3 are N, and A 2 is CH.
  • a 4 is C-R Y , and A 5 is N; or B.
  • a 4 is C-R Y , and A 5 is CH; or C.
  • a 4 is CH, and A 5 is N; or D.
  • a 4 is N, and A 5 is CH; or E.
  • a 4 is CH, and A 5 is CH.
  • the group or groups R Y are independently: A.
  • R Y is hydrogen, C1-C3alkyl, C1-C3haloalkyl, hydroxy, C1-C3alkoxy, C1-C3haloalkoxy, halogen, CN, or cyclopropyl; or B.
  • R Y is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, or cyclopropyl; or C.
  • R Y is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, or cyclopropyl; or D.
  • R Y is hydrogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, or cyclopropyl; or E. R Y is hydrogen, methyl, trifluoromethyl, methoxy, or cyclopropyl; or F. R Y is hydrogen, methyl, or trifluoromethyl; or G. R Y is hydrogen. [0042] In preferred embodiments of each aspects of the invention: 82949 FF 9 A. One or two of A 1 , A 2 , and A 3 are nitrogen, and the other or others are CH; and one or two of A 4 and A 5 are CH; or B.
  • a 1 , A 2 , and A 3 are nitrogen, and the other or others are CH; A 4 is CH, and A 5 is CH; or C.
  • a 1 is N, A 2 is CH, A 3 is CH, A 4 is CH, and A 5 is CH; or D.
  • a 1 is CH, A 2 is CH, A 3 is N, A 4 is CH, and A 5 is CH; or E.
  • a 1 is N, A 2 is CH, A 3 is N, A 4 is CH, and A 5 is CH.
  • a 1 is N, A 2 is CH, A 3 is N, A 4 is CH, and A 5 is CH.
  • R is hydrogen, methyl, ethyl, 2,2-difluoroethyl, or 2,2,2-trifluoroethyl.
  • the bicyclic ring containing A 1 , A 2 , A 3 , A 4 and A 5 may be abbreviated as T: the staggered line represents the connection of T to the remainder of the compound, for instance to the -N(R 1 )C(R 3 )Q moiety in compounds of formula (I).
  • T the staggered line represents the connection of T to the remainder of the compound, for instance to the -N(R 1 )C(R 3 )Q moiety in compounds of formula (I).
  • R 1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B.
  • R 1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; or C.
  • R 1 is hydrogen, methyl, or cyclopropylmethyl; or D.
  • R 1 is hydrogen or methyl; or E.
  • R 1 is hydrogen; or F.
  • R 1 is methyl.
  • R 1 is hydrogen, methyl, or cyclopropylmethyl; or R 1 is hydrogen or methyl. In more preferred embodiments of each aspects of the invention, R 1 is hydrogen or methyl. [0048] In an embodiment of each aspect of the invention: A.
  • R 2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C6cycloalkyl, phenyl, piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl, pyrrolidin-1-yl, C3- C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, or C1-C4haloalkylsulfonyl; or B.
  • R 2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C4cycloalkyl, phenyl, C3-C4cycloalkylC1-C4alkyl, or C1-C4haloalkylsulfonyl; or C.
  • R 2a is fluoro, chloro, bromo, iodo, C1-C3haloalkyl, methoxy, ethoxy, C1-C3haloalkoxy, phenyl, C3-C4cycloalkylC1-C4alkyl, or C1-C2haloalkylsulfonyl; or 82949 FF 10 D.
  • R 2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C6cycloalkyl, phenyl, or C1-C4haloalkylsulfonyl; or E.
  • R 2a is halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or C1-C4haloalkylsulfonyl; or F.
  • R 2a is hydrogen, halogen, or C1-C3haloalkyl; or G.
  • R 2a is hydrogen, halogen, C1-C3fluoroalkyl, or C1-C3fluoroalkylsulfonyl; or H.
  • R 2a is hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or I.
  • R 2a is trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or J. R 2a is trifluoromethyl, chloro, or bromo; or K. R 2a is chloro.
  • A. R 2b is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C6cycloalkyl, phenyl, or C1-C4haloalkylsulfonyl; or B.
  • R 2b is halogen, C1-C3haloalkyl, C1-C3alkoxy, or C1-C3haloalkoxy; or C. R 2b is C1-C3fluoroalkyl, or C1-C3fluoroalkylsulfonyl; or D. R 2b is hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or E. R 2b is trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or F. R 2b is trifluoromethyl, chloro, or bromo; or G.
  • R 2b is trifluoromethyl, chloro, or iodo; or H. R 2b is trifluoromethyl, or chloro; or I. R 2b is trifluoromethyl or iodo; or J. R 2b is trifluoromethyl.
  • A. R 2a and R 2b are independently hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or B. R 2a and R 2b are independently trifluoromethyl, chloro, bromo, or iodo; or C.
  • R 2a and R 2b are differently selected from the group consisting of trifluoromethyl, chloro, bromo, and iodo; or D.
  • R 2a and R 2b are independently trifluoromethyl, chloro, or iodo; or E.
  • R 2a is trifluoromethyl, chloro, or bromo, and R 2b is trifluoromethyl; or F.
  • R 2a is chloro, and R 2b is trifluoromethyl or chloro; or G.
  • R 2a is chloro, and R 2b is trifluoromethyl or iodo; or H.
  • R 2a is chloro, and R 2b is trifluoromethyl.
  • R 3 is methyl or trifluoromethyl; or B. R 3 is methyl. [0052] In preferred embodiments of each aspect of the invention, R 3 is methyl. [0053] In an embodiment of each aspect of the invention: A. Q is Q a ; or B. Q is Q b . [0054] In an embodiment of each aspect of the invention, Q is Q a and 82949 FF 11 A.
  • R 5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; or B. R 5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or C.
  • R 5 is hydrogen, halogen, or C1-C3alkyloxy; or D. R 5 is hydrogen, halogen, or C1-C3alkyl; or E. R 5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, 2-methoxyethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylcarbonyl, methoxycarbonyl, or 1,3,4-oxadiazol-2-yl; or F. R 5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; or G.
  • R 5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or H.
  • R 5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, or 2-methoxyethoxy; or I.
  • R 5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; or J.
  • R 5 is hydrogen, cyclopropyl, or methoxy; or K.
  • R 5 is hydrogen. [0055]
  • Q is Q a , and A.
  • R 5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or B. R 5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, or 2-methoxyethoxy; or C. R 5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; or D. R 5 is hydrogen, cyclopropyl, or methoxy; or E. R 5 is hydrogen.
  • Q a is selected from Q a -1 to Q a -16: Q a -5 Q a -6 Q a -7 Q a -8 82949 FF 12
  • Q a is Q a -1, Q a -4, Q a -5 Q a -6, Q a -7, Q a -10, or Q a -15.
  • Q a is Q a -1, Q a -6, Q a -7, Q a -10, or Q a -15. More preferably, Q a is Q a -1 or Q a -15. Most preferably, Q a is Q a -1.
  • Q is Q b and A.
  • R 5a is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B.
  • R 5a is hydrogen, halogen, or C1-C3alkyloxy; or C.
  • R 5a is hydrogen, halogen, or C 1 -C 3 alkyl; or D.
  • R 5a is hydrogen, chloro, fluoro, methyl, cyclopropyl, trifluoromethyl, methoxy, difluoromethoxy, or cyano; or E.
  • R 5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy; or F. R 5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy ; or G. R 5a is hydrogen, fluoro, chloro, cyano, methyl, or methoxy H. R 5a is hydrogen; and A. R 5b is hydrogen, halogen, C 1 -C 3 alkyl, or C 3 -C 4 cycloalkyl; or B. R 5b is hydrogen, halogen, or C1-C3alkyloxy; or C.
  • R 5b is hydrogen, halogen, or C1-C3alkyl; or D. R 5b is hydrogen, chloro, fluoro, or methoxy; or E. R 5b is hydrogen, fluoro, or methoxy; or F. R 5b is hydrogen. [0059] In preferred embodiments where Q is Q b , 82949 FF 13 A. R 5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy and R 5b is hydrogen, fluoro, or methoxy; or B.
  • R 5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy
  • R 5b is hydrogen, chloro, fluoro, or methoxy
  • C is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy
  • R 5b is hydrogen, fluoro, or methoxy
  • D is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy
  • R 5b is hydrogen
  • one of R 5a and R 5b is hydrogen, the other is hydrogen, fluoro, chloro, cyano, methyl, or methoxy; or F.
  • R 5a and R 5b are hydrogen, the other is hydrogen, fluoro, chloro, methyl, or methoxy; or G.
  • R 5a is hydrogen
  • R 5b is hydrogen, fluoro, or methoxy; or H.
  • R 5a and R 5b are hydrogen.
  • Q b is selected from Q b -1 to Q b -13: 82949 FF 14
  • Q b is Q b -1, Q b -2, Q b -3, Q b -5, Q b -6, Q b -8, Q b -9, Q b -10, or Q b -11.
  • Q b is Q b -1, Q b -2, Q b -3, Q b -5, Q b -8, Q b -9, Q b -10, or Q b -11. More preferably, Q b is Q b -1, Q b -2, Q b -3, Q b -5, Q b -8, Q b -10, or Q b -11, or Q b is Q b -1, Q b -3, Q b -5, Q b -10, or Q b - 11. In preferred embodiments, Q b is Q b -1. [0062] In an embodiment of each aspect of the invention, where Q is Q a : A.
  • R 4 is pyrimidin-4-yl, pyrimidin-2-yl, pyrazin-2-yl, thiazol-2-yl, each of which, independently of each other, is substituted with a single -N(R 11 )C(O)OR 10 ; or B.
  • R 4 is R 4 -1, R 4 -2, R 4 -3, R 4 -4, or R 4 -5; or C.
  • R 4 is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R 11 )C(O)OR 10 ; or D.
  • R 4 is pyrimidinyl substituted with a single -N(R 11 )C(O)OR 10 ; or E.
  • R 4 is R 4 -3, R 4 -4, or R 4 -5; or F. R 4 is R 4 -3 or R 4 -5; or G. R 4 is R 4 -5; or H. R 4 is R 4 -3.
  • Q is Q b :
  • R 4a is pyrimidin-4-yl, pyrimidin-2-yl, pyrazin-2-yl, thiazol-2-yl, pyrazol-1-yl, or 1,2,4-triazol-1-yl, each of which, independently of each other, is substituted with a single -N(R 11 )C(O)OR 10 ; or B.
  • R 4a is R 4a -1, R 4a -2, R 4a -3, R 4a -4, R 4a -5, R 4a -6, or R 4a -7: 82949 FF 15 ; or C.
  • R 4a is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R 11 )C(O)OR 10 ; or D.
  • R 4a is pyrimidinyl substituted with a single -N(R 11 )C(O)OR 10 ; or E.
  • R 4a is R 4a -3 or R 4a -5; or F.
  • R 4a is R 4a -5; or G.
  • R 4a is R 4a -3.
  • the pyridyl, pyrimidinyl, pyrazinyl, and thiazolyl groups of R 4 and R 4a are each connected to the respective ring via a carbon atom.
  • a carbon atom of the pyridyl, pyrimidinyl, pyrazinyl, and thiazolyl groups of R 4 and R 4a is linked to Q a or Q b .
  • the group -N(R 11 )C(O)OR 10 is in the meta or para position with respect to the link of R 4 or R 4a to the remainder of the compound.
  • Q is Q a or Q b , such as Q a -1 or Q b -1:
  • A. R 10 is C1-C4alkyl, C3-C6cycloalkyl, cyanoC3-C6cycloalkyl, or C1-C3alkoxy-C1-C3alkyl; or B.
  • R 10 is C1-C4alkyl, or C3-C6cycloalkyl; or C.
  • R 10 is methyl, ethyl, isopropyl, tert-butyl, or C3-C4cycloalkyl; or D.
  • R 10 is methyl, ethyl, isopropyl, tert-butyl, or cyclopropyl; or E. R 10 is methyl, ethyl, isopropyl, or cyclopropyl; or F. R 10 is methyl.
  • Q is Q a or Q b , such as Q a -1 or Q b -1:
  • R 11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxy-C1-C3alkyl, or C1-C3alkoxy; or B.
  • R 11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, or C1-C3alkoxy; or C. R 11 is hydrogen, C1-C3alkyl, or cyclopropyl; or 82949 FF 16 D.
  • R 11 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or methoxy; or E.
  • R 11 is hydrogen, methyl, ethyl, or methoxy; or F.
  • R 11 is hydrogen, methyl, or methoxy; or G.
  • R 11 is hydrogen or methyl.
  • R 10 and R 11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl or 2,4-dioxo-3-oxazolidinyl, each of which, independently of each other, is substituted with one or two methyl, ethyl, or isopropyl; or B.
  • R 10 and R 11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl substituted with one or two C1-C3alkyl; and the C1-C3alkyl is methyl or ethyl; or C.
  • R 10 and R 11 form, together with the fragment -NC(O)O- to which they are attached, a 2,4- dioxo-3-oxazolidinyl substituted with one or two C1-C3alkyl; and the C1-C3alkyl is methyl or ethyl.
  • R X is halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or CN; or B.
  • R X is fluoro, chloro, bromo, methoxy, difluoromethoxy, or cyano.
  • R Z is oxo, halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or CN; or B.
  • R Z is oxo, fluoro, chloro, bromo, methoxy, difluoromethoxy, or cyano.
  • a 1 is C-R Y or N;
  • a 2 is CH;
  • a 3 is CH or N;
  • a 4 is CH;
  • a 5 is CH;
  • R 1 is hydrogen, methyl, or cyclopropylmethyl;
  • R 2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3-C6cycloalkyl, phenyl, piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl, pyrrolidin-1-yl, C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, or C1-C4haloalkylsulfonyl;
  • R 2b is hydrogen, trifluoromethyl, chloro, bromo, i
  • a 1 is C-R Y or N
  • a 2 is CH or N
  • a 3 is CH or N
  • a 4 is C-R Y or N
  • a 5 is CH or N
  • R Y is hydrogen, methyl, trifluoromethyl, methoxy, or cyclopropyl
  • R 1 is hydrogen, methyl, or cyclopropylmethyl
  • R 2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1- C3alkoxy, C1-C3haloalkoxy, C3-C6cycloalkyl, phenyl, piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1- yl, pyrrolidin-1-yl, C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, or C
  • a 1 is C-R Y or N
  • a 2 is CH or N
  • a 3 is CH or N
  • a 4 is C-R Y or N
  • a 5 is CH or N
  • R Y is hydrogen, methyl, or trifluoromethyl
  • Q is Q b
  • R 5a and R 5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl
  • R 4a is R 4a -1, R 4a - 2, R 4a -3, R 4a -4, R 4a -5, R 4a -6, or R 4a -7
  • R 10 is methyl, ethyl, isopropyl, or cyclopropyl
  • R 11 is hydrogen or methyl.
  • compounds of formula (I) are made available where A 1 is N; A 2 is CH; A 3 is N; A 4 is CH; A 5 is CH; R 1 is hydrogen or methyl; R 2a and R 2b are independently trifluoromethyl, chloro, or iodo; R 3 is methyl; Q is Q a ; R 4 is R 4 -3 or R 4 -5; R 5 is hydrogen; R 10 is methyl, ethyl, isopropyl, or cyclopropyl; and R 11 is hydrogen, methyl, or methoxy.
  • compounds of formula (I) are made available where A 1 is N; A 2 is CH; A 3 is N; A 4 is CH; A 5 is CH; R 1 is hydrogen or methyl; R 2a is chloro, R 2b is trifluoromethyl or iodo; R 3 is methyl; Q is Q a ; R 4 is R 4 -3, R 4 -4, or R 4 -5; R 5 is hydrogen; R 10 is methyl, ethyl, isopropyl, or tert-butyl; and R 11 is hydrogen, methyl, or methoxy; or where R 10 and R 11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3-oxazolidinyl or 2,4-dioxo-3-oxazolidinyl group.
  • compounds of formula (I) are preferred where A 1 is N; A 2 is CH; A 3 is N; A 4 is CH; A 5 is CH; R 1 is hydrogen; R 2a is chloro, R 2b is trifluoromethyl or iodo; R 3 is methyl; Q is Q a ; R 4 is R 4 - 3 or R 4 -5; R 5 is hydrogen; R 10 is methyl or ethyl; and R 11 is hydrogen or methyl.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N- dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium 82949 FF 19 complex, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,
  • 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 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
  • a base such as an inorganic base, for instance sodium, potassium or cesium carbonate
  • an organic base such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance, methanol.
  • a reducing agent such as for example hydrogen
  • a hydride such as sodium borohydride
  • a catalyst such as a hydrogenation catalyst, for example palladium on carbon
  • an acid such as acetic acid
  • a Lewis acid such as zinc bromide or titanium(IV) isopropoxide
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • a base such as an inorganic base, for instance potassium carbonate
  • organic base such as, for example, triethylamine.
  • reaction of an amine of the formula IVa with a compound of the formula VII gives a compound of the formula (I) wherein R 1 is H and A 1 , A 2 , A 3 , A 4 , A 5 , R 2a , R 2b , R 3 and Q have the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • 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.
  • reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula VII can be treated with a reducing agent, followed by reaction with a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula V, wherein the leaving group Q is a sulfonate, for instance a mesylate.
  • This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a base such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol.
  • the reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.
  • a compound of the formula Ia wherein A 1 , A 2 , A 3 , A 4 , A 5 , R 2a , R 2b , R 3 and Q have the same meaning as given above for compounds of the formula (I)
  • a compound of the formula VI wherein R 1 has the same meaning as given above for compounds of the formula (I), except that R 1 is different from hydrogen
  • X 3 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (I), wherein A 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 2a , R 2b , R 3 and Q 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 acetonitrile, N,N-dimethylformamide (DMF) or N,N- dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, 82949 FF 22 triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, N,N-dimethylformamide (DMF) or N,N- dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an in
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, toluene, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, optionally in the presence of a quaternary ammonium salt, for instance tetrabutylammonium bromide (TBAB), 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 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
  • XIII is N,N-dimethylformamide dimethyl acetal, also named DMF-DMA, when R 5 is hydrogen and each of R 20 , R 21 , R 22 and R 23 are methyl) gives compounds of the formula XI, wherein A 1 , A 2 , A 3 , A 4 , A 5 , R 2a , R 2b and R 3 have the same meaning as given above for compounds of the formula (I), and in which R 5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl, and each of R 20 and R 21 are independently of each other C1-C4alkyl, or R 20 , R 21 together with the nitrogen to which they are bound represent a pyrrolidine, piperidine or morpholine radical.
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether or dioxane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50 °C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether or dioxane
  • a temperature range of -100 to +300 °C preferably between ambient temperature and 100 °C, or between
  • This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, or between ambient temperature and 80 °C.
  • a solvent such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid
  • compounds of the formula XIIa or a tautomer thereof, or a salt thereof, a particular subset of compounds of the formula XII, wherein R 10 and R 11 have the same meaning as given above for compounds of the formula (I) can be prepared by reacting compounds of the formula XII-1, wherein R 10 and R 11 have the same meaning as given above for compounds of the formula (I), and in which Xb is a leaving group, such as for example 82949 FF 24 a halogen or a sulfonate, preferably Br or Cl (even more preferably Cl), with hydrazine or with hydrazine hydrate, or salts thereof.
  • Xb is a leaving group, such as for example 82949 FF 24 a halogen or a sulfonate, preferably Br or Cl (even more preferably Cl)
  • the reaction can be carried out neat or in a solvent, such as for instance water, or alcohols such as methanol, ethanol or isopropanol, or methoxy cyclopentane, at temperatures between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 90- 100 °C, optionally under microwave conditions.
  • a solvent such as for instance water, or alcohols such as methanol, ethanol or isopropanol, or methoxy cyclopentane
  • Compounds of the formula Ik can be prepared by the reaction of an amine of the formula IIIf, or a salt thereof, 82949 FF 25 wherein R 1 , R 3 , R 4 and R 5 are as described in formula (I), with a compound of the formula II wherein A 1 , A 2 , A 3 , A 4 , A 5 , R 2a and R 2b are as described in formula (I) and X 1 is a leaving group, such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.
  • Compounds of formula Ic can be made, for example, as outlined in Scheme 7.
  • R 4a -M1 is a metal, such as for instance lithium, or –MgCl, or –ZnBr, or –B(OH)2; or R 4a -M1 represents a boronate, such as a pinacol ester of a boronic acid, or a stannane such as R 4a -Sn(n-Bu)3.
  • Such transformations are known to a person skilled in the art as Suzuki-, Kumada-, Negishi- or Stille-coupling reactions, respectively.
  • Such reactions are carried out in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst, 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.
  • the reaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance Cu
  • 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.
  • This reaction is done with or without a solvent, preferentially in a solvent.
  • the reaction mixture is heated, the reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath.
  • compound XVII can be reacted with a compound of the formula XV to give intermediate XVIII. This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate XIV to the compound of formula Ic.
  • the intermediate XVIII is reacted with amine IVa to give a compound of the formula Ic, wherein R 1 is hydrogen and A 1 , A 2 , A 3 , A 4 , A 5 , R 2a , R 2b , R 3 and R 4a have the same meaning as given above for compounds of the formula (I).
  • This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound XVII to intermediate XVI.
  • the intermediate compound of the formula XVIII can be reacted with an amine of the formula XIX to give the intermediate of the formula IIIa.
  • the intermediate compounds of formulas XIV, XVI, XVIII and IIIa can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.
  • Compounds of the formula XVII are known, or they can be prepared by methods known to a person skilled in the art.
  • Compounds of the formula Id can be prepared by the reaction of an amine of the formula IIIb, or a salt thereof wherein R 1 , R 3 , R 4a , R 5a and R 5b are as described in formula (I) with a compound of the formula II wherein A 1 , A 2 , A 3 , A 4 , A 5 , R 2a and R 2b are as described in formula (I) and X 1 is a leaving group, such as a halogen or a sulfonate, for instance chloride.
  • the chemistry is described in more detail in Scheme 8.
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.
  • a solvent such as an organic solvent, for instance acetonitrile
  • 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.
  • Amines of formula IIIc may be obtained by biocatalyzed deracemization of amines of formula IIId. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.
  • compounds of formula IIIc, or a salt thereof can be obtained from compounds of the formula XXII, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), following the synthesis described in Scheme 10.
  • Amines of formula IIIc, or a salt thereof may be obtained from intermediates of formula XXII, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example
  • Such intermediates of formula XXII wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula XXI, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula XXI with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine, such
  • amines of formula IIIc may be obtained by reduction of azides of formula XXIII, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen.
  • Azides of formula XXIII may be obtained by treatment of alcohols of formula XXI, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • an azidation reagent such as diphenyl phosphoryl azide
  • a solvent such as toluene or THF
  • a base such as DBU.
  • Alcohols of formula XXI may be obtained by enantioselective reduction of ketones of formula XXIV, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I).
  • reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)- TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • compounds of formula IIIc may also be prepared as outlined in Scheme 11.
  • Scheme 11 Amines of formula IIIc, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be prepared by deprotection of amines of formula XXV, wherein R 3 , R 4a , R 5a , and R 5b are as described in formula (I), for instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane.
  • a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane.
  • Amines of formula XXV can be obtained by condensation of diamines of formula XXVII, wherein R 5a , and R 5b are as described in formula (I), on diketones of formula XXVI, wherein R 3 , and R 4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ.
  • Diketones of formula XXVI may be formed by oxidation of hydroxyketones of formula XXVII wherein R 3 , and R 4a are as described in formula (I).
  • This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/Bu4NHSO4.
  • solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof
  • base for instance triethylamine or alternatively sodium hypochlorite
  • a catalyst such as TEMPO/Bu4NHSO4.
  • Hydroxyketones of formula XXVII may be synthesized by cross-benzoin condensation between aldehydes of formula XXIX, wherein R 4a is as described in formula (I), and aldehydes of formula XXVIII, wherein R 3 is as described in formula (I).
  • Aldehydes of formula XXVIII are commercially available in chiral form, like for instance Boc-L- alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36-9).
  • Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt in the presence of a base such as potassium tert-butoxide or N,N-isopropylethylamine in a suitable solvent such as DCM or THF at a temperature between -20 °C and the boiling point of the solvent.
  • organocatalyst such as a triazolium salt or a thiazolium salt
  • a base such as potassium tert-butoxide or N,N-isopropylethylamine
  • a suitable solvent such as DCM or THF
  • Amines of formula XXXIV can be prepared by deracemization procedure method, which involves for example, a selective acylation of one enantiomer. Such an example is described more in details in Scheme 13.
  • Chemoenzymatic resolution biocatalyst e.g. lipase or protease acylating agent e.g.
  • XXXIV may be obtained by biocatalyzed deracemization of amines of formula XXXIVa, wherein R 3 , R 5a , and R 5b are as in formula (I) and X07 is a leaving group such as bromine, chlorine or iodine.
  • a lipase e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20 °C to 100 °C.
  • acyl donor e.g. ethyl methoxyacetate or vinyl acetate
  • suitable solvent such as acetonitrile or methyl tert-butyl ether
  • Chiral auxiliaries of formula XXXVI are for instance mandelic acid or (1R)-menthylchloroformate.
  • Intermediates of formula XXXVII can be formed by coupling of a chiral auxiliary of formula XXXVI, wherein X 0 is a leaving group, such as chlorine, with amines of the formula XXXIVa following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493.
  • Amines of formula XXXIV, or a salt thereof may be obtained from intermediates of formula XXIIa, wherein R 3 , R 5a , and R 5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert- butyloxycarbonyl) group),
  • Such intermediates of formula XXIIa wherein R 3 , R 5a , and R 5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N- phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula XXIa, wherein R 3 , R 5a , and R 5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula XXIa with an azodicarboxylate, such as diethyl
  • amines of formula XXXIV may be obtained by reduction of azides of formula XXIIIa, wherein R 3 , R 5a , and R 5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen.
  • Azides of formula XXIIIa may be obtained by treatment of alcohols of formula XXIa with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.
  • Alcohols of formula XXIa may be obtained by enantioselective reduction of ketones of formula XXIVa, wherein R 3 , R 5a , and R 5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide.
  • Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • catalysts for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4.
  • Chem.2018, 83, 930 at temperatures between 20-200°C, preferably room temperature to 100°C, provides compounds of formula (XXXIX-2), wherein R 2a , R 2b , A 4 and A 5 are as described in formula (I), and X 08 is Cl, Br or I (preferably Br or I).
  • compounds of the formula (Ie) may be prepared by reacting compounds of the formula (XL-1), or a salt thereof, with compounds of the formula HOC(O)OR 10 (XL-b-1), wherein R 10 is as defined for compounds of the formula (I), in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide or propanephosphonic acid cyclic anhydride (T3P ® ), under similar conditions as described above.
  • a dehydration reagent for instance a peptide coupling reagent, such as, for example, a carbodiimide or propanephosphonic acid cyclic anhydride (T3P ® .
  • trans-cyclohexyldiamine) or 1,10-phenanthroline optionally in the presence of a base, such as sodium, potassium or cesium carbonate, or potassium phosphate, or an organic base, such as, for example, triethylamine, N,N-diisopropylethylamine or pyridine, in inert solvents such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2- trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or mixtures thereof, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally under microwave
  • H2NR 11 is ammonia
  • ammonium hydroxide solution of ammonia in water
  • inert organic solvents such as ethyl acetate, dioxane or methanol
  • ammonia surrogates such as ammonium salts (for instance ammonium chloride).
  • compounds of the formula (Ie), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 , A 5 , R 10 and R 11 are as defined for compounds of the formula (I) can be prepared by reacting compounds of the formula (XL-2), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 and A 5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with compounds of the formula HN(R 11 )C(O)OR 10 (XL-c), wherein R 10 and R 11 are as defined for compounds of the formula (I), optionally in the presence of a catalyst, for example palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(di
  • a catalyst for
  • 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.
  • Compounds of the formula (XL-3), or a free base thereof, wherein R 3 is as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), and X- is an anion, can be prepared from compounds of the formula (XL-4), wherein R 3 is as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), by treatment with an acid, such as the acids listed above.
  • the reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, 2-methyltetrahydro-furan, dichloromethane or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents.
  • a solvent for instance an organic solvent, such as in methanol, tetrahydrofuran, 2-methyltetrahydro-furan, 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.
  • sodium, potassium or cesium carbonate or a hydroxide ((e.g. sodium or potassium hydroxide), in an inert solvent such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, under conditions well known to those skilled in the art.
  • Compounds of the formula (Ie-1), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 , A 5 and R 10 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XL- 1a), or a salt thereof, wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 and A 5 are as defined for compounds of the formula (I), with compounds of the formula X 04 -C(O)OR 10 (XL-b), wherein R 10 is as defined for compounds of the formula (I) and X 04 is halogen, preferably chlorine, or alternatively with compounds of the formula HOC(O)OR 10 (XL-b-1), wherein R 10 is as defined for compounds of the formula (I), under conditions already described above in Scheme 17 (transformation XL-1 into Ie).
  • Scheme 19 [0163] Alternatively, as outlined in Scheme 19, compounds of the formula (Ie), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 , A 5 , R 10 and R 11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XL-6), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 , A 5 and R 11 are as defined for compounds of the formula (I), with alcohol compounds of the formula (XL-e), wherein R 10 is as defined for compounds of the formula (I).
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +200 °C, preferably between ambient temperature and 120 °C, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, sodium hydride, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +200 °C, preferably between ambient temperature and 120 °C, optionally in the presence of a 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 82949 FF 41 base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran, ethyl acetate, N
  • compounds of the formula (Ie-1), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 , A 5 and R 10 are as defined for compounds of the formula (I), may be prepared by reacting compounds of the formula (XL-5), wherein R 2a , R 2b , R 1 , R 3 , A 1 , A 2 , A 3 , A 4 and A 5 are as defined for compounds of the formula (I), with alcohol compounds of the formula (XL-e), wherein R 10 is as defined for compounds of the formula (I).
  • the reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +200 °C, preferably between ambient temperature and 120 °C, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, sodium hydride, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.
  • a solvent such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100
  • Such compounds of the formula (XL-5) 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 (Ie-1) may be prepared in a one-pot two steps process by (i) reacting compounds of the formula (XL-1), in which R 11 is hydrogen, with phosgene (or a surrogate thereof) with in situ formation of compounds of the formula (XL-5) which are not isolated; followed by (ii) addition of a compound of formula (XL-e) to form the compounds of the formula (Ie-1).
  • Alcohol compounds of the formula (XL-e), wherein R 10 is as defined for compounds of the formula (I), and the compound of the formula (XL-f), phenyl chloroformate, are known, commercially available or may be prepared by methods known to a person skilled in the art.
  • Compounds of the formula (XLI-2), wherein R 1 , R 3 , R 10 and R 11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XLI-3), or a salt thereof, wherein R 1 , R 3 and R 11 are as defined for compounds of the formula (I), with compounds of the formula X 04 -C(O)OR 10 (XL-b), wherein R 10 is as defined for compounds of the formula (I) and X 04 is halogen, preferably chlorine, under analogous conditions already described above in Scheme 17 (transformation XL-1 into Ie).
  • compounds of the formula (XLI-2), wherein R 1 , R 3 , R 10 and R 11 are as defined for compounds of the formula (I) may be prepared by reacting compounds of the formula (XLI-4), wherein R 1 and R 3 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with compounds of the formula HN(R 11 )C(O)OR 10 (XL-c), wherein R 10 and R 11 are as defined for compounds of the formula (I), under analogous conditions already described above in Scheme 17 (transformation XL-2 into Ie).
  • Compounds of the formula (XLI-4), wherein R 1 and R 3 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), can be prepared by reacting compounds of the formula (XLI-7), wherein R 1 and R 3 are as defined for compounds of the formula (I), with hydrazine compounds of the formula (XLI-6) or a tautomer thereof, or a salt thereof, wherein Xa is a halogen, preferably Br or Cl (even more preferably Cl), under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib).
  • Scheme 21 82949 FF 44 [0177]
  • compounds of the formula (XLI-2), wherein R 1 , R 3 , R 10 and R 11 are as defined for compounds of the formula (I), except that R 11 is different from hydrogen may be prepared by reacting compounds of the formula (XLI-2a), wherein R 1 , R 3 and R 10 are as defined for compounds of the formula (I), with compounds of the formula (XL-d), wherein R 11 has the same meaning as given above for compounds of the formula (I), except that R 11 is different from hydrogen, and wherein X 06 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, under analogous conditions already described above in Scheme 18 (transformation Ie-1 into Ie).
  • a leaving group such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate
  • Compounds of the formula (XLI-2a), wherein R 1 , R 3 and R 10 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XLI-3a), or a salt thereof, wherein R 1 and R 3 are as defined for compounds of the formula (I), with compounds of the formula X 04 -C(O)OR 10 (XL-b), wherein R 10 is as defined for compounds of the formula (I) and X 04 is halogen, preferably chlorine, or alternatively with compounds of the formula HOC(O)OR 10 (XL-b-1), wherein R 10 is as defined for compounds of the formula (I), under conditions already described above in Scheme 17 (transformation XL-1 into Ie).
  • 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).
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. [0182] The reactions are advantageously carried out in a temperature range from approximately - 80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • an inorganic salt which forms, for example silver chloride is insoluble and thus precipitates from the reaction mixture.
  • the compounds of formula (I) which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each 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 82949 FF 46 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 differ
  • N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2O2/urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • Tables A-1 to A-90 and Tables B-1 to B-90 can be prepared according to the methods described above.
  • the examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I-A) and (I-B): Tables A-1 to A-90 (formula I-A)
  • Table A-1 provides 21 compounds A-1.001 to A-1.021 of formula I-A wherein R 1 is H, R 10 is Me, R 11 is H and T is as defined in table X.
  • Table A-2 provides 21 compounds A-2.001 to A-2.021 of formula I-A wherein R 1 is H, R 10 is Me, R 11 is Me and T is as defined in table X.
  • Table A-3 provides 21 compounds A-3.001 to A-3.021 of formula I-A wherein R 1 is H, R 10 is Me, R 11 is Et and T is as defined in table X.
  • Table A-4 provides 21 compounds A-4.001 to A-4.021 of formula I-A wherein R 1 is H, R 10 is Me, R 11 is iPr and T is as defined in table X.
  • Table A-5 provides 21 compounds A-5.001 to A-5.021 of formula I-A wherein R 1 is H, R 10 is Me, R 11 is Cyp and T is as defined in table X.
  • Table A-6 provides 21 compounds A-6.001 to A-6.021 of formula I-A wherein R 1 is H, R 10 is Me, R 11 is OMe and T is as defined in table X.
  • Table A-7 provides 21 compounds A-7.001 to A-7.021 of formula I-A wherein R 1 is H, R 10 is Et, R 11 is H and T is as defined in table X.
