WO2024068947A1 - Microbiocidal pyrazole derivatives - Google Patents

Microbiocidal pyrazole derivatives Download PDF

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Publication number
WO2024068947A1
WO2024068947A1 PCT/EP2023/077096 EP2023077096W WO2024068947A1 WO 2024068947 A1 WO2024068947 A1 WO 2024068947A1 EP 2023077096 W EP2023077096 W EP 2023077096W WO 2024068947 A1 WO2024068947 A1 WO 2024068947A1
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formula
methyl
compound
compounds
phenyl
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PCT/EP2023/077096
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French (fr)
Inventor
Andrew Edmunds
Christopher Charles SCARBOROUGH
Atul Mahajan
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Syngenta Crop Protection Ag
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Publication of WO2024068947A1 publication Critical patent/WO2024068947A1/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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • A01P3/00—Fungicides

Definitions

  • the present invention relates to microbiocidal pyrazole derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to preparation of these pyrazole derivatives, to intermediates useful in the preparation of these pyrazole derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to the use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.
  • R1 is selected from hydrogen, C1-C4 alkyl, C2-C4alkenyl, C2-C4 alkynyl, or C3-C6cycloalkyl
  • R 2 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4haloalkyl, C3- C6cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl- carbonimidoyl, or C1-C4 alkoxycarbonyl;
  • R 3 is selected from hydrogen, halogen, or C1-C4 alkyl;
  • R 4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the invention.
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
  • a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms wherein a fungicidally effective amount of a compound of 82714_FF 3 formula (I) according to the invention, or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof.
  • a compound of formula (I) according to the invention as a fungicide.
  • the use may exclude methods for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • 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- C4 alkane- or arylsulfonic acids which are unsubstituted or substituted
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • 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 ethyl-, die
  • 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.
  • substituents are indicated as being “optionally substituted”, this means that they may or may not carry one or more identical or different substituents, e.g., one, two or three R x substituents.
  • C1-C6alkyl substituted by 1, 2 or 3 halogens may include, but not be limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, - CF3, -CH2CF3 or -CF2CH3 groups.
  • C1-C6alkoxy substituted by 1, 2 or 3 halogens may include, but not be limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.
  • optionally substituted means that the referred group is unsubstituted or substituted.
  • halogen or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.
  • amino means a -NH2 group.
  • cyano means a -CN group.
  • hydroxyl or “hydroxy” means an -OH group.
  • carboxylic acid means a -COOH group.
  • C1-Cn-alkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n- pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,
  • C2-Cn-alkenyl refers to a straight or branched alkenyl chain moiety having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-l -enyl, but-2-enyl.
  • C2-Cn-alkynyl refers to a straight or branched alkynyl chain moiety having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl
  • C3-Cn-cycloalkyl refers to three (3) to n membered cycloalkyl radical such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C1-Cn-alkoxy refers to a straight-chain or branched saturated alkyl radical having one (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 and 1,1-dimethylethoxy.
  • C2-Cn-alkenyloxy refers to a straight-chain or branched alkenyl chain having two (2) to n carbon atoms (as mentioned above) which is attached via an oxygen atom.
  • C1-Cn-haloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2-chloro-2
  • C1-C2fluoroalkyl would refer to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.
  • C2-Cn-haloalkenyl or “C2-Cn-haloalkynyl” as used herein refers to a C2-Cn-alkenyl or C2-Cn-alkynyl radical respectively substituted with one or more halogen atoms which may be the same or different.
  • C 3 -C n -halocycloalkyl or “C 1 -C n -haloalkoxy” as used herein refers to a C 3 -C n -cycloalkyl radical or C 1 -C n - alkoxyl radical respectively substituted with one or more halo atoms which may be the same or different.
  • C1-Cn-alkylthio“ or “C1-Cn-alkylsulfanyl“ refers to a C1-Cn-alkyl group linked through a sulfur atom.
  • C1-Cn-alkoxycarbonyl-C1-C6-alkyl refers to a C1-Cn-alkyl radical substituted by a “C1- Cn-alkoxycarbonyl group.
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S.
  • heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.
  • heteroaryl-C1-Cn-alkyl or “heteroaryl- C3-Cn-cycloalkyl” refers to an C1-Cn-alkyl or C3-Cn-cycloalkyl radical respectively substituted by a heteroaryl group.
  • the heteroaryl-C1-Cn-alkyl or heteroaryl-C3-Cn-cycloalkyl radical may be substituted on heteroaryl, alkyl and/or cycloalkyl group as appropriate.
  • controlling refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
  • the 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.
  • 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, using known techniques and by observing results obtained under analogous circumstances.
  • room temperature or “RT” or “rt” refer to a temperature of about 15° C to about 35° C.
  • rt can refer to a temperature of about 20° C to about 30° C.
  • R1 is selected from C1-C4 alkyl.
  • R1 is methyl, ethyl or isopropyl.
  • R 1 is methyl.
  • R 2 is selected from hydrogen, halogen, C1-C6 alkyl, C3-C6cycloalkyl, C1-C2 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C2 alkyl-carbonimidoyl, or N-hydroxy-C-C1-C2 alkyl-carbonimidoyl.