  • Table A-8 provides 21 compounds A-8.001 to A-8.021 of formula I-A wherein R 1 is H, R 10 is Et, R 11 is Me and T is as defined in table X.
  • Table A-9 provides 21 compounds A-9.001 to A-9.021 of formula I-A wherein R 1 is H, R 10 is Et, R 11 is Et and T is as defined in table X.
  • Table A-10 provides 21 compounds A-10.001 to A-10.021 of formula I-A wherein R 1 is H, R 10 is Et, R 11 is iPr and T is as defined in table X.
  • Table A-11 provides 21 compounds A-11.001 to A-11.021 of formula I-A wherein R 1 is H, R 10 is Et, R 11 is Cyp and T is as defined in table X.
  • Table A-12 provides 21 compounds A-12.001 to A-12.021 of formula I-A wherein R 1 is H, R 10 is Et, R 11 is OMe and T is as defined in table X.
  • Table A-13 provides 21 compounds A-13.001 to A-13.021 of formula I-A wherein R 1 is H, R 10 is iPr, R 11 is H and T is as defined in table X.
  • Table A-14 provides 21 compounds A-14.001 to A-14.021 of formula I-A wherein R 1 is H, R 10 is iPr, R 11 is Me and T is as defined in table X.
  • Table A-15 provides 21 compounds A-15.001 to A-15.021 of formula I-A wherein R 1 is H, R 10 is iPr, R 11 is Et and T is as defined in table X.
  • Table A-16 provides 21 compounds A-16.001 to A-16.021 of formula I-A wherein R 1 is H, R 10 is iPr, R 11 is iPr and T is as defined in table X.
  • Table A-17 provides 21 compounds A-17.001 to A-17.021 of formula I-A wherein R 1 is H, R 10 is iPr, R 11 is Cyp and T is as defined in table X.
  • Table A-18 provides 21 compounds A-18.001 to A-18.021 of formula I-A wherein R 1 is H, R 10 is iPr, R 11 is OMe and T is as defined in table X.
  • Table A-19 provides 21 compounds A-19.001 to A-19.021 of formula I-A wherein R 1 is H, R 10 is Cyp, R 11 is H and T is as defined in table X.
  • Table A-20 provides 21 compounds A-20.001 to A-20.021 of formula I-A wherein R 1 is H, R 10 is Cyp, R 11 is Me and T is as defined in table X.
  • Table A-21 provides 21 compounds A-21.001 to A-21.021 of formula I-A wherein R 1 is H, R 10 is Cyp, R 11 is Et and T is as defined in table X.
  • Table A-22 provides 21 compounds A-22.001 to A-22.021 of formula I-A wherein R 1 is H, R 10 is Cyp, R 11 is iPr and T is as defined in table X.
  • Table A-23 provides 21 compounds A-23.001 to A-23.021 of formula I-A wherein R 1 is H, R 10 is Cyp, R 11 is Cyp and T is as defined in table X.
  • Table A-24 provides 21 compounds A-24.001 to A-24.021 of formula I-A wherein R 1 is H, R 10 is Cyp, R 11 is OMe and T is as defined in table X.
  • Table A-25 provides 21 compounds A-25.001 to A-25.021 of formula I-A wherein R 1 is H, R 10 is tBu, R 11 is H and T is as defined in table X.
  • Table A-26 provides 21 compounds A-26.001 to A-26.021 of formula I-A wherein R 1 is H, R 10 is tBu, R 11 is Me and T is as defined in table X.
  • Table A-27 provides 21 compounds A-27.001 to A-27.021 of formula I-A wherein R 1 is H, R 10 is tBu, R 11 is Et and T is as defined in table X.
  • Table A-28 provides 21 compounds A-28.001 to A-28.021 of formula I-A wherein R 1 is H, R 10 is tBu, R 11 is iPr and T is as defined in table X.
  • Table A-29 provides 21 compounds A-29.001 to A-29.021 of formula I-A wherein R 1 is H, R 10 is tBu, R 11 is Cyp and T is as defined in table X.
  • Table A-30 provides 21 compounds A-30.001 to A-30.021 of formula I-A wherein R 1 is H, R 10 is tBu, R 11 is OMe and T is as defined in table X.
  • Table A-31 provides 21 compounds A-31.001 to A-31.021 of formula I-A wherein R 1 is CH3, R 10 is Me, R 11 is H and T is as defined in table X.
  • Table A-32 provides 21 compounds A-32.001 to A-32.021 of formula I-A wherein R 1 is CH3, R 10 is Me, R 11 is Me and T is as defined in table X.
  • Table A-33 provides 21 compounds A-33.001 to A-33.021 of formula I-A wherein R 1 is CH3, R 10 is Me, R 11 is Et and T is as defined in table X.
  • Table A-34 provides 21 compounds A-34.001 to A-34.021 of formula I-A wherein R 1 is CH3, R 10 is Me, R 11 is iPr and T is as defined in table X.
  • Table A-35 provides 21 compounds A-35.001 to A-35.021 of formula I-A wherein R 1 is CH3, R 10 is Me, R 11 is Cyp and T is as defined in table X.
  • Table A-36 provides 21 compounds A-36.001 to A-36.021 of formula I-A wherein R 1 is CH3, R 10 is Me, R 11 is OMe and T is as defined in table X. 82949 FF 49
  • Table A-37 provides 21 compounds A-37.001 to A-37.021 of formula I-A wherein R 1 is CH3, R 10 is Et, R 11 is H and T is as defined in table X.
  • Table A-38 provides 21 compounds A-38.001 to A-38.021 of formula I-A wherein R 1 is CH3, R 10 is Et, R 11 is Me and T is as defined in table X.
  • Table A-39 provides 21 compounds A-39.001 to A-39.021 of formula I-A wherein R 1 is CH3, R 10 is Et, R 11 is Et and T is as defined in table X.
  • Table A-40 provides 21 compounds A-40.001 to A-40.021 of formula I-A wherein R 1 is CH3, R 10 is Et, R 11 is iPr and T is as defined in table X.
  • Table A-41 provides 21 compounds A-41.001 to A-41.021 of formula I-A wherein R 1 is CH3, R 10 is Et, R 11 is Cyp and T is as defined in table X.
  • Table A-42 provides 21 compounds A-42.001 to A-42.021 of formula I-A wherein R 1 is CH3, R 10 is Et, R 11 is OMe and T is as defined in table X.
  • Table A-43 provides 21 compounds A-43.001 to A-43.021 of formula I-A wherein R 1 is CH3, R 10 is iPr, R 11 is H and T is as defined in table X.
  • Table A-44 provides 21 compounds A-44.001 to A-44.021 of formula I-A wherein R 1 is CH3, R 10 is iPr, R 11 is Me and T is as defined in table X.
  • Table A-45 provides 21 compounds A-45.001 to A-45.021 of formula I-A wherein R 1 is CH3, R 10 is iPr, R 11 is Et and T is as defined in table X.
  • Table A-46 provides 21 compounds A-46.001 to A-46.021 of formula I-A wherein R 1 is CH3, R 10 is iPr, R 11 is iPr and T is as defined in table X.
  • Table A-47 provides 21 compounds A-47.001 to A-47.021 of formula I-A wherein R 1 is CH3, R 10 is iPr, R 11 is Cyp and T is as defined in table X.
  • Table A-48 provides 21 compounds A-48.001 to A-48.021 of formula I-A wherein R 1 is CH3, R 10 is iPr, R 11 is OMe and T is as defined in table X.
  • Table A-49 provides 21 compounds A-49.001 to A-49.021 of formula I-A wherein R 1 is CH3, R 10 is Cyp, R 11 is H and T is as defined in table X.
  • Table A-50 provides 21 compounds A-50.001 to A-50.021 of formula I-A wherein R 1 is CH3, R 10 is Cyp, R 11 is Me and T is as defined in table X.
  • Table A-51 provides 21 compounds A-51.001 to A-51.021 of formula I-A wherein R 1 is CH3, R 10 is Cyp, R 11 is Et and T is as defined in table X.
  • Table A-52 provides 21 compounds A-52.001 to A-52.021 of formula I-A wherein R 1 is CH3, R 10 is Cyp, R 11 is iPr and T is as defined in table X.
  • Table A-53 provides 21 compounds A-53.001 to A-53.021 of formula I-A wherein R 1 is CH3, R 10 is Cyp, R 11 is Cyp and T is as defined in table X.
  • Table A-54 provides 21 compounds A-54.001 to A-54.021 of formula I-A wherein R 1 is CH3, R 10 is Cyp, R 11 is OMe and T is as defined in table X.
  • Table A-55 provides 21 compounds A-55.001 to A-55.021 of formula I-A wherein R 1 is CH3, R 10 is tBu, R 11 is H and T is as defined in table X.
  • Table A-56 provides 21 compounds A-56.001 to A-56.021 of formula I-A wherein R 1 is CH3, R 10 is tBu, R 11 is Me and T is as defined in table X. 82949 FF 50
  • Table A-57 provides 21 compounds A-57.001 to A-57.021 of formula I-A wherein R 1 is CH3, R 10 is tBu, R 11 is Et and T is as defined in table X.
  • Table A-58 provides 21 compounds A-58.001 to A-58.021 of formula I-A wherein R 1 is CH3, R 10 is tBu, R 11 is iPr and T is as defined in table X.
  • Table A-59 provides 21 compounds A-59.001 to A-59.021 of formula I-A wherein R 1 is CH3, R 10 is tBu, R 11 is Cyp and T is as defined in table X.
  • Table A-60 provides 21 compounds A-60.001 to A-60.021 of formula I-A wherein R 1 is CH3, R 10 is tBu, R 11 is OMe and T is as defined in table X.
  • Table A-61 provides 21 compounds A-61.001 to A-61.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is H and T is as defined in table X.
  • Table A-62 provides 21 compounds A-62.001 to A-62.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is Me and T is as defined in table X.
  • Table A-63 provides 21 compounds A-63.001 to A-63.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is Et and T is as defined in table X.
  • Table A-64 provides 21 compounds A-64.001 to A-64.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is iPr and T is as defined in table X.
  • Table A-65 provides 21 compounds A-65.001 to A-65.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is Cyp and T is as defined in table X.
  • Table A-66 provides 21 compounds A-66.001 to A-66.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is OMe and T is as defined in table X.
  • Table A-67 provides 21 compounds A-67.001 to A-67.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is H and T is as defined in table X.
  • Table A-68 provides 21 compounds A-68.001 to A-68.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is Me and T is as defined in table X.
  • Table A-69 provides 21 compounds A-69.001 to A-69.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is Et and T is as defined in table X.
  • Table A-70 provides 21 compounds A-70.001 to A-70.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is iPr and T is as defined in table X.
  • Table A-71 provides 21 compounds A-71.001 to A-71.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is Cyp and T is as defined in table X.
  • Table A-72 provides 21 compounds A-72.001 to A-72.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is OMe and T is as defined in table X.
  • Table A-73 provides 21 compounds A-73.001 to A-73.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is H and T is as defined in table X.
  • Table A-74 provides 21 compounds A-74.001 to A-74.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is Me and T is as defined in table X.
  • Table A-75 provides 21 compounds A-75.001 to A-75.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is Et and T is as defined in table X.
  • Table A-76 provides 21 compounds A-76.001 to A-76.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is iPr and T is as defined in table X.
  • Table A-77 provides 21 compounds A-77.001 to A-77.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is Cyp and T is as defined in table X.
  • Table A-78 provides 21 compounds A-78.001 to A-78.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is OMe and T is as defined in table X.
  • Table A-79 provides 21 compounds A-79.001 to A-79.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is H and T is as defined in table X.
  • Table A-80 provides 21 compounds A-80.001 to A-80.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is Me and T is as defined in table X.
  • Table A-81 provides 21 compounds A-81.001 to A-81.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is Et and T is as defined in table X.
  • Table A-82 provides 21 compounds A-82.001 to A-82.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is iPr and T is as defined in table X.
  • Table A-83 provides 21 compounds A-83.001 to A-83.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is Cyp and T is as defined in table X.
  • Table A-84 provides 21 compounds A-84.001 to A-84.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is OMe and T is as defined in table X.
  • Table A-85 provides 21 compounds A-85.001 to A-85.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is H and T is as defined in table X.
  • Table A-86 provides 21 compounds A-86.001 to A-86.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is Me and T is as defined in table X.
  • Table A-87 provides 21 compounds A-87.001 to A-87.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is Et and T is as defined in table X.
  • Table A-88 provides 21 compounds A-88.001 to A-88.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is iPr and T is as defined in table X.
  • Table A-89 provides 21 compounds A-89.001 to A-89.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is Cyp and T is as defined in table X.
  • Table A-90 provides 21 compounds A-90.001 to A-90.021 of formula I-A wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is OMe and T is as defined in table X.
  • Tables B-1 to B-90 (formula I-B) [0286] Table B-1 provides 21 compounds B-1.001 to B-1.021 of formula I-B wherein R 1 is H, R 10 is Me, R 11 is H and T is as defined in table X. [0287] Table B-2 provides 21 compounds B-2.001 to B-2.021 of formula I-B wherein R 1 is H, R 10 is Me, R 11 is Me and T is as defined in table X. [0288] Table B-3 provides 21 compounds B-3.001 to B-3.021 of formula I-B wherein R 1 is H, R 10 is Me, R 11 is Et and T is as defined in table X.
  • Table B-4 provides 21 compounds B-4.001 to B-4.021 of formula I-B wherein R 1 is H, R 10 is Me, R 11 is iPr and T is as defined in table X.
  • Table B-5 provides 21 compounds B-5.001 to B-5.021 of formula I-B wherein R 1 is H, R 10 is Me, R 11 is Cyp and T is as defined in table X. 82949 FF 52
  • Table B-6 provides 21 compounds B-6.001 to B-6.021 of formula I-B wherein R 1 is H, R 10 is Me, R 11 is OMe and T is as defined in table X.
  • Table B-7 provides 21 compounds B-7.001 to B-7.021 of formula I-B wherein R 1 is H, R 10 is Et, R 11 is H and T is as defined in table X.
  • Table B-8 provides 21 compounds B-8.001 to B-8.021 of formula I-B wherein R 1 is H, R 10 is Et, R 11 is Me and T is as defined in table X.
  • Table B-9 provides 21 compounds B-9.001 to B-9.021 of formula I-B wherein R 1 is H, R 10 is Et, R 11 is Et and T is as defined in table X.
  • Table B-10 provides 21 compounds B-10.001 to B-10.021 of formula I-B wherein R 1 is H, R 10 is Et, R 11 is iPr and T is as defined in table X.
  • Table B-11 provides 21 compounds B-11.001 to B-11.021 of formula I-B wherein R 1 is H, R 10 is Et, R 11 is Cyp and T is as defined in table X.
  • Table B-12 provides 21 compounds B-12.001 to B-12.021 of formula I-B wherein R 1 is H, R 10 is Et, R 11 is OMe and T is as defined in table X.
  • Table B-13 provides 21 compounds B-13.001 to B-13.021 of formula I-B wherein R 1 is H, R 10 is iPr, R 11 is H and T is as defined in table X.
  • Table B-14 provides 21 compounds B-14.001 to B-14.021 of formula I-B wherein R 1 is H, R 10 is iPr, R 11 is Me and T is as defined in table X.
  • Table B-15 provides 21 compounds B-15.001 to B-15.021 of formula I-B wherein R 1 is H, R 10 is iPr, R 11 is Et and T is as defined in table X.
  • Table B-16 provides 21 compounds B-16.001 to B-16.021 of formula I-B wherein R 1 is H, R 10 is iPr, R 11 is iPr and T is as defined in table X.
  • Table B-17 provides 21 compounds B-17.001 to B-17.021 of formula I-B wherein R 1 is H, R 10 is iPr, R 11 is Cyp and T is as defined in table X.
  • Table B-18 provides 21 compounds B-18.001 to B-18.021 of formula I-B wherein R 1 is H, R 10 is iPr, R 11 is OMe and T is as defined in table X.
  • Table B-19 provides 21 compounds B-19.001 to B-19.021 of formula I-B wherein R 1 is H, R 10 is Cyp, R 11 is H and T is as defined in table X.
  • Table B-20 provides 21 compounds B-20.001 to B-20.021 of formula I-B wherein R 1 is H, R 10 is Cyp, R 11 is Me and T is as defined in table X.
  • Table B-21 provides 21 compounds B-21.001 to B-21.021 of formula I-B wherein R 1 is H, R 10 is Cyp, R 11 is Et and T is as defined in table X.
  • Table B-22 provides 21 compounds B-22.001 to B-22.021 of formula I-B wherein R 1 is H, R 10 is Cyp, R 11 is iPr and T is as defined in table X.
  • Table B-23 provides 21 compounds B-23.001 to B-23.021 of formula I-B wherein R 1 is H, R 10 is Cyp, R 11 is Cyp and T is as defined in table X.
  • Table B-24 provides 21 compounds B-24.001 to B-24.021 of formula I-B wherein R 1 is H, R 10 is Cyp, R 11 is OMe and T is as defined in table X.
  • Table B-25 provides 21 compounds B-25.001 to B-25.021 of formula I-B wherein R 1 is H, R 10 is tBu, R 11 is H and T is as defined in table X. 82949 FF 53
  • Table B-26 provides 21 compounds B-26.001 to B-26.021 of formula I-B wherein R 1 is H, R 10 is tBu, R 11 is Me and T is as defined in table X.
  • Table B-27 provides 21 compounds B-27.001 to B-27.021 of formula I-B wherein R 1 is H, R 10 is tBu, R 11 is Et and T is as defined in table X.
  • Table B-28 provides 21 compounds B-28.001 to B-28.021 of formula I-B wherein R 1 is H, R 10 is tBu, R 11 is iPr and T is as defined in table X.
  • Table B-29 provides 21 compounds B-29.001 to B-29.021 of formula I-B wherein R 1 is H, R 10 is tBu, R 11 is Cyp and T is as defined in table X.
  • Table B-30 provides 21 compounds B-30.001 to B-30.021 of formula I-B wherein R 1 is H, R 10 is tBu, R 11 is OMe and T is as defined in table X.
  • Table B-31 provides 21 compounds B-31.001 to B-31.021 of formula I-B wherein R 1 is CH3, R 10 is Me, R 11 is H and T is as defined in table X.
  • Table B-32 provides 21 compounds B-32.001 to B-32.021 of formula I-B wherein R 1 is CH3, R 10 is Me, R 11 is Me and T is as defined in table X.
  • Table B-33 provides 21 compounds B-33.001 to B-33.021 of formula I-B wherein R 1 is CH3, R 10 is Me, R 11 is Et and T is as defined in table X.
  • Table B-34 provides 21 compounds B-34.001 to B-34.021 of formula I-B wherein R 1 is CH3, R 10 is Me, R 11 is iPr and T is as defined in table X.
  • Table B-35 provides 21 compounds B-35.001 to B-35.021 of formula I-B wherein R 1 is CH3, R 10 is Me, R 11 is Cyp and T is as defined in table X.
  • Table B-36 provides 21 compounds B-36.001 to B-36.021 of formula I-B wherein R 1 is CH3, R 10 is Me, R 11 is OMe and T is as defined in table X.
  • Table B-37 provides 21 compounds B-37.001 to B-37.021 of formula I-B wherein R 1 is CH3, R 10 is Et, R 11 is H and T is as defined in table X.
  • Table B-38 provides 21 compounds B-38.001 to B-38.021 of formula I-B wherein R 1 is CH3, R 10 is Et, R 11 is Me and T is as defined in table X.
  • Table B-39 provides 21 compounds B-39.001 to B-39.021 of formula I-B wherein R 1 is CH3, R 10 is Et, R 11 is Et and T is as defined in table X.
  • Table B-40 provides 21 compounds B-40.001 to B-40.021 of formula I-B wherein R 1 is CH3, R 10 is Et, R 11 is iPr and T is as defined in table X.
  • Table B-41 provides 21 compounds B-41.001 to B-41.021 of formula I-B wherein R 1 is CH3, R 10 is Et, R 11 is Cyp and T is as defined in table X.
  • Table B-42 provides 21 compounds B-42.001 to B-42.021 of formula I-B wherein R 1 is CH3, R 10 is Et, R 11 is OMe and T is as defined in table X.
  • Table B-43 provides 21 compounds B-43.001 to B-43.021 of formula I-B wherein R 1 is CH3, R 10 is iPr, R 11 is H and T is as defined in table X.
  • Table B-44 provides 21 compounds B-44.001 to B-44.021 of formula I-B wherein R 1 is CH3, R 10 is iPr, R 11 is Me and T is as defined in table X.
  • Table B-45 provides 21 compounds B-45.001 to B-45.021 of formula I-B wherein R 1 is CH3, R 10 is iPr, R 11 is Et and T is as defined in table X.
  • Table B-46 provides 21 compounds B-46.001 to B-46.021 of formula I-B wherein R 1 is CH3, R 10 is iPr, R 11 is iPr and T is as defined in table X.
  • Table B-47 provides 21 compounds B-47.001 to B-47.021 of formula I-B wherein R 1 is CH3, R 10 is iPr, R 11 is Cyp and T is as defined in table X.
  • Table B-48 provides 21 compounds B-48.001 to B-48.021 of formula I-B wherein R 1 is CH3, R 10 is iPr, R 11 is OMe and T is as defined in table X.
  • Table B-49 provides 21 compounds B-49.001 to B-49.021 of formula I-B wherein R 1 is CH3, R 10 is Cyp, R 11 is H and T is as defined in table X.
  • Table B-50 provides 21 compounds B-50.001 to B-50.021 of formula I-B wherein R 1 is CH3, R 10 is Cyp, R 11 is Me and T is as defined in table X.
  • Table B-51 provides 21 compounds B-51.001 to B-51.021 of formula I-B wherein R 1 is CH3, R 10 is Cyp, R 11 is Et and T is as defined in table X.
  • Table B-52 provides 21 compounds B-52.001 to B-52.021 of formula I-B wherein R 1 is CH3, R 10 is Cyp, R 11 is iPr and T is as defined in table X.
  • Table B-53 provides 21 compounds B-53.001 to B-53.021 of formula I-B wherein R 1 is CH3, R 10 is Cyp, R 11 is Cyp and T is as defined in table X.
  • Table B-54 provides 21 compounds B-54.001 to B-54.021 of formula I-B wherein R 1 is CH3, R 10 is Cyp, R 11 is OMe and T is as defined in table X.
  • Table B-55 provides 21 compounds B-55.001 to B-55.021 of formula I-B wherein R 1 is CH3, R 10 is tBu, R 11 is H and T is as defined in table X.
  • Table B-56 provides 21 compounds B-56.001 to B-56.021 of formula I-B wherein R 1 is CH3, R 10 is tBu, R 11 is Me and T is as defined in table X.
  • Table B-57 provides 21 compounds B-57.001 to B-57.021 of formula I-B wherein R 1 is CH3, R 10 is tBu, R 11 is Et and T is as defined in table X.
  • Table B-58 provides 21 compounds B-58.001 to B-58.021 of formula I-B wherein R 1 is CH3, R 10 is tBu, R 11 is iPr and T is as defined in table X.
  • Table B-59 provides 21 compounds B-59.001 to B-59.021 of formula I-B wherein R 1 is CH3, R 10 is tBu, R 11 is Cyp and T is as defined in table X.
  • Table B-60 provides 21 compounds B-60.001 to B-60.021 of formula I-B wherein R 1 is CH3, R 10 is tBu, R 11 is OMe and T is as defined in table X.
  • Table B-61 provides 21 compounds B-61.001 to B-61.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is H and T is as defined in table X.
  • Table B-62 provides 21 compounds B-62.001 to B-62.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is Me and T is as defined in table X.
  • Table B-63 provides 21 compounds B-63.001 to B-63.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is Et and T is as defined in table X.
  • Table B-64 provides 21 compounds B-64.001 to B-64.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is iPr and T is as defined in table X.
  • Table B-65 provides 21 compounds B-65.001 to B-65.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is Cyp and T is as defined in table X. 82949 FF 55
  • Table B-66 provides 21 compounds B-66.001 to B-66.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Me, R 11 is OMe and T is as defined in table X.
  • Table B-67 provides 21 compounds B-67.001 to B-67.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is H and T is as defined in table X.
  • Table B-68 provides 21 compounds B-68.001 to B-68.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is Me and T is as defined in table X.
  • Table B-69 provides 21 compounds B-69.001 to B-69.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is Et and T is as defined in table X.
  • Table B-70 provides 21 compounds B-70.001 to B-70.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is iPr and T is as defined in table X.
  • Table B-71 provides 21 compounds B-71.001 to B-71.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is Cyp and T is as defined in table X.
  • Table B-72 provides 21 compounds B-72.001 to B-72.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Et, R 11 is OMe and T is as defined in table X.
  • Table B-73 provides 21 compounds B-73.001 to B-73.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is H and T is as defined in table X.
  • Table B-74 provides 21 compounds B-74.001 to B-74.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is Me and T is as defined in table X.
  • Table B-75 provides 21 compounds B-75.001 to B-75.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is Et and T is as defined in table X.
  • Table B-76 provides 21 compounds B-76.001 to B-76.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is iPr and T is as defined in table X.
  • Table B-77 provides 21 compounds B-77.001 to B-77.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is Cyp and T is as defined in table X.
  • Table B-78 provides 21 compounds B-78.001 to B-78.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is iPr, R 11 is OMe and T is as defined in table X.
  • Table B-79 provides 21 compounds B-79.001 to B-79.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is H and T is as defined in table X.
  • Table B-80 provides 21 compounds B-80.001 to B-80.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is Me and T is as defined in table X.
  • Table B-81 provides 21 compounds B-81.001 to B-81.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is Et and T is as defined in table X.
  • Table B-82 provides 21 compounds B-82.001 to B-82.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is iPr and T is as defined in table X.
  • Table B-83 provides 21 compounds B-83.001 to B-83.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is Cyp and T is as defined in table X.
  • Table B-84 provides 21 compounds B-84.001 to B-84.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is Cyp, R 11 is OMe and T is as defined in table X.
  • Table B-85 provides 21 compounds B-85.001 to B-85.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is H and T is as defined in table X. 82949 FF 56
  • Table B-86 provides 21 compounds B-86.001 to B-86.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is Me and T is as defined in table X.
  • Table B-87 provides 21 compounds B-87.001 to B-87.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is Et and T is as defined in table X.
  • Table B-88 provides 21 compounds B-88.001 to B-88.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is iPr and T is as defined in table X.
  • Table B-89 provides 21 compounds B-89.001 to B-89.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is Cyp and T is as defined in table X.
  • Table B-90 provides 21 compounds B-90.001 to B-90.021 of formula I-B wherein R 1 is CH2- cyclopropyl, R 10 is tBu, R 11 is OMe and T is as defined in table X.
  • Table X Substituent definitions of T Index T Index T Index T 1 8 15 2 9 16 3 10 17 82949 FF 57 Index T Index T Index T 4 11 18 5 12 19 6 13 20 7 14 21 [0376]
  • Me represents methyl
  • Et represents ethyl
  • iPr represents isopropyl
  • Cyp represents cyclopropyl
  • tBu represents tert-butyl.
  • a compound of formula XL-1 where A 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 2a , R 2b , R 3 and R 11 are as defined for compounds of formula (I); for instance, where R 3 is methyl, T is as defined in Table X above, and R 1 and R 11 are as defined in Tables A-1 to A-90, preferably R 1 is hydrogen or methyl, and R 11 is hydrogen or methyl; and 82949 FF 58 ⁇ A compound of formula XL-1-13, which corresponds to a subset of compounds of formula XL- 1 where A 1 and A 3 are N, A 2 , A 4 and A 5 are CH, and where R 1 , R 2a , R 2b , R 3 , and R 11 are as defined for compounds of formula XL-1: ⁇ A compound of formula XL-6, where A 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 2a , R 2a
  • 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, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivor
  • ⁇ from the order Anoplura for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.
  • ⁇ from the order Coleoptera for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna s
  • Trogoderma spp. ⁇ from the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., O
  • ⁇ from the order Hemiptera for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocor
  • Vespa spp. ⁇ from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminata; ⁇ from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chry
  • ⁇ from the order Orthoptera for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp., and Schistocerca spp.
  • ⁇ from the order Psocoptera for example, Liposcelis spp.
  • Siphonaptera for example, Ceratophyllus spp., Ctenocephalides spp.
  • Thysanoptera for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; ⁇ from the order Thysanura, for example, Lepisma saccharina.
  • the invention may also relate to a method of controlling damage to plant and 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, 82949 FF 63 Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H.
  • the active ingredients according to the invention can be used for controlling, i.e.
  • pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, 82949 FF 64 Cinnamon
  • compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I.
  • Iresines spp. Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.
  • the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A.
  • Daucus carota Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the compounds of formula (I) are particularly suitable for control of ⁇ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans, and sugarcane); ⁇ a pest of the order Lepidoptera, for example, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn); ⁇ a pest of the order Thysanoptera,
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vip1, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, 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
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1FA 2 , Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • 82949 FF 66 Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP 0374753 A, WO 93/07278, WO 95/34656, EP 0427529 A, EP 451878 A and WO 03/052073.
  • transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP 0367474 A, EP 0401979 A and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1FA 2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810. 82949 FF 67 4.
  • MON 863 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • CP4 EPSPS obtained from Agrobacterium sp. strain CP4
  • Roundup® contains glyphosate
  • Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis- related proteins" (PRPs, see e.g. EP 0392225 A).
  • PRPs pathogenesis- related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP 0392225 A, WO 95/33818 and EP 0353191 A.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP 0392225 A); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g.
  • compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention provides a compound of the first aspect for use in therapy.
  • the present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal.
  • the present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal.
  • 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.
  • the term "preventing" when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal.
  • the term "animal" when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal.
  • Non-human mammals include, but are not limited to, livestock animals and companion animals.
  • Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses.
  • Companion animals include, but are not limited to, dogs, cats and rabbits.
  • a "parasite” is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense.
  • An “endoparasite” is a parasite which lives in the host animal.
  • An “ectoparasite” is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice).
  • the Acari (or Acarina) sub-class comprises ticks and mites.
  • Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros.
  • Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus 82949 FF 69 gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates.
  • Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera.
  • Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis.
  • Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes.
  • Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola ovis and Bovicola bovis.
  • the term "effective amount" when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal.
  • the effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • the compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally ' and subcutaneously. Topical administration is preferred.
  • Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip.
  • the compounds of the invention may be administered by means of an ear tag or collar.
  • Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts.
  • Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS indoor residual spraying
  • a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005/113886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g.
  • Ataenius spp. e.g. Black turfgrass ataenius, A. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls (Margarodes spp.)
  • mole crickets tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Examples of such parasites are: ⁇ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Chrysomyia spppp
  • Siphonapta for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. ⁇
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. ⁇
  • Blattarida for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., 82949 FF 74 Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • a compound TX controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more 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., Rhop
  • a compound TX controls one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp.
  • the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.
  • a compound TX controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, 82949 FF 75 Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella +
  • a compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B-90, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.
  • a compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B-90, and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
  • advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
  • certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera.
  • TX means "one compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B-90, and Table P): (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX
  • Israelensis + TX Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thuringiensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec.
  • lecontei NPV + TX nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp.
  • TX trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc- call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp.
  • acridum + TX Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO 2020/193387) + TX,
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain AQ153 + TX, 82949 FF 88 Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • TX Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX
  • NRRL 305408 + TX, Mycorrhizae spp. (AMykor®, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp.
  • TX Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, P
  • TX Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp.
  • Rhizobia Distal®, Vault®
  • Rhizoctonia + TX Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp.
  • TX Sordaria fimicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces 82949 FF 90 hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX,
  • Trichoderma asperellum T34 Biocontrol®
  • TX Trichoderma atroviride
  • Trichoderma gamsii TX
  • Trichoderma hamatum TH 382 + TX Trichoderma harzianum rifai (Mycostar®) + TX
  • Trichoderma harzianum T-22 Trianum-P®, PlantShield HC®, RootShield®, Trianum-G® + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp.
  • TX maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • TX Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp.
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus,
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, CAS Number: 2643947-26-4 + TX, Chondroster
  • NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX
  • Bacillus pumilus in particular strain BU F-33, having NRRL Accession No. 50185 (CARTISSA® from BASF, EPA Reg. No.71840-19) + TX
  • Bacillus subtilis CX-9060 from Certis USA LLC
  • Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai 82949 FF 93 Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S.
  • Patent No.7,094,592 + TX Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S.
  • Patent No.6,060,051 available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US
  • TX Paenibacillus polymyxa
  • strain AC-1 e.g. TOPSEED® from Green Biotech Company Ltd.
  • TX Paenibacillus sp. strain having Accession No. NRRL B- 50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX, Pantoea agglomerans, in particular strain E325 (Accession No.
  • NRRL B-21856 (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO 2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No.1-3936, CNCM No.1- 3937, CNCM No.1-3938 or CNCM No.1-3939 (WO 2010/086790)
  • DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX
  • Bacillus amyloliquefaciens in particular strain D747 (available as Double NickelTM from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No.7,094,592) + TX
  • Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX
  • Bacillus licheniformis in particular strain SB3086, having Accession No.
  • ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having Accession No. B-30890 (available as BMJ TGAI® or WG and LifeGardTM from Certis USA LLC) + TX, Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No.
  • Patent No.5,061,495 + TX Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No.
  • DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No.
  • PRORADIX® from Sourcon Padena + TX
  • Streptomyces griseoviridis strain K61 also known as Streptomyces galbus strain K61
  • DSM 7206 Streptomyces galbus strain K61
  • MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf.
  • BIOKUPRUMTM by AgriLife + TX
  • Chaetomium globosum available as RIVADIOM® by Rivale
  • TX Cladosporium cladosporioides
  • strain H39 having Accession No. CBS122244, US 2010/0291039 (by Stichting Moowgrass Onderzoek) + TX
  • Coniothyrium minitans in particular strain CON/M/91-8 (Accession No. DSM9660, e.g.
  • strain ICC 080 having Accession No. IMI 392151 (e.g., BIO-TAMTM from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938, CNCM No.1-3939 (WO 2010/086790) from Lesaffre et Compag
  • T- Gro from Andermatt Biocontrol + TX
  • Trichoderma atroviride strain 77B T77 from Andermatt Biocontrol
  • Trichoderma atroviride strain ATCC 20476 IMI 206040
  • Trichoderma atroviride strain LC52 e.g. Tenet by Agrimm Technologies Limited
  • Trichoderma atroviride strain LU132 e.g. Sentinel from Agrimm Technologies Limited
  • TX Trichoderma atroviride strain NMI no. V08/002388 + TX
  • Trichoderma atroviride strain NMI no. V08/002389 + TX Trichoderma atroviride strain NMI no.
  • Patent No.8,431,120 (from Bi-PA)) + TX, Trichoderma atroviride,strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A.