  • R 3 is selected from hydrogen, halogen, or C1-C2 alky.
  • R 3 is hydrogen, fluorine, chlorine, or methyl. More preferably R 3 is hydrogen or methyl. Even more preferably R 3 is hydrogen.
  • R 4 is hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4-alkylcarbonyl, or C1-C4- alkoxycarbonyl.
  • R 4 is hydrogen, chlorine, fluorine, C1-C3-alkyl, cyano, or CO2Me. More preferably R 4 is hydrogen, methyl, ethyl, isopropyl, or cyano.
  • R 4 is hydrogen or methyl. In one embodiment R 4 is hydrogen. In another embodiment R 4 is methyl. 82714_FF 7
  • R 5 and R 6 are independently selected from hydrogen or C1-C2-alkyl. Preferably R 5 and R 6 are independently selected from hydrogen or methyl. More preferably R 5 and R 6 are hydrogen.
  • Q is selected from Q1, Q2, Q3 or Q4: Preferably, Q is selected from Q1, Q2, or Q3: More preferably, Q is Q1: wherein R 10 , R 11 , R 12 and R 13 are as defined above.
  • R 12 and R 13 are independently selected from hydrogen, halogen, cyano, C1- C4 alkyl, or C1-C4 alkoxy.
  • R 12 and R 13 are independently selected from hydrogen, chlorine, bromine, fluorine, or methyl. More preferably R 12 and R 13 are hydrogen.
  • R 10 and R 11 are independently selected from hydrogen, halogen, hydroxy, cyano, amino, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4alkenyloxy, C2-C4 alkynyloxy, 82714_FF 8 C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-4alkylamino, N,N-diC1- 4alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy- C 1 -C 4 alkyl-carbonimid
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3alkenyloxy, C2-C3 alkynyloxy, C1- C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1- C 2 alkylcarbonyl, N-C 1 -C 2 alkoxy-C-C 1 -C 2 alkyl-carbonimidoyl, N-hydroxy-C 1 -C 2 alkyl- carbonimidoyl, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylaminocarbonyl
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1- C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3alkenyloxy, C2-C3 alkynyloxy, C1- C 2 alkylsulfanyl, C 1 -C 2 alkylsulfnyl, C 1 -C 2 alkylsulfonyl, C 1 -C 2 alkoxy-C 1 -C 2 alkyl, C 1 -C 3 alkoxycarbonyl, C 1 - C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, N-hydroxy-C1-C2 alkyl-carbonimidoyl, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkyl, di
  • R 10 and R 11 are independently selected from hydrogen, chloro, fluoro, bromo, methoxy, cyano, amino, carboxy, 2-cyanophenyl, 3-cyanophenyl, 4- cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3- chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1- yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1- cyanocyclopropyl.
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein said 5- or 6- membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6- membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl.
  • R 10 and R 11 are independently selected from hydrogen, chloro, bromo, methoxy, cyano, amino, 2-cyanophenyl, 3-cyanophenyl, 4- cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1-cyanocyclopropyl. Even more preferably R 10 and R 11 are independently selected from hydrogen, chloro, bromo, cyano, or amino.
  • Q is selected from Q1, Q2, Q3, or Q4:
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R 12 and R 13 are hydrogen.
  • Q is selected from Q1, Q2, Q3, or Q4; wherein R 10 and R 11 are independently selected from hydrogen, halogen, cyano, or amino; and R 12 and R 13 are hydrogen.
  • Q is selected from Q1, Q2, or Q3: R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R 12 and R 13 are hydrogen.
  • Q is selected from Q1, Q2, or Q3; wherein R 10 and R 11 are independently selected from hydrogen, halogen, cyano, or amino; and R12 and R13 are hydrogen. More preferably Q is Q1 R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R 12 and R 13 are hydrogen.
  • Q is Q1; wherein R 10 and R 11 are independently selected from hydrogen, halogen, cyano, or amino; and R 12 and R 13 are hydrogen.
  • a 1 is selected from CR 7 or N;
  • a 2 is selected from CR 8 or N;
  • a 3 is selected from CR 9 or N; wherein at least two of A 1 , A 2 and A 3 are selected from N.
  • a 1 is selected from CR 7 ; and
  • a 2 and A 3 are N.
  • a 1 and A 2 are N; and A 3 is selected from CR 9 .
  • a 1 is N;
  • a 2 is CR 8 , and A 3 is N.
  • a 1 , A 2 , and A 3 are N. In another embodiment of the invention A 1 and A 2 are N, and A 3 is CR 9 . In still another embodiment of the invention A 1 is CR 7 ; A 2 is CR 8 , and A 3 is N. In still another embodiment of the invention A 1 is N; A 2 is CR 8 , and A 3 is CR 9 . In still another embodiment of the invention A 1 is CR 7 ; A 2 is N; and A 3 is CR 9 In an embodiment of the invention R 7 , R 8 , and R 9 are independently selected from hydrogen, C1-C4 alkyl, C2- C4 alkenyl, C1-C4 haloalkyl, or C2-C4 alkynyl.
  • R 7 , R 8 , and R 9 are independently selected from hydrogen, halogen, methyl, ortrifluoromethyl. More preferably R 7 , R 8 , and R 9 are hydrogen.