  • Trichoderma gamsii strain ICC080 IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.
  • + TX Trichoderma harmatum + TX
  • Trichoderma harmatum having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g.
  • Trichodex® from Makhteshim, US + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro), + TX, Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g.
  • Trichoderma polysporum strain IMI 206039 e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden
  • TX Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX
  • Trichoderma virens also known as Gliocladium virens
  • strain GL-21 e.g. SoilGard by Certis, US
  • TX Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No.
  • ATCC 20906 (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No.
  • NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
  • TX Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No.
  • WCS850 deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IFTM from TerraMax, Inc.) + TX, Azotobacter chroococcum, in particular strain H
  • NRRL B-5015 + TX
  • Bacillus amyloliquefaciens in particular strain FZB42 e.g. RHIZOVITAL® from ABiTEP, DE
  • Bacillus amyloliquefaciens in particular strain IN937a + TX Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX
  • Bacillus amyloliquefaciens SB3281 ATCC # PTA-7542, WO 2017/205258
  • Bacillus amyloliquefaciens TJ1000 available as QUIKROOTS® from Novozymes
  • Bacillus cereus family member EE128 NRRL No.
  • YIELD SHIELD® from Bayer Crop Science, DE
  • + TX Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B- 50421 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g.
  • BIOBOOST® from Brett Young Seeds + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company 82949 FF 97 Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g.
  • PRORADIX® from Sourcon Padena + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g.
  • Trichoderma atroviride strain SC1 (described in WO 2009/116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g.
  • aizawai in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp.
  • serotype H-7 e.g. FLORBAC® WG from Valent BioSciences, US
  • TX Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX
  • israeltaki strain ABTS 351 + TX Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis 82949 FF 98 subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g.
  • MBI206 TGAI and ZELTO® from Marrone Bio Innovations + TX
  • Chromobacterium subtsugae in particular strain PRAA4-1T e.g. MBI-203, e.g. GRANDEVO® from Marrone Bio Innovations
  • TX Chromobacterium subtsugae in particular strain PRAA4-1T
  • MBI-203 e.g. GRANDEVO® from Marrone Bio Innovations
  • TX Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX
  • Paenibacillus popilliae (formerly Bacillus popilliae, e.g. MILKY SPORE POWDERTM or MILKY SPORE GRANULARTM from St. Gabriel Laboratories) + TX
  • Serratia entomophila e.g.
  • ATCC74250 e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation
  • TX Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017/066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX; Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, of Adoxophyes orana (summer fruit tortrix) granul
  • Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp.
  • Heads Up® 82949 FF 99 (Saponins of Quinoa) from Heads Up plant Protectants, CA) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from STK) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (FRACTURE® from FMC) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (PROBLAD® from Certis EU) + TX, Pyrethrins + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX from Marrone Bio) + TX, RequiemTM Insecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX,
  • the designation is not a "common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name”, a “traditional name”, a “compound name” or a “development code” is used or, if neither one of those designations nor a "common name” is used, an "alternative name” is employed.
  • "CAS Reg. No” means the Chemical Abstracts Registry Number.
  • the active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-90 , Tables B-1 to B-90, and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-90 , Tables B-1 to B-90, and Table P, and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or
  • the compounds and mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.
  • the mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-90 , Tables B-1 to B-90, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention.
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl-formamide, dimethyl sulfoxide, 1,4- dioxane, diprop
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula-tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: ⁇ active ingredient: 1 to 95 %, preferably 60 to 90 % ⁇ surface-active agent: 1 to 30 %, preferably 5 to 20 % ⁇ liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts: ⁇ active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % ⁇ solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: ⁇ active ingredient: 5 to 75 %, preferably 10 to 50 % ⁇ water: 94 to 24 %, preferably 88 to 30 % ⁇ surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: ⁇ active ingredient: 0.5 to 90 %, preferably 1 to 80 % ⁇ surface-
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • the mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity.
  • Suitable additions to active ingredients are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredi-ent can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • the compounds of formula (I) of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the 82949 FF 105 compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula (I).
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • the compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m 2 .
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - [0472] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20 % [0473] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % [0474] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % [0478]
  • 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.
  • FF 108 such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % [0479] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • "Mp" means melting point in degrees Celsius (°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 [0482] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive 82949 FF 109 and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • Method 2 [0483] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 5000°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range: 110 to 800 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector.
  • an electrospray source Polyity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 5000°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/
  • Method 3 [0484] 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.
  • an electrospray source Polarity: Positive and Negative Polarity Switch
  • Example E1 Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P1) 82949 FF 110 [0485] A microwave vial was charged with 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol- 3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-8) (0.15 g, 0.33 mmol), methyl carbamate (0.037 g, 0.49 mmol), [1-(2-diphenylphosphanyl-1-naphthyl)-2-naphthyl]-diphenyl-phosphane (BINAP,
  • Example E2 Alternative preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin- 4-yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P1) [0488] To a mixture of 4,6-dichloro-8-(trifluoromethyl)quinazoline (prepared as described in WO 2021/083936) (0.12 g, 0.45 mmol) and [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4- triazol-3-yl]ethyl]ammonium chloride (I-3) (0.15 g, 0.49 mmol) in tetrahydrofuran (4 mL) was added triethylamine (0.14 g, 1.35 mmol) dropwise at room temperature.
  • Example E3 Preparation of ethyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (compound P2) [0491] To a solution of 6-chloro-N-[(1S)-1-[2-[6-(methylamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]- 8-(trifluoromethyl)quinazolin-4-amine (I-10) (0.10 g, 0.22 mmol) in tetrahydrofuran (2 mL) were added ethyl chloroformate (0.24 g, 2.22 mmol) and triethylamine (0.05 g, 0.44 mmol) at 0°C.
  • Example E4 Preparation of ethyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P6) [0493] To a solution of N-[(1S)-1-[2-(6-amino-pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-N- methyl-8-(trifluoromethyl)quinazolin-4-amine (I-12) (0.1 g, 0.22 mmol) in acetonitrile (4 mL) were added ethyl chloroformate (0.24 g, 2.22 mmol) and potassium carbonate (0.06 g, 0.67 mmol).
  • Example E5 Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P5)
  • Step 1 Preparation of phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-14) (I-14) [0495]
  • phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (I-15) can be obtained from intermediate (I-10) with above protocol.
  • phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-16) can be obtained from intermediate (I-12) with above protocol.
  • LCMS (method 3): retention time 1.27 min, m/z 570/572 [M+H] + .
  • phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (I-17) can be obtained from intermediate (I-13) with above protocol.
  • Step 2 Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P5) [0500] To a solution of phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-14) (0.1 g, 0.18 mmol) in isopropanol (4 mL) was added potassium carbonate (0.02 g, 0.18 mmol) and reaction mixture was stirred at 80°C for 45 minutes.
  • Example E6 Preparation of tert-butyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P19) 82949 FF 114 Step 1: Preparation of 6-chloro-8-(trifluoromethyl)-3H-quinazolin-4-one (I-20) (I-20) [0502] To a solution of 2-amino-5-chloro-3-(trifluoromethyl)benzonitrile (CAS 74396-76-2) (500 mg, 2.27 mmol) in formic acid (4.5 mL) was added sulfuric acid (0.192 mL, 1.5 equiv.) dropwise and the reaction mixture was heated to 80°C for 1 hour.
  • Step 2 Preparation of 4,6-dichloro-8-(trifluoromethyl)quinazoline (I-21) (I-21) [0504] A suspension of 6-chloro-8-(trifluoromethyl)-3H-quinazolin-4-one (I-20) (1.0 g, 4.02 mmol) and N,N-dimethylformamide (0.0629 mL, 0.80 mmol, 0.2 equiv.) in thionyl chloride (10 mL) was heated at 79°C for 5 hours. After cooling to room temperature, the mixture was diluted with toluene and poured carefully into ice and water.
  • Step 4 Preparation of (E,2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]-N- (dimethylaminomethylene)propanamide (I-23) (I-23) [0508]
  • (2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]propanamide (I- 22) (0.15 g, 0.44 mmol, 1.0 equiv.)
  • CPME (1.05 mL)
  • N,N-dimethylformamide dimethyl acetal DMF-DMA
  • Step 5 Preparation of tert-butyl N-(6-hydrazinopyrimidin-4-yl)carbamate (I-24) [0511] Tert-butyl (6-chloropyrimidin-4-yl)carbamate (CAS 1849595-31-8) (0.2 g, 0.87 mmol, 1 equiv.) was suspended in 2-propanol (1 mL). Hydrazine hydrate (0.164 g, 3 equiv.) was added, and the mixture was stirred at 90°C for 2 hours. After cooling to room temperature, the reaction mixture was diluted with water and ethanol. The formed precipitate was isolated by filtration and washed with a mixture of ethanol and water.
  • Step 6 Preparation of tert-butyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino] ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P19) [0513] Tert-butyl N-(6-hydrazinopyrimidin-4-yl)carbamate (I-24) (0.119 g, 0.53 mmol, 1.2 equiv.) dissolved in acetic acid (1.16 mL) was added to the mixture obtained in Example E6, step 4 above (solution A containing (I-23), assumed 0.44 mmol) at room temperature.
  • Example E7 Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (compound P12)
  • Step 1 Preparation of 6-chloro-N-[(1S)-1-[2-[6-(methoxyamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]- 8-(trifluoromethyl)quinazolin-4-amine (I-18) (I-18) [0515] A mixture in a pressure vessel of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol- 3-yl]ethyl]-8-(trifluoromethyl)qui
  • Step 2 Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (compound P11) 82949 FF 118 [0517]
  • a solution of 6-chloro-N-[(1S)-1-[2-[6-(methoxyamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]- 8-(trifluoromethyl)quinazolin-4-amine (I-18) 200 mg, 1 equiv.) in acetonitrile (2 mL) was treated with potassium carbonate (0.447 g, 10.5 equiv.) and methyl chloroformate (0.410 g, 10 equiv.).
  • Step 3 Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (compound P12) [0519] To a solution of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (P11) (80 mg, 1 equiv.) in acetonitrile (0.8 mL) were added cesium carbonate (100 mg, 2 equiv.), followed by methyl iodide (218 mg, 10 equiv.).
  • Example E8 Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]- methyl-amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (compound P14) 82949 FF 119
  • Step 1 Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P7) [0521] To a solution of phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl
  • reaction mixture was stirred at 20°C for 5 hours, then at 80°C for 15 minutes, after which it was diluted with water and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo.
  • Step 2 Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (compound P14) [0523] To a solution of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (P7) (80 mg, 1 equiv.) in acetonitrile (0.8 mL) 82949 FF 120 were added potassium carbonate (39 mg, 2 equiv.) and iodomethane (20 mg, 10 equiv.).
  • reaction mixture was stirred at 20°C for 4 hours, then poured into water and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo.
  • Example PI-1 Preparation of [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-3)
  • Step 1 Preparation of tert-butyl N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-1) (I-1) [0525]
  • a solution of tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (CAS 2694010-23-4, prepared as described for example in WO 2021/165195) (5.00 g, 15.40 mmol) in ammonia (7M in methanol) (39.60 mL, 27
  • Step 2 Preparation of methyl N-[6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (I-2) [0528] To a mixture of tert-butyl N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-1) (1.90 g, 6.22 mmol) and potassium carbonate (2.58 g, 18.67 mmol) in acetonitrile (28.5 mL) was added methyl chloroformate (1.18 g, 0.96 mL, 12.44 mmol) at room temperature.
  • Step 3 Preparation of [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-3) [0531] To a suspension of methyl N-[6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (I-2) (1.60 g, 4.40 mmol) in CPME (32 mL) was added hydrochloric acid (4M in dioxane) (2.02 mL, 66 mmol) at room temperature.
  • Example PI-2 Preparation of N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (trifluoromethyl)quinazolin-4-amine (I-9) (I-9) Step 1: Preparation of [(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 7) [0534] To a solution of tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (CAS 2694010-23-4, prepared as described for example in WO 2021/165195) (20.0 g, 61.58 mmol) in 1,4-dioxane (200 mL)
  • Step 3 Preparation of N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (trifluoromethyl)quinazolin-4-amine (I-9) (I-9) [0538] A pressure vessel was charged with 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4- triazol-3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-8) (2 g, 4.39 mmol) and 1,4-dioxane (20 mL).
  • N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-N-methyl-8- (trifluoromethyl)quinazolin-4-amine (I-12) can be obtained from intermediate (I-11) with above protocol.
  • Example PI-3 Preparation of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-N- methyl-8-(trifluoromethyl)quinazolin-4-amine(I-11) (I-11) [0543] To a solution of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine (I-8) (4 g, 8.79 mmol) in acetonitrile (40 mL) were added iodomethane (5.50 mL, 87.87 mmol) and cesium carbonate (5.73 g, 17.57 mmol) at room temperature.
  • iodomethane 5.50 mL, 87.87 m
  • Example PI-4 Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]thiazol-5-amine (I-19) 82949 FF 125 (I-19) Step 1: Preparation of 6-chloro-N-[(1S)-1-[2-(5-nitrothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine [0545] To a solution of (NE,2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]-N- (dimethylaminomethylene)propanamide (2.2 g, 5.6 mmol) (prepared in analogy to descriptions found in WO 2021/083936) and (5-nitrothia
  • Step 2 Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]thiazol-5-amine (I-19) [0547] To a solution of 6-chloro-N-[(1S)-1-[2-(5-nitrothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine (700 mg, 1.41 mmol) in methanol (14 mL) was added palladium on charcoal (Pd/C, 75 mg, 10% Pd).
  • Example PI-5 Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium 2,2,2- trifluoroacetate (I-28) (I-28) Step 1: Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-27) (I-27) [0549] To a solution of tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (1.8 g, 9.56 mmol) in 2-methyltetrahydrofuran (29 mL) was added N,N-dimethylformamide dimethyl acetal (14.35 mmol) at room temperature.
  • Step 2 Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium 2,2,2- trifluoroacetate (I-28) 82949 FF 127 (I-28) [0551] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-27) (2.0 g, 5.42 mmol) in trifluoromethylbenzene (40 mL) was added 2,2,2-trifluoroacetic acid (10 mL) at RT dropwise.
  • Example B1 Activity against Chilo suppressalis (Striped rice stemborer) [0555] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well).
  • the samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation.
  • Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • the following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P13, P14, P16, P17, P18, P19.
  • Example B2 Activity against Diabrotica balteata (Corn root worm)
  • Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
  • the following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P13, P14, P17, P19.
  • Example B3 Activity against Euschistus heros (Neotropical Brown Stink Bug) [0559] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10’000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. 82949 FF 139 The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. [0560] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P8, P13.
  • Example B4 Activity against Myzus persicae (Green peach aphid).
  • Test compounds prepared from 10’000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation. [0562] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: P1, P10.
  • Example B5 Activity against Plutella xylostella (Diamond back moth) [0563] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10’000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.
  • the samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation.
  • Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • the following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P13, P14, P16, P17, P18, P19.
  • Example B7 Activity against Frankliniella occidentalis (Western flower thrips).
  • Feeding/Contact activity Bean leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation. [0568] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P13.

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Abstract

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

Description

82949 FF 1 PESTICIDALLY ACTIVE QUINAZOLINE COMPOUNDS TECHNICAL FIELD [0001] The present invention relates to pesticidally active quinazoline compounds, e.g. as active ingredients, which have pesticidal activity, in particular insecticidally active quinazoline compounds. The invention also relates to the preparation of these quinazoline compounds, to intermediates useful in the preparation of these quinazoline compounds, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of these quinazoline compounds, to preparation of these compositions and to the use of these quinazoline compounds or compositions in agriculture or horticulture, for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina. BACKGROUND [0002] WO 2021/083936, WO 2021/148639, WO 2021/177160, WO 2022/268648, WO 2023/104714, WO 2023/247360, and WO 2024/110554 describe certain quinazoline, quinazolinone and quinoline compounds. BRIEF SUMMARY [0003] It has now surprisingly been found that certain novel quinazoline compounds have pesticidal activity. Hence, the present invention accordingly relates, in a first aspect, to a compound of the formula (I):
Figure imgf000002_0001
wherein: A1, A2, and A3 are, independently from each other, N or C-RY; A4 and A5 are, independently from each other, N or C-RY;
Figure imgf000002_0002
the staggered line represents the connection of Q to the rest of compound of the formula (I); 82949 FF 2 R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a and R2b are independently hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3-C6cycloalkylcarbonyl, C1-C3cyanoalkyl, C1-C3cyanoalkoxy, OR6, NO2, SF5, CN, C(O)NH2, C(O)OH, C(S)NH2, C3-C6cycloalkyl, phenyl, heteroaryl, piperidin-2-one-1-yl, pyridin-2-one-1- yl, azetidin-1-yl, pyrrolidin-1-yl, C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, C1- C4alkylsulfanyl, C1-C4alkylsulfonyl, or C1-C4alkylsulfinyl; each of said C3-C6cycloalkyl, C3-C6cycloalkylcarbonyl, phenyl, heteroaryl, C1-C4alkylsulfanyl, C1-C4alkylsulfonyl, and C1-C4alkylsulfinyl being optionally substituted with one, two or three independently selected RX substituents; each of said piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl, pyrrolidin-1-yl, and C3- C6cycloalkylC1-C3alkoxy being optionally substituted with one or two independently selected RX substituents; said C3-C6cycloalkylC1-C4alkyl being optionally substituted with one or two independently selected RZ substituents; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidinyl, pyrazinyl, or thiazolyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R4a is pyridinyl, pyrimidinyl, pyrazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3- C4cycloalkyl; R6 is phenyl, benzyl, heteroaryl, or C3-C6cycloalkyl, each of which is optionally substituted with one, two or three independently selected RX substituents; R10 is C1-C4alkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxy-C1- C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, C1-C3alkyl, C1-C3cyanoalkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1- C3alkoxy-C1-C3alkyl, C1-C3haloalkyl, hydroxy, or C1-C3alkoxy; or R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl or 2,4-dioxo-3-oxazolidinyl, each of which, independently of each other, is substituted with one or two C1-C3alkyl; RX is halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1- C4haloalkylsulfanyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4alkylsulfanyl, C1- C4alkylsulfinyl, C1-C4alkylsulfonyl, NO2, SF5, CN, C(O)NH2, or C(S)NH2; RY is hydrogen, C1-C3alkyl, C1-C3haloalkyl, hydroxy, C1-C3alkoxy, C1-C3haloalkoxy, halogen, CN, or cyclopropyl; RZ is oxo, halogen, C1-C3 alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or CN; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of the compound of formula (I). 82949 FF 3 [0004] The present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I). [0005] In a second aspect, the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient. [0006] In a third aspect, the present invention makes available a method of combating and controlling pests, such as insects, acarines, nematodes, or molluscs, which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally, such as insecticidally, acaricidally, nematicidally, or molluscicidally, effective amount of a compound as defined in the first aspect or of a composition as defined in the second aspect. [0007] In a fourth aspect, the present invention makes available a method for the protection of plant propagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which comprises treating the propagation material or the site where the propagation material is planted, with an effective amount of a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect. [0008] In a fifth aspect, the present invention makes available a plant propagation material, such as a seed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as defined in the first aspect or of a composition as defined in the second aspect. [0009] The present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof. DETAILED DESCRIPTION [0010] Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or 82949 FF 4 dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. [0011] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form. [0012] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. [0013] The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation. [0014] The term "C1-Cnalkyl" as used herein refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2- dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl. [0015] The term "C1-Cnhaloalkyl" as used herein refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2- fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3- dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3- pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1- (bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly "C1-C2fluoroalkyl" refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. [0016] The term "C1-Cnalkoxy" as used herein refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1- methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. The term "haloC1-Cnalkoxy" as used herein refers to a C1-Cnalkoxy radical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different halo atom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy. [0017] The term "C1-Cncyanoalkyl" as used herein refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in 82949 FF 5 these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3- cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like. [0018] The term "C3-Cncycloalkyl" as used herein refers to a saturated monocyclic hydrocarbon radical attached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. [0019] The term "cyanoC3-C4cycloalkyl" as used herein refers to a cyclopropyl or cyclobutyl radical where one of the hydrogen atoms in these radicals is replaced by a cyano group. [0020] The term "C3-Cncycloalkylcarbonyl" as used herein refers to a C3-Cncycloalkyl radical bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. Similarly the terms "C1-Cnalkylcarbonyl", "C1-Cnalkoxycarbonyl", "phenyloxycarbonyl" and "benzyloxycarbonyl" as used herein refers to an C1-Cnalkyl, C1-Cnalkoxy, phenyloxy and benzyloxy group bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. [0021] The term "C3-C4cycloalkylC1-C2alkyl" as used herein refers to a cyclopropyl or cyclobutyl radical bonded via a methylene or ethylene bridge to the rest of the molecule. When the C3- C4cycloalkylC1-C2alkyl radical is substituted, the substituent(s) can be bonded to the C3-C4cycloalkyl radical and/or to the C1-C2alkyl bridge. [0022] The term "C1-Cnalkylsulfanyl" as used herein refers to a C1-Cnalkyl moiety linked through a sulfur atom. Similarly, the term "C1-Cnhaloalkylthio" or "C1-Cnhaloalkylsulfanyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through a sulfur atom. Similarly, the term "C3-Cncycloalkylsulfanyl" refers to 3-n membered cycloalkyl moiety linked through a sulfur atom. [0023] The term "C1-Cnalkylsulfinyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, the term "C1-Cnhaloalkylsulfinyl " or "C1-Cnhaloalkylsulfinyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, the term "C3-Cncycloalkylsulfinyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom of the S(=O) group. [0024] The term "C1-Cnalkylsulfonyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly, the term "C1-Cnhaloalkylsulfonyl " or "C1-Cnhaloalkylsulfonyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly, the term "C3-Cncycloalkylsulfonyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom of the S(=O)2 group. [0025] The term "C2-Cnalkenyl" as used herein refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl. [0026] The term "C2-Cnalkynyl" as used herein refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl. [0027] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl. [0028] The terms 2-oxo-3-oxazolidinyl and 2,4-dioxo-3-oxazolidinyl as used herein refer to the following two radicals, where the staggered line represents the point of attachment of the radical to the rest of the compound: 82949 FF 6 2-oxo-3-oxazolidinyl 2,4-dioxo-3-oxazolidinyl [0029] The term "heteroaryl" as used herein refers to a 5- or 6-membered aromatic monocyclic ring having 1, 2 or 3 heteroatoms independently selected from N, O and S. Preferably, heteroaryls are linked to the remainder of the compound via a carbon atom of the aromatic monocyclic ring. Examples are heteroaryls J-1 to J-40 shown in Table J below, where the staggered line represents the connection of the heteroaryl to the remainder of the compound. Preferred heteroaryl include pyridyl, pyrimidyl, and pyrazolyl. Table J: Heteroaryl J-1 to J-41:
Figure imgf000007_0001
82949 FF 7
Figure imgf000008_0001
J-37 J-38 J-39 J-40 J-41 [0030] The term "optionally substituted" as used herein means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, "C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms" means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3-C4cycloalkyl substituted with 2 halo atoms. [0031] As used herein, the term "controlling" refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced. [0032] As used herein, the term "pest" refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest. [0033] As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect. [0034] 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. [0035] As one of ordinary skill in the art will appreciate, compounds of formula (I) contain a stereogenic centre which is indicated with an asterisk in formula (I*) below:
Figure imgf000008_0002
where R1, R2a, R2b, R3, Q, A1, A2, A3, A4, and A5 are as defined in the first aspect. [0036] The present invention contemplates both racemates and individual enantiomers. Compounds of formula (I'a) having a preferred stereochemistry are set out below: 82949 FF 8
Figure imgf000009_0001
[0037] Particularly preferred compounds of the present invention are compounds of formula (I’a) where R1, R2a, R2b, R3, Q, A1, A2, A3, A4, and A5 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. [0038] Embodiments according to the invention are provided as set out below. [0039] In an embodiment of each aspect of the invention: A. A1, A2 and A3 are, independently from each other, N or C-RY, with the proviso that at least one of A1, A2, and A3, is C-RY ; or B. A1 and A3 are N and A2 is CRY; or C. A1, A2 and A3 are, independently from each other, N or CH; or D. A1, A2 and A3 are, independently from each other, N or CH, with the proviso that at least one of A1, A2, and A3 is CH; or E. A1 is N, and A2 and A3 are CH; or F. A1 and A2 CH, and A3 is N; or G. A1 and A3 are N, and A2 is CH. [0040] In an embodiment of each aspect of the invention: A. A4 is C-RY , and A5 is N; or B. A4 is C-RY , and A5 is CH; or C. A4 is CH, and A5 is N; or D. A4 is N, and A5 is CH; or E. A4 is CH, and A5 is CH. [0041] In the embodiments where A1, A2, A3, A4, or A5 are C-RY, the group or groups RY are independently: A. RY is hydrogen, C1-C3alkyl, C1-C3haloalkyl, hydroxy, C1-C3alkoxy, C1-C3haloalkoxy, halogen, CN, or cyclopropyl; or B. RY is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, or cyclopropyl; or C. RY is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, or cyclopropyl; or D. RY is hydrogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, or cyclopropyl; or E. RY is hydrogen, methyl, trifluoromethyl, methoxy, or cyclopropyl; or F. RY is hydrogen, methyl, or trifluoromethyl; or G. RY is hydrogen. [0042] In preferred embodiments of each aspects of the invention: 82949 FF 9 A. One or two of A1, A2, and A3 are nitrogen, and the other or others are CH; and one or two of A4 and A5 are CH; or B. One or two of A1, A2, and A3 are nitrogen, and the other or others are CH; A4 is CH, and A5 is CH; or C. A1 is N, A2 is CH, A3 is CH, A4 is CH, and A5 is CH; or D. A1 is CH, A2 is CH, A3 is N, A4 is CH, and A5 is CH; or E. A1 is N, A2 is CH, A3 is N, A4 is CH, and A5 is CH. [0043] In more preferred embodiments of each aspect of the invention, A1 is N, A2 is CH, A3 is N, A4 is CH, and A5 is CH. [0044] It may be noted that the motif A1=A2-A3 may also represent NR-C(=O)-N, where R is hydrogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, or C1-C3haloalkoxy. For instance, R is hydrogen, methyl, ethyl, 2,2-difluoroethyl, or 2,2,2-trifluoroethyl. [0045] Throughout the description, the bicyclic ring containing A1, A2, A3, A4 and A5 may be abbreviated as T:
Figure imgf000010_0001
the staggered line represents the connection of T to the remainder of the compound, for instance to the -N(R1)C(R3)Q moiety in compounds of formula (I). [0046] In an embodiment of each aspect of the invention: A. R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B. R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; or C. R1 is hydrogen, methyl, or cyclopropylmethyl; or D. R1 is hydrogen or methyl; or E. R1 is hydrogen; or F. R1 is methyl. [0047] In preferred embodiments of each aspects of the invention, R1 is hydrogen, methyl, or cyclopropylmethyl; or R1 is hydrogen or methyl. In more preferred embodiments of each aspects of the invention, R1 is hydrogen or methyl. [0048] In an embodiment of each aspect of the invention: A. R2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C6cycloalkyl, phenyl, piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl, pyrrolidin-1-yl, C3- C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, or C1-C4haloalkylsulfonyl; or B. R2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C4cycloalkyl, phenyl, C3-C4cycloalkylC1-C4alkyl, or C1-C4haloalkylsulfonyl; or C. R2a is fluoro, chloro, bromo, iodo, C1-C3haloalkyl, methoxy, ethoxy, C1-C3haloalkoxy, phenyl, C3-C4cycloalkylC1-C4alkyl, or C1-C2haloalkylsulfonyl; or 82949 FF 10 D. R2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C6cycloalkyl, phenyl, or C1-C4haloalkylsulfonyl; or E. R2a is halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or C1-C4haloalkylsulfonyl; or F. R2a is hydrogen, halogen, or C1-C3haloalkyl; or G. R2a is hydrogen, halogen, C1-C3fluoroalkyl, or C1-C3fluoroalkylsulfonyl; or H. R2a is hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or I. R2a is trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or J. R2a is trifluoromethyl, chloro, or bromo; or K. R2a is chloro. [0049] In an embodiment of each aspect of the invention: A. R2b is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3- C6cycloalkyl, phenyl, or C1-C4haloalkylsulfonyl; or B. R2b is halogen, C1-C3haloalkyl, C1-C3alkoxy, or C1-C3haloalkoxy; or C. R2b is C1-C3fluoroalkyl, or C1-C3fluoroalkylsulfonyl; or D. R2b is hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or E. R2b is trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or F. R2b is trifluoromethyl, chloro, or bromo; or G. R2b is trifluoromethyl, chloro, or iodo; or H. R2b is trifluoromethyl, or chloro; or I. R2b is trifluoromethyl or iodo; or J. R2b is trifluoromethyl. [0050] In preferred embodiments of each aspect of the invention: A. R2a and R2b are independently hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; or B. R2a and R2b are independently trifluoromethyl, chloro, bromo, or iodo; or C. R2a and R2b are differently selected from the group consisting of trifluoromethyl, chloro, bromo, and iodo; or D. R2a and R2b are independently trifluoromethyl, chloro, or iodo; or E. R2a is trifluoromethyl, chloro, or bromo, and R2b is trifluoromethyl; or F. R2a is chloro, and R2b is trifluoromethyl or chloro; or G. R2a is chloro, and R2b is trifluoromethyl or iodo; or H. R2a is chloro, and R2b is trifluoromethyl. [0051] In an embodiment of each aspect of the invention: A. R3 is methyl or trifluoromethyl; or B. R3 is methyl. [0052] In preferred embodiments of each aspect of the invention, R3 is methyl. [0053] In an embodiment of each aspect of the invention: A. Q is Qa; or B. Q is Qb. [0054] In an embodiment of each aspect of the invention, Q is Qa and 82949 FF 11 A. R5 is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; or B. R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or C. R5 is hydrogen, halogen, or C1-C3alkyloxy; or D. R5 is hydrogen, halogen, or C1-C3alkyl; or E. R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, 2-methoxyethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylcarbonyl, methoxycarbonyl, or 1,3,4-oxadiazol-2-yl; or F. R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; or G. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or H. R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, or 2-methoxyethoxy; or I. R5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; or J. R5 is hydrogen, cyclopropyl, or methoxy; or K. R5 is hydrogen. [0055] In preferred embodiments of each aspect of the invention, Q is Qa, and A. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2- methoxyethoxy; or B. R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, or 2-methoxyethoxy; or C. R5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; or D. R5 is hydrogen, cyclopropyl, or methoxy; or E. R5 is hydrogen. [0056] For instance, Qa is selected from Qa-1 to Qa-16:
Figure imgf000012_0001
Qa-5 Qa-6 Qa-7 Qa-8 82949 FF 12
Figure imgf000013_0001
[0057] In an embodiment of each aspect of the invention, Qa is Qa-1, Qa-4, Qa-5 Qa-6, Qa-7, Qa-10, or Qa-15. Preferably, Qa is Qa-1, Qa-6, Qa-7, Qa-10, or Qa-15. More preferably, Qa is Qa-1 or Qa-15. Most preferably, Qa is Qa-1. [0058] In another embodiment of each aspect of the invention, Q is Qb and A. R5a is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R5a is hydrogen, halogen, or C1-C3alkyloxy; or C. R5a is hydrogen, halogen, or C1-C3alkyl; or D. R5a is hydrogen, chloro, fluoro, methyl, cyclopropyl, trifluoromethyl, methoxy, difluoromethoxy, or cyano; or E. R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy; or F. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy ; or G. R5a is hydrogen, fluoro, chloro, cyano, methyl, or methoxy H. R5a is hydrogen; and A. R5b is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; or B. R5b is hydrogen, halogen, or C1-C3alkyloxy; or C. R5b is hydrogen, halogen, or C1-C3alkyl; or D. R5b is hydrogen, chloro, fluoro, or methoxy; or E. R5b is hydrogen, fluoro, or methoxy; or F. R5b is hydrogen. [0059] In preferred embodiments where Q is Qb, 82949 FF 13 A. R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy and R5b is hydrogen, fluoro, or methoxy; or B. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy , and R5b is hydrogen, chloro, fluoro, or methoxy; or C. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy , and R5b is hydrogen, fluoro, or methoxy; or D. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy and R5b is hydrogen; or E. one of R5a and R5b is hydrogen, the other is hydrogen, fluoro, chloro, cyano, methyl, or methoxy; or F. one of R5a and R5b is hydrogen, the other is hydrogen, fluoro, chloro, methyl, or methoxy; or G. R5a is hydrogen, and R5b is hydrogen, fluoro, or methoxy; or H. R5a and R5b are hydrogen. [0060] For instance, Qb is selected from Qb-1 to Qb-13:
Figure imgf000014_0001
82949 FF 14
Figure imgf000015_0001
[0061] In an embodiment of each aspect of the invention, Qb is Qb-1, Qb-2, Qb-3, Qb-5, Qb-6, Qb-8, Qb-9, Qb-10, or Qb-11. Preferably, Qb is Qb-1, Qb-2, Qb-3, Qb-5, Qb-8, Qb-9, Qb-10, or Qb-11. More preferably, Qb is Qb-1, Qb-2, Qb-3, Qb-5, Qb-8, Qb-10, or Qb-11, or Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb- 11. In preferred embodiments, Qb is Qb-1. [0062] In an embodiment of each aspect of the invention, where Q is Qa: A. R4 is pyrimidin-4-yl, pyrimidin-2-yl, pyrazin-2-yl, thiazol-2-yl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10 ; or B. R4 is R4-1, R4-2, R4-3, R4-4, or R4 -5; or
Figure imgf000015_0002
C. R4 is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; or D. R4 is pyrimidinyl substituted with a single -N(R11)C(O)OR10; or E. R4 is R4-3, R4-4, or R4 -5; or F. R4 is R4-3 or R4 -5; or G. R4 is R4 -5; or H. R4 is R4-3. [0063] In an embodiment of each aspect of the invention, where Q is Qb: A. R4a is pyrimidin-4-yl, pyrimidin-2-yl, pyrazin-2-yl, thiazol-2-yl, pyrazol-1-yl, or 1,2,4-triazol-1-yl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; or B. R4a is R4a-1, R4a-2, R4a-3, R4a-4, R4a-5, R4a-6, or R4a-7: 82949 FF 15
Figure imgf000016_0001
; or C. R4a is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; or D. R4a is pyrimidinyl substituted with a single -N(R11)C(O)OR10; or E. R4a is R4a-3 or R4a-5; or F. R4a is R4a-5; or G. R4a is R4a-3. [0064] The pyridyl, pyrimidinyl, pyrazinyl, and thiazolyl groups of R4 and R4a are each connected to the respective ring via a carbon atom. In other words, a carbon atom of the pyridyl, pyrimidinyl, pyrazinyl, and thiazolyl groups of R4 and R4a is linked to Qa or Qb. [0065] In preferred embodiments of each aspect of the invention, the group -N(R11)C(O)OR10 is in the meta or para position with respect to the link of R4 or R4a to the remainder of the compound. [0066] In an embodiment of each aspect of the invention, where Q is Qa or Qb, such as Qa-1 or Qb-1: A. R10 is C1-C4alkyl, C3-C6cycloalkyl, cyanoC3-C6cycloalkyl, or C1-C3alkoxy-C1-C3alkyl; or B. R10 is C1-C4alkyl, or C3-C6cycloalkyl; or C. R10 is methyl, ethyl, isopropyl, tert-butyl, or C3-C4cycloalkyl; or D. R10 is methyl, ethyl, isopropyl, tert-butyl, or cyclopropyl; or E. R10 is methyl, ethyl, isopropyl, or cyclopropyl; or F. R10 is methyl. [0067] In an embodiment of each aspect of the invention, where Q is Qa or Qb, such as Qa-1 or Qb-1: A. R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxy-C1-C3alkyl, or C1-C3alkoxy; or B. R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, or C1-C3alkoxy; or C. R11 is hydrogen, C1-C3alkyl, or cyclopropyl; or 82949 FF 16 D. R11 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or methoxy; or E. R11 is hydrogen, methyl, ethyl, or methoxy; or F. R11 is hydrogen, methyl, or methoxy; or G. R11 is hydrogen or methyl. [0068] In an embodiment of each aspect of the invention, where Q is Qa or Qb, such as Qa-1 or Qb-1: A. R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl or 2,4-dioxo-3-oxazolidinyl, each of which, independently of each other, is substituted with one or two methyl, ethyl, or isopropyl; or B. R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl substituted with one or two C1-C3alkyl; and the C1-C3alkyl is methyl or ethyl; or C. R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2,4- dioxo-3-oxazolidinyl substituted with one or two C1-C3alkyl; and the C1-C3alkyl is methyl or ethyl. [0069] In an embodiment of each aspect of the invention, A. RX is halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or CN; or B. RX is fluoro, chloro, bromo, methoxy, difluoromethoxy, or cyano. [0070] In an embodiment of each aspect of the invention, A. RZ is oxo, halogen, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or CN; or B. RZ is oxo, fluoro, chloro, bromo, methoxy, difluoromethoxy, or cyano. [0071] Accordingly, the present invention makes available a compound of formula (I) having the substituents A1, A2, A3, A4, A5, Q (i.e. Qa with R4, or Qb with R4a), R1, R2a and R2b, R3, R10, R11, RX, RY, and RZ, as defined above, in all combinations and each permutation. [0072] For instance, compounds of formula (I) are made available, where A1 is C-RY or N; A2 is CH; A3 is CH or N; A4 is CH; A5 is CH; R1 is hydrogen, methyl, or cyclopropylmethyl; R2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C3-C6cycloalkyl, phenyl, piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl, pyrrolidin-1-yl, C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, or C1-C4haloalkylsulfonyl; R2b is hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; R3 is C1-C3alkyl or C1-C3haloalkyl; Q is Qa or Qb; R4 is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R4a is pyrimidinyl substituted with a single -N(R11)C(O)OR10; R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1- C3alkoxy, or C3-C4cycloalkyl; R10 is C1-C4alkyl, C3-C6cycloalkyl, cyanoC3-C6cycloalkyl, or C1-C3alkoxy- C1-C3alkyl; R11 is hydrogen, C1-C3alkyl, or cyclopropyl; and RY is hydrogen, methyl, or trifluoromethyl. [0073] Compounds of formula (I) are made available, where A1 is C-RY or N; A2 is CH or N; A3 is CH or N; A4 is C-RY or N; A5 is CH or N; RY is hydrogen, methyl, trifluoromethyl, methoxy, or cyclopropyl; R1 is hydrogen, methyl, or cyclopropylmethyl; R2a is hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1- C3alkoxy, C1-C3haloalkoxy, C3-C6cycloalkyl, phenyl, piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1- yl, pyrrolidin-1-yl, C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, or C1-C4haloalkylsulfonyl; R2b is halogen, C1-C3haloalkyl, C1-C3alkoxy, or C1-C3haloalkoxy; R3 is methyl; Q is Qa; R4 is pyridinyl, pyrimidinyl, pyrazinyl, or thiazolyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; R10 is methyl, ethyl, isopropyl, tert-butyl, or C3-C4cycloalkyl; and R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, or C1-C3alkoxy. 82949 FF 17 [0074] Compounds of formula (I) are made available, where A1 is N; A2 is CH; A3 is N; A4 and A5 are CH; R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a and R2b are independently hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; R3 is C1-C3alkyl or C1-C3haloalkyl; Q is Qa; R4 is R4-1, R4-2, R4-3, R4-4, or R4 -5; R5 is hydrogen; R10 is C1-C4alkyl, C3-C6cycloalkyl, cyanoC3- C6cycloalkyl, or C1-C3alkoxy-C1-C3alkyl; and R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, or C1- C3alkoxy. [0075] Compounds of formula (I) are also made available, where A1 is C-RY or N; A2 is CH or N; A3 is CH or N; A4 is C-RY or N; A5 is CH or N; RY is hydrogen, methyl, or trifluoromethyl; Q is Qb; R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R4a is R4a-1, R4a- 2, R4a-3, R4a-4, R4a-5, R4a-6, or R4a-7; R10 is methyl, ethyl, isopropyl, or cyclopropyl; and R11 is hydrogen or methyl. [0076] In addition, compounds of formula (I) are made available, where A1 is CH or N; A2 is CH; A3 is CH or N; A4 is CH; A5 is CH or N; R1 is hydrogen, methyl, or cyclopropylmethyl; R2a and R2b are independently hydrogen, trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; R3 is C1-C3alkyl or C1-C3haloalkyl; Q is Qa or Qb; R4 is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R4a is pyridinyl or pyrimidinyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, 2-methoxyethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, methylcarbonyl, methoxycarbonyl, or 1,3,4-oxadiazol-2-yl; R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy; R5b is hydrogen, chloro, fluoro, or methoxy; R10 is methyl, ethyl, isopropyl, tert-butyl, or C3-C4cycloalkyl; and R11 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or methoxy. [0077] Compounds of formula (I) are made available, where A1 is N; A2 is CH; A3 is N; A4 and A5 are CH; R1 is hydrogen or methyl; R2a is chloro; R2b is trifluoromethyl; R3 is methyl; Q is Qa and R4 is R4-1, R4-2, R4-3, R4-4, or R4 -5; or Q is Qb and R4 is R4-1, R4-2, R4-3, R4-4, or R4 -5; R5a and R5b are hydrogen; and R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl substituted with one or two C1-C3alkyl. [0078] Compounds of formula (I) are also made available, where A1 is N; A2 is CH; A3 is N; A4 and A5 are CH; R1 is hydrogen or methyl; R2a is chloro; R2b is trifluoromethyl; R3 is methyl; Q is Qa; R4 is R4-3; R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; and R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3-oxazolidinyl or 2,4-dioxo-3-oxazolidinyl, each of which, independently of each other, is substituted with one or two methyl, ethyl, or isopropyl. [0079] Compounds of formula (I) are also made available, where A1 is N; A2 is CH; A3 is N; A4 and A5 are CH; R1 is hydrogen or methyl; R2a is chloro; R2b is trifluoromethyl; R3 is methyl; Q is Qa; R4 is R4-3; R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; R10 is methyl, ethyl, isopropyl, or cyclopropyl; and R11 is hydrogen or methyl. [0080] Also made available are compounds of formula (I) where A1 is N; A2 is CH; A3 is N; A4 is CH; A5 is CH; R1 is hydrogen or methyl; R2a and R2b are independently trifluoromethyl, chloro, or iodo; R3 is 82949 FF 18 methyl or trifluoromethyl; Q is Qa; R4 is R4-1, R4-2, R4-3, R4-4, or R4 -5; R5 is hydrogen; R10 is methyl, ethyl, isopropyl, or cyclopropyl; and R11 is hydrogen, methyl, ethyl, or methoxy. [0081] Preferably, compounds of formula (I) are made available where A1 is N; A2 is CH; A3 is N; A4 is CH; A5 is CH; R1 is hydrogen or methyl; R2a and R2b are independently trifluoromethyl, chloro, or iodo; R3 is methyl; Q is Qa; R4 is R4-3 or R4-5; R5 is hydrogen; R10 is methyl, ethyl, isopropyl, or cyclopropyl; and R11 is hydrogen, methyl, or methoxy. [0082] More preferably, compounds of formula (I) are made available where A1 is N; A2 is CH; A3 is N; A4 is CH; A5 is CH; R1 is hydrogen or methyl; R2a is chloro, R2b is trifluoromethyl or iodo; R3 is methyl; Q is Qa; R4 is R4-3, R4-4, or R4-5; R5 is hydrogen; R10 is methyl, ethyl, isopropyl, or tert-butyl; and R11 is hydrogen, methyl, or methoxy; or where R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3-oxazolidinyl or 2,4-dioxo-3-oxazolidinyl group. [0083] For instance, compounds of formula (I) are preferred where A1 is N; A2 is CH; A3 is N; A4 is CH; A5 is CH; R1 is hydrogen; R2a is chloro, R2b is trifluoromethyl or iodo; R3 is methyl; Q is Qa; R4 is R4- 3 or R4-5; R5 is hydrogen; R10 is methyl or ethyl; and R11 is hydrogen or methyl. Synthesis [0084] Compounds of formula (I) can be prepared by those skilled in the art following known methods. More specifically compounds of formulae (I), and (I’a), and intermediates therefor can be prepared as described below in the schemes and examples. Certain stereogenic centers have been left unspecified for the clarity and are not intended to limit the teaching of the schemes in any way. [0085] Compounds of formula (I) can be made, for example, as outlined in Scheme 1.