  • Z 1 is selected from C1-C4 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C 3 -C 6 -cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S, and wherein any of said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C2-C4-alkynyl, C1-C4 alkylsulfanyl, C1-C4 al
  • Z 1 is selected from C1-C3 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6- cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1, 2 or 3 heteroatoms individually selected from N, O or S, and wherein any of said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.
  • Z 1 is selected from C1-C3 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6- cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, O or S, and wherein any of said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.
  • Z 1 is selected from 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro- 2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4- fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5- fluoro-2-thienyl, 2-
  • Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2- chlorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3- 82714_FF 12 fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, or phenyl.
  • Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6- trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4- difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl.
  • Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.
  • Z 1 is selected from C1-C4 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6-cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1, 2 or 3 heteroatoms individually selected from N, O or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C 1 -C 4 haloalkoxy, or C 1 -C 4 alkoxy, and wherein said C 3 -C 6 -cycloalkyl is unsubstituted or substitute
  • Z 1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and -5 to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4alkyl, or C1-C4alkoxy.
  • Z 1 is selected from 1- methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro- 2-pyridyl, 2-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2- thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2- methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or methyl.
  • Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 3,5-difluoro-2- furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2- fluorophenyl, 4-fluorophenyl, or phenyl.
  • Z 1 is selected from phenyl, a 5- to 6- membered heteroaryl, or C3-C6- cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl.
  • Z 1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6- membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy.
  • the present invention accordingly, makes available a compound of formula (I) having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , A 1 , A 2 , A 3 , Q (Q-1, Q2, Q3, Q4, and Q5) and Z 1 with reference to formula (I) as defined above in all combinations / each permutation.
  • Embodiments according to the invention are provided as set out below.
  • R 1 is selected from hydrogen, C1-C6 alkyl, C2-C6alkenyl, C2-C6 alkynyl, or C3-C6cycloalkyl
  • R 2 is selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3- C6cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl- carbonimidoyl, or C 1 -C 6 alkoxycarbonyl;
  • R 3 is selected from hydrogen, halogen or C1-C4 alkyl;
  • R 4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-
  • the compound of formula (I) may be a compound of formula (Ia): Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention, and A is selected from the group consisting of: and R 7 , R 8 and C4 haloalkyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention,
  • A is selected from A1, A2, A3, A4, A5, A6, A7, or A9, and
  • R 7 , R 8 and R 9 are hydrogen, halogen, methyl, or trifluoromethyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4, and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A9, and R 7 , R 8 and R 9 are hydrogen.
  • R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention, A is selected from arrow the bond to the Z 1 group, and R 7 is C1-C4 haloalkyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4, and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention,
  • A is selected from A1, A2, or A3, and
  • R 7 is hydrogen, halogen, methyl, or trifluoromethyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4, and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3, and R 7 is hydrogen.
  • R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4, and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2. More preferably, in the compound of formula (Ia) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4, and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2.
  • A is selected from A1, or A2; R 7 is hydrogen; and Q is Q1.
  • R 10 , R 11 , R 12 , R 13 ,and Z 1 are as defined for the compounds of formula (I) according to the present invention
  • R 1 is C1-C4-alkyl, 82714_FF 17
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • A is A1, or A2
  • R 7 is hydrogen
  • Q is Q1, Q2 or Q3
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl
  • R 12 and R 13 are independently selected from hydrogen
  • R 1 is C 1 -C 4 -alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • A is A1, or A2
  • R 7 is hydrogen
  • Q is Q1
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano or methyl
  • R 12 and R 13 are selected from hydrogen
  • Z 1 is selected from phenyl
  • the compound of formula (Ia) may be a compound of formula (Ia-A), wherein A is A1: 82714_FF 18 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4, and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q, R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R5 and R6 are independently selected from hydrogen or methyl
  • Q is Q1, Q2, or Q3,
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q is Q1
  • the compound of formula (Ia) may be a compound of formula (Ia-B), wherein A is A2: wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4 and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q, R 10 , R 11 , R 12 , R 13 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C 1 -C 4 -alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q is Q1, Q2, or Q3, 82714_FF 20
  • R 10 and R 11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C 3 -C 6 -cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl
  • R 12 and R 13 are hydrogen
  • Z 1 is selected from phenyl
  • R 1 is C 1 -C 4 -alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q is Q1
  • the compound of formula (Ia) may be a compound of formula (Ia-C), wherein A is A3, and wherein R 7 is hydrogen: wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q, R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for the compounds of formula (II) according to the present invention.
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q is Q1, Q2 or Q3
  • R 1 is C1-C4-alkyl
  • R 2 is hydrogen, fluorine, chlorine, or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Q is Q1
  • the presence of one or more possible asymmetric carbon atoms in any of the compounds of formula (I), (Ia), (Ia-A), (Ia-B) and (Ia-C) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
  • the compound of formula (I) according to the invention is selected from compounds listed in any one of Tables C-1 to C-21 or compounds listed in Table P. More preferably the compound of formula (I) according to the invention is selected from compounds listed in Table P.
  • the compound of formula (I) is selected from N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazoleamide
  • the compound of formula (I) is selected from N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazoleamide
  • an intermediate compound of formula (III) or a salt thereof: R 6 and Q correspond to the same definitions as for the compounds of formula (I) according to the present invention.