Figure imgf000019_0001
Scheme 1 [0086] Reaction of a compound of the formula II, wherein A1, A2, A3, A4, A5, R2a and R2b are as defined above for compounds of the formula (I), and wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, with a compound of formula III, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I), gives a compound of the formula (I), wherein A1, A2, A3, A4, A5, R1, R2a, R2b, R3 and Q have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N- dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium 82949 FF 19 complex, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0087] Compounds of the formula II, wherein A1, A2, A3, A4, A5, R2a and R2b are as defined above for compounds of the formula (I), are either known, or can be prepared in analogy to descriptions found for example in WO 2021/083936 and WO 2021/177160, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000020_0001
V III VII Scheme 2 [0088] Compounds of formula III, or a salt thereof, wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I), can be made, for example, as outlined in Scheme 2. Treatment of a compound of the formula V, wherein R3 and Q have the same meaning as given above for compounds of the formula (I) and wherein X2 is a leaving group, such as a halogen or sulfonate, for instance bromide, with an amine of the formula XIX, or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), gives compounds of the formula III, or a salt thereof, wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0089] Alternatively, treatment of a compound of the formula VII, wherein R3 and Q have the same meaning as given above for compounds of the formula (I), with an amine of the formula XIX, or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), gives compounds of the formula III, or a salt thereof, wherein Q, R1 and R3 have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, for the alkylation of amines and for the reductive alkylation of amines (e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid, at room temperature, analogous to WO 2002/088073; or alternatively, by the use of a combination of Ti(i-OiPr)4 and NaBH4 as described in Synthesis 2003 (14), 2206) are well known to a person skilled 82949 FF 20 in the art. The amines of formula XIX, or a salt thereof, wherein R1 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000021_0001
Scheme 3 [0090] Alternatively, compounds of formula (I) can be made, for example, as outlined in Scheme 3. Reaction of an amine of the formula IV with a compound of the formula V, wherein X2 is a leaving group, such as a halogen or sulfonate, for instance bromide, gives a compound of formula (I), wherein A1, A2, A3, A4, A5, R1, R2a, R2b, R3 and Q have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art. [0091] Alternatively, reaction of an amine of the formula IVa with a compound of the formula VII gives a compound of the formula (I) wherein R1 is H and A1, A2, A3, A4, A5, R2a, R2b, R3 and Q have the same meaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, such as for example hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of - 100 to +300 °C, preferably between ambient temperature and 200 °C. [0092] Such methods for the reductive alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art.
Figure imgf000021_0002
VIII V VII Scheme 4 [0093] Compounds of formula V can be made, for example, as outlined in Scheme 4. Treatment of a compound of the formula VIII with a halogenating agent, such as chlorine or bromine or N- bromosuccinimide, for example, gives compound of the formula V, wherein the leaving group Q is a 82949 FF 21 halogen, for instance chloride or bromide. This reaction is done with or without a solvent, preferably in a solvent, with or without an additive, such as a radical starter, such as, for example, benzoyl peroxide or azoisobutyronirile. 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. [0094] Alternatively, a compound of the formula VII can be treated with a reducing agent, followed by reaction with a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula V, wherein the leaving group Q is a sulfonate, for instance a mesylate. This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, and it can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. A suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. [0095] 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 amines of formula VII and the compounds of formula VIII are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000022_0001
Scheme 5 [0096] Alternatively, compounds of formula (I) wherein R1 is different from hydrogen can be made, for example, as outlined in Scheme 5. A compound of the formula Ia, wherein A1, A2, A3, A4, A5, R2a, R2b, R3 and Q have the same meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula VI, wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X3 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (I), wherein A1, A2, A3, A4, A5, R1, R2a, R2b, R3 and Q 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 acetonitrile, N,N-dimethylformamide (DMF) or N,N- dimethylacetamide (DMA), or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, 82949 FF 22 triethylamine, diisopropylethylamine or pyridine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art, and are described for example in WO 2021/083936. [0097] Compounds of the formula (VI), wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X3 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, are either known, or they can be prepared by methods known to a person skilled in the art.
Figure imgf000023_0001
Scheme 6 [0098] Compounds of formula Ib can be made, for example, as outlined in Scheme 6. Reaction of a compound of the formula II, wherein A1, A2, A3, A4, A5, R2a and R2b have the same meaning as given above for compounds of the formula (I), and wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, with a compound of formula IX, or a salt thereof, wherein R3 has the same meaning as given above for compounds of the formula (I), gives a compound of the formula X, wherein A1, A2, A3, A4, A5, R2a, R2b and R3 have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, toluene, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, optionally in the presence of a quaternary ammonium salt, for instance tetrabutylammonium bromide (TBAB), 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 sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. 82949 FF 23 [0099] Subsequent treatment of compound of the formula X, wherein A1, A2, A3, A4, A5, R2a, R2b and R3 have the same meaning as given above for compounds of the formula (I), with compounds of the formula XIII, wherein R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl, and in which each of R20, R21, R22 and R23 are independently of each other C1-C4alkyl, or in which each of R22 and R23 are independently of each other C1-C4alkyl and R20, R21 together with the nitrogen to which they are bound represent a pyrrolidine, piperidine or morpholine radical (e.g. XIII is N,N-dimethylformamide dimethyl acetal, also named DMF-DMA, when R5 is hydrogen and each of R20, R21, R22 and R23 are methyl) gives compounds of the formula XI, wherein A1, A2, A3, A4, A5, R2a, R2b and R3 have the same meaning as given above for compounds of the formula (I), and in which R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl, and each of R20 and R21 are independently of each other C1-C4alkyl, or R20, R21 together with the nitrogen to which they are bound represent a pyrrolidine, piperidine or morpholine radical. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether or dioxane, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50 °C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. [0100] Further reaction of compound of the formula XI, wherein A1, A2, A3, A4, A5, R2a, R2b and R3 have the same meaning as given above for compounds of the formula (I), and in which R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl, and each of R20 and R21 are independently of each other C1-C4alkyl, or R20, R21 together with the nitrogen to which they are bound represent a pyrrolidine, piperidine or morpholine radical, with hydrazine compounds of formula XII or a tautomer thereof, or a salt thereof, wherein R4 has the same meaning as given above for compounds of the formula (I), gives the compound of formula Ib, wherein A1, A2, A3, A4, A5, R2a, R2b, R3 and R4 have the same meaning as given above for compounds of the formula (I), and in which R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of 1,4-dioxane and acetic acid, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, or between ambient temperature and 80 °C. Within this sequence of transformations, the intermediate compounds of formula X and of formula XI can be used as crude products for the subsequent step, or they can be purified, for instance by chromatography or precipitation, and used in purified form for the next transformation. [0101] Compounds of the formula IX, or a salt thereof, wherein R3 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. Hydrazine compounds of formula XII or a tautomer thereof, or a salt thereof, wherein R4 has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. For example, compounds of the formula XIIa or a tautomer thereof, or a salt thereof, a particular subset of compounds of the formula XII, wherein R10 and R11 have the same meaning as given above for compounds of the formula (I), can be prepared by reacting compounds of the formula XII-1, wherein R10 and R11 have the same meaning as given above for compounds of the formula (I), and in which Xb is a leaving group, such as for example 82949 FF 24 a halogen or a sulfonate, preferably Br or Cl (even more preferably Cl), with hydrazine or with hydrazine hydrate, or salts thereof. The reaction can be carried out neat or in a solvent, such as for instance water, or alcohols such as methanol, ethanol or isopropanol, or methoxy cyclopentane, at temperatures between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at 90- 100 °C, optionally under microwave conditions.
Figure imgf000025_0001
[0102] Compounds of the formula XIIa, or a salt thereof, wherein R10 and R11 have the same meaning as given above for compounds of the formula (I), may exist in different tautomeric forms, such as XIIa- 1 and/or XIIa-2, or salts thereof, in which R10 and R11 have the same meaning as given above for compounds of the formula (I):
Figure imgf000025_0002
[0103] This invention covers all such tautomers and mixtures thereof in all proportions. [0104] Compounds of the formula XII-1, wherein R10 and R11 have the same meaning as given above for compounds of the formula (I), and in which Xb is a leaving group, such as for example a halogen or a sulfonate, preferably Br or Cl (even more preferably Cl), are either known, or they can be prepared by methods known to a person skilled in the art. [0105] Compounds of the formula Ik
Figure imgf000025_0003
can be prepared by the reaction of an amine of the formula IIIf, or a salt thereof, 82949 FF 25
Figure imgf000026_0001
wherein R1, R3, R4 and R5 are as described in formula (I), with a compound of the formula II
Figure imgf000026_0002
wherein A1, A2, A3, A4, A5, R2a and R2b are as described in formula (I) and X1 is a leaving group, such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.
Figure imgf000026_0003
[0106] Compounds of formula Ic can be made, for example, as outlined in Scheme 7. Reaction of a compound of the formula XVII (wherein X05 is a leaving group such as chlorine, bromine, iodine, arysulfonate, alkylsulfonate or trifluoromethanesulfonate) with an amine of the formula XIX gives compounds of the formula XVI. 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 82949 FF 26 instance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, for the reductive alkylation of amines are well known to a person skilled in the art. [0107] Subsequent reaction of the intermediate of the formula XVI with a compound of the formula II gives a compound of the formula XIV. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. [0108] Subsequently, the intermediate of the formula XIV is reacted with a compound of the formula XV to give the compound of formula Ic, wherein A1, A2, A3, A4, A5, R2a, R2b, R1, R3 and R4a have the same meaning as given above for compounds of the formula (I), and M1 in R4a-M1 is a metal, such as for instance lithium, or –MgCl, or –ZnBr, or –B(OH)2; or R4a-M1 represents a boronate, such as a pinacol ester of a boronic acid, or a stannane such as R4a-Sn(n-Bu)3. Such transformations are known to a person skilled in the art as Suzuki-, Kumada-, Negishi- or Stille-coupling reactions, respectively. Such reactions are carried out in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, in the presence of a catalyst, such as a metal catalyst, for instance a palladium catalyst, and a ligand, such as for example a phosphine ligand, or an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand. The reaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance CuI. The reaction is done with or without a base, which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or 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. Where the reaction mixture is heated, the reaction can be conducted under microwave irradiation or with conventional heating, such as heating the reaction vessel in an oil bath. [0109] By an alternative route, compound XVII can be reacted with a compound of the formula XV to give intermediate XVIII. This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate XIV to the compound of formula Ic. [0110] Subsequently, the intermediate XVIII is reacted with amine IVa to give a compound of the formula Ic, wherein R1 is hydrogen and A1, A2, A3, A4, A5, R2a, R2b, 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 XVII to intermediate XVI. [0111] By yet another alternative route, the intermediate compound of the formula XVIII can be reacted with an amine of the formula XIX to give the intermediate of the formula IIIa. This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound XVII to intermediate XVI. [0112] Subsequently, the intermediate of the formula IIIa is reacted with a compound of the formula II to give the compound of the formula Ic, wherein A1, A2, A3, A4, A5, R2a, R2b, R1, R3 and R4a have the 82949 FF 27 same meaning as given above for compounds of the formula (I). This reaction is done essentially under the same conditions as described above for the transformation of intermediate XVI to intermediate XIV. [0113] Within these different multistep sequences, the intermediate compounds of formulas XIV, XVI, XVIII and IIIa can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation. Compounds of the formula XVII are known, or they can be prepared by methods known to a person skilled in the art. [0114] Compounds of the formula Id
Figure imgf000028_0001
can be prepared by the reaction of an amine of the formula IIIb, or a salt thereof
Figure imgf000028_0002
wherein R1, R3, R4a, R5a and R5b are as described in formula (I) with a compound of the formula II
Figure imgf000028_0003
wherein A1, A2, A3, A4, A5, R2a and R2b are as described in formula (I) and X1 is a leaving group, such as a halogen or a sulfonate, for instance chloride. [0115] The chemistry is described in more detail in Scheme 8.
Figure imgf000028_0004
Scheme 8 82949 FF 28 [0116] Reaction of a compound of the formula II, wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, with a compound of formula IIIb gives a compound of the formula Id, wherein A1, A2, A3, A4, A5, R1, R2a, R2b, R3, R4a, R5a and R5b have the same meaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the 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. [0117] The formation of compounds of formula IIIb is outlined in Scheme 9:
Figure imgf000029_0001
Scheme 9 [0118] Compounds of formula IIIb can be prepared by treatment of compounds of formula IIIc, wherein R3, R4a, R5a, and R5b are as described in formula (I), with compounds of formula XX wherein R1a is for example H, methyl or cyclopropyl, e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid at room temperature analogous to WO 2002/088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206). [0119] Amines of formula IIIc may be obtained by biocatalyzed deracemization of amines of formula IIId. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem.2007, 72, 6918-6923 or Adv. Synth. Catal.2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem.1991, 56, 2656-2665 or J. Am. Chem. Soc.2015, 137, 3996−4009. [0120] In an alternative process, compounds of formula IIIc, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be obtained from compounds of the formula XXII, wherein R3, R4a, R5a, and R5b are as described in formula (I), following the synthesis described in Scheme 10. 82949 FF 29
Figure imgf000030_0005
Figure imgf000030_0001
Nucleophilic substitution deprotection
Figure imgf000030_0002
Figure imgf000030_0003
Figure imgf000030_0004
[0121] Amines of formula IIIc, or a salt thereof, may be obtained from intermediates of formula XXII, wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9. [0122] Such intermediates of formula XXII, wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula XXI, wherein R3, R4a, R5a, and R5b are as described in formula (I), by a Mitsunobu reaction, which involves treating alcohols of formula XXI with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide (HNPhth) or bis(tert- butoxycarbonyl)amine(HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed with inversion of the stereocenter, as described for instance in Chem. Rev.2009, 109, 2551-2651. [0123] Alternatively, amines of formula IIIc may be obtained by reduction of azides of formula XXIII, wherein R3, R4a, R5a, and R5b are as described in formula (I), by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula XXIII may be obtained by treatment of alcohols of formula XXI, wherein R3, R4a, R5a, and R5b are as described in formula (I), with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU. Such 82949 FF 30 processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literature for instance in Adv. Synth. Catal.2018, 360, 2157–2165. [0124] Alcohols of formula XXI may be obtained by enantioselective reduction of ketones of formula XXIV, wherein R3, R4a, R5a, and R5b are as described in formula (I). Such reductions can be done using a catalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)- TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607. [0125] Alternatively, compounds of formula IIIc may also be prepared as outlined in Scheme 11.
Figure imgf000031_0001
Scheme 11 [0126] Amines of formula IIIc, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be prepared by deprotection of amines of formula XXV, wherein R3, R4a, R5a, and R5b are as described in formula (I), for instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane. [0127] Amines of formula XXV can be obtained by condensation of diamines of formula XXVII, wherein R5a, and R5b are as described in formula (I), on diketones of formula XXVI, wherein R3, and R4a are as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ. [0128] Diketones of formula XXVI may be formed by oxidation of hydroxyketones of formula XXVII wherein R3, and R4a are as described in formula (I). This oxidation can involve for instance SO3-pyridine in presence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO/Bu4NHSO4. Examples of such oxidations can be found in the literature, for instance in Synlett, 2014, 25, 596 or J. Am. Chem. Soc.1990, 112, 5290-5313. 82949 FF 31 [0129] Hydroxyketones of formula XXVII may be synthesized by cross-benzoin condensation between aldehydes of formula XXIX, wherein R4a is as described in formula (I), and aldehydes of formula XXVIII, wherein R3 is as described in formula (I). [0130] Aldehydes of formula XXVIII are commercially available in chiral form, like for instance Boc-L- alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36-9). Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt in the presence of a base such as potassium tert-butoxide or N,N-isopropylethylamine in a suitable solvent such as DCM or THF at a temperature between -20 °C and the boiling point of the solvent. Examples of catalysts for such transformations have been described in the literature for instance in J. Am. Chem. Soc.2014, 136, 7539-7542 or in Org. Lett.2016, 18, 4518- 4521.
Figure imgf000032_0001
Scheme 12 [0131] As outlined in Scheme 12, compounds of formula Id can be alternatively prepared by reaction of compounds of formula XXX (wherein A1, A2, A3, A4, A5, R1, R2a, R2b, R3, R5a, and R5b are as defined in formula (I) and X07 is a leaving group like, for example, chlorine, bromine, iodine) with compounds of formula XXXI (Stille reaction; R4a in XXXI is as defined in formula I) or compounds of formula XXXII (Suzuki-Miyaura reaction; R4a in XXXII is as defined in formula (I) and W is a boronic acid B(OH)2 group, or a corresponding boronate, such as a pinacol ester of said boronic acid) in the presence of a palladium catalyst as described in detail in Scheme 7. 82949 FF 32 [0132] Compounds of formula XXX can be prepared by coupling of amines of formula XXXIII and compounds of formula II, wherein A1, A2, A3, A4, A5, R2a, R2b and X1 are described in Scheme 1, under the conditions described in detail in Scheme 1. Under the same conditions, if R1 = H, compounds of formula XXX may be obtained directly from compounds of formula XXXIV. [0133] Compounds of formula XXXIII can be prepared by treatment of compounds of formula XXXIV, with compounds of formula XX (wherein R1a is for example H, methyl or cyclopropyl), e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid at room temperature analogous to WO 2002/088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206). [0134] Amines of formula XXXIV can be prepared by deracemization procedure method, which involves for example, a selective acylation of one enantiomer. Such an example is described more in details in Scheme 13. Chemoenzymatic resolution biocatalyst e.g. lipase or protease acylating agent e.g. ethyl methoxyacetate or vinyl acetate
Figure imgf000033_0001
solvent e.g. ACN or TBME
Figure imgf000033_0002
T = 20 to 100 °C XXXIVa XXXIV X07 = Cl, Br, I, OMs, OTs or OTf X07 = Cl, Br, I, OMs, OTs or OTf Scheme 13 [0135] Amines of formula XXXIV may be obtained by biocatalyzed deracemization of amines of formula XXXIVa, wherein R3, R5a, and R5b are as in formula (I) and X07 is a leaving group such as bromine, chlorine or iodine. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem. 2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem.1991, 56, 2656-2665 or J. Am. Chem. Soc.2015, 137, 3996−4009. [0136] Alternatively, resolution of amines of formula XXXIVa to give amines of formula XXXIV may be achieved using a chiral auxiliary, as described in Scheme 14: 82949 FF 33
Figure imgf000034_0001
Scheme 14 [0137] Amines of formula XXXIV can be prepared from intermediates of formula XXXVII, wherein R3, R5a, and R5b are as in compounds of the formula (I), X07 is a leaving group such as bromine, chlorine or iodine, and X12* is a chiral auxiliary, by treatment with acids such as HCl or bases such as NaOH. Chiral auxiliaries of formula XXXVI are for instance mandelic acid or (1R)-menthylchloroformate. Intermediates of formula XXXVII can be formed by coupling of a chiral auxiliary of formula XXXVI, wherein X0 is a leaving group, such as chlorine, with amines of the formula XXXIVa following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493. [0138] Alternatively, amines of formula XXXIV, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be formed as described in Scheme 15:
Figure imgf000034_0002
Figure imgf000034_0003
Z3 = NPhth or Boc2N X07 = Cl, Br, I, OMs, OTs or OTf Nucleophilic substitution deprotection
Figure imgf000034_0005
Figure imgf000034_0004
Figure imgf000034_0006
Scheme 15 82949 FF 34 [0139] Amines of formula XXXIV, or a salt thereof, may be obtained from intermediates of formula XXIIa, wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert- butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as for example in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471- 16019-9. [0140] Such intermediates of formula XXIIa, wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N- phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula XXIa, wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction, which involves treating alcohols of formula XXIa with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and of an amine such as phthalimide(HNPhth) or bis(tert- butoxycarbonyl)amine (HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed with inversion of the stereocenter, as described for instance in Chem. Rev.2009, 109, 2551-2651. [0141] Alternatively, amines of formula XXXIV may be obtained by reduction of azides of formula XXIIIa, wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula XXIIIa may be obtained by treatment of alcohols of formula XXIa with an azidation reagent such as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU. Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literature for instance in Adv. Synth. Catal.2018, 360, 2157–2165. [0142] Alcohols of formula XXIa may be obtained by enantioselective reduction of ketones of formula XXIVa, wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen or sulfonate, for instance bromide. Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as for example HCOOH/Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607. [0143] Compounds of formula (II), wherein R2a, R2b, A1, A2, A3, A4 and A5 are as described in formula (I), and wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, can be prepared by following descriptions found in, for example, WO 2021/083936, WO 2021/148639 and WO 2021/177160. 82949 FF 35
Figure imgf000036_0001
[0144] In particular, compounds of the formula (IIa), a subset of compounds of the formula (II), wherein A1 and A3 are N, A2 is CH and X1 is Cl, and in which R2a, R2b, A4 and A5 are as described in formula (I), can be prepared according to reaction Scheme 16.
Figure imgf000036_0002
Scheme 16 [0145] Compounds of formula (XXXIX-1), wherein R2a, R2b, A4 and A5 are as described in formula (I), are either known, or they can be prepared by methods known to a person skilled in the art. For example, reacting a compound of formula (XXXIX-3), wherein R2a, R2b, A4 and A5 are as described in formula (I), with an electrophilic halogenating reagent, such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), in an inert solvent, such as chloroform, carbon tetrachloride, 1,2- dichloroethane, acetic acid, ethers, acetonitrile, N,N-dimethylformamide or hexafluoroisopropanol (as described for example in J. Org. Chem.2018, 83, 930), at temperatures between 20-200°C, preferably room temperature to 100°C, provides compounds of formula (XXXIX-2), wherein R2a, R2b, A4 and A5 are as described in formula (I), and X08 is Cl, Br or I (preferably Br or I). Cyanation of compounds of formula (XXXIX-2) with, for example, copper(I) cyanide, in a solvent such as N,N-dimethylformamide DMF, at temperatures such as 100 °C, provides compounds of formula (XXXIX-1), wherein R2a, R2b, A4 and A5 are as described in formula (I) (procedure analogous to for instance WO 2005/100298, page 44). [0146] Treatment of compounds of formula (XXXIX-1) with formic acid and sulfuric acid, at temperatures between 80 and 100 °C, following procedures analogous to for example WO 2018/206539, page 80, provides compounds of formula (XXXVIII), or tautomers thereof, wherein R2a, R2b, A4 and A5 are as described in formula (I). [0147] Subsequent conversion of compounds of formula (XXXVIII), or tautomers thereof, to compounds of formula (IIa) is accomplished via methods known to the person skilled in the art, for example by treatment with thionyl chloride (alternatively phosphorus oxychloride), optionally in presence 82949 FF 36 of catalytic N,N-dimethylformamide, preferably at reflux, analogous to descriptions found in, for example, WO 2015/54572, page 263. [0148] Compounds of the formula (XXXVIII), wherein R2a, R2b, A4 and A5 are as described in formula (I), may exist in different tautomeric forms, such as (XXXVIII-1) and/or (XXXVIII-2), in which R2a, R2b, A4 and A5 are as described in formula (I):
Figure imgf000037_0001
[0149] This invention covers all such tautomers and mixtures thereof in all proportions.