  • R 6 and Q correspond to the same definitions as for the compounds of formula (I) according to the present invention.
  • 82714_FF 23 The intermediate compounds of formula (III) possess the same definitions for R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Q as for the compounds of formula (I) according to the invention and their corresponding preferences.
  • an intermediate compound of formula (IIb) or a salt thereof wherein A 1 , A 2 , A 3 and Z 1 are defined as for the compounds of formula (I) according to the present invention.
  • the intermediate compounds of formula (IIb) possess the same definitions for A 1 , A 2 , A 3 and Z 1 as for the compounds of formula (I) according to the invention and their corresponding preferences.
  • the compound of formula (IIb) may be a compound of formula (IIba), wherein R 7 is hydrogen, R 0 is C1-C6 alkyl, A 1 , A 2 , A 3 are N, and Z 1 is as defined for the compounds of formula (I) according to the present invention.
  • asymmetric carbon atoms in a compound of formula (III) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
  • the compounds of formula (I) as defined in any of the embodiments of the present invention can be made as shown in the following Schemes 1 to 15, in which, unless otherwise stated, the definition of each variable is as defined above in any of the embodiments according to the invention.
  • the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
  • compounds of formula (I) may be prepared from compounds of formula (III) or a salt thereof, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , and Q are as defined above for the compound of formula (I) by reaction with a compound of formula (II), wherein A 1 , A 2 , A 3 , and Z 1 are as defined above for the compound of formula (I). This reaction is shown in Scheme 1.
  • compounds of formula (IIa), where G 0 is halogen are formed by treatment of compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic quantities of N,N-dimethylformamide (DMF) in inert solvents such as methylene dichloride (CH2Cl2) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C.
  • DMF N,N-dimethylformamide
  • inert solvents such as methylene dichloride (CH2Cl2) or tetrahydrofuran (THF)
  • compounds of formula (I) may be prepared by treatment of compounds of formula (II) with dicyclohexyl carbodiimide (DCC), 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5- b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (IIa), wherein G 0 is G 01 , G 02 or G 03 as set forth below (Scheme 2), in an inert solvent, e.g.
  • DCC dicyclohexyl carbodiimide
  • EDC 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide
  • HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5- b]pyridinium 3-oxide
  • a compound of formula (II) can also be activated by reaction with a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (IIa), wherein G 0 is G 04 as set forth below, as described for example in Synthesis 2013, 45, 1569. Further reaction with an amine (or a salt thereof) of the compound of formula (III) leads to compounds of formula (I).
  • a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (IIa), wherein G 0 is G 04 as set forth below, as described for example in Synthesis 2013, 45, 1569.
  • Grignard reagents R 5 MgBr or R 6 MgBr, wherein R 5 and R 6 are as defined above for the compound of formula (I) may be added as nucleophiles to compounds of formula (IV), sequentially or simultaneously, to allow more highly substituted amines of formula (III) to be prepared.
  • Such Grignard additions to nitriles are carried out in an inert solvent such as diethyl ether, tert-butylmethyl ether, and cyclopentyl methyl ether in the presence of a Lewis acid such as Ti(O- i Pr)4 (see Synlett 2007, (4), 652-654). This reaction is shown in Scheme 3.
  • compounds of formula (IV), wherein R 1 , R 2 , R 3 , R 4 , R 10 , R 11 , R 12 , R 13 , and Q are as defined above for the compound of formula (I) and R 4 is different from hydrogen may be prepared by a person skilled in the art by deprotonation of compound of formula (IVa), wherein R 4 is hydrogen and R 1 , R 2 , R 3 and Q are as defined above for the compound of formula (I), using a strong base such as n-butyl lithium or sodium hydride at cryogenic temperatures in an inert solvent such as tetrahydrofuran, followed by addition of a suitable alkylating agent R 4 -X 0 , wherein X 0 is halogen, for example iodomethane.
  • Compounds of formula (IVa), wherein R 4 is hydrogen and R 1 , R 2 , R 3 , R 10 , R 11 , R 12 , R 13 , and Q are as defined above for the compound of formula (I), may be prepared from alcohols of formula (V) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a nonpolar solvent such as dichloromethane at temperatures between 0°C and the boiling point of the reaction mixture.
  • TMSCN cyanotrimethylsilane
  • Compounds of formula (V) may be prepared from compounds of formula (VI), respectively from any of compounds of formula (VIa), (VIb), (VIc), (VId) or (VIe), as shown in Scheme 5.
  • 82714_FF 27 As shown in Scheme 5, compounds of formula (VII), wherein R 1 , R 2 ,R 3 , R 10 , R 11 , R 12 , R 13 , are as defined above for the compound of formula (I) and X 01 is bromo or iodo, are metalated with an appropriate reagent such as turbo Grignard (isopropylmagnesium chloride-lithium chloride complex), or an alkyl lithium, such as n-butyl lithium to give an intermediate Grignard or alkyl lithium reagent (M is MgX 01 or Lithium).