Figure imgf000037_0002
Scheme 17 [0150] Compounds of the formula (Ie), a subset of compounds of formula (I), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5, R10 and R11 are as defined for compounds of the formula (I), can be prepared (Scheme 17) from compounds of the formula (XL-1), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R11 are as defined for compounds of the formula (I), by treatment with compounds of the formula X04-C(O)OR10 (XL-b), wherein R10 is as defined for compounds of the formula (I) and X04 is halogen, preferably chlorine, 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, N,N-diisopropylethylamine or pyridine, optionally in the presence of a catalyst (such as 4-dimethylaminopyridine DMAP), in an inert solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene, at temperatures between 0 and 50°C, under standard amide bond formation 82949 FF 37 conditions known to a person skilled in the art. Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. [0151] Alternatively, compounds of the formula (Ie) may be prepared by reacting compounds of the formula (XL-1), or a salt thereof, with compounds of the formula HOC(O)OR10 (XL-b-1), wherein R10 is as defined for compounds of the formula (I), in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide or propanephosphonic acid cyclic anhydride (T3P®), under similar conditions as described above. [0152] Compounds of the formula (XL-1), or a salt thereof, wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R11 are as defined for compounds of the formula (I), can be prepared from compounds of the formula (XL-2), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), by treatment with amine compounds of the formula H2NR11 (XL-a), or a salt thereof, wherein R11 is as defined for compounds of the formula (I), optionally in the presence of a copper catalyst, such as copper powder, copper(I) iodide or copper sulfate, or mixtures thereof, optionally in the presence of a ligand, for example a diamine ligand (e.g. trans-cyclohexyldiamine) or 1,10-phenanthroline, optionally in the presence of a base, such as sodium, potassium or cesium carbonate, or potassium phosphate, or an organic base, such as, for example, triethylamine, N,N-diisopropylethylamine or pyridine, in inert solvents such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2- trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or mixtures thereof, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally under microwave irradiation or pressurized conditions using an autoclave. In the particular amination reaction featuring amine compound of the formula H2NR11 (XL-a), wherein R11 is hydrogen (i.e. H2NR11 is ammonia), it may be advantageous to use ammonium hydroxide (solution of ammonia in water), a solution of ammonia in inert organic solvents, such as ethyl acetate, dioxane or methanol, or ammonia surrogates such as ammonium salts (for instance ammonium chloride). [0153] Alternatively, compounds of the formula (Ie), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5, R10 and R11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XL-2), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with compounds of the formula HN(R11)C(O)OR10 (XL-c), wherein R10 and R11 are as defined for compounds of the formula (I), optionally in the presence of a catalyst, for example palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, optionally in form of a chloroform adduct), or a palladium pre-catalyst such as for example tert-BuBrettPhos Pd G3 [(2-Di-tert-butylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2- (2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate or BrettPhos Pd G3 [(2-di- cyclohexylphosphino-3,6-dimethoxy-2′,4′,6′- triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′ - biphenyl)]palladium(II) methanesulfonate, or XantPhos Pd G3 [(4,5-bis(diphenylphosphino)-9,9- dimethylxanthene)-2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate, and optionally in the 82949 FF 38 presence of a ligand, for example BINAP, SPhos, t-BuBrettPhos or Xantphos, in the presence of a base, such as sodium, potassium or cesium carbonate, sodium hydroxide or potassium phosphate, in an inert solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, toluene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidine or dimethyl sulfoxide, at temperatures between 60-180°C, optionally under microwave irradiation. [0154] Compounds of the formula (XL-2), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), except that R1 is different from hydrogen, and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), can be prepared by reacting compounds of the formula (XL-2a), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), except that R1 is hydrogen, and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with a compound of the formula VI, wherein R1 has the same meaning as given above for compounds of the formula (I), except that R1 is different from hydrogen, and wherein X3 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, under conditions already described above in Scheme 5. [0155] Compounds of the formula (XL-2a), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), except that R1 is hydrogen, and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), can be prepared by reacting compounds of the formula (II), wherein R2a, R2b, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), and wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, with compounds of the formula (XL-3), or a free base thereof, wherein R3 is as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), and X- is an anion, under analogous conditions already described above in Scheme 1. The anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid. A great number of such acids are known to a person skilled in the art. [0156] Compounds of the formula (XL-3), or a free base thereof, wherein R3 is as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), and X- is an anion, can be prepared from compounds of the formula (XL-4), wherein R3 is as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), by treatment with an acid, such as the acids listed above. The reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, 2-methyltetrahydro-furan, 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. [0157] Certain compounds of the formula (XL-4), wherein R3 is as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), are known for example from WO 2021/224323 or WO 2021/165195, or they can be made by known methods. [0158] The following compounds are either known, commercially available, or may be prepared according to methods known to a person skilled in the art: 82949 FF 39 ^ compounds XL-a of the formula: H2NR11 , or a salt thereof, wherein R11 is as defined for compounds of the formula (I) ^ compounds XL-b of the formula: X04-C(O)OR10 , wherein R10 is as defined for compounds of the formula (I) and X04 is halogen, preferably chlorine ^ compounds XL-b-1 of the formula: HOC(O)OR10 , wherein R10 is as defined for compounds of the formula (I) ^ compounds XL-c of the formula: HN(R11)C(O)OR10, wherein R10 and R11 are as defined for compounds of the formula (I)
Figure imgf000040_0001
Scheme 18 [0159] Alternatively, as outlined in Scheme 18, compounds of the formula (Ie), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5, R10 and R11 are as defined for compounds of the formula (I), except that R11 is different from hydrogen, may be prepared (Scheme 18) by reacting compounds of the formula (Ie-1), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R10 are as defined for compounds of the formula (I), with compounds of the formula (XL-d), wherein R11 has the same meaning as given above for compounds of the formula (I), except that R11 is different from hydrogen, and wherein X06 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, in the presence of a base, such as sodium hydride or an alkaline earth metal hydride, a carbonate (e.g. sodium, potassium or cesium carbonate) or a hydroxide ((e.g. sodium or potassium hydroxide), in an inert solvent such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, under conditions well known to those skilled in the art. [0160] Compounds of the formula (Ie-1), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R10 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XL- 1a), or a salt thereof, wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5are as defined for compounds of the formula (I), with compounds of the formula X04-C(O)OR10 (XL-b), wherein R10 is as defined for compounds of the formula (I) and X04 is halogen, preferably chlorine, or alternatively with compounds of the formula HOC(O)OR10 (XL-b-1), wherein R10 is as defined for compounds of the formula (I), under conditions already described above in Scheme 17 (transformation XL-1 into Ie). [0161] Compounds of the formula (XL-1a), or a salt thereof, wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5are as defined for compounds of the formula (I), are a particular subset of compounds of the formula (XL-1) described in Scheme 17. [0162] Compounds of the formula (XL-d), wherein R11 has the same meaning as given above for compounds of the formula (I), except that R11 is different from hydrogen, and wherein X06 is a leaving 82949 FF 40 group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, are either known, commercially available or may be prepared by methods known to a person skilled in the art.
Figure imgf000041_0001
Scheme 19 [0163] Alternatively, as outlined in Scheme 19, compounds of the formula (Ie), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5, R10 and R11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XL-6), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R11 are as defined for compounds of the formula (I), with alcohol compounds of the formula (XL-e), wherein R10 is as defined for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +200 °C, preferably between ambient temperature and 120 °C, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, sodium hydride, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. It may be advantageous to make use of the alcohol HOR10 (XL-e) as both reactant and solvent. [0164] Compounds of the formula (XL-6), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XL- 1), or a salt thereof, wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R11 are as defined for compounds of the formula (I), with the compound of the formula (XL-f). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +200 °C, preferably between ambient temperature and 120 °C, optionally in the presence of a 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 82949 FF 41 base, such as, for example, triethylamine, diisopropylethylamine or pyridine. Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. [0165] Alternatively, compounds of the formula (Ie-1), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5 and R10 are as defined for compounds of the formula (I), may be prepared by reacting compounds of the formula (XL-5), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5are as defined for compounds of the formula (I), with alcohol compounds of the formula (XL-e), wherein R10 is as defined for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N- dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +200 °C, preferably between ambient temperature and 120 °C, and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, sodium hydride, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine. It may be advantageous to make use of the alcohol HOR10 (XL-e) as both reactant and solvent. [0166] Compounds of the formula (XL-5), wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5are as defined for compounds of the formula (I), may be prepared by reacting compounds of the formula (XL-1a), or a salt thereof, wherein R2a, R2b, R1, R3, A1, A2, A3, A4 and A5are as defined for compounds of the formula (I) [i.e. compounds of the formula (XL-1), in which R11 is hydrogen], with phosgene, or phosgene surrogates such as di- or triphosgene, in the presence of a base, such as triethylamine, diisopropylethylamine or pyridine, in an inert solvent such as acetonitrile, 2-methyltetrahydrofuran, 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 (XL-5) may be worked up and isolated, or alternatively may form in situ and can be used as such in a next step. A person skilled in the art will hence recognize that compounds of the formula (Ie-1) may be prepared in a one-pot two steps process by (i) reacting compounds of the formula (XL-1), in which R11 is hydrogen, with phosgene (or a surrogate thereof) with in situ formation of compounds of the formula (XL-5) which are not isolated; followed by (ii) addition of a compound of formula (XL-e) to form the compounds of the formula (Ie-1). [0167] Alcohol compounds of the formula (XL-e), wherein R10 is as defined for compounds of the formula (I), and the compound of the formula (XL-f), phenyl chloroformate, are known, commercially available or may be prepared by methods known to a person skilled in the art.
82949 FF 42
Figure imgf000043_0001
Scheme 20 [0168] Alternatively, as outlined in Scheme 20, compounds of the formula (Ie), wherein R2a, R2b, R1, R3, A1, A2, A3, A4, A5, R10 and R11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XLI-1), or a free base thereof, wherein R1, R3, R10 and R11 are as defined for compounds of the formula (I), and in which X- is an anion which has the same meaning as given above in Scheme 17, with compounds of the formula (II), wherein R2a, R2b, A1, A2, A3, A4 and A5 are as defined for compounds of the formula (I), and wherein X1 is a leaving group, such as a halogen or sulfonate, for instance chloride, under analogous conditions already described above in Scheme 1 (transformation II + III into I). [0169] Compounds of the formula (XLI-1), or a free base thereof, wherein R1, R3, R10 and R11 are as defined for compounds of the formula (I), and in which X- is an anion which has the same meaning as given above in Scheme 17, can be prepared by treating compounds of the formula (XLI-2), wherein R1, R3, R10 and R11 are as defined for compounds of the formula (I), with an acid, such as the acids listed above in Scheme 17, under analogous conditions already described above in said Scheme 17 (transformation XL-4 into XL-3). [0170] Compounds of the formula (XLI-2), wherein R1, R3, R10 and R11 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XLI-3), or a salt thereof, wherein R1, R3 and R11 are as defined for compounds of the formula (I), with compounds of the formula X04-C(O)OR10 (XL-b), wherein R10 is as defined for compounds of the formula (I) and X04 is halogen, preferably chlorine, under analogous conditions already described above in Scheme 17 (transformation XL-1 into Ie). 82949 FF 43 [0171] Compounds of the formula (XLI-3), or a salt thereof, wherein R1, R3 and R11 are as defined for compounds of the formula (I), can be prepared from compounds of the formula (XLI-4), wherein R1 and R3 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), by treatment with amine compounds of the formula H2NR11 (XL-a), or a salt thereof, wherein R11 is as defined for compounds of the formula (I), under analogous conditions already described above in Scheme 17 (transformation XL-2 into XL-1). [0172] Alternatively, compounds of the formula (XLI-2), wherein R1, R3, R10 and R11 are as defined for compounds of the formula (I), may be prepared by reacting compounds of the formula (XLI-4), wherein R1 and R3 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), with compounds of the formula HN(R11)C(O)OR10 (XL-c), wherein R10 and R11 are as defined for compounds of the formula (I), under analogous conditions already described above in Scheme 17 (transformation XL-2 into Ie). [0173] Compounds of the formula (XLI-4), wherein R1 and R3 are as defined for compounds of the formula (I), and in which Xa is a halogen, preferably Br or Cl (even more preferably Cl), can be prepared by reacting compounds of the formula (XLI-7), wherein R1 and R3 are as defined for compounds of the formula (I), with hydrazine compounds of the formula (XLI-6) or a tautomer thereof, or a salt thereof, wherein Xa is a halogen, preferably Br or Cl (even more preferably Cl), under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib). [0174] Compounds of the formula (XLI-7), wherein R1 and R3 are as defined for compounds of the formula (I), are known, for instance from WO 2021/083936 or WO 2021/165195, or they can be made in analogy to descriptions found therein. Compounds of the formula (XLI-6) or a tautomer thereof, or a salt thereof, wherein Xa is a halogen, preferably Br or Cl (even more preferably Cl), are known or even commercially available, or they can be made by known methods. [0175] Compounds of the formula (XLI-6) or a salt thereof, wherein Xa is a halogen, preferably Br or Cl (even more preferably Cl), may exist in different tautomeric forms, such as (XLI-6-1) and/or (XLI-6- 2), or salts thereof, in which Xa is a halogen, preferably Br or Cl (even more preferably Cl):
Figure imgf000044_0001
[0176] This invention covers all such tautomers and mixtures thereof in all proportions.
Figure imgf000044_0002
Scheme 21 82949 FF 44 [0177] Alternatively, as outlined in Scheme 21, compounds of the formula (XLI-2), wherein R1, R3, R10 and R11 are as defined for compounds of the formula (I), except that R11 is different from hydrogen, may be prepared by reacting compounds of the formula (XLI-2a), wherein R1, R3 and R10 are as defined for compounds of the formula (I), with compounds of the formula (XL-d), wherein R11 has the same meaning as given above for compounds of the formula (I), except that R11 is different from hydrogen, and wherein X06 is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, under analogous conditions already described above in Scheme 18 (transformation Ie-1 into Ie). [0178] Compounds of the formula (XLI-2a), wherein R1, R3 and R10 are as defined for compounds of the formula (I), can be prepared by reacting compounds of the formula (XLI-3a), or a salt thereof, wherein R1 and R3 are as defined for compounds of the formula (I), with compounds of the formula X04-C(O)OR10 (XL-b), wherein R10 is as defined for compounds of the formula (I) and X04 is halogen, preferably chlorine, or alternatively with compounds of the formula HOC(O)OR10 (XL-b-1), wherein R10 is as defined for compounds of the formula (I), under conditions already described above in Scheme 17 (transformation XL-1 into Ie). [0179] Compounds of the formula (XLI-3a), or a salt thereof, wherein R1 and R3 are as defined for compounds of the formula (I), are a particular subset of compounds of the formula (XLI-3) described in Scheme 20. [0180] Depending on the procedure or the reaction conditions, the reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). [0181] The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. [0182] The reactions are advantageously carried out in a temperature range from approximately - 80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C. 82949 FF 45 [0183] Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step. [0184] Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent. [0185] Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent. [0186] Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture. [0187] Depending on the procedure or the reaction conditions, the compounds of formula (I), which have salt-forming properties can be obtained in free form or in the form of salts. [0188] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case. [0189] Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography. [0190] Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for 82949 FF 46 example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents. [0191] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry. [0192] N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000/15615. [0193] It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity. [0194] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form. [0195] The compounds of formula (I) according to the following Tables A-1 to A-90 and Tables B-1 to B-90 can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I-A) and (I-B):
Figure imgf000047_0001
Tables A-1 to A-90 (formula I-A) [0196] Table A-1 provides 21 compounds A-1.001 to A-1.021 of formula I-A wherein R1 is H, R10 is Me, R11 is H and T is as defined in table X. For example, compound A-90.001 is 82949 FF 47
Figure imgf000048_0001
[0197] Table A-2 provides 21 compounds A-2.001 to A-2.021 of formula I-A wherein R1 is H, R10 is Me, R11 is Me and T is as defined in table X. [0198] Table A-3 provides 21 compounds A-3.001 to A-3.021 of formula I-A wherein R1 is H, R10 is Me, R11 is Et and T is as defined in table X. [0199] Table A-4 provides 21 compounds A-4.001 to A-4.021 of formula I-A wherein R1 is H, R10 is Me, R11 is iPr and T is as defined in table X. [0200] Table A-5 provides 21 compounds A-5.001 to A-5.021 of formula I-A wherein R1 is H, R10 is Me, R11 is Cyp and T is as defined in table X. [0201] Table A-6 provides 21 compounds A-6.001 to A-6.021 of formula I-A wherein R1 is H, R10 is Me, R11 is OMe and T is as defined in table X. [0202] Table A-7 provides 21 compounds A-7.001 to A-7.021 of formula I-A wherein R1 is H, R10 is Et, R11 is H and T is as defined in table X. [0203] Table A-8 provides 21 compounds A-8.001 to A-8.021 of formula I-A wherein R1 is H, R10 is Et, R11 is Me and T is as defined in table X. [0204] Table A-9 provides 21 compounds A-9.001 to A-9.021 of formula I-A wherein R1 is H, R10 is Et, R11 is Et and T is as defined in table X. [0205] Table A-10 provides 21 compounds A-10.001 to A-10.021 of formula I-A wherein R1 is H, R10 is Et, R11 is iPr and T is as defined in table X. [0206] Table A-11 provides 21 compounds A-11.001 to A-11.021 of formula I-A wherein R1 is H, R10 is Et, R11 is Cyp and T is as defined in table X. [0207] Table A-12 provides 21 compounds A-12.001 to A-12.021 of formula I-A wherein R1 is H, R10 is Et, R11 is OMe and T is as defined in table X. [0208] Table A-13 provides 21 compounds A-13.001 to A-13.021 of formula I-A wherein R1 is H, R10 is iPr, R11 is H and T is as defined in table X. [0209] Table A-14 provides 21 compounds A-14.001 to A-14.021 of formula I-A wherein R1 is H, R10 is iPr, R11 is Me and T is as defined in table X. [0210] Table A-15 provides 21 compounds A-15.001 to A-15.021 of formula I-A wherein R1 is H, R10 is iPr, R11 is Et and T is as defined in table X. [0211] Table A-16 provides 21 compounds A-16.001 to A-16.021 of formula I-A wherein R1 is H, R10 is iPr, R11 is iPr and T is as defined in table X. 82949 FF 48 [0212] Table A-17 provides 21 compounds A-17.001 to A-17.021 of formula I-A wherein R1 is H, R10 is iPr, R11 is Cyp and T is as defined in table X. [0213] Table A-18 provides 21 compounds A-18.001 to A-18.021 of formula I-A wherein R1 is H, R10 is iPr, R11 is OMe and T is as defined in table X. [0214] Table A-19 provides 21 compounds A-19.001 to A-19.021 of formula I-A wherein R1 is H, R10 is Cyp, R11 is H and T is as defined in table X. [0215] Table A-20 provides 21 compounds A-20.001 to A-20.021 of formula I-A wherein R1 is H, R10 is Cyp, R11 is Me and T is as defined in table X. [0216] Table A-21 provides 21 compounds A-21.001 to A-21.021 of formula I-A wherein R1 is H, R10 is Cyp, R11 is Et and T is as defined in table X. [0217] Table A-22 provides 21 compounds A-22.001 to A-22.021 of formula I-A wherein R1 is H, R10 is Cyp, R11 is iPr and T is as defined in table X. [0218] Table A-23 provides 21 compounds A-23.001 to A-23.021 of formula I-A wherein R1 is H, R10 is Cyp, R11 is Cyp and T is as defined in table X. [0219] Table A-24 provides 21 compounds A-24.001 to A-24.021 of formula I-A wherein R1 is H, R10 is Cyp, R11 is OMe and T is as defined in table X. [0220] Table A-25 provides 21 compounds A-25.001 to A-25.021 of formula I-A wherein R1 is H, R10 is tBu, R11 is H and T is as defined in table X. [0221] Table A-26 provides 21 compounds A-26.001 to A-26.021 of formula I-A wherein R1 is H, R10 is tBu, R11 is Me and T is as defined in table X. [0222] Table A-27 provides 21 compounds A-27.001 to A-27.021 of formula I-A wherein R1 is H, R10 is tBu, R11 is Et and T is as defined in table X. [0223] Table A-28 provides 21 compounds A-28.001 to A-28.021 of formula I-A wherein R1 is H, R10 is tBu, R11 is iPr and T is as defined in table X. [0224] Table A-29 provides 21 compounds A-29.001 to A-29.021 of formula I-A wherein R1 is H, R10 is tBu, R11 is Cyp and T is as defined in table X. [0225] Table A-30 provides 21 compounds A-30.001 to A-30.021 of formula I-A wherein R1 is H, R10 is tBu, R11 is OMe and T is as defined in table X. [0226] Table A-31 provides 21 compounds A-31.001 to A-31.021 of formula I-A wherein R1 is CH3, R10 is Me, R11 is H and T is as defined in table X. [0227] Table A-32 provides 21 compounds A-32.001 to A-32.021 of formula I-A wherein R1 is CH3, R10 is Me, R11 is Me and T is as defined in table X. [0228] Table A-33 provides 21 compounds A-33.001 to A-33.021 of formula I-A wherein R1 is CH3, R10 is Me, R11 is Et and T is as defined in table X. [0229] Table A-34 provides 21 compounds A-34.001 to A-34.021 of formula I-A wherein R1 is CH3, R10 is Me, R11 is iPr and T is as defined in table X. [0230] Table A-35 provides 21 compounds A-35.001 to A-35.021 of formula I-A wherein R1 is CH3, R10 is Me, R11 is Cyp and T is as defined in table X. [0231] Table A-36 provides 21 compounds A-36.001 to A-36.021 of formula I-A wherein R1 is CH3, R10 is Me, R11 is OMe and T is as defined in table X. 82949 FF 49 [0232] Table A-37 provides 21 compounds A-37.001 to A-37.021 of formula I-A wherein R1 is CH3, R10 is Et, R11 is H and T is as defined in table X. [0233] Table A-38 provides 21 compounds A-38.001 to A-38.021 of formula I-A wherein R1 is CH3, R10 is Et, R11 is Me and T is as defined in table X. [0234] Table A-39 provides 21 compounds A-39.001 to A-39.021 of formula I-A wherein R1 is CH3, R10 is Et, R11 is Et and T is as defined in table X. [0235] Table A-40 provides 21 compounds A-40.001 to A-40.021 of formula I-A wherein R1 is CH3, R10 is Et, R11 is iPr and T is as defined in table X. [0236] Table A-41 provides 21 compounds A-41.001 to A-41.021 of formula I-A wherein R1 is CH3, R10 is Et, R11 is Cyp and T is as defined in table X. [0237] Table A-42 provides 21 compounds A-42.001 to A-42.021 of formula I-A wherein R1 is CH3, R10 is Et, R11 is OMe and T is as defined in table X. [0238] Table A-43 provides 21 compounds A-43.001 to A-43.021 of formula I-A wherein R1 is CH3, R10 is iPr, R11 is H and T is as defined in table X. [0239] Table A-44 provides 21 compounds A-44.001 to A-44.021 of formula I-A wherein R1 is CH3, R10 is iPr, R11 is Me and T is as defined in table X. [0240] Table A-45 provides 21 compounds A-45.001 to A-45.021 of formula I-A wherein R1 is CH3, R10 is iPr, R11 is Et and T is as defined in table X. [0241] Table A-46 provides 21 compounds A-46.001 to A-46.021 of formula I-A wherein R1 is CH3, R10 is iPr, R11 is iPr and T is as defined in table X. [0242] Table A-47 provides 21 compounds A-47.001 to A-47.021 of formula I-A wherein R1 is CH3, R10 is iPr, R11 is Cyp and T is as defined in table X. [0243] Table A-48 provides 21 compounds A-48.001 to A-48.021 of formula I-A wherein R1 is CH3, R10 is iPr, R11 is OMe and T is as defined in table X. [0244] Table A-49 provides 21 compounds A-49.001 to A-49.021 of formula I-A wherein R1 is CH3, R10 is Cyp, R11 is H and T is as defined in table X. [0245] Table A-50 provides 21 compounds A-50.001 to A-50.021 of formula I-A wherein R1 is CH3, R10 is Cyp, R11 is Me and T is as defined in table X. [0246] Table A-51 provides 21 compounds A-51.001 to A-51.021 of formula I-A wherein R1 is CH3, R10 is Cyp, R11 is Et and T is as defined in table X. [0247] Table A-52 provides 21 compounds A-52.001 to A-52.021 of formula I-A wherein R1 is CH3, R10 is Cyp, R11 is iPr and T is as defined in table X. [0248] Table A-53 provides 21 compounds A-53.001 to A-53.021 of formula I-A wherein R1 is CH3, R10 is Cyp, R11 is Cyp and T is as defined in table X. [0249] Table A-54 provides 21 compounds A-54.001 to A-54.021 of formula I-A wherein R1 is CH3, R10 is Cyp, R11 is OMe and T is as defined in table X. [0250] Table A-55 provides 21 compounds A-55.001 to A-55.021 of formula I-A wherein R1 is CH3, R10 is tBu, R11 is H and T is as defined in table X. [0251] Table A-56 provides 21 compounds A-56.001 to A-56.021 of formula I-A wherein R1 is CH3, R10 is tBu, R11 is Me and T is as defined in table X. 82949 FF 50 [0252] Table A-57 provides 21 compounds A-57.001 to A-57.021 of formula I-A wherein R1 is CH3, R10 is tBu, R11 is Et and T is as defined in table X. [0253] Table A-58 provides 21 compounds A-58.001 to A-58.021 of formula I-A wherein R1 is CH3, R10 is tBu, R11 is iPr and T is as defined in table X. [0254] Table A-59 provides 21 compounds A-59.001 to A-59.021 of formula I-A wherein R1 is CH3, R10 is tBu, R11 is Cyp and T is as defined in table X. [0255] Table A-60 provides 21 compounds A-60.001 to A-60.021 of formula I-A wherein R1 is CH3, R10 is tBu, R11 is OMe and T is as defined in table X. [0256] Table A-61 provides 21 compounds A-61.001 to A-61.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is H and T is as defined in table X. [0257] Table A-62 provides 21 compounds A-62.001 to A-62.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is Me and T is as defined in table X. [0258] Table A-63 provides 21 compounds A-63.001 to A-63.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is Et and T is as defined in table X. [0259] Table A-64 provides 21 compounds A-64.001 to A-64.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is iPr and T is as defined in table X. [0260] Table A-65 provides 21 compounds A-65.001 to A-65.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is Cyp and T is as defined in table X. [0261] Table A-66 provides 21 compounds A-66.001 to A-66.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is OMe and T is as defined in table X. [0262] Table A-67 provides 21 compounds A-67.001 to A-67.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is H and T is as defined in table X. [0263] Table A-68 provides 21 compounds A-68.001 to A-68.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is Me and T is as defined in table X. [0264] Table A-69 provides 21 compounds A-69.001 to A-69.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is Et and T is as defined in table X. [0265] Table A-70 provides 21 compounds A-70.001 to A-70.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is iPr and T is as defined in table X. [0266] Table A-71 provides 21 compounds A-71.001 to A-71.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is Cyp and T is as defined in table X. [0267] Table A-72 provides 21 compounds A-72.001 to A-72.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is OMe and T is as defined in table X. [0268] Table A-73 provides 21 compounds A-73.001 to A-73.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is H and T is as defined in table X. [0269] Table A-74 provides 21 compounds A-74.001 to A-74.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is Me and T is as defined in table X. [0270] Table A-75 provides 21 compounds A-75.001 to A-75.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is Et and T is as defined in table X. [0271] Table A-76 provides 21 compounds A-76.001 to A-76.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is iPr and T is as defined in table X. 82949 FF 51 [0272] Table A-77 provides 21 compounds A-77.001 to A-77.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is Cyp and T is as defined in table X. [0273] Table A-78 provides 21 compounds A-78.001 to A-78.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is OMe and T is as defined in table X. [0274] Table A-79 provides 21 compounds A-79.001 to A-79.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is H and T is as defined in table X. [0275] Table A-80 provides 21 compounds A-80.001 to A-80.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is Me and T is as defined in table X. [0276] Table A-81 provides 21 compounds A-81.001 to A-81.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is Et and T is as defined in table X. [0277] Table A-82 provides 21 compounds A-82.001 to A-82.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is iPr and T is as defined in table X. [0278] Table A-83 provides 21 compounds A-83.001 to A-83.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is Cyp and T is as defined in table X. [0279] Table A-84 provides 21 compounds A-84.001 to A-84.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is OMe and T is as defined in table X. [0280] Table A-85 provides 21 compounds A-85.001 to A-85.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is H and T is as defined in table X. [0281] Table A-86 provides 21 compounds A-86.001 to A-86.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is Me and T is as defined in table X. [0282] Table A-87 provides 21 compounds A-87.001 to A-87.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is Et and T is as defined in table X. [0283] Table A-88 provides 21 compounds A-88.001 to A-88.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is iPr and T is as defined in table X. [0284] Table A-89 provides 21 compounds A-89.001 to A-89.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is Cyp and T is as defined in table X. [0285] Table A-90 provides 21 compounds A-90.001 to A-90.021 of formula I-A wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is OMe and T is as defined in table X. Tables B-1 to B-90 (formula I-B) [0286] Table B-1 provides 21 compounds B-1.001 to B-1.021 of formula I-B wherein R1 is H, R10 is Me, R11 is H and T is as defined in table X. [0287] Table B-2 provides 21 compounds B-2.001 to B-2.021 of formula I-B wherein R1 is H, R10 is Me, R11 is Me and T is as defined in table X. [0288] Table B-3 provides 21 compounds B-3.001 to B-3.021 of formula I-B wherein R1 is H, R10 is Me, R11 is Et and T is as defined in table X. [0289] Table B-4 provides 21 compounds B-4.001 to B-4.021 of formula I-B wherein R1 is H, R10 is Me, R11 is iPr and T is as defined in table X. [0290] Table B-5 provides 21 compounds B-5.001 to B-5.021 of formula I-B wherein R1 is H, R10 is Me, R11 is Cyp and T is as defined in table X. 82949 FF 52 [0291] Table B-6 provides 21 compounds B-6.001 to B-6.021 of formula I-B wherein R1 is H, R10 is Me, R11 is OMe and T is as defined in table X. [0292] Table B-7 provides 21 compounds B-7.001 to B-7.021 of formula I-B wherein R1 is H, R10 is Et, R11 is H and T is as defined in table X. [0293] Table B-8 provides 21 compounds B-8.001 to B-8.021 of formula I-B wherein R1 is H, R10 is Et, R11 is Me and T is as defined in table X. [0294] Table B-9 provides 21 compounds B-9.001 to B-9.021 of formula I-B wherein R1 is H, R10 is Et, R11 is Et and T is as defined in table X. [0295] Table B-10 provides 21 compounds B-10.001 to B-10.021 of formula I-B wherein R1 is H, R10 is Et, R11 is iPr and T is as defined in table X. [0296] Table B-11 provides 21 compounds B-11.001 to B-11.021 of formula I-B wherein R1 is H, R10 is Et, R11 is Cyp and T is as defined in table X. [0297] Table B-12 provides 21 compounds B-12.001 to B-12.021 of formula I-B wherein R1 is H, R10 is Et, R11 is OMe and T is as defined in table X. [0298] Table B-13 provides 21 compounds B-13.001 to B-13.021 of formula I-B wherein R1 is H, R10 is iPr, R11 is H and T is as defined in table X. [0299] Table B-14 provides 21 compounds B-14.001 to B-14.021 of formula I-B wherein R1 is H, R10 is iPr, R11 is Me and T is as defined in table X. [0300] Table B-15 provides 21 compounds B-15.001 to B-15.021 of formula I-B wherein R1 is H, R10 is iPr, R11 is Et and T is as defined in table X. [0301] Table B-16 provides 21 compounds B-16.001 to B-16.021 of formula I-B wherein R1 is H, R10 is iPr, R11 is iPr and T is as defined in table X. [0302] Table B-17 provides 21 compounds B-17.001 to B-17.021 of formula I-B wherein R1 is H, R10 is iPr, R11 is Cyp and T is as defined in table X. [0303] Table B-18 provides 21 compounds B-18.001 to B-18.021 of formula I-B wherein R1 is H, R10 is iPr, R11 is OMe and T is as defined in table X. [0304] Table B-19 provides 21 compounds B-19.001 to B-19.021 of formula I-B wherein R1 is H, R10 is Cyp, R11 is H and T is as defined in table X. [0305] Table B-20 provides 21 compounds B-20.001 to B-20.021 of formula I-B wherein R1 is H, R10 is Cyp, R11 is Me and T is as defined in table X. [0306] Table B-21 provides 21 compounds B-21.001 to B-21.021 of formula I-B wherein R1 is H, R10 is Cyp, R11 is Et and T is as defined in table X. [0307] Table B-22 provides 21 compounds B-22.001 to B-22.021 of formula I-B wherein R1 is H, R10 is Cyp, R11 is iPr and T is as defined in table X. [0308] Table B-23 provides 21 compounds B-23.001 to B-23.021 of formula I-B wherein R1 is H, R10 is Cyp, R11 is Cyp and T is as defined in table X. [0309] Table B-24 provides 21 compounds B-24.001 to B-24.021 of formula I-B wherein R1 is H, R10 is Cyp, R11 is OMe and T is as defined in table X. [0310] Table B-25 provides 21 compounds B-25.001 to B-25.021 of formula I-B wherein R1 is H, R10 is tBu, R11 is H and T is as defined in table X. 82949 FF 53 [0311] Table B-26 provides 21 compounds B-26.001 to B-26.021 of formula I-B wherein R1 is H, R10 is tBu, R11 is Me and T is as defined in table X. [0312] Table B-27 provides 21 compounds B-27.001 to B-27.021 of formula I-B wherein R1 is H, R10 is tBu, R11 is Et and T is as defined in table X. [0313] Table B-28 provides 21 compounds B-28.001 to B-28.021 of formula I-B wherein R1 is H, R10 is tBu, R11 is iPr and T is as defined in table X. [0314] Table B-29 provides 21 compounds B-29.001 to B-29.021 of formula I-B wherein R1 is H, R10 is tBu, R11 is Cyp and T is as defined in table X. [0315] Table B-30 provides 21 compounds B-30.001 to B-30.021 of formula I-B wherein R1 is H, R10 is tBu, R11 is OMe and T is as defined in table X. [0316] Table B-31 provides 21 compounds B-31.001 to B-31.021 of formula I-B wherein R1 is CH3, R10 is Me, R11 is H and T is as defined in table X. [0317] Table B-32 provides 21 compounds B-32.001 to B-32.021 of formula I-B wherein R1 is CH3, R10 is Me, R11 is Me and T is as defined in table X. [0318] Table B-33 provides 21 compounds B-33.001 to B-33.021 of formula I-B wherein R1 is CH3, R10 is Me, R11 is Et and T is as defined in table X. [0319] Table B-34 provides 21 compounds B-34.001 to B-34.021 of formula I-B wherein R1 is CH3, R10 is Me, R11 is iPr and T is as defined in table X. [0320] Table B-35 provides 21 compounds B-35.001 to B-35.021 of formula I-B wherein R1 is CH3, R10 is Me, R11 is Cyp and T is as defined in table X. [0321] Table B-36 provides 21 compounds B-36.001 to B-36.021 of formula I-B wherein R1 is CH3, R10 is Me, R11 is OMe and T is as defined in table X. [0322] Table B-37 provides 21 compounds B-37.001 to B-37.021 of formula I-B wherein R1 is CH3, R10 is Et, R11 is H and T is as defined in table X. [0323] Table B-38 provides 21 compounds B-38.001 to B-38.021 of formula I-B wherein R1 is CH3, R10 is Et, R11 is Me and T is as defined in table X. [0324] Table B-39 provides 21 compounds B-39.001 to B-39.021 of formula I-B wherein R1 is CH3, R10 is Et, R11 is Et and T is as defined in table X. [0325] Table B-40 provides 21 compounds B-40.001 to B-40.021 of formula I-B wherein R1 is CH3, R10 is Et, R11 is iPr and T is as defined in table X. [0326] Table B-41 provides 21 compounds B-41.001 to B-41.021 of formula I-B wherein R1 is CH3, R10 is Et, R11 is Cyp and T is as defined in table X. [0327] Table B-42 provides 21 compounds B-42.001 to B-42.021 of formula I-B wherein R1 is CH3, R10 is Et, R11 is OMe and T is as defined in table X. [0328] Table B-43 provides 21 compounds B-43.001 to B-43.021 of formula I-B wherein R1 is CH3, R10 is iPr, R11 is H and T is as defined in table X. [0329] Table B-44 provides 21 compounds B-44.001 to B-44.021 of formula I-B wherein R1 is CH3, R10 is iPr, R11 is Me and T is as defined in table X. [0330] Table B-45 provides 21 compounds B-45.001 to B-45.021 of formula I-B wherein R1 is CH3, R10 is iPr, R11 is Et and T is as defined in table X. 82949 FF 54 [0331] Table B-46 provides 21 compounds B-46.001 to B-46.021 of formula I-B wherein R1 is CH3, R10 is iPr, R11 is iPr and T is as defined in table X. [0332] Table B-47 provides 21 compounds B-47.001 to B-47.021 of formula I-B wherein R1 is CH3, R10 is iPr, R11 is Cyp and T is as defined in table X. [0333] Table B-48 provides 21 compounds B-48.001 to B-48.021 of formula I-B wherein R1 is CH3, R10 is iPr, R11 is OMe and T is as defined in table X. [0334] Table B-49 provides 21 compounds B-49.001 to B-49.021 of formula I-B wherein R1 is CH3, R10 is Cyp, R11 is H and T is as defined in table X. [0335] Table B-50 provides 21 compounds B-50.001 to B-50.021 of formula I-B wherein R1 is CH3, R10 is Cyp, R11 is Me and T is as defined in table X. [0336] Table B-51 provides 21 compounds B-51.001 to B-51.021 of formula I-B wherein R1 is CH3, R10 is Cyp, R11 is Et and T is as defined in table X. [0337] Table B-52 provides 21 compounds B-52.001 to B-52.021 of formula I-B wherein R1 is CH3, R10 is Cyp, R11 is iPr and T is as defined in table X. [0338] Table B-53 provides 21 compounds B-53.001 to B-53.021 of formula I-B wherein R1 is CH3, R10 is Cyp, R11 is Cyp and T is as defined in table X. [0339] Table B-54 provides 21 compounds B-54.001 to B-54.021 of formula I-B wherein R1 is CH3, R10 is Cyp, R11 is OMe and T is as defined in table X. [0340] Table B-55 provides 21 compounds B-55.001 to B-55.021 of formula I-B wherein R1 is CH3, R10 is tBu, R11 is H and T is as defined in table X. [0341] Table B-56 provides 21 compounds B-56.001 to B-56.021 of formula I-B wherein R1 is CH3, R10 is tBu, R11 is Me and T is as defined in table X. [0342] Table B-57 provides 21 compounds B-57.001 to B-57.021 of formula I-B wherein R1 is CH3, R10 is tBu, R11 is Et and T is as defined in table X. [0343] Table B-58 provides 21 compounds B-58.001 to B-58.021 of formula I-B wherein R1 is CH3, R10 is tBu, R11 is iPr and T is as defined in table X. [0344] Table B-59 provides 21 compounds B-59.001 to B-59.021 of formula I-B wherein R1 is CH3, R10 is tBu, R11 is Cyp and T is as defined in table X. [0345] Table B-60 provides 21 compounds B-60.001 to B-60.021 of formula I-B wherein R1 is CH3, R10 is tBu, R11 is OMe and T is as defined in table X. [0346] Table B-61 provides 21 compounds B-61.001 to B-61.