  • turbo Grignard isopropylmagnesium chloride-lithium chloride complex
  • an alkyl lithium such as n-butyl lithium to give an intermediate Grignard or alkyl lithium
  • Such metal insertions into C-X01 bonds are well known to those skilled in the art and are generally carried out at temperatures between -78°C to rt, in inert solvents such as ethers, e.g., tert-butyl methyl ether or tetrahydrofuran and the like.
  • Solutions of the metalated species (VIIa) are then treated with compounds of formula (VI), respectively (VIa), (VIb), (VIc), (VId), or (VIe) to give compounds of formula (V). Similar reactions of these type have been described in for example WO 2012/102297 and Bio. Med. Chem. Lett.2017, 27(17), 4044-4050 (X 01 is Br, n-butyl lithium) and Angew. Chem.
  • a further synthesis of compounds of formula (I) involves treatment of compounds of formula (VIII) with a base, such as sodium hydride or n-butyl lithium, in an inert solvent, such as tetrahydrofuran, and subsequent alkylation with compounds of formula (IX), wherein R 4 is as described under formula (I) and X 02 is a leaving group such as halogen, mesylate or tosylate, to yield compounds of formula (X).
  • a base such as sodium hydride or n-butyl lithium
  • an inert solvent such as tetrahydrofuran
  • compounds of formula (IIba), wherein A 1 , A 2 , A 3 are N and Z 1 is as described in for formula (I), can be prepared by reacting a compound of formula (XIX): is phenyl or p-tolyl, with compounds of formula (XVI), in the presence of a base, e.g., pyridine at temperatures from -50°C to 50°C to yield compounds of formula (IIba).
  • a base e.g., pyridine
  • Such reactions have good precedence in the literature, for example Chem. Comm.2017, 53(69), 9620-9623, Angew. Chem. Int. Ed. 2017, 56(47), 15044-15048, and J. Am. Chem. Soc. 2016, 138(44), 14609-14615.
  • sequence begins with diazotation of compounds of formula (XVIII) as previously described vide supra and then treatment of the diazionium salt with a compound of formula (XXII), wherein R 0 is C1-C6alkyl, in the presence of in the presence of a mild base, for example sodium acetate to yield compounds of formula (XXIII).
  • a mild base for example sodium acetate
  • Compounds of formula (XXIII), wherein Z 1 and R 0 are as previously defined are then treated 82714_FF 34 with aqueous ammonia in a miscible organic solvent, for example tetrahydrofuran or 2-methyl tetrahydrofuran, at temperatures between 0°C to 30°C, to give compounds of formula (XXIV).
  • Compounds of formula (IIb) may also be prepared by alkylation of compounds of formula (XX) (XXIV) (XXIV) wherein Z 1 is as previously described under formula I and X 0 is halogen, preferably chlorine, bromine or iodine in the presence of a base, for example and alkaline earth metal base such as NaOH, KOH, LiOH, Cs2CO3, K2CO3 and the like, in inert aprotic or protic solvents.
  • a base for example and alkaline earth metal base such as NaOH, KOH, LiOH, Cs2CO3, K2CO3 and the like, in inert aprotic or protic solvents.
  • alkylation’s are well known to those skilled in the art and have been used in this context to prepare compounds of formula (IIb) as described for example in WO14/168221; WO10/043000; and WO14/32498.
  • compounds of formula (I), wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 are as defined above for the compounds of formula (I), and X 04 is halogen, preferably bromine or chlorine, e.g., compounds of formula (Ia): 82714_FF 35 such as palladium catalysed carbonylations, Suzuki reactions, Stille couplings, copper catalysed introduction of sulphonyl groups, haloalkyl groups, and cyano moieties, as well as SnAr reactions with a variety of nucleophiles.
  • Scheme 13 82714_FF 36 As shown in Scheme 13, compounds of formula (I), wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 are as defined above for the compound of formula (I), and R 9 is cyano, namely compounds of formula (Ib), can be obtained from compound of formula (Ia) by treatment with an inorganic cyanide source such as CuCN an inert solvent such as dimethylformamide (DMF) or N-methyl-2-pyrrolidone at temperatures between 0°C and 150°C.
  • an inorganic cyanide source such as CuCN
  • an inert solvent such as dimethylformamide (DMF) or N-methyl-2-pyrrolidone
  • the reaction is catalyzed by a palladium-based catalyst, for example tetrakis(triphenylphosphine)-palladium or (1,1'-bis(diphenylphosphino)- ferrocene)dichloropalladium-dichloromethane (1:1 complex), in presence of a base, like sodium carbonate or cesium fluoride, in a solvent or a solvent mixture, like, for example, a mixture of 1,2-dimethoxyethane and water, or dioxane and water, or methyl tetrahydrofuran and water, preferably under inert atmosphere.
  • the reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture.
  • compounds of formula (Ic) can be prepared by a Stille reaction of compounds of formula (XXVIb), wherein Yb2 is a trialkyl tin derivative, preferably tri-n-butyl tin, with compounds of formula (Ia).
  • Such Stille reactions are carried out in the presence of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium(0) or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium- dichloromethane (1:1 complex), in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive, such as cesium fluoride, or lithium chloride, and optionally in the presence of a further 82714_FF 37 catalyst, for example copper(I) iodide.