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is H and T is as defined in table X. [0347] Table B-62 provides 21 compounds B-62.001 to B-62.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is Me and T is as defined in table X. [0348] Table B-63 provides 21 compounds B-63.001 to B-63.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is Et and T is as defined in table X. [0349] Table B-64 provides 21 compounds B-64.001 to B-64.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is iPr and T is as defined in table X. [0350] Table B-65 provides 21 compounds B-65.001 to B-65.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is Cyp and T is as defined in table X. 82949 FF 55 [0351] Table B-66 provides 21 compounds B-66.001 to B-66.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Me, R11 is OMe and T is as defined in table X. [0352] Table B-67 provides 21 compounds B-67.001 to B-67.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is H and T is as defined in table X. [0353] Table B-68 provides 21 compounds B-68.001 to B-68.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is Me and T is as defined in table X. [0354] Table B-69 provides 21 compounds B-69.001 to B-69.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is Et and T is as defined in table X. [0355] Table B-70 provides 21 compounds B-70.001 to B-70.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is iPr and T is as defined in table X. [0356] Table B-71 provides 21 compounds B-71.001 to B-71.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is Cyp and T is as defined in table X. [0357] Table B-72 provides 21 compounds B-72.001 to B-72.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Et, R11 is OMe and T is as defined in table X. [0358] Table B-73 provides 21 compounds B-73.001 to B-73.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is H and T is as defined in table X. [0359] Table B-74 provides 21 compounds B-74.001 to B-74.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is Me and T is as defined in table X. [0360] Table B-75 provides 21 compounds B-75.001 to B-75.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is Et and T is as defined in table X. [0361] Table B-76 provides 21 compounds B-76.001 to B-76.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is iPr and T is as defined in table X. [0362] Table B-77 provides 21 compounds B-77.001 to B-77.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is Cyp and T is as defined in table X. [0363] Table B-78 provides 21 compounds B-78.001 to B-78.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is iPr, R11 is OMe and T is as defined in table X. [0364] Table B-79 provides 21 compounds B-79.001 to B-79.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is H and T is as defined in table X. [0365] Table B-80 provides 21 compounds B-80.001 to B-80.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is Me and T is as defined in table X. [0366] Table B-81 provides 21 compounds B-81.001 to B-81.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is Et and T is as defined in table X. [0367] Table B-82 provides 21 compounds B-82.001 to B-82.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is iPr and T is as defined in table X. [0368] Table B-83 provides 21 compounds B-83.001 to B-83.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is Cyp and T is as defined in table X. [0369] Table B-84 provides 21 compounds B-84.001 to B-84.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is Cyp, R11 is OMe and T is as defined in table X. [0370] Table B-85 provides 21 compounds B-85.001 to B-85.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is H and T is as defined in table X. 82949 FF 56 [0371] Table B-86 provides 21 compounds B-86.001 to B-86.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is Me and T is as defined in table X. [0372] Table B-87 provides 21 compounds B-87.001 to B-87.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is Et and T is as defined in table X. [0373] Table B-88 provides 21 compounds B-88.001 to B-88.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is iPr and T is as defined in table X. [0374] Table B-89 provides 21 compounds B-89.001 to B-89.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is Cyp and T is as defined in table X. [0375] Table B-90 provides 21 compounds B-90.001 to B-90.021 of formula I-B wherein R1 is CH2- cyclopropyl, R10 is tBu, R11 is OMe and T is as defined in table X. Table X: Substituent definitions of T Index T Index T Index T 1 8 15 2 9 16 3 10 17 82949 FF 57 Index T Index T Index T 4 11 18 5 12 19 6 13 20 7 14 21 [0376] In Tables A-1 to A-90 and Tables B-1 to B-90, "Me" represents methyl, "Et" represents ethyl, "iPr" represents isopropyl, "Cyp" represents cyclopropyl, and "tBu" represents tert-butyl. [0377] Also made available are certain intermediate compounds of formulae XL-1, XL-1-13, XL-6, XL-6-13, XLI-1, XLI-2, and XLI-3, or other intermediate compounds shown in Schemes 1 to 21, some of which are novel. For example: ^ A compound of formula XL-1, where A1, A2, A3, A4, A5, R1, R2a, R2b, R3 and R11 are as defined for compounds of formula (I); for instance, where R3 is methyl, T is as defined in Table X above, and R1 and R11 are as defined in Tables A-1 to A-90, preferably R1 is hydrogen or methyl, and R11 is hydrogen or methyl; and 82949 FF 58 ^ A compound of formula XL-1-13, which corresponds to a subset of compounds of formula XL- 1 where A1 and A3 are N, A2, A4 and A5 are CH, and where R1, R2a, R2b, R3, and R11 are as defined for compounds of formula XL-1:
Figure imgf000059_0001
^ A compound of formula XL-6, where A1, A2, A3, A4, A5, R1, R2a, R2b, R3 and R11 are as defined for compounds of formula (I); for instance, where R3 is methyl, T is as defined in Table X above, and R1 and R11 are as defined in Tables A-1 to A-90, preferably R1 is hydrogen or methyl, and R11 is hydrogen or methyl; and ^ A compound of formula XL-6-13, which corresponds to a subset of compounds of formula XL- 6 where A1 and A3 are N, A2, A4 and A5 are CH, and where R1, R2a, R2b, R3, and R11 are as defined for compounds of formula XL-6:
Figure imgf000059_0002
^ A compound of formula XLI-1, where R1, R3, R10 and R11 are as defined for compounds of formula (I), and X- is an anion, such as Cl- or CF3COO-; for instance, where R3 is methyl and R1, R10 and R11 are as defined in Tables A-1 to A-90, preferably where R1 is hydrogen, R10 is methyl and R11 is hydrogen or methyl: 82949 FF 59
Figure imgf000060_0001
XLI-1 ^ A compound of formula XLI-2, where R1, R3, R10, and R11 are as defined for compounds of formula (I); for instance, where R3 is methyl and R1, R10, and R11 are as defined in Tables A-1 to A- 90, preferably where R1 is hydrogen, R10 is methyl and R11 is hydrogen or methyl:
Figure imgf000060_0002
^ A compound of formula XLI-3, where R1, R3, R11 are as defined for compounds of formula (I); for instance, where R3 is methyl and R1 and R11 are as defined in Tables A-1 to A-90, preferably where R1 is hydrogen and R11 is hydrogen or methyl:
Figure imgf000060_0003
[0378] Also made available are certain intermediate compounds: as shown below: ^ A compound of formulae X or XI, where A1, A2, A3, A4, A5, R2a, R2b, R3 and R5 are as defined for compounds of formula (I), and R20 and R21 are independently of each other C1-C4alkyl, or R20 and R21 together with the nitrogen to which they are bound to, form a pyrrolidine, piperidine or morpholine radical; for instance, where R3 is methyl, R5 is hydrogen, T is as defined in Table X above, and R20 and R21 are methyl: 82949 FF 60
Figure imgf000061_0001
^ A compound of formulae X-13 or XI-13, where R2a, R2b, R3 and R5 are as defined for compounds of formula (I), and R20 and R21 are independently of each other C1-C4alkyl, or R20 and R21 together with the nitrogen to which they are bound to, form a pyrrolidine, piperidine or morpholine radical; for instance, where R3 is methyl, R5 is hydrogen, and R20 and R21 are methyl:
Figure imgf000061_0002
[0379] The compounds of formula (I) according to the invention are preventively and/or curatively valuable ac-tive ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate. [0380] Examples of the above mentioned animal pests are: ^ from the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; ^ from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; ^ from the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, 82949 FF 61 Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae spp., Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.; ^ from the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; ^ from the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp., Thyanta spp , Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae , Unaspis citri, Zygina flammigera, Zyginidia scutellaris ; 82949 FF 62 ^ from the order Hymenoptera, for example, Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; ^ from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminata; ^ from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.; ^ from the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; ^ from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp., and Schistocerca spp.; ^ from the order Psocoptera, for example, Liposcelis spp.; ^ from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; ^ from the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; ^ from the order Thysanura, for example, Lepisma saccharina. [0381] In a further aspect, the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, 82949 FF 63 Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.. [0382] The compounds of the invention may also have activity against the molluscs. Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides. [0383] 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. [0384] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, 82949 FF 64 Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants. [0385] The compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens. [0386] For example the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants. [0387] For example the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba. [0388] 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. [0389] 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). 82949 FF 65 [0390] The compounds of formula (I) are particularly suitable for control of ^ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans, and sugarcane); ^ a pest of the order Lepidoptera, for example, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn); ^ a pest of the order Thysanoptera, such as the family Thripidae, for example, one or more of Thrips tabaci and Frankliniella occidentalis (preferably in vegetables); and ^ soil pests (such as of the order Coleoptera), for example, the species Diabrotica balteata, Agriotes spp. and Leptinotarsa decemlineata (preferably in vegetables and corn). [0391] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. [0392] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize- RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA- reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. [0393] In the context of the present invention there are to be understood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). 82949 FF 66 [0394] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP 0374753 A, WO 93/07278, WO 95/34656, EP 0427529 A, EP 451878 A and WO 03/052073. [0395] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP 0367474 A, EP 0401979 A and WO 90/13651. [0396] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera). [0397] Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1FA2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); Nature-Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®. [0398] Further examples of such transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 82949 FF 67 4. MON 863 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 × MON 810 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. [0399] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch). [0400] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis- related proteins" (PRPs, see e.g. EP 0392225 A). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP 0392225 A, WO 95/33818 and EP 0353191 A. 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. [0401] 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. [0402] Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode. [0403] Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art. [0404] 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 0392225 A); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) 82949 FF 68 or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906). [0405] Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type. [0406] 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. [0407] 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. [0408] 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. [0409] The term "controlling" when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation. [0410] The term "treating" when used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease. [0411] The term "preventing" when used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal. [0412] The term "animal" when used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses. Companion animals include, but are not limited to, dogs, cats and rabbits. [0413] A "parasite" is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense. An "endoparasite" is a parasite which lives in the host animal. An "ectoparasite" is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice). The Acari (or Acarina) sub-class comprises ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus 82949 FF 69 gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates. Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera. Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis. Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola ovis and Bovicola bovis. [0414] The term "effective amount" when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal. The effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances. [0415] The compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally' and subcutaneously. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip. In the alternative, the compounds of the invention may be administered by means of an ear tag or collar. [0416] Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts. Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, S.M., et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977). One skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as a salt, such as a hydrochloride salt, using techniques and conditions well known to one of ordinary skill in the art. In addition, one skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as the corresponding free base from the corresponding salt. [0417] The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, 82949 FF 70 the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents. [0418] In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents. [0419] Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005/113886 or WO 2007/090739. [0420] Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees. [0421] In the field of tree injection/trunk treatment, the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A. Examples of exotic woodborers of economic importance. Family Species Host or Crop Infested Buprestidae Agrilus planipennis Ash Cerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandrus crassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperda Conifers Table B. Examples of native woodborers of economic importance. Family Species Host or Crop Infested Buprestidae Agrilus anxius Birch Agrilus politus Willow, Maple 82949 FF 71 Family Species Host or Crop Infested Agrilus sayi Bayberry, Sweetfern Agrilus vittaticolllis Apple, Pear, Cranberry, Serviceberry, Hawthorn Chrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry, Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut, Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum, Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texania campestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplar Cerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak, Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytus acuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Eastern hophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust, Honeylocust, Yellow-poplar, Chestnut, Osage- orange, Sassafras, Lilac, Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood, Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleaf hackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant, Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood, Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, Mulberry Oncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood, Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit trees Saperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory, Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak, Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, Elm 82949 FF 72 Family Species Host or Crop Infested Dendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wild cherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut, Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, Pine Phloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry, Mountain-ash Pseudopityophthorus Oak, American beech, Black cherry, Chickasaw pruinosus plum, Chestnut, Maple, Hickory, Hornbeam, Hophornbeam Sesiidae Paranthrene simulans Oak, American chestnut Sannina uroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine, Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum, Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedon scitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Black cherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark, Bayberry Vitacea polistiformis Grape [0422] 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. [0423] In particular, the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and Tomarus spp., ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.). 82949 FF 73 [0424] 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). [0425] The present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs. [0426] 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. [0427] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. [0428] Examples of such parasites are: ^ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.. ^ Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.. ^ Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.. ^ Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. ^ Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. ^ Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.. ^ Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.. ^ Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., 82949 FF 74 Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.. [0429] The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings. [0430] The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina. [0431] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B- 90, and Table P”) controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. [0432] The compounds of formulae I, and I’a, or salts 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. [0433] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B- 90, and Table P”) controls one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp and Chilo spp. [0434] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis. [0435] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B- 90, and Table P”) controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, 82949 FF 75 Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilaparvata lugens + TX, Myzus persicae + TX, Chrysodeixis incIudens + TX, Aphis craccivora + TX, Diabrotica balteata + TX, Rhopalosiphum Padi + TX, and Chilo suppressalis + TX. [0436] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B-90, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops. [0437] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B-90, 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). [0438] Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been surprisingly found that certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera. [0439] The following combinations of a compound of formula I with another active substance in a weight ratio of 1:1 are preferred (where the abbreviation “TX” means "one compound selected from the compounds defined in Tables A-1 to A-90, Tables B-1 to B-90, and Table P): (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-11- enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en- 1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, 1,2-dibromo-3- chloropropane + TX, 1,2-dichloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 14-methyloctadec-1-ene + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 2- (octylthio)ethanol + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5- methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4-(quinoxalin-2- ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5-methyl-6- thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, Adoxophyes orana GV + TX, afidopyropen + TX, afoxolaner + TX, Agrobacterium radiobacter + TX, AKD-3088 + TX, alanycarb + TX, aldicarb + TX, aldoxycarb + TX, allethrin + TX, 82949 FF 76 alpha-cypermethrin + TX, alphamethrin + TX, alpha-multistriatin + TX, Amblyseius spp. + TX, amidoflumet + TX, amino acids + TX, aminocarb + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, Autographa californica NPV + TX, AZ 60541 + TX, azadirachtin + TX, azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ175 (ATCC Accession No.55608) + TX, Bacillus sp. AQ177 (ATCC Accession No.55609) + TX, Bacillus sp. AQ178 (ATCC Accession No.53522) + TX, Bacillus sphaericus Neide + TX, Bacillus subtilis AQ153 (ATCC Accession No.55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus subtilis unspecified + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No B- 21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. Aizawai + TX, Bacillus thuringiensis subsp. Israelensis + TX, Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thuringiensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, Beauveria brongniartii + TX, benclothiaz + TX, benomyl + TX, bensultap + TX, benzoximate + TX, benzpyrimoxan + TX, betacyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, bioresmethrin + TX, bis(tributyltin) oxide + TX, bisazir + TX, bistrifluron + TX, bisulflufen + TX, brevicomin + TX, broflanilide + TX, brofluthrinate + TX, bromoacetamide + TX, bromophos-ethyl + TX, bronopol + TX, busulfan + TX, butocarboxim + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butylpyridaben + TX, cadusafos + TX, calcium arsenate + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbosulfan + TX, cartap + TX, CAS number: 1594624-87-9 + TX, CAS number: 1922957-47-8 + TX, CAS number: 1255091-74-7 + TX, CAS number: 1365070-72-9 + TX, CAS number: 1445683-71-5 + TX, CAS number: 1445684-82-1 + TX, CAS number: 1594626-19-3 + TX, CAS number: 1594637-65-6 + TX, CAS number: 1632218- 00-8 + TX, CAS number: 1808115-49-2 + TX, CAS number: 1922957-46-7 + TX, CAS number: 1922957-48-9 + TX, CAS number: 1956329-03-5 + TX, CAS number: 1990457-52-7 + TX, CAS number: 1990457-55-0 + TX, CAS number: 1990457-57-2 + TX, CAS number: 1990457-66-3 + TX, CAS number: 1990457-77-6 + TX, CAS number: 1990457-85-6 + TX, CAS number: 2032403-97-5 + TX, CAS number: 2044701-44-0 + TX, CAS number: 2095470-94-1 + TX, CAS Number: 2128706-04- 5 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2133042-31-4 + TX, CAS number: 2133042- 44-9 + TX, CAS number: 2171099-09-3 + TX, CAS number: 2220132-55-6 + TX, CAS number: 2396747-83-2 + TX, CAS number: 2408220-91-5 + TX, CAS number: 2408220-94-8 + TX, CAS number: 2415706-16-8 + TX, CAS number: 2615135-05-0 + TX, CAS number: 2719848-60-7 + TX, CAS number: RNA (Leptinotarsa decemlineata-specific recombinant double-stranded interfering GS2) + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloropicrin + TX, chloroprallethrin + TX, chlorpyrifos + TX, chromafenozide + TX, Chrysoperla carnea + TX, clenpirin + TX, cloethocarb + 82949 FF 77 TX, clothianidin + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper dioctanoate + TX, copper hydroxide + TX, copper sulfate + TX, cresol + TX, crufomate + TX, Cryptolaemus montrouzieri + TX, cuelure + TX, cyanofenphos + TX, cyantraniliprole + TX, cybutryne + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxaprid + TX, Cydia pomonella GV + TX, cyenopyrafen + TX, cyetpyrafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cylohalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyproflanilide + TX, cyromazine + TX, cytokinins + TX, Dacnusa sibirica + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, diafenthiuron + TX, dialifos + TX, diamidafos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dichlofenthion + TX, dichlone + TX, dichlorophen + TX, dicliphos + TX, dicloromezotiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea + TX, dimatif + TX, dimethoate + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimpropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzofos + TX, dipyrithione + TX, disparlure + TX, D-limonene + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8,10- dien-1-yl acetate + TX, dodicin + TX, dominicalure + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, empenthrin + TX, Encarsia formosa + TX, endothal + TX, endrin + TX, eprinomectin + TX, epsilon - momfluorothrin + TX, epsilon-metofluthrin + TX, Eretmocerus eremicus + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, ethoprophos + TX, ethyl 4-methyloctanoate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, etofenprox + TX, etoxazole + TX, etpyrafen + TX, eugenol + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones, vitamins, EDTA-chelated copper, zinc, and iron + TX, famphur + TX, fenaminosulf + TX, fenamiphos + TX, fenazaquin + TX, fenfluthrin + TX, fenitrothion + TX, fenmezoditiaz + TX, fenobucarb + TX, fenothiocarb + TX, fenoxycarb + TX, fenpropathrin + TX, fenpyrad + TX, fenpyroximate + TX, fensulfothion + TX, fenthion + TX, fentin + TX, fentinacetate + TX, fenvalerate + TX, ferric phosphate + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, fluchlordiniliprole + TX, flucitrinate + TX, flucycloxuron + TX, flucythrinate + TX, fluensulfone [318290-98-1] + TX, fluensulfone + TX, flufenerim + TX, flufenprox + TX, flufiprole + TX, fluhexafon + TX, flumethrin + TX, fluopyram + TX, flupyradifurone + TX, flupyrimin + TX, flupyroxystrobin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, formaldehyde + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, furfural + TX, gamma-cyhalothrin + TX, Gossyplure® (1:1 mixture of the (Z,E) and (Z,Z) isomers of hexadeca- 7,11-dien-1-yl-acetate) + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, Granulovirus + TX, guadipyr + TX, GY-81 + TX, halfenprox + TX, halofenozide + TX, Harpin + TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, hemel + TX, hempa + TX, heptafluthrin + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexalure + TX, hexamide + TX, hexythiazox + TX, Hippodamia convergens + TX, hydramethylnon + TX, hydrargaphen + TX, hydrated lime + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, Indazapyroxamet + TX, indoxacarb + 82949 FF 78 TX, iodomethane + TX, iprodione + TX, ipsdienol + TX, ipsenol + TX, isamidofos + TX, isazofos + TX, isocycloseram + TX, Isoflualanam (CAS number: 2892524-05-7) + TX, isothioate + TX, ivermectin + TX, japonilure + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, lambda-cyhalothrin + TX, ledprona + TX, lepimectin + TX, Leptomastix dactylopii + TX, lineatin + TX, litlure + TX, looplure + TX, lotilaner + TX, lufenuron + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, mecarphon + TX, medlure + TX, megatomoic acid + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Metarhizium spp. + TX, metepa + TX, methiocarb + TX, methiotepa + TX, methomyl + TX, methoquin-butyl + TX, methoxyfenozide + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methylneodecanamide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime + TX, momfluorothrin + TX, morzid + TX, moxidectin + TX, muscalure + TX, Muscodor albus 620 (NRRL Accession No.30547) + TX, Muscodor roseus A3-5 (NRRL Accession No.30548) + TX, Myrothecium verrucaria composition + TX, nabam + TX, NC-184 + TX, Neem tree based products + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, ostramone + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, parathion-ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, penfluron + TX, pentachlorophenol + TX, permethrin + TX, phenothrin + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, Phytoseiulus persimilis + TX, picaridin + TX, pioxaniliprole + TX, piperazine + TX, piperonylbutoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, potassium and molybdenum and EDTA-chelated manganese + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, prallethrin + TX, probenazole + TX, profenofos + TX, profluthrin + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyrethrum + TX, pyridaben + TX, pyridalyl + TX, pyridin-4-amine + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, quinoclamine + TX, quinonamid + TX, resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663) + TX, sarolaner + TX, S-bioallethrin + TX, sebufos + TX, selamectin + TX, siglure + TX, silafluofen + TX, simazine + TX, sodium pentachlorophenoxide + TX, sordidin + TX, spidoxamat + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Spodoptera frugiperda Nucleopolyhedrovirus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema 82949 FF 79 feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Streptomyces galbus (NRRL Accession No. 30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulfiflumin (CAS number: 2377084- 09-6) + TX, sulfoxaflor + TX, tazimcarb + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tecloftalam + TX, tefluthrin + TX, temephos + TX, tepa + TX, terbam + TX, terbufos + TX, terpenoid blend + TX, tetrachlorantraniliprole + TX, tetrachlorothiophene + TX, tetradec-11-en-1-yl acetate + TX, tetradiphon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiosultap + TX, thiotepa + TX, tigolaner + TX, tiorantraniliprole + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, tretamine + TX, triazamate + TX, triazophos + TX, triazuron + TX, tributyltin oxide + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, Trichogramma spp. + TX, trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc- call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp. + TX, xylenols + TX, YI-5302 + TX, zeatin + TX, zeta-Cypermethrin + TX; N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N- [(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-ethyl-N’-[5- methoxy-2-methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO 2019/110427) + TX, (3',4',5'-trifluoro- biphenyl-2-yl)-amide + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methanone (these compounds may be prepared from the methods described in WO 2017/220485) + TX, (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound may be prepared from the methods described in WO 2014/006945) + TX, (5-methyl-2- pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca-7,9-dien- 1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate, + TX, (R)-3-(difluoromethyl)- 1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl- pent-3-enamide + TX, , [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4- yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, 1-(4,5-dimethylbenzimidazol-1- yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3- dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl- 82949 FF 80 isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO 2017/025510) + TX, 1,1-bis(4- chlorophenyl)-2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dibromo-3- chloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 10-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 1-bromo-2-chloroethane + TX, 1-dichloro-1-nitroethane + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1- yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4-yl) pyridine- 3- carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1- dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl- indan-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4- yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(octylthio)ethanol + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2- dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2,6-Dimethyl- 1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound may be prepared from the methods described in WO 2011/138281) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4- triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1- yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2- imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2018/065414) + TX, 2- thiocyanatoethyl laurate + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H- cyclopenta[e]benzimidazole (these compounds may be prepared from the methods described in WO 2016/156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 3-(4- chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4- yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-[2-(1- chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3- chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared 82949 FF 81 from the methods described in WO 2016/156290) + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-chloro-6- methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4- carboxylic acid + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1, 3- dimethyl- 1H- pyrazol- 5- amine + TX, 4-(2,6- difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2- chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(quinoxalin-2- ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl- isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4- [5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 4-[[6-[2-(2,4- difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4- [[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1- yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3- pyridyl)methoxy]pyridazin-3-one + TX, 4-chlorophenyl phenyl sulfone + TX, 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5- (1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, 5-methyl-6-thioxo- 1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4- dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4- dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4- methylbenzimidazol-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro- ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391) + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2- c]isothiazole-3-carbonitrile + TX, 6-isopentenylaminopurine + TX, 8-fluoro-N-[(1R)-1-[(3- fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3- fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-hydroxyquinoline sulfate + TX, acethion + TX, acetoprole + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, acrylonitrile + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, aldoxycarb + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-chlorohydrin + TX, alpha-ecdysone + TX, alpha-multistriatin + TX, aluminium phosphide + TX, Amblyseius spp. + TX, amectotractin + TX, ametoctradin + TX, amidithion + TX, amidothioate + TX, aminocarb + TX, aminopyrifen + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasine + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancymidol + TX, anilazine + TX, anisiflupurin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, aramite + TX, arsenous oxide + TX, athidathion + TX, Autographa californica NPV + TX, 82949 FF 82 azaconazole + TX, azamethiphos + TX, azobenzene + TX, azothoate + TX, azoxystrobin + TX, Bacillus sphaericus Neide + TX, Bacillus thuringiensis delta endotoxins + TX, barium carbonate + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, Beauveria brongniartii + TX, benalaxyl + TX, benclothiaz + TX, benomyl + TX, benoxafos + TX, benthiavalicarb + TX, benzothiostrobin + TX, benzovindiflupyr + TX, benzyl benzoate + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, bis(tributyltin) oxide + TX, bisazir + TX, bisthiosemi + TX, bitertanol + TX, bixafen + TX, blasticidin-S + TX, borax + TX, bordeaux mixture + TX, boscalid + TX, brevicomin + TX, brodifacoum + TX, brofenvalerate + TX, bromadiolone + TX, bromethalin + TX, bromfenvinfos + TX, bromoacetamide + TX, bromocyclen + TX, bromo-DDT + TX, bromophos + TX, bromopropylate + TX, bromuconazole + TX, bronopol + TX, bufencarb + TX, bupirimate + TX, buprofezin + TX, busulfan + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, butacarb + TX, butathiofos + TX, butocarboxim + TX, butonate + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, camphechlor + TX, captafol + TX, captan + TX, carbanolate + TX, carbendazim + TX, carbon disulfide + TX, carbon tetrachloride + TX, carbophenothion + TX, carboxin + TX, cartap hydrochloride + TX, CAS Number: 2132414-04-9 + TX, CAS Number: 2344721-61-3 + TX, cevadine + TX, chinomethionat + TX, chloralose + TX, chlorbenside + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloroform + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron + TX, chloroneb + TX, chlorophacinone + TX, chloropicrin + TX, chloropropylate + TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorthiophos + TX, chlozolinate + TX, cholecalciferol + TX, Chrysoperla carnea + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, cismethrin + TX, cis-resmethrin + TX, clocythrin + TX, closantel + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX, coumachlor + TX, coumafuryl + TX, coumaphos + TX, coumatetralyl + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, coumithoate + TX, coumoxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, crotoxyphos + TX, crufomate + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, CS 708 + TX, cuelure + TX, cufraneb + TX, cyanofenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclethrin + TX, cyclobutrifluram + TX, Cydia pomonella GV + TX, cyflufenamid + TX, cymiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinins + TX, Dacnusa sibirica + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb + TX, decarbofuran + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, diamidafos + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofenthion + TX, dichlofluanid + TX, dichlone + TX, dichlorophen + TX, dichlorvos + TX, dichlozoline + TX, dicliphos + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicresyl + TX, 82949 FF 83 dicyclanil + TX, dicyclopentadiene + TX, dieldrin + TX, dienochlor + TX, diethofencarb + TX, diethyl 5- methylpyrazol-3-yl phosphate + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difethialone + TX, diflovidazin + TX, Diglyphus isaea + TX, dilor + TX, dimatif + TX, dimefluthrin + TX, dimefox + TX, dimetan + TX, dimethirimol + TX, dimethomorph + TX, dimethrin + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimethylvinphos + TX, dimetilan + TX, dimoxystrobin + TX, dinex + TX, dinex-diclexine + TX, diniconazole + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, dinosulfon + TX, dinoterbon + TX, diofenolan + TX, dioxabenzofos + TX, dioxathion + TX, diphacinone + TX, diphenyl sulfone + TX, dipymetitrone + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, dithianon + TX, dithicrofos + TX, DNOC + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, DSP + TX, d- tetramethrin + TX, ecdysterone + TX, edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, endothal + TX, endothion + TX, enestroburin + TX, enoxastrobin + TX, EPBP + TX, epoxicon- azole + TX, eprinomectin + TX, Eretmocerus eremicus + TX, ergocalciferol + TX, etaphos + TX, ethaboxam + TX, ethiofencarb + TX, ethirimol + TX, ethoate-methyl + TX, ethyl 1-[[4-[(Z)-2-ethoxy- 3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090) + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2- yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4- carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4- carboxylate (this compound may be prepared from the methods described in WO 2018/158365) + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol with nerolidol + TX, fenamidone + TX, fenaminosulf + TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, fenethacarb + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrad + TX, fenpyrazamine + TX, fenpyroximate + TX, fenson + TX, fensulfothion + TX, fenthion + TX, fenthion-ethyl + TX, fentin + TX, fentrifanil + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, flocoumafen + TX, florylpicoxamid + TX, fluazinam + TX, flubeneteram + TX, flubenzimine + TX, flucofuron + TX, flucycloxuron + TX, fludioxonil + TX, fluenetil + TX, flufenoxadiazam + TX, flufenoxystrobin + TX, fluindapyr + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluorbenside + TX, fluoroacetamide + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin + TX, fluoxytioconazole + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, FMC 1137 + TX, folpet + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, fosetyl-aluminium + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, frontalin + TX, fuberidazole + TX, furalaxyl + TX, furametpyr + TX, furathiocarb + TX, furethrin + TX, furfural + TX, gamma-HCH + TX, glyodin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + 82949 FF 84 TX, grandlure IV + TX, guazatine + TX, guazatine acetates + TX, halfenprox + TX, HCH + TX, hemel + TX, hempa + TX, HEOD + TX, heptachlor + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecyl cyclopropanecarboxylate + TX, hexalure + TX, hexamide + TX, HHDN + TX, Hippodamia convergens + TX, hydrargaphen + TX, hydrated lime + TX, hydrogen cyanide + TX, hymexazol + TX, hyquincarb + TX, imanin + TX, imazalil + TX, imibencon- azole + TX, iminoctadine + TX, inpyrfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidofos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrin + TX, isofenphos + TX, isofetamid + TX, isoflucypram + TX, isolane + TX, isoprothiolane + TX, isopyrazam + TX, isotianil + TX, isoxathion + TX, japonilure + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kadethrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kelevan + TX, kinetin + TX, kinoprene + TX, kresoxim-methyl + TX, lead arsenate + TX, Leptomastix dactylopii + TX, leptophos + TX, lindane + TX, lineatin + TX, lirimfos + TX, litlure + TX, looplure + TX, lvbenmixianan + TX, lythidathion + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, malonoben + TX, Mamestra brassicae NPV + TX, mancopper + TX, mancozeb + TX, mandestrobin + TX, mandipropamid + TX, maneb + TX, mazidox + TX, m-cumenyl methylcarbamate + TX, mecarbam + TX, mecarphon + TX, medlure + TX, mefentrifluconazole + TX, megatomoic acid + TX, menazon + TX, mepanipyrim + TX, meperfluthrin + TX, mephosfolan + TX, mepronil + TX, mercuric oxide + TX, mercurous chloride + TX, mesulfen + TX, mesulfenfos + TX, metalaxyl + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO 2020/193387) + TX, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy- prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds may be prepared from the methods described in WO 2020/079111) + TX, methyl (Z)-3-methoxy-2-[2- methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N-[[4-[1-(2,6-difluoro-4- isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]- 2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl- phenyl]methyl]carbamate + TX, methylchloroform + TX, methylene chloride + TX, methylneodecanamide + TX, metiram + TX, metolcarb + TX, metominostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, MGK 264 + TX, milbemycin oxime + TX, mipafox + TX, 82949 FF 85 mirex + TX, monocrotophos + TX, morphothion + TX, morzid + TX, moxidectin + TX, muscalure + TX, myclobutanil + TX, myclozoline + TX, Myrothecium verrucaria composition + TX, N-((1R)-1-benzyl-3- chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO 2017/153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3- enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO 2017/153380) + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine + TX, N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N,2- dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N,N- dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689) + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro- quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)- 1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl- butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8- fluoro-quinoline-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N- [2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2- chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016/202742) + TX, N'-[4-(4,5-dichlorothiazol-2- yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO 2015/155075) + TX, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)- 3-pyridyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in IPCOM000249876D) + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N- ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]- N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N- ethyl-N-methyl-formamidine + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzamide (these compounds may be prepared from the methods described in WO 2018/202428) + TX, N’-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl- phenyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO 2018/228896) + TX, nabam + TX, naftalofos + TX, naled + TX, naphthalene + TX, NC-170 + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nerolidol + TX, N-ethyl-2-methyl-N- [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N’-[5-methoxy-2- methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nifluridide + TX, nikkomycins + TX, N-isopropyl-N’-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1- 82949 FF 86 phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrilacarb 1:1 zinc chloride complex + TX, nitrothal-isopropyl + TX, N-methoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol- 3-yl]benzenecarbothioamide + TX, norbormide + TX, nuarimol + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, ofurace + TX, oleic acid + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, orysastrobin + TX, ostramone + TX, oxadixyl + TX, oxamate + TX, oxathiapiprolin + TX, oxine-copper + TX, oxolinic acid + TX, oxycarboxin + TX, oxydeprofos + TX, oxydisulfoton + TX, oxytetracycline + TX, paclobutrazole + TX, Paecilomyces fumosoroseus + TX, para-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penflufen + TX, penfluron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, PH 60-38 + TX, phenamacril + TX, phenkapton + TX, phosacetim + TX, phosalone + TX, phosdiphen + TX, phosfolan + TX, phosglycin + TX, phosnichlor + TX, phosphamidon + TX, phosphine + TX, phosphorus + TX, phoxim-methyl + TX, phthalide + TX, Phytoseiulus persimilis + TX, picarbutrazox + TX, picaridin + TX, picoxystrobin + TX, pindone + TX, piperazine + TX, piperonyl butoxide + TX, piprotal + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, polychloroterpenes + TX, polynactins + TX, polyoxins + TX, potassium arsenite + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, potassium thiocyanate + TX, pp'-DDT + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, probenazole + TX, prochloraz + TX, proclonol + TX, procymidone + TX, profluthrin + TX, promacyl + TX, promecarb + TX, propamocarb + TX, propiconazole + TX, propineb + TX, propoxur + TX, propyl isomer + TX, proquinazid + TX, prothidathion + TX, prothioconazole + TX, prothiofos + TX, prothoate + TX, pydiflumetofen + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, pyrapropoyne + TX, pyraziflumid + TX, pyrazophos + TX, pyresmethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyribencarb + TX, pyridachlometyl + TX, pyridaphenthion + TX, pyridin-4-amine + TX, pyrifenox + TX, pyrimethanil + TX, pyrimitate + TX, pyrimorph + TX, pyrinuron + TX, pyriofenone + TX, pyrisoxazole + TX, pyroquilon + TX, quassia + TX, quinalphos + TX, quinalphos-methyl + TX, quinoclamine + TX, quinofumelin + TX, quinonamid + TX, quinothion + TX, quinoxyfen + TX, quintiofos + TX, quintozene + TX, R-1492 + TX, rafoxanide + TX, resmethrin + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, R-metalaxyl + TX, rotenone + TX, ryania + TX, ryanodine + TX, S421 + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sebufos + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesasmolin + TX, SI-0009 + TX, siglure + TX, simazine + TX, simeconazole + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium fluoroacetate + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium tetrathiocarbonate + TX, sodium thiocyanate + TX, sophamide + TX, sordidin + TX, spiroxamine + TX, SSI-121 + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, 82949 FF 87 sulcofuron + TX, sulcofuron-sodium + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfoxide + TX, sulfur + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tau-fluvalinate + TX, tazimcarb + TX, TDE + TX, tebuconazole + TX, tebufloquin + TX, tebupirimfos + TX, tecloftalam + TX, temephos + TX, tepa + TX, TEPP + TX, terallethrin + TX, terbam + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)- phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, tetrachloroethane + TX, tetrachlorothiophene + TX, tetraconazole + TX, tetradec-11-en-1-yl acetate + TX, tetradifon + TX, tetramethylfluthrin + TX, tetrasul + TX, thallium sulfate + TX, thiabendazole + TX, thiafenox + TX, thiapronil + TX, thicrofos + TX, thifluzamide + TX, thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodiazole copper + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap + TX, thiosultap-sodium + TX, thiotepa + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tolclofos-methyl + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tretamine + TX, triadimefon + TX, triadimenol + TX, triamiphos + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, triazuron + TX, tributyltin oxide + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma spp. + TX, triclopyricarb + TX, tricyclazole + TX, tridemorph + TX, trifenmorph + TX, trifenofos + TX, trifloxystrobin + TX, triflumizole + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, Typhlodromus occidentalis + TX, uredepa + TX, validamycin + TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenols + TX, zeatin + TX, zetamethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiazole + TX, zineb + TX, ziram + TX, zolaprofos + TX; Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®) in particular strain CNMC 1-1582 (e.g. VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis strain HB-2 (Biostart™ formerly Rhizoboost®) + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus sphaericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain AQ153 + TX, 82949 FF 88 Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis (Novodor®, BtBooster) + TX, Bacillus thuringiensis var. aizawai (XenTari®, DiPel®) + TX, bacteria spp. (GROWMEND®, GROWSWEET®, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES®, Mycotrol O®, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz®, Schweizer Beauveria®, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium chlorocephalum + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®, Madex®, Madex® Plus, Madex Max, Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera 82949 FF 89 nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isaria fumosorosea (previously known as Paecilomyces fumosoroseus strain, PFR-97®, PreFeRal®) + TX, Isoflavone formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus in particular strain A3-5 (Accession No. NRRL 30548) + TX, Mycorrhizae spp. (AMykor®, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta/ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal®, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor (SARRITOR®) + TX, Sclerotinia minor + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces 82949 FF 90 hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P®, PlantShield HC®, RootShield®, Trianum-G® + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp. + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus + TX; AGNIQUE® MMF + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X® e.g. AZATIN XL from Certis, US) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, essentials oils of Labiatae (Botania®) + TX, extract of neem oil (Trilogy®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, garlic + TX, Glycinebetaine (Greenstim®) + TX, kaolin (Screen®) + TX, lemongrass oil (GreenMatch®) + TX, Melaleuca alternifolia extract (also called tea tree oil) (Timorex Gold®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pine oil (Retenol®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia®, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, storage glucam of brown algae (Laminarin®) + TX, thyme oil + TX; (E,Z)-7,9-Dodecadien-1-yl acetate + TX, (E,Z,Z)-3,8,11 Tetradecatrienyl acetate + TX, (Z,Z,E)- 7,11,13-Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, Biolure® + TX, blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Calcium acetate + TX, Check- Mate® + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Lavandulyl senecioate + TX, Leafroller pheromone (3M MEC – LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + 82949 FF 91 TX, Scenturion® + TX, Starbar Premium Fly Bait®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX; Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris (Thripex®, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii®, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris- System®) + TX, Aphelinus abdominalis (Apheline®, Aphiline®), + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Aphelinus-System®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®, Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus®, Digline®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max®, Encarline®, En-Strip®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Enermix®, Ercal®, Eretline e®, Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar®, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Feltiline®) + TX, Feltiella acarisuga (Spidend®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis bacteriophora (NemaShield HB®, Nemaseek®, Terranem-Nam®, Terranem®, Larvanem®, B-Green®, NemAttack ®, Nematop®) + TX, Heterorhabditis megidis (Nemasys H®, BioNem H®, Exhibitline hm®, Larvanem- M®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System®, Entomite-A®) + TX, Hypoaspis miles (Hypoline m®, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus 82949 FF 92 testaceipes + TX, Macrolophus caliginosus (Mirical-N®, Macroline c®, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I®, Oriline i®) + TX, Orius laevigatus (Thripor-L®, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex®, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®) + TX, Steinernema feltiae (NemaShield®, Nemasys F®, BioNem F®, Steinernema-System®, NemAttack®, Nemaplus®, Exhibitline sf®, Scia-rid®, Entonem®) + TX, Steinernema kraussei (Nemasys L®, BioNem L®, Exhibitline srb®) + TX, Steinernema riobrave (BioVector®, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, CAS Number: 2643947-26-4 + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta traps (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct®, Ni-HIBIT Gold CST®) + TX, fatty acids derived from a natural by-product of extra virgin olive oil (FLIPPER®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, Spider venom + TX, Sticky traps (Trapline YF®, Rebell Amarillo®) + TX, SuffOil-X® + TX, Traps (Takitrapline y + b®) + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX, Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No. 50185 (CARTISSA® from BASF, EPA Reg. No.71840-19) + TX, Bacillus subtilis CX-9060 from Certis USA LLC, Bacillus sp., in particular strain D747 (available as DOUBLE NICKEL® from Kumiai 82949 FF 93 Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S. Patent No.7,094,592 + TX, Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL Accession No. B-21661 and described in U.S. Patent No.6,060,051, available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US) + TX, Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Paenibacillus sp. strain having Accession No. NRRL B- 50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX, Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO 2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No.1-3936, CNCM No.1- 3937, CNCM No.1-3938 or CNCM No.1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX; Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX, Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014/028521) (STARGUS® from Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No.7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX, Bacillus licheniformis, in particular strain SB3086, having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAF™ from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having Accession No. B-30890 (available as BMJ TGAI® or WG and LifeGard™ from Certis USA LLC) + TX, Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No.6,245,551) + TX, Bacillus subtilis CX-9060 from Certis USA LLC + TX, Bacillus subtilis IAB/BS03 (AVIV™ from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) + TX, Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX, Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX, Bacillus subtilis strain MBI 600 (available as SUBTILEX from 82949 FF 94 BASF SE), having Accession Number NRRL B-50595, U.S. Patent No.5,061,495 + TX, Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016/020371) from BASF SE + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX, Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017/019448 (e.g., HOWLER™ and ZIO® from AgBiome Innovations, US) + TX, Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescens strain A506 (e.g. BLIGHTBAN® A506 by NuFarm) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf. Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® from Novozymes) + TX; Trichoderma atroviride strain T11 (IMI352941/ CECT20498) + TX, Ampelomyces quisqualis strain AQ10, having Accession No. CNCM 1-807 (e.g., AQ 10® by IntrachemBio Italia) + TX, Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta/ChemChina) + TX, Aureobasidium pullulans, in particular blastospores of strain DSM 14941 + TX, Aureobasidium pullulans, in particular blastospores of strain DSM14940 + TX, Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH) + TX, Chaetomium cupreum (Accession No. CABI 353812) (e.g. BIOKUPRUM™ by AgriLife) + TX, Chaetomium globosum (available as RIVADIOM® by Rivale) + TX, Cladosporium cladosporioides, strain H39, having Accession No. CBS122244, US 2010/0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM9660, e.g. Contans ® from Bayer CropScience Biologics GmbH) + TX, Cryptococcus flavescens, strain 3C (NRRL Y-50378), + TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST FUNGUS®), Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection) + TX, Gliocladium catenulatum (Synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g. Prestop ® by Lallemand) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea) strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain ’IK726’, Australasian Plant Pathol.2007,36(2):95-101) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue A.G. (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed 82949 FF 95 treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 2003, 83(3): 519-524) + TX, Metschnikowia fructicola, in particular strain NRRL Y-30752 + TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, WO 2015/067800) from BASF SE + TX, mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No. CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having Accession No. IMI 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No.1-3936, CNCM No.1-3937, CNCM No.1-3938, CNCM No.1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR + TX, Saccharomyces cerevisiae, in particular strain LASO2 (from Agro-Levures et Dérivés) + TX, Simplicillium lanosoniveum + TX, strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro + TX, strain WRL-076 (NRRL Y- 30842), U.S. Patent No.7,579,183 + TX, Talaromyces flavus, strain V117b + TX, Trichoderma asperelloides JM41R (Accession No. NRRL B-50759) (TRICHO PLUS® from BASF SE) + TX, Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. ECO- HOPE® from Kumiai Chemical Industry) + TX, Trichoderma asperellum, in particular, strain kd (e.g. T- Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (T77 from Andermatt Biocontrol) + TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX, Trichoderma atroviride strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX, Trichoderma atroviride strain LU132 (e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08/002388 + TX, Trichoderma atroviride strain NMI no. V08/002389 + TX, Trichoderma atroviride strain NMI no. V08/002390 + TX, Trichoderma atroviride strain no. V08/002387 + TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009/116106 and U.S. Patent No.8,431,120 (from Bi-PA)) + TX, Trichoderma atroviride,strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma harmatum + TX, Trichoderma harmatum, having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro), + TX, Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g. Root-Pro by Mycontrol) + TX, 82949 FF 96 Trichoderma polysporum strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX, Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX, Trichoderma virens (also known as Gliocladium virens) in particular strain GL-21 (e.g. SoilGard by Certis, US) + TX, Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No. NM 99/06216 (e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IF™ from TerraMax, Inc.) + TX, Azotobacter chroococcum, in particular strain H23 + TX, Azotobacter vinelandii, in particular strain ATCC 12837 + TX, Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015) + TX, Bacillus amyloliquefaciens in particular strain FZB42 (e.g. RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens in particular strain IN937a + TX, Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC # PTA-7542, WO 2017/205258) + TX, Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus in particular strain BP01 (ATCC 55675, e.g. MEPICHLOR® from Arysta Lifescience, US) + TX, Bacillus mycoides BT155 (NRRL No. B-50921) + TX, Bacillus mycoides BT46-3 (NRRL No. B-50922) + TX, Bacillus mycoides EE118 (NRRL No. B-50918) + TX, Bacillus mycoides EE141 (NRRL No. B-50916) + TX, Bacillus pumilus in particular strain GB34 (e.g. YIELD SHIELD® from Bayer Crop Science, DE), + TX, Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B- 50421 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No.13/330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g. SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE) + TX, Bacillus tequilensis in particular strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7 + TX, Bradyrhizobium japonicum (e.g. OPTIMIZE® from Novozymes) + TX, Delftia acidovorans in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company 82949 FF 97 Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g. CROPAID® from Cropaid Ltd UK) + TX; Myrothecium verrucaria strain AARC-0255 (e.g. DiTera™ from Valent Biosciences) + TX, Penicillium bilaii strain ATCC 22348 (e.g. JumpStart® from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89/030550, e.g. BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472 e.g. Polyversum from Bioprepraty, CZ) + TX, Rhizopogon amylopogon (Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Rhizopogon fulvigleba (e.g. Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Talaromyces flavus strain V117b + TX, Trichoderma asperellum strain (Eco-T from Plant Health Products, ZA) + TX, Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride in particular strain no. V08/002387 + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain no. NMI No. V08/002388 + TX, Trichoderma atroviride strain no. NMI No. V08/002389 + TX, Trichoderma atroviride strain no. NMI No. V08/002390 + TX, Trichoderma atroviride strain SC1 (described in WO 2009/116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g. SoilGard® from Certis, USA) + TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g. Dutch Trig from Tree Care Innovations) + TX; Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc.), + TX, Bacillus amyloliquefaciens in particular strain PTS-4838 (e.g. AVEO from Valent Biosciences, US), + TX, Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC), + TX, Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US), + TX, Bacillus thuringiensis israelensis strain BMP 144 (e.g. AQUABAC® by Becker Microbial Products IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis 82949 FF 98 subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensis strain Buibui + TX, Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global) + TX, Brevibacillus laterosporus + TX, Burkholderia spp. in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319, WO 2011/106491 and WO 2013/032693, e.g. MBI206 TGAI and ZELTO® from Marrone Bio Innovations), + TX, Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI-203, e.g. GRANDEVO® from Marrone Bio Innovations) + TX, Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX, Paenibacillus popilliae (formerly Bacillus popilliae, e.g. MILKY SPORE POWDER™ or MILKY SPORE GRANULAR™ from St. Gabriel Laboratories) + TX, Serratia entomophila (e.g. INVADE® by Wrightson Seeds) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708) + TX, Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX, Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX; Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (Accession No. DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (Accession No. ATCC74250, e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017/066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX; Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX; Burkholderia spp. in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp. + TX, Agrobacterium spp. + TX, Azorhizobium caulinodans + TX, Azospirillum spp. + TX, Azotobacter spp. + TX, Bradyrhizobium spp. + TX, Gigaspora monosporum + TX; Allium sativum (NEMGUARD from Eco-Spray, BRALIC from ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae extract in particular oilseed rape powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Chenopodium quinoa saponin extract from quinoa seeds (e.g. Heads Up® 82949 FF 99 (Saponins of Quinoa) from Heads Up plant Protectants, CA) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from STK) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (FRACTURE® from FMC) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (PROBLAD® from Certis EU) + TX, Pyrethrins + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX from Marrone Bio) + TX, Requiem™ Insecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX, ryania/ryanodine + TX, Symphytum officinale + TX, Tanacetum vulgare + TX, Thymol + TX, Thymol mixed with Geraniol (CEDROZ from Eden Research) + TX, Thymol mixed with Geraniol and Eugenol (MEVALONE from Eden Research) + TX, Triact 70 + TX, TriCon + TX, Tropaeulum majus + TX, Urtica dioica + TX, Veratrin + TX, Viscum album + TX; mercuric oxide + TX, octhilinone + TX, thiophanate-methyl + TX; MGK 264 + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-isovalerylindan-1,3-dione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, alpha-bromadiolone + TX, alpha-chlorohydrin + TX, aluminium phosphide + TX, anthraquinone + TX, antu + TX, arsenous oxide + TX, barium carbonate + TX, benoxacor + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, calcium cyanide + TX, chloralose + TX, chlorophacinone + TX, cholecalciferol + TX, cloquintocet (including cloquintocet-mexyl) + TX, copper naphthenate + TX, copper oxychloride + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, cyprosulfamide + TX, diazinon + TX, dichlormid + TX, dicyclopentadiene + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, farnesol + TX, farnesol with nerolidol + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluxofenim + TX, furilazole + TX, gamma-HCH + TX, guazatine + TX, guazatine acetates + TX, HCH + TX, hydrogen cyanide + TX, imanin + TX, iodomethane + TX, isoxadifen (including isoxadifen-ethyl) + TX, lindane + TX, magnesium phosphide + TX, MB-599 + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX, methiocarb + TX, methyl bromide + TX, nerolidol + TX, norbormide + TX, petroleum oils + TX, phosacetim + TX, phosphine + TX, phosphorus + TX, pindone + TX, piperonyl butoxide + TX, piprotal + TX, potassium arsenite + TX, probenazole + TX, propyl isomer + TX, pyridin-4-amine + TX, pyrinuron + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, S421 + TX, scilliroside + TX, sesamex + TX, sesasmolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thiram + TX, trimethacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX. [0440] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added 82949 FF 100 hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html. [0441] Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number. [0442] The active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables A-1 to A-90 , Tables B-1 to B-90, and Table P, with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-90 , Tables B-1 to B-90, and Table P, and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight. [0443] The compounds and mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body. [0444] The mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-90 , Tables B-1 to B-90, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention. [0445] The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, micro-emulsifiable concentrates, oil- 82949 FF 101 in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents. [0446] 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. [0447] The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated. [0448] The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl-formamide, dimethyl sulfoxide, 1,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, 82949 FF 102 propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. [0449] 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. [0450] A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981). [0451] Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers. [0452] The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010. 82949 FF 103 [0453] The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula-tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations. [0454] The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha. [0455] 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 % [0456] Formulation types include an emulsifiable concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. A short definition of formulation types may be found in the OECD Guidance for Industry Data Submissions on Plant Protection Products and their Active Substances (Revision 2 May 2005), Appendix 2. 82949 FF 104 [0457] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use. [0458] Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations. [0459] The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides. [0460] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention. [0461] The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha. [0462] A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredi-ent can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field. [0463] The compounds of formula (I) of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the 82949 FF 105 compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds. [0464] The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds. [0465] The present invention also comprises seeds coated or treated with or containing a compound of formula (I). The term "coated or treated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I). [0466] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds. [0467] The compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m2. The greater efficacy can be observed by an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). [0468] In each aspect and embodiment of the invention, "consisting essentially" and inflections thereof are a preferred embodiment of "comprising" and its inflections, and "consisting of" and inflections thereof are a preferred embodiment of "consisting essentially of" and its inflections. [0469] The disclosure in the present application makes available each and every combination of embodiments disclosed herein. [0470] It should be noted that the disclosure herein in respect of a compound of formula (I) applies equally in respect of a compound of each of formulae (I*), (I’a) and Tables A-1 to A-90 and Tables B-1 to B-90. EXAMPLES Formulation Examples 82949 FF 106 [0471] The following Examples further illustrate, but do not limit, the invention. Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - [0472] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration. Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20 % [0473] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment. Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % [0474] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. 82949 FF 107 Dusts a) b) c) Active ingredients 5 % 6 % 4 % Talcum 95 % - - Kaolin - 94 % - mineral filler - - 96 % [0475] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruded granules Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % Kaolin 82 % [0476] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Coated granules Active ingredients 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % [0477] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % [0478] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using 82949 FF 108 such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % [0479] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Slow Release Capsule Suspension [0480] 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. Preparatory Examples [0481] "Mp" means melting point in degrees Celsius (°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: [0482] Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive 82949 FF 109 and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 1.5 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 1.0 min, 100% B isocratic for 0.2min, 100-10% B in 0.05min, 10% B isocratic for 0.05 min. Method 2: [0483] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 41 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 5000°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range: 110 to 800 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, Temp: 40 °C, PDA Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B = Acetonitrile + 0.05 % HCOOH, gradient: 10-100% B in 1.3 min; Flow (ml/min) 0.6. Method 3: [0484] Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector. Column: Acquity UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B = Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-50% B; 0.2-0.6 min 50-100% B; 0.6-1.3 min 100% B; 1.3-1.4 min 100-10% B; 1.4-1.6 min 10% B; Flow (mL/min) 0.6. Example E1: Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P1)
Figure imgf000110_0001
82949 FF 110 [0485] A microwave vial was charged with 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol- 3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-8) (0.15 g, 0.33 mmol), methyl carbamate (0.037 g, 0.49 mmol), [1-(2-diphenylphosphanyl-1-naphthyl)-2-naphthyl]-diphenyl-phosphane (BINAP, 0.021 g, 0.033 mmol), sodium carbonate (0.070 g, 0.66 mmol) and toluene (3 mL). The mixture was flushed with nitrogen for 5 minutes, then Pd2(dba)3 (0.015 g, 0.017 mmol) was added and the vial was sealed. The reaction mixture was heated in the microwave at 100°C for 2 h. The reaction mass was filtered through a celite bed, the bed washed with EtOAc and the combined filtrate concentrated in vacuo. The crude product was purified using reverse phase chromatography to afford methyl N-[6-[5-[(1S)-1-[[6-chloro-8- (trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (0.02 g) as a white solid. [0486] 1H NMR (DMSO-d6) δ: 11.14 (br s, 1H), 9.12 (br d, 1H), 8.97 (d, 1H), 8.81 (s, 1H), 8.40 (s, 1H), 8.37 (s, 1H), 8.22 (d, 1H), 8.18 (s, 1H), 6.49 (quint, 1H), 3.76 (s, 3H), 1.74 (d, 3H). [0487] Similarly, 3-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]pyrimidin-4-yl]oxazolidin-2-one (P16) can be obtained from intermediate (I-8) following above protocol in analogy when replacing methyl carbamate with 1,3-oxazolidin-2-one. LCMS (method 3): retention time 1.13 min, m/z 506/508 [M+H]+. Example E2: Alternative preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin- 4-yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P1)
Figure imgf000111_0001
[0488] To a mixture of 4,6-dichloro-8-(trifluoromethyl)quinazoline (prepared as described in WO 2021/083936) (0.12 g, 0.45 mmol) and [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4- triazol-3-yl]ethyl]ammonium chloride (I-3) (0.15 g, 0.49 mmol) in tetrahydrofuran (4 mL) was added triethylamine (0.14 g, 1.35 mmol) dropwise at room temperature. The mixture was heated at 70°C for 1 h, then diluted with water and the precipitated solid was filtered, washed with water and dried. The crude was adsorbed on celite and purified by reverse phase column chromatography (H2O/ACN eluent) to afford methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (0.103 g) as a white solid. LCMS (method 3): retention time 1.14 min, m/z 494/496 [M+H]+. [0489] 1H NMR (DMSO-d6) δ: 11.14 (br s, 1H), 9.10 (br d, 1H), 8.96 (d, 1H), 8.81 (s, 1H), 8.40 (s, 1H), 8.37 (s, 1H), 8.22 (d, 1H), 8.17 (s, 1H), 6.48 (quint, 1H), 3.75 (s, 3H), 1.73 (d, 3H). [0490] Similarly, methyl N-[6-[5-[(1S)-1-[(6-chloro-8-iodo-quinazolin-4-yl)amino]ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (P18) can be obtained from intermediate (I-3) following above protocol in 82949 FF 111 analogy when replacing 4,6-dichloro-8-(trifluoromethyl)quinazoline with 4,6-dichloro-8-iodo-quinazoline (CAS 100949-33-5). LCMS (method 3): retention time 1.12 min, m/z 552/554 [M+H]+. Example E3: Preparation of ethyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (compound P2)
Figure imgf000112_0001
[0491] To a solution of 6-chloro-N-[(1S)-1-[2-[6-(methylamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]- 8-(trifluoromethyl)quinazolin-4-amine (I-10) (0.10 g, 0.22 mmol) in tetrahydrofuran (2 mL) were added ethyl chloroformate (0.24 g, 2.22 mmol) and triethylamine (0.05 g, 0.44 mmol) at 0°C. The reaction mixture was stirred for 2 h at room temperature, then diluted with water and the precipitated solid filtered, washed with water and dried in vacuo to afford ethyl N-[6-[5-[(1S)-1-[[6-chloro-8- (trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (0.053 g) as a white solid. LCMS (method 3): retention time 1.27 min, m/z 522/524 [M+H]+. [0492] 1H NMR (DMSO-d6) δ: 9.12 (br d,1H), 8.98 (s, 1H), 8.81 (s, 1H), 8.46 (s, 1H), 8.22-8.26 (m, 1H), 8.15 (s, 1H), 8.03 (s, 1H), 6.41 (quint, 1H), 4.07 (Q, 2H), 3.55 (s, 3H),1.71 (br d, 3H), 1.23 (br t, 3H). Example E4: Preparation of ethyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P6)