  • a palladium catalyst for example tetrakis(triphenylphosphine)palladium(0) or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium- dichloromethane (1:1 complex
  • an inert solvent such as DMF, acetonitrile, or dioxane
  • compounds of formula (Ia) can be carbonylated to give compounds of formula (I), namely compounds of formula (Ih) with R 14 C1-C4 alkyl, wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 are as defined above for the compound of formula (I),
  • compounds of formula (Ia) are reacted with carbon monoxide, usually under pressure, in the presence of metal catalyst such as a palladium catalyst (for example, palladium(II) acetate, [1,1'- bis(diphenylphosphino)ferrocene] palladium(II) dichloride (Pd(dppf)Cl2), bis(triphenylphosphine)palladium(II) dichloride (PdCl2(PPh3)2) or bis(diphen
  • Such compounds of formula (Ih) can be easily saponified to compounds of formula (Ii) under conditions known to those skilled in the art, for example conditions such as aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature, or up to refluxing conditions.
  • conditions such as aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature, or up to refluxing conditions.
  • halide anions preferably chloride anions, originating from, for example, lithium chloride (or alternatively, sodium or potassium chloride)
  • solvents such as N,N-dimethylformamide, N,N- dimethylacetamide or N-methyl-2-pyrrolidone
  • reaction temperatures for such an O-demethylation range preferably from 20°C to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation.
  • Compounds of formula (Ii) can be converted to amides of formula (I), namely compounds of formula (Ij) with R 15 and R 16 are independently hydrogen or C1-C4 alkyl, wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 are as defined for the compound of formula (I).
  • Curtius rearrangement compounds of formula (Ij) are treated with an organo-azide in the presence of a suitable base and optionally in the presence or absence of Lewis acids, in an inert solvent at temperatures between 50°C and 200°C.
  • organo-azide include TMSN3, sodium azide, diphenyl phosphoryl azide or tosyl azide and suitable solvent may be toluene, xylene, THF or acetonitrile.
  • suitable Lewis acids may include Zn(OTf)2 amongst others.
  • the isocyanates formed in the rearrangement react with water to form carbamates which decarboxylate under the reaction conditions to the corresponding amines of formula (lk).
  • the reactions can be carried out in alcohols, e.g., t-butyl alcohol, allowing the t-butyl carbamates to be isolated. These in turn can be cleaved in a separate step by methods known to those skilled in the art with acids (such as trifluoroacetic acid) to yield compounds of formula (Ik). Examples of such Curtius reactions have been reported, for example, in Org. Lett.2005, 7, 4107-4110, J. Med.Chem. 2006, 49(12), 3614-3627, and Tetrahedron 1974, 30, 2151-2157.
  • a compound of formula (I) as defined in any of the embodiments of the present invention can be converted in a manner known per se into another compound as defined in any of the embodiments of the present invention 82714_FF 40 by replacing one or more substituents of the starting compound in the customary manner by (an)other substituent(s) according to the invention.
  • compounds of formula (I) can be further transformed to further derivatives of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C-C-bond forming reactions in the presence of metal catalysts, heteroatom-carbon bond formation in the presence of metal catalysts, oxidation, and reduction.
  • alkylation nucleophilic substitution, elimination, C-C-bond forming reactions in the presence of metal catalysts, heteroatom-carbon bond formation in the presence of metal catalysts, oxidation, and reduction.
  • salts of compounds of formula (I) may be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • 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 tautomer’s 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 herein below, even when stereochemical details are not mentioned specifically in each case.
  • the compounds of formula (I) of the present invention exhibit an asymmetric carbon atom at the bis-benzylic position: A skilled person would be well aware that both enantiomers are within the scope of the invention.
  • 82714_FF 41 Diastereomeric mixtures or racemic 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.
  • Enantiomeric 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 com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities,
  • 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. 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.
  • compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns.
  • SFC supercritical fluid chromatography
  • Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention.
  • the compounds of formula (I) of the present invention exhibit two asymmetric carbon atoms. The relationship between enantiomers and diastereomers of compounds of formula (I) is shown below.
  • R 1 , R2, R3, R4, R5, R6, R7, R8, R9, A1, A2, A3, Q, R10, R11, R12, R13, and Z1 are as defined for formula (I) are within the scope of the invention.
  • R1, R2, R3, R4, R5, R6, R7, R8, R9, A1, A2, A3, Q, R 10 , R 11 , R 12 , R 13 , and Z 1 are as defined for formula (I) and are within the scope of the invention.
  • 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.
  • the compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • the compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man.
  • novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants.
  • the compounds of formula (I) can be used to inhibit or destroy the pests that occur on plants 82714_FF 43 or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) according to the invention is applied to the plants, to parts thereof or the locus thereof.
  • controlling when used in context of infestation of plants or plant propagation material and /or harvest food crops 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.
  • preventing when used in context of infestation of plants or plant propagation material and /or harvest food crops refers to the avoidance of a symptom due to microbial attack or fungal infections (growth of fungi). It is also possible to use a compound of formula (I) according to the invention as a fungicide.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • compounds of formula (I) may also be possible to use compounds of formula (I) according to the invention as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown.
  • the active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds of formula (I) according to the invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g., lumber, wall boards and paint.
  • the compounds of formula (I) according to the invention are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia 82714_FF 44 lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising B.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. including P. oryzae, Pythium spp. including P.
  • the compounds of formula (I) according to the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees, or evergreens, for example conifers, as well as for tree injection, pest management and the like.
  • target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), millet, oats
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, 82714_FF 45 rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, 82714_FF 45 rosemary, sage and thyme
  • legumes for example beans
  • useful plants is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxida
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g., imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
  • useful plants is to be understood as also including useful 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.
  • YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Bollgard I® (cotton variety that expresses a CryIA(c) toxin); Bollgard II® (cotton variety that
  • crops is to be understood as including also crop plants which have been so transformed using recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins 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 82714_FF 46 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 oxida
  • delta-endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO2002/015701).
  • 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 WO2003/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO2003/052073.
  • transgenic plants are generally known to a 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 WO95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO90/13651.
  • 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 butterflies (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 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 express
  • transgenic crops 82714_FF 47.
  • Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 2003/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • the compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Alternaria species in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solani in potatoes and vegetables; Uncinula necator in grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium in cucurbits; Leveillula taurica in cucurbits and solanacious crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymospetoria spp. in cereals.
  • phytopathogenic diseases especially phytopathogenic fungi such as Alternaria species in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solani in potatoes and vegetables; Uncinul
  • locus as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes.
  • plants there can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.
  • the compounds of formula (I) according to the invention may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation.
  • compositions may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g., in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants e.g., for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO97/33890.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended.
  • Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor.
  • these concentrates are diluted in water and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents.
  • a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents.
  • 82714_FF 49 these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter.
  • Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and granular carbon.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein said active ingredient is dispersed in finely divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2- butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 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,
  • Water is generally the carrier of choice for the dilution of concentrates.
  • suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation.
  • Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2 ethylhexyl) sulfosuccinate; sorbi
  • compositions of the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, and sticking agents.
  • biocidal active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention.
  • these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank.
  • These further biocidal 82714_FF 51 active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators. Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
  • the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No.
  • the compounds of formula (I) according to the invention are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants.
  • the compounds of formula (I) according to the invention may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemical usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the invention, an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use.
  • Agricultural carriers are well known in the art.
  • said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
  • the compound of formula (I) according to the invention may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imi
  • suitable additional active ingredients include the following: petroleum oils, 1,1-bis(4-chlorophenyl)- 2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4- chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carboxy
  • lecontei NPV, Orius spp. Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en- 1-yl acetate
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP0357460, EP0444964 and EP0594291.
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US5,015,630, WO94/15944 and WO95/22552. Additional anthelmintic agents include the benzimidazoles such 82714_FF 59 as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class.
  • Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US5,478,855, US4,639,771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO96/11945, WO93/19053, WO 93/25543, EP0626375, EP0382173, WO94/19334, EP0382173, and EP0503538.
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • terpene alkaloids for example those described in WO95/19363 or WO04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, hep
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan- 3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, beta- cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, 82714_FF 60 cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • antiparasitics acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydr
  • Biological agents Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • TX means one compound selected from the group consisting of compounds of formula (I), (Ia), (Ia-A), (Ia-B) or (Ia-C), or one compound selected from the group consisting of the compounds as represented in Tables C- 1 to C-21 or a compound as listed in Table P (below): a compound selected from the group of substances consisting of petroleum oils + TX, 1,1-bis(4-chlorophenyl)- 2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + T
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • the compounds in this paragraph may be prepared from the methods described in WO2017/055473, WO2017/055469, WO2017/093348 and WO2017/118689; 2-[6-(4- chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO2016/156290);
  • 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 mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of 82714_FF 69 a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound selected from the compounds of formula (I),) (Ia), (Ia-A), (Ia-B), (Ia-C), or one compound selected from the group consisting of the compounds as represented in Tables C-1 to C-21 or a compound as listed in Table P (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • 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).
  • Another aspect of the invention is related to the use of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • plants e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
  • a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the
  • Controlling or preventing means reducing infestation by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I) according to the invention, or an agrochemical composition which contains at least one compound of formula (I), is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula (I) according to the invention can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g., in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation e.g., a composition containing the compound of formula (I) according to the invention and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • g a.i./ha refers to the application rate given in gram [g ] of active ingredient [a.i.] per unit of surface [ha].
  • the unit hectare is the metric unit of area that equals a square with 100 m side (1 hm 2 ) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.
  • rates of 0.001 to 50 g of a compound of formula (I) per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • compositions comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • the compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro- emulsion (ME), an oil dispersion (OD), an oil miscible flowable (O
  • compositions may be produced in conventional manner, e.g., by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers, and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers, and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g., as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g., as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g., as slow-release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts, and adjuvant(s), the active agent consisting of at least the compound of formula (I) according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.
  • the end user will normally employ diluted formulations. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline, compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts: 82714_FF 72 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
  • the compounds according to the following Tables C-1 to C-21 may 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).
  • the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
  • the disclosure in the present application makes available each and every combination of embodiments disclosed herein.
  • the compounds according to the following Tables C-1 to C-21 may 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).