Figure imgf000112_0002
[0493] To a solution of N-[(1S)-1-[2-(6-amino-pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-N- methyl-8-(trifluoromethyl)quinazolin-4-amine (I-12) (0.1 g, 0.22 mmol) in acetonitrile (4 mL) were added ethyl chloroformate (0.24 g, 2.22 mmol) and potassium carbonate (0.06 g, 0.67 mmol). The reaction mixture was stirred at room temperature for 5 h, then diluted with water and the precipitated solid was filtered. The crude material was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford ethyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl-amino]ethyl]-1,2,4-triazol-1- 82949 FF 112 yl]pyrimidin-4-yl]carbamate (37 mg) as a white solid. LCMS (method 3): retention time 1.23 min, m/z 522/524 [M+H]+. [0494] 1H NMR (DMSO-d6) δ: 11.04 (s, 1H), 8.52 (s, 1H), 8.33 (d, 1H), 8.31 (s, 1H), 8.22 (d, 1H), 8.16 (d, 1H), 8.14 (d,1H), 6.76 (Q, 1H), 4.20 (Q, 2H), 3.24 (s, 3H), 1.83 (d, 3H), 1.26 (t, 3H). Example E5: Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P5)
Figure imgf000113_0001
Step 1: Preparation of phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-14)
Figure imgf000113_0002
(I-14) [0495] To a solution of N-[(1S)-1-[2-(6-amino-pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (trifluoromethyl)quinazolin-4-amine (I-9) (0.1 g, 0.23 mmol) in acetonitrile (4 mL) were added potassium carbonate (0.07 g, 0.69 mmol) and phenyl chloroformate (0.09 g, 0.57 mmol). The reaction mixture was stirred at room temperature for 19 h, diluted with water and the precipitated solid filtered and dried. The crude material was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford phenyl N-[6-[5- [(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4- yl]carbamate (96 mg) as a pale yellow solid. LCMS (method 3): retention time 1.22 min, m/z 556/558 [M+H]+. [0496] 1H NMR (CDCl3) δ: 8.97 (d, 1H), 8.84 (s, 1H), 8.75 (d, 1H), 8.62 (s, 1H), 8.25 (br d,1H), 8.09 (s, 1H), 8.01 (d, 1H), 7.86 (d, 1H), 7.43-7.51 (m, 2H), 7.29-7.38 (m, 2H), 7.24-7.28 (m, 1H), 6.69 (quint, 1H), 1.85 (d, 3H). 82949 FF 113 [0497] Similarly, phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (I-15) can be obtained from intermediate (I-10) with above protocol. LCMS (method 3): retention time 1.19 min, m/z 570/572 [M+H]+. [0498] Similarly, phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-16) can be obtained from intermediate (I-12) with above protocol. LCMS (method 3): retention time 1.27 min, m/z 570/572 [M+H]+. [0499] Similarly, phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (I-17) can be obtained from intermediate (I-13) with above protocol. LCMS (method 3): retention time 1.19 min, m/z 584/586 [M+H]+. Step 2: Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P5)
Figure imgf000114_0001
[0500] To a solution of phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-14) (0.1 g, 0.18 mmol) in isopropanol (4 mL) was added potassium carbonate (0.02 g, 0.18 mmol) and reaction mixture was stirred at 80°C for 45 minutes. The reaction mixture was cooled to room temperature, diluted with water and the product extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (56 mg) as a white solid. LCMS (method 3): retention time 1.23 min, m/z 522/524 [M+H]+. [0501] 1H NMR (CDCl3) δ: 8.85 (s, 1H), 8.71 (s, 1H), 8.65 (s, 2H), 8.32 (br s, 1H), 8.09 (br d, 2H), 7.96 (s, 1H), 6.75 (quint,1H), 5.13 (m, 1H), 1.87 (br d, 3H), 1.39 (d, 6H). Example E6: Preparation of tert-butyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P19) 82949 FF 114
Figure imgf000115_0001
Step 1: Preparation of 6-chloro-8-(trifluoromethyl)-3H-quinazolin-4-one (I-20)
Figure imgf000115_0002
(I-20) [0502] To a solution of 2-amino-5-chloro-3-(trifluoromethyl)benzonitrile (CAS 74396-76-2) (500 mg, 2.27 mmol) in formic acid (4.5 mL) was added sulfuric acid (0.192 mL, 1.5 equiv.) dropwise and the reaction mixture was heated to 80°C for 1 hour. After cooling to room temperature, the mixture was diluted with ice cold water (4.5 mL). The formed precipitate was isolated by filtration, the solid washed with cold water and dried in vacuo to afford 6-chloro-8-(trifluoromethyl)-3H-quinazolin-4-one (I-20). LCMS (method 1): retention time 0.87 min, m/z 249/251 [M+H]+. [0503] 1H NMR (400 MHz, DMSO-d6) δ ppm 12.79 (br s, 1H), 8.34 (m, 1H), 8.30 (s, 1H), 8.24 (m, 1H). Step 2: Preparation of 4,6-dichloro-8-(trifluoromethyl)quinazoline (I-21)
Figure imgf000115_0003
(I-21) [0504] A suspension of 6-chloro-8-(trifluoromethyl)-3H-quinazolin-4-one (I-20) (1.0 g, 4.02 mmol) and N,N-dimethylformamide (0.0629 mL, 0.80 mmol, 0.2 equiv.) in thionyl chloride (10 mL) was heated at 79°C for 5 hours. After cooling to room temperature, the mixture was diluted with toluene and poured carefully into ice and water. After further dilution with EtOAc, the layers were separated, the aqueous phase extracted three times with ethyl acetate, the combined organic layers washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford 4,6-dichloro-8- 82949 FF 115 (trifluoromethyl)quinazoline (I-21) as a white solid. LCMS (method 1): retention time 1.10 min, m/z 267/269 [M+H]+. [0505] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.29 (s, 1H), 8.61 (m, 1H), 8.59 (m, 1H). Step 3: Preparation of (2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]propanamide (I-22)
Figure imgf000116_0001
(I-22) [0506] To a suspension of L-alaninamide hydrochloride (synonym: (S)-2-aminopropanamide hydrochloride; CAS 33208-99-0) (0.593 g, 4.66 mmol, 1.1 equiv.) in toluene (15 mL) were added tetrabutylammonium bromide (0.137 g, 0.1 equiv.) and triethylamine (1.31 mL, 2.2 equiv.). The reaction mixture was stirred for 10 minutes at room temperature, then 4,6-dichloro-8-(trifluoromethyl)quinazoline (I-21) (1.155 g, 4.24 mmol, 1.0 equiv.) dissolved in toluene (6 mL) was added and the resulting suspension was stirred at 110°C for 14 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate (20 ml) and water (20 ml), and the layers were separated. The aqueous phase was extracted three times with ethyl acetate, the combined organic layers washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was triturated with diisopropyl ether (3 mL), filtered, the solid rinsed with more of the same solvent, then dried in vacuo to afford (2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]propanamide (I-22). LCMS (method 1): retention time 0.88 min, m/z 319/321 [M+H]+. [0507] 1H NMR (DMSO-d6) δ ppm 8.91 (s, 1H), 8.62 (d, 1H), 8.58 (s, 1H), 8.17 (s, 1H), 7.54 (br s, 1H), 7.04 (br s, 1H), 4.73 (quint, 1H), 1.49 (d, 3H). Step 4: Preparation of (E,2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]-N- (dimethylaminomethylene)propanamide (I-23)
Figure imgf000116_0002
(I-23) [0508] To a suspension of (2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]propanamide (I- 22) (0.15 g, 0.44 mmol, 1.0 equiv.) in CPME (1.05 mL) was added N,N-dimethylformamide dimethyl acetal (DMF-DMA) (0.065 g, 0.53 mmol, 1.2 equiv.) and the reaction mixture was stirred at 50°C for 30 minutes. LCMS analysis indicated formation of the title compound (I-23). LCMS (method 1): retention time 0.78 min, m/z 374/376 [M+H]+. Compound (I-23) was not isolated in pure form, but above mixture containing (I-23) was used directly in the following step (solution A). [0509] 1H NMR characterization of compound (I-23): a similar reaction was performed as described above with (2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]propanamide (I-22) (0.25 g, 0.74 82949 FF 116 mmol, 1.0 equiv.) and DMF-DMA (0.109 g, 0.88 mmol, 1.2 equiv.) in perdeuterotoluene (toluene-d8, 1.75 mL). The mixture was stirred at 50°C for 2 hours. The progression of the reaction was followed by submitting samples of the mixture to NMR spectroscopy. A final sample of the reaction mixture was diluted with DMSO-d6 and submitted to 1H NMR analysis to show the title compound (I-23). [0510] 1H NMR (DMSO-d6 / trace of toluene-d8) δ ppm 8.98 (d, 1H), 8.68 (d, 1H), 8.59 (s, 1H), 8.48 (s, 1H), 8.11 (d, 1H), 4.97 (quint, 1H), 3.30-3.20 (m, 6 H), 1.60 (d, 3H). Step 5: Preparation of tert-butyl N-(6-hydrazinopyrimidin-4-yl)carbamate (I-24)
Figure imgf000117_0001
[0511] Tert-butyl (6-chloropyrimidin-4-yl)carbamate (CAS 1849595-31-8) (0.2 g, 0.87 mmol, 1 equiv.) was suspended in 2-propanol (1 mL). Hydrazine hydrate (0.164 g, 3 equiv.) was added, and the mixture was stirred at 90°C for 2 hours. After cooling to room temperature, the reaction mixture was diluted with water and ethanol. The formed precipitate was isolated by filtration and washed with a mixture of ethanol and water. After drying tert-butyl N-(6-hydrazinopyrimidin-4-yl)carbamate (I-24) was obtained as a white solid. LCMS (method 1): retention time 0.45 min, m/z 226 [M+H]+. [0512] 1H NMR (DMSO-d6) δ ppm: 9.52-9.63 (m, 1 H), 8.09-8.20 (m, 1 H), 8.05 (s, 1 H), 7.14 (br s, 1 H), 4.22-4.30 (m, 2 H), 1.47 (s, 9 H). Step 6: Preparation of tert-butyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino] ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P19)
Figure imgf000117_0002
[0513] Tert-butyl N-(6-hydrazinopyrimidin-4-yl)carbamate (I-24) (0.119 g, 0.53 mmol, 1.2 equiv.) dissolved in acetic acid (1.16 mL) was added to the mixture obtained in Example E6, step 4 above (solution A containing (I-23), assumed 0.44 mmol) at room temperature. The resulting reaction mixture was stirred at 80°C for 45 minutes. After cooling to room temperature (formation of a precipitate), the mixture was diluted with water and the resulting suspension was filtered. The residue was washed with CPME and water several times. The wet colourless solid was dried in vacuo at 45°C for 45 minutes to afford tert-butyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino] ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (P19) as a white solid. LCMS (method 1): retention time 1.16 min, m/z 536/538 [M+H]+. 82949 FF 117 [0514] 1H NMR (400 MHz, DMSO-d6) δ ppm 10.77 (s, 1H), 9.10 (d, J=6.9Hz, 1H), 8.96 (d, J=1.8Hz, 1H), 8.78 (d, J=1.1Hz, 1H), 8.41 (s, 1H), 8.35 (d, J=1.1Hz, 1H), 8.22 (d, J=1.8Hz, 1H), 8.17 (s, 1H), 6.50 (quint, J=6.9Hz, 1H), 1.74 (d, J=6.9Hz, 3H), 1.50 (s, 9H). Example E7: Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (compound P12)
Figure imgf000118_0001
Step 1: Preparation of 6-chloro-N-[(1S)-1-[2-[6-(methoxyamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]- 8-(trifluoromethyl)quinazolin-4-amine (I-18)
Figure imgf000118_0002
(I-18) [0515] A mixture in a pressure vessel of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol- 3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-8) (1.0 g, 1 equiv.), O-methylhydroxylamine hydrochloride (1.835 g, 10 equiv.) and triethylamine (2.23 g, 10 equiv.) in tetrahydrofuran (20 mL) was stirred at 80°C for 15 hours. After cooling, the reaction mixture was filtered and the filter residue washed with ethyl acetate. The combined filtrates were concentrated under reduced pressure and the residue purified by combiflash (ethyl acetate/cyclohexane eluent) to afford 6-chloro-N-[(1S)-1-[2-[6- (methoxyamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-18) as a colourless solid. LCMS (method 3): retention time 1.23 min, m/z 466/468 [M+H]+. [0516] 1H NMR (DMSO-d6) δ 11.03 (s, 1H), 9.10 (d, 1H), 8.98 (d, 1H), 8.56 (s, 1H), 8.42 (s, 1H), 8.22 (d, 1H), 8.13 (s, 1H), 7.08 (s, 1H), 6.50 (m, 1H), 3.74 (s, 3H), 1.73 (d, 3H). Step 2: Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (compound P11) 82949 FF 118
Figure imgf000119_0001
[0517] A solution of 6-chloro-N-[(1S)-1-[2-[6-(methoxyamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]- 8-(trifluoromethyl)quinazolin-4-amine (I-18) (200 mg, 1 equiv.) in acetonitrile (2 mL) was treated with potassium carbonate (0.447 g, 10.5 equiv.) and methyl chloroformate (0.410 g, 10 equiv.). The reaction mixture was stirred at 20°C for one hour, then poured into 50 mL of water. The formed precipitate was isolated by filtration and dried in vacuo to afford methyl N-[6-[5-[(1S)-1-[[6-chloro-8- (trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (P11) as a solid. LCMS (method 3): retention time 1.15 min, m/z 524/526 [M+H]+. [0518] 1H NMR (DMSO-d6) δ 9.13 (d, 1H), 9.02 (br s, 1H), 8.97 (br s, 1H), 8.39 (br s, 1H), 8.30 (br s, 1H), 8.22 (s, 1H), 8.20 (s, 1H), 6.49 (m, 1H), 3.92 (s, 3H), 3.90 (s, 3H), 1.75 (br d, 3H). Step 3: Preparation of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (compound P12)
Figure imgf000119_0002
[0519] To a solution of methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4- yl]amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (P11) (80 mg, 1 equiv.) in acetonitrile (0.8 mL) were added cesium carbonate (100 mg, 2 equiv.), followed by methyl iodide (218 mg, 10 equiv.). The reaction mixture was stirred at 20°C for 22 hours, then filtered through a celite bed and the filtrate evaporated. The residue was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford methyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl-amino]ethyl]-1,2,4- triazol-1-yl]pyrimidin-4-yl]-N-methoxy-carbamate (P12) as a yellow solid. LCMS (method 3): retention time 1.18 min, m/z 538/540 [M+H]+. [0520] 1H NMR (CDCl3) δ 8.56 (s, 1H), 8.40 (s, 1H), 8.40 (s, 1H), 8.00 (br s, 3H), 6.87 (q, 1H), 4.00 (s, 3H), 3.95 (s, 3H), 3.41 (s, 3H), 1.94 (d, 3H). Example E8: Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]- methyl-amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (compound P14) 82949 FF 119
Figure imgf000120_0001
Step 1: Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (compound P7)
Figure imgf000120_0002
[0521] To a solution of phenyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (I-16) (150 mg, 1 equiv.) in acetonitrile (6 mL) were added potassium carbonate (26 mg, 1 equiv.) and isopropanol (17 mg, 1.1 equiv.). The reaction mixture was stirred at 20°C for 5 hours, then at 80°C for 15 minutes, after which it was diluted with water and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo. The residue was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8- (trifluoromethyl)quinazolin-4-yl]-methyl-amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (P7) as a colourless solid. LCMS (method 3): retention time 1.27 min, m/z 536/538 [M+H]+. [0522] 1H NMR (DMSO-d6) δ 10.95 (s, 1H), 8.52 (s, 1H), 8.33 (s, 1H), 8.31 (s, 1H), 8.21 (s, 1H), 8.15 (s, 1H), 8.13 (s, 1H), 6.76 (q, 1H), 4.95 (hept, 1H), 3.24 (s, 3H), 1.82 (br d, 3H), 1.28 (br d, 6H). Step 2: Preparation of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (compound P14)
Figure imgf000120_0003
[0523] To a solution of isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (P7) (80 mg, 1 equiv.) in acetonitrile (0.8 mL) 82949 FF 120 were added potassium carbonate (39 mg, 2 equiv.) and iodomethane (20 mg, 10 equiv.). The reaction mixture was stirred at 20°C for 4 hours, then poured into water and the product extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo. The residue was purified by combiflash (ethyl acetate/cyclohexane eluent) to afford isopropyl N-[6-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]-methyl- amino]ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]-N-methyl-carbamate (P14) as a solid. LCMS (method 3): retention time 1.33 min, m/z 550/552 [M+H]+. [0524] 1H NMR (CDCl3) δ 8.67 (d, 1H), 8.59 (s, 1H), 8.25 (d, 1H), 8.02 (s, 2H), 7.96 (d, 1H), 6.87 (q, 1H), 5.13 (hept, 1H), 3.49 (s, 3H), 3.34 (s, 3H), 1.95 (d, 3H), 1.40 (d, 6H). Preparation of intermediates Example PI-1: Preparation of [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-3)
Figure imgf000121_0001
Step 1: Preparation of tert-butyl N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-1)
Figure imgf000121_0002
(I-1) [0525] A solution of tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (CAS 2694010-23-4, prepared as described for example in WO 2021/165195) (5.00 g, 15.40 mmol) in ammonia (7M in methanol) (39.60 mL, 277.1 mmol) was heated at 100 °C for 1h in a sealed vessel. The reaction mixture was concentrated, the crude adsorbed on celite and purified by reverse phase column chromatography using H2O and ACN as eluent to afford tert-butyl N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)- 1,2,4-triazol-3-yl]ethyl]carbamate (1.9 g) as a white solid. LCMS (method 3): retention time 0.98 min, m/z 306 [M+H]+. [0526] 1H NMR (DMSO-d6) δ: 8.38 (s, 1H), 8.10 (s, 1H), 7.47 (br d, 1H), 7.33 (br s, 2H), 6.84 (s, 1H), 5.72 (quint, 1H), 1.40 ( d, 3H), 1.33 (s, 9H). 82949 FF 121 [0527] Similarly, tert-butyl N-[(1S)-1-[2-[6-(methylamino)pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]carbamate (I-4) can be obtained following above protocol in analogy when replacing ammonia with methylamine. LCMS (method 3): retention time 1.00 min, m/z 320 [M+H]+. Step 2: Preparation of methyl N-[6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (I-2)
Figure imgf000122_0001
[0528] To a mixture of tert-butyl N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (I-1) (1.90 g, 6.22 mmol) and potassium carbonate (2.58 g, 18.67 mmol) in acetonitrile (28.5 mL) was added methyl chloroformate (1.18 g, 0.96 mL, 12.44 mmol) at room temperature. The reaction mixture was stirred at room temperature for 1 h, diluted with water, and the precipitated solid was filtered, washed with water and dried to afford crude methyl-N-[6-[5-[(1S)-1-(tert- butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]pyrimidin-4-yl]carbamate (1.60 g) as a white solid. This material was used as such in the next step. LCMS (method 3): retention time 1.03 min, m/z 308 [M+H- tBu]+ and 264 [M+H-Boc]+. [0529] 1H NMR (DMSO-d6) δ: 11.15 (s, 1H), 8.83 (s, 1H), 8.35 (s, 1H), 8.21 (s, 1H), 7.55 (br d, 1H), 5.75 (quint, 1H), 3.75 (s, 3H), 1.43 (d, 3H), 1.33 (s, 9H). [0530] Similarly, methyl N-[6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]pyrimidin- 4-yl]-N-methyl-carbamate (I-5) can be obtained from intermediate (I-4) following above protocol in analogy. LCMS (method 3): retention time 0.99 min, m/z 378 [M+H]+. Step 3: Preparation of [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-3)
Figure imgf000122_0002
[0531] To a suspension of methyl N-[6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1- yl]pyrimidin-4-yl]carbamate (I-2) (1.60 g, 4.40 mmol) in CPME (32 mL) was added hydrochloric acid (4M in dioxane) (2.02 mL, 66 mmol) at room temperature. The reaction mixture was stirred at room 82949 FF 122 temperature for 20 h. The precipitated solid was filtered, washed with CPME and dried in vacuo to afford [(1S)-1-[2-[6-(methoxycarbonylamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]ammonium chloride (1.30 g) as a light yellow solid. LCMS (method 3): retention time 0.19 min, m/z 264 [M+H]+ of the corresponding free base. [0532] 1H NMR (DMSO-d6) δ: 11.22 (s, 1H), 8.91 (br s, 3H), 8.87 (s, 1H), 8.43 (s, 1H), 8.39 (s, 1H), 5.41-5.52 (m, 1H), 3.76 (s, 3H), 1.65 (d, 3H). [0533] Similarly, [(1S)-1-[2-[6-[methoxycarbonyl(methyl)amino]pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]ammonium 2,2,2-trifluoroacetate (I-6) can be obtained from intermediate (I-5) in analogy by treatment with trifluoroacetic acid under conditions known to a person skilled in the art. LCMS (method 3): retention time 0.18 min, m/z 278 [M+H]+ of the corresponding free base. Example PI-2: Preparation of N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (trifluoromethyl)quinazolin-4-amine (I-9)
Figure imgf000123_0001
(I-9) Step 1: Preparation of [(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I- 7)
Figure imgf000123_0002
[0534] To a solution of tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3- yl]ethyl]carbamate (CAS 2694010-23-4, prepared as described for example in WO 2021/165195) (20.0 g, 61.58 mmol) in 1,4-dioxane (200 mL) was added a hydrochloric acid solution (4M in dioxane) (77.0 mL, 308 mmol) at room temperature. The reaction mixture was stirred at room temperature for 25 hours, the formed precipitate isolated by filtration, and the solid dried in vacuo to afford [(1S)-1-[2-(6- chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]ammonium chloride (I-7) as a white solid. LCMS (method 3): retention time 0.20 min, m/z 225/227 [M+H]+ of the corresponding free base. [0535] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.14 (d, 1H), 8.88 (br s, 3H), 8.51 (s, 1H), 8.14 (d, 1H), 5.46 (br m, 1 H), 1.65 (d, 3H). 82949 FF 123 Step 2: Preparation of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine (I-8)
Figure imgf000124_0001
(I-8) [0536] To a mixture of 4,6-dichloro-8-(trifluoromethyl)quinazoline (prepared as described in WO 2021/083936) (9.0 g, 33.70 mmol) and [(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3- yl]ethyl]ammonium chloride (I-7) (9.24 g, 35.39 mmol) in tetrahydrofuran (90 mL) was added triethylamine (10.34 g, 14.2 mL, 101.11 mmol) at room temperature. The reaction mixture was stirred at 70°C for 1 hour, then diluted with water (1000 mL), the formed precipitate isolated by filtration, the solid washed with water and dried in vacuo to afford 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4- triazol-3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-8) as a pale yellowish solid. LCMS (method 3): retention time 1.33 min, m/z 455/457 [M+H]+. [0537] 1H NMR (400 MHz, CDCl3) δ ppm 9.08 (s, 1H), 8.54 (s, 2H), 8.19 (s, 2H), 7.96 (d, 1H), 7.77 (s, 1H), 6.66 (quint, 1H), 1.87 (d, 3H). Step 3: Preparation of N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-8- (trifluoromethyl)quinazolin-4-amine (I-9)
Figure imgf000124_0002
(I-9) [0538] A pressure vessel was charged with 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4- triazol-3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-8) (2 g, 4.39 mmol) and 1,4-dioxane (20 mL). The vessel was filled with ammonia gas under stirring to a pressure of 4 bar. The mixture was heated at 120°C for 3 h. After cooling the reaction mixture was diluted with water, the precipitated solid filtered, washed with water and dried in vacuo to afford N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3- yl]ethyl]-6-chloro-8-(trifluoromethyl)quinazolin-4-amine (1.4 g) as a white solid. LCMS (method 3): retention time 1.09 min, m/z 436/438 [M+H]+. [0539] 1H NMR (DMSO-d6) δ: 9.09 (br d, 1H), 8.96 (s, 1H), 8.41 (s, 1H), 8.38 (s, 1H), 8.20 (s, 1H), 8.08 (s, 1H), 7.36 (br s, 2H), 6.89 (s, 1H), 6.47 (quint, 1H), 1.71 (d, 3H). 82949 FF 124 [0540] Similarly, 6-chloro-N-[(1S)-1-[2-[6-(methylamino)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine (I-10) can be obtained from intermediate (I-8) with above protocol when replacing ammonia with methylamine. LCMS (method 3): retention time 1.12 min, m/z 450/452 [M+H]+. [0541] Similarly, N-[(1S)-1-[2-(6-aminopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-6-chloro-N-methyl-8- (trifluoromethyl)quinazolin-4-amine (I-12) can be obtained from intermediate (I-11) with above protocol. LCMS (method 3): retention time 1.24 min, m/z 450/452 [M+H]+. [0542] Similarly, 6-chloro-N-methyl-N-[(1S)-1-[2-[6-(methylamino)pyrimidin-4-yl]-1,2,4-triazol-3- yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine (I-13) can be obtained from intermediate (I-11) with above protocol when replacing ammonia with methylamine. LCMS (method 3): retention time 1.15 min, m/z 464/466 [M+H]+. Example PI-3: Preparation of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-N- methyl-8-(trifluoromethyl)quinazolin-4-amine(I-11)
Figure imgf000125_0001
(I-11) [0543] To a solution of 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine (I-8) (4 g, 8.79 mmol) in acetonitrile (40 mL) were added iodomethane (5.50 mL, 87.87 mmol) and cesium carbonate (5.73 g, 17.57 mmol) at room temperature. The reaction mixture was stirred at 80°C for 6 h. The mixture was cooled to room temperature, diluted with water and the product extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by combiflash using ethyl acetate and cyclohexane as eluent to afford 6-chloro-N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4- triazol-3-yl]ethyl]-N-methyl-8-(trifluoromethyl)quinazolin-4-amine (1.7 g) as a pale yellow solid. LCMS (method 3): retention time 1.26 min, m/z 469/471 [M+H]+. [0544] 1H NMR (CDCl3) δ: 8.49-8.55 (m, 2H), 8.01-8.07 (m, 4H), 6.88 (Q, 1H), 3.50 (s, 3H), 1.94 (d,3H). Example PI-4: Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]thiazol-5-amine (I-19) 82949 FF 125
Figure imgf000126_0001
(I-19) Step 1: Preparation of 6-chloro-N-[(1S)-1-[2-(5-nitrothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine
Figure imgf000126_0002
[0545] To a solution of (NE,2S)-2-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]-N- (dimethylaminomethylene)propanamide (2.2 g, 5.6 mmol) (prepared in analogy to descriptions found in WO 2021/083936) and (5-nitrothiazol-2-yl)hydrazine (CAS 26245-59-0) (6.2 mmol) in 2-methyl- tetrahydrofuran (14mL) were added 4Å molecular sieves (0.2 g) and acetic acid (14 mL). The reaction mixture was heated at 80°C for 2 h, then concentrated in vacuo. The residue was purified by combiflash using a neutral alumina column (ethyl acetate in cyclohexane) to afford 6-chloro-N-[(1S)-1-[2-(5- nitrothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]-8-(trifluoromethyl)quinazolin-4-amine as a solid. LCMS (method 3): retention time 1.19 min, m/z 471 [M+H]+. [0546] 1H NMR (400 MHz, CDCl3) δ ppm 8.68 (s, 1H), 8.52 (s, 1H), 8.02-8.08 (m, 2H), 8.00 (s, 1H), 7.48 (br s, 1H), 6.56 (m, 1H), 1.84 (br d, 3H). Step 2: Preparation of 2-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]-1,2,4- triazol-1-yl]thiazol-5-amine (I-19)
Figure imgf000126_0003
[0547] To a solution of 6-chloro-N-[(1S)-1-[2-(5-nitrothiazol-2-yl)-1,2,4-triazol-3-yl]ethyl]-8- (trifluoromethyl)quinazolin-4-amine (700 mg, 1.41 mmol) in methanol (14 mL) was added palladium on charcoal (Pd/C, 75 mg, 10% Pd). The reaction mixture was degassed under vacuum and backfilled with nitrogen three times, then stirred under a 10 bar molecular hydrogen pressure for 3 hours. The pressure 82949 FF 126 was carefully released and the vessel flushed with nitrogen. The mixture was filtered through a celite bed and the filtrate concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate in cyclohexane) to afford 2-[5-[(1S)-1-[[6-chloro-8-(trifluoromethyl)quinazolin-4-yl]amino]ethyl]- 1,2,4-triazol-1-yl]thiazol-5-amine (I-19). LCMS (method 3): retention time 1.08 min, m/z 441/443 [M+H]+. [0548] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.09 (d, 1H), 8.98 (d, 1H), 8.43 (s, 1H), 8.24 (d, 1H), 8.02 (s, 1H), 6.65 (s, 1H), 6.11 (quint, 1H), 5.95 (br s, 2H), 1.69 (d, 3H). Example PI-5: Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium 2,2,2- trifluoroacetate (I-28)
Figure imgf000127_0001
(I-28) Step 1: Preparation of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-27)
Figure imgf000127_0002
(I-27) [0549] To a solution of tert-butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (1.8 g, 9.56 mmol) in 2-methyltetrahydrofuran (29 mL) was added N,N-dimethylformamide dimethyl acetal (14.35 mmol) at room temperature. The resulting reaction mixture was stirred at 40°C for 1.5 hour, then concentrated in vacuo to get the crude intermediate tert-butyl N-[(1S)-2-[(E)-dimethylamino-methyleneamino]-1-methyl- 2-oxo-ethyl]carbamate. [0550] 1,4-Dioxane (9.6 mL), acetic acid (9.6 mL) and 2-bromo-5-hydrazinylpyrazine (CAS 1001050- 24-3) (1.6 g, 95%, 8.04 mmol) were added to this intermediate and the mixture was stirred at 80°C for 2 hours, then cooled to room temperature and poured over water and EtOAc. The phases were separated, the aqueous layer extracted with EtOAc, the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by combiflash (ethyl acetate in cyclohexane) to afford tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)- 1,2,4-triazol-3-yl]ethyl]carbamate (I-27) as a gum. LCMS (method 1): retention time 0.95 min, m/z 369/371 [M+H]+. Step 2: Preparation of [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium 2,2,2- trifluoroacetate (I-28) 82949 FF 127
Figure imgf000128_0001
(I-28) [0551] To a solution of tert-butyl N-[(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (I-27) (2.0 g, 5.42 mmol) in trifluoromethylbenzene (40 mL) was added 2,2,2-trifluoroacetic acid (10 mL) at RT dropwise. The reaction mixture was stirred at room temperature for 2.5 h, then concentrated in vacuo. TBME was added to the thick oily residue, the mixture stirred at RT and the formed solid filtered, then dried in vacuo to afford [(1S)-1-[2-(5-bromopyrazin-2-yl)-1,2,4-triazol-3-yl]ethyl]ammonium 2,2,2- trifluoroacetate (I-28) as an off-white solid. LCMS (method 3): retention time 0.29 min, m/z 269/271 [M+H]+ of the corresponding free base. [0552] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.08 (s, 1H), 8.93 (s, 1H), 8.61 (br s, 3H), 8.50 (s, 1H), 5.27 (br q, 1H), 1.60 (d, 3H). [0553] Abbreviations used in synthesis schemes and preparatory examples ACN acetonitrile CPME cyclopentyl methyl ether (or methoxy cyclopentane) BINAP [1-(2-diphenylphosphanyl-1-naphthyl)-2-naphthyl]-diphenyl-phosphane Boc t-butoxycarbonyl DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCM dichloromethane DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DMA N,N-dimethylacetamide DMF N,N-dimethylformamide DMF-DMA N,N-dimethylformamide dimethyl acetal DMSO dimethyl sulfoxide DMSO-d6 deuterated dimethylsulfoxide DPEN diphenylethylenediamine Et3N triethylamine EtOAc ethyl acetate HCl hydrochloric acid Ms methanesulfonyl (mesyl) nBu, tBu n-butyl, t-butyl NaOH sodium hydroxide NPhth phthalimide-1-yl OMs mesylate group OTf triflate group 82949 FF 128 OTs tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride TBME tert-butyl methyl ether TEA triethylamine TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl Tf trifluoromethanesulfonyl (triflyl) TFA trifluoroacetic acid THF tetrahydrofuran Ts p-toluenesulfonyl (tosyl) XantPhos Pd G3 [(4,5-bis(diphenylphosphino)-9,9-dimethylxanthene)-2-(2′-amino-1,1′- biphenyl)]palladium(II) methanesulfonate XPhos 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl aq. aqueous °C degrees Celsius equiv. equivalent h hour(s) LC/MS or LCMS liquid chromatography mass spectrometry M molar MHz megahertz min minutes mp or M.P. melting point NMR nuclear magnetic resonance ppm parts per million RT room temperature Rt retention time Table P: Compounds of Formula (I) [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000129_0001
82949 FF 129 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000130_0001
Figure imgf000130_0002
Figure imgf000130_0003
Figure imgf000130_0004
Figure imgf000130_0005
Figure imgf000130_0006
82949 FF 130 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000131_0001
Figure imgf000131_0002
Figure imgf000131_0003
Figure imgf000131_0004
3
Figure imgf000131_0005
82949 FF 131 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed) 3
Figure imgf000132_0001
Figure imgf000132_0002
Figure imgf000132_0003
3
Figure imgf000132_0004
82949 FF 132 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000133_0001
Figure imgf000133_0002
Figure imgf000133_0003
Table Q: Intermediate compounds [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000133_0004
82949 FF 133 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed) 3
Figure imgf000134_0001
Figure imgf000134_0002
Figure imgf000134_0003
3
Figure imgf000134_0004
82949 FF 134 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000135_0001
Figure imgf000135_0002
3
Figure imgf000135_0003
Figure imgf000135_0004
Figure imgf000135_0005
82949 FF 135 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000136_0001
Figure imgf000136_0002
Figure imgf000136_0003
Figure imgf000136_0004
Figure imgf000136_0005
82949 FF 136 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000137_0001
Figure imgf000137_0002
Figure imgf000137_0003
Figure imgf000137_0004
82949 FF 137 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed)
Figure imgf000138_0003
Figure imgf000138_0004
tert-butyl N-[(1S)-1-[2-(5- I-27 bromopyrazin-2-yl)-1,2,4- 0.95 369/371 1 triazol-3-yl]ethyl]carbamate
Figure imgf000138_0001
[(1S)-1-[2-(5-bromopyrazin-2- 269/271 yl)-1,2,4-triazol-3- of the I-28 0.29 3 yl]ethyl]ammonium 2,2,2- free trifluoroacetate base
Figure imgf000138_0002
Figure imgf000138_0005
82949 FF 138 [M+H]+ Rt Metho Entry IUPAC name Structure (measur (min) d ed) 225/227 [(1S)-1-[2-(5-chloropyrazin-2- of the I-30 yl)-1,2,4-triazol-3- 0.21 3 free yl]ethyl]ammonium chloride base
Figure imgf000139_0001
Biological Examples [0554] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm. Example B1: Activity against Chilo suppressalis (Striped rice stemborer) [0555] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0556] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P13, P14, P16, P17, P18, P19. Example B2: Activity against Diabrotica balteata (Corn root worm) [0557] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation. [0558] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P13, P14, P17, P19. Example B3: Activity against Euschistus heros (Neotropical Brown Stink Bug) [0559] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10’000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. 82949 FF 139 The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. [0560] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P8, P13. Example B4: Activity against Myzus persicae (Green peach aphid). Intrinsic activity [0561] Test compounds prepared from 10’000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation. [0562] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: P1, P10. Example B5: Activity against Plutella xylostella (Diamond back moth) [0563] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10’000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation. [0564] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P8, P10, P11, P13, P14, P16, P17, P18, P19. Example B6: Activity against Spodoptera littoralis (Egyptian cotton leaf worm) [0565] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. [0566] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P13, P14, P16, P17, P18, P19. Example B7: Activity against Frankliniella occidentalis (Western flower thrips). Feeding/Contact activity [0567] Bean leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 4 days after infestation. [0568] The following compounds resulted in at least 80% growth inhibition at an application rate of 200 ppm: P13.

Claims

82949 FF 140 CLAIMS 1. A compound of the formula (I)
Figure imgf000141_0001
wherein: A1, A2, and A3 are, independently from each other, N or C-RY; A4 and A5 are, independently from each other, N or C-RY;
Figure imgf000141_0002
, where the staggered line represents the connection of Q to the rest of compound of the formula (I); R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a and R2b are independently hydrogen, halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1- C3haloalkoxy, C3-C6cycloalkylcarbonyl, C1-C3cyanoalkyl, C1-C3cyanoalkoxy, OR6, NO2, SF5, CN, C(O)NH2, C(O)OH, C(S)NH2, C3-C6cycloalkyl, phenyl, heteroaryl, piperidin-2-one-1-yl, pyridin-2-one-1- yl, azetidin-1-yl, pyrrolidin-1-yl, C3-C6cycloalkylC1-C4alkyl, C3-C6cycloalkylC1-C3alkoxy, C1- C4alkylsulfanyl, C1-C4alkylsulfonyl, or C1-C4alkylsulfinyl; each of said C3-C6cycloalkyl, C3-C6cycloalkylcarbonyl, phenyl, heteroaryl, C1-C4alkylsulfanyl, C1-C4alkylsulfonyl, and C1-C4alkylsulfinyl being optionally substituted with one, two or three independently selected RX substituents; each of said piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl, pyrrolidin-1-yl, and C3- C6cycloalkylC1-C3alkoxy being optionally substituted with one or two independently selected RX substituents; said C3-C6cycloalkylC1-C4alkyl being optionally substituted with one or two independently selected RZ substituents; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidinyl, pyrazinyl, or thiazolyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; R4a is pyridinyl, pyrimidinyl, pyrazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is substituted with a single -N(R11)C(O)OR10; 82949 FF 141 R5, R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3- C4cycloalkyl; R6 is phenyl, benzyl, heteroaryl, or C3-C6cycloalkyl, each of which is optionally substituted with one, two or three independently selected RX substituents; R10 is C1-C4alkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxy-C1- C3alkyl, or C1-C4haloalkyl; R11 is hydrogen, C1-C3alkyl, C1-C3cyanoalkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1- C3alkoxy-C1-C3alkyl, C1-C3haloalkyl, hydroxy, or C1-C3alkoxy; or R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3- oxazolidinyl or 2,4-dioxo-3-oxazolidinyl, each of which, independently of each other, is substituted with one or two C1-C3alkyl; RX is halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1- C4haloalkylsulfanyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, NO2, SF5, CN, C(O)NH2, or C(S)NH2; RY is hydrogen, C1-C3alkyl, C1-C3haloalkyl, hydroxy, C1-C3alkoxy, C1-C3haloalkoxy, halogen, CN, or cyclopropyl; RZ is oxo, halogen, C1-C3 alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, or CN; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula (I). 2. The compound according to claim 1, wherein Q is Qa and R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, or 2-methoxyethoxy; preferably R5 is hydrogen. 3. The compound according to claim 1 or 2, wherein R4 is R4-1, R4-2, R4-3, R4-4, or R4 -5:
Figure imgf000142_0001
preferably R4 is R4-3, R4-4 or R4-5; more preferably R4 is R4-3 or R4-5; where the staggered line represents the connection of R4 to Qa. 4. The compound according to claim 1, wherein Q is Qb; R4a is R4a-1, R4a-2, R4a-3, R4a-4, R4a-5, R4a-6, or R4a-7: 82949 FF 142
Figure imgf000143_0001
preferably R4a is R4a-3; where the staggered line represents the connection of R4a to Qb; and wherein one of R5a and R5b is hydrogen, and the other is hydrogen, fluoro, chloro, methyl, or methoxy; preferably both R5a and R5b are hydrogen. 5. The compound according to any one of claims 1 to 4, wherein R10 is methyl, ethyl, isopropyl, tert-butyl or cyclopropyl; and R11 is hydrogen, methyl, or methoxy. 6. The compound according to any one of claims 1 to 4, wherein R10 and R11 form, together with the fragment -NC(O)O- to which they are attached, a 2-oxo-3-oxazolidinyl or 2,4-dioxo-3-oxazolidinyl, each of which, independently of each other, is substituted with one or two C1-C3alkyl. 7. The compound according to any one of claims 1 to 6, wherein A1 is N, A2 is CH, A3 is N, A4 is CH, and A5 is CH. 8. The compound according to any one of claims 1 to 7, wherein R2a is trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; and R2b is trifluoromethyl, chloro, bromo, iodo, or trifluoromethylsulfonyl; preferably where R2a is chloro, and R2b is trifluoromethyl, or iodo. 9. The compound according to any one of claims 1 to 8, wherein R3 is methyl. 10. The compound according to any one of claims 1 to 9, wherein R1 is hydrogen, methyl, or cyclopropylmethyl; preferably R1 is hydrogen or methyl. 11. A composition comprising a compound as defined in any one of claims 1 to 10, one or more auxiliaries and diluent, and optionally one or more other active ingredient. 82949 FF 143 12. A method (i) of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in any one of claims 1 to 10, or of a composition as defined in claim 11; or (ii) for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the plant propagation material or the site where the propagation material is planted, with an effective amount of a compound as defined in any one of claims 1 to 10, or of a composition as defined in claim 11; or (iii) of controlling parasites in or on an animal in need thereof, comprising administering an effective amount of a compound as defined in any one of claims 1 to 10, or of a composition as defined in claim 11. 13. A plant propagation material, such as a seed, comprising, or coated with, or treated with, or adhered thereto, a compound as defined in any one of claims 1 to 10, or a composition as defined in claim 11. 14. A compound of the formula XL-1, XL-1-13, XL-6, or XL-6-13:
Figure imgf000144_0001
XL-6 XL-6-13 82949 FF 144 wherein A1, A2, A3, A4, A5, R1, R2a, R2b, R3, and R11 are as defined in claims 1, 5, 7, 8, 9 and 10. 15. A compound of the formula XLI-1, XLI-2, or XLI-3:
Figure imgf000145_0001
wherein R1, R3, R10 and R11 are as defined are as defined in claims 1, 5, 9 and 10; and X- is an anion, such as Cl- or CF3COO-.
Figure imgf000145_0002
wherein A1, A2, A3, A4, A5, R2a, R2b, R3 and R5 are as defined in claims 1, 2, 4, 7, 8, and 9; and R20 and R21 are independently of each other C1-C4alkyl, or R20 and R21 together with the nitrogen to which they are bound to, form a pyrrolidine, piperidine or morpholine radical.
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