  • Table A This table discloses 20 substituent definitions G of the formula (I) 82714_FF 73 wherein G is of formula defined below: Index G Index G l] l] Table B: This table discloses 14 substituent definitions Q of the Formula (I) Index Q 82714_FF 74
  • Tables C-1 to C-21 disclose specific compounds of the invention of formula (I), wherein Q and G substituents are as defined in tables A and B.
  • Table C-1 This table provides 20 compounds C-1.01 to C-1.20 of formula (I) wherein R 2 , R 4 , R 5 , R 6 are H, Q is Q-1 as defined in Table B, and G is as defined in Table A.
  • compound C-1.01 has the following structure: Compound C-1.01 C-2.01 to C-2.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-1 as defined in Table B, and G is as defined in Table A.
  • compound C-2.05 has the following structure: Compound C-2.05 C-3.01 to C-3.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • compound C-3.11 has the following structure; Compound C-3.11 C-4.01 to C-4.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-5 This table provides 20 compounds C-5.01 to C-5.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-6 This table provides 20 compounds C-6.01 to C-6.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A. 82714_FF 75
  • Table C-7 This table provides 20 compounds C7.01 to C-7.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-6 as defined in Table B, and G is as defined in Table A.
  • Table C-8 This table provides 20 compounds C8.01 to C-8.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-7 as defined in Table B, and G is as defined in Table A.
  • Table C-9 This table provides 12 compounds C-9.01 to C-9.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-8 as defined in Table B, and G is as defined in Table A.
  • compound C-9.03 has the following structure: Compound C-9.03 C-10.01 to C-10.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-9 as defined in Table B, and G is as defined in Table A.
  • Table C-11 This table provides 20 compounds C-11.01 to C-11.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-10 as defined in Table B, and G is as defined in Table A.
  • Table C-12 This table provides 20 compounds C-12.01 to C-12.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-11 as defined in Table B, and G is as defined in Table A.
  • Table C-13 This table provides 20 compounds C-13.01 to C-13.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-12 as defined in Table B, and G is as defined in Table A.
  • Table C-14 This table provides 20 compounds C-14.01 to C-14.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-13 as defined in Table B, and G is as defined in Table A.
  • Table C-15 This table provides 20 compounds C-15.01 to C-15.20 of formula (I) wherein R 2 , R 5 , R 6 are H, R 4 is CH3, Q is Q-14 as defined in Table B, and G is as defined in Table A.
  • compound C-15.12 has the following structure: Compound C-15.12 82714_FF 76
  • Table C-16 This table provides 20 compounds C-16.01 to C-16.20 of formula (I) wherein R 5 , R 6 are H, R 2 and R 4 are CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-17 This table provides 20 compounds C-17.01 to C-17.20 of formula (I) wherein R 5 , R 6 are H, R 2 and R 4 are CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-18 This table provides 20 compounds C-18.01 to C-18.20 of formula (I) wherein R 5 , R 6 are H, R 2 and R 4 are CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • compound C-18.01 has the following structure: Table C-19: This table provides 20 compounds C-19.01 to C-19.20 of formula (I) wherein R 5 , R 6 are H, R 2 is Cl, R 4 is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-20 This table provides 20 compounds C-20.01 to C-20.20 of formula (I) wherein R 5 , R 6 are H, R 2 is Cl, R 4 is CH 3 , Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-21 This table provides 20 compounds C-21.01 to C-21.20 of formula (I) wherein R 5 , R 6 are H, R 2 is Cl, R 4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • compound C-21.01 has the following structure: Compound C-21.04 EXAMPLES The Examples which follow serve to illustrate the invention and are not meant in any way to limit the invention.
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, if necessary, for example 60 ppm, 20 ppm or 2 ppm.
  • Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • temperatures are given in degrees Celsius (°C) and “m.p.” means melting point.
  • LC/MS or LC-MS or LCMS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows. 82714_FF 77 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS ( 1 H) and CFCl3 ( 19 F) 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)-.
  • LCMS Method A Spectra were recorded on a Mass Spectrometer from Waters Corp. (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • LCMS Method C Spectra were recorded on a Mass Spectrometer from Waters Corp. (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source. 82714_FF 78 Optimized Mass Parameter: Ionisation method: Electrospray (ESI); Polarity: Positive and Negative Polarity Switch; Scan Type: Full Scan; Capillary (kV): 3.00; Cone Voltage (V): 41.00; Source Temperature (°C): 150; Desolvation Gas Flow (L/Hr): 1000; Desolvation Temperature (°C): 500; Gas Flow @ Cone (L/Hr): 50; Mass range: 110 to 1000 Da Gradient conditions: Solvent A: water with 0.1% formic acid: acetonitrile: 95: 5 v/v; Solvent B: acetonitrile with 0.05% formic acid Time (minutes) A (%) B (%) Flow rate (ml/min) 0
  • LCMS Method F Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector.
  • an electrospray source Polyity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - - 20 % The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % 82714_FF 80 calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Dusts a) b) c) Active ingredients 5 % 6 % 4 % Talcum 95 % - - Kaolin - 94 % - mineral filler - - 96 % Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 % 82714_FF 81
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo-emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • EG
  • the compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below. “Mp” means melting point in °C (grad Celsius). Free radicals represent methyl groups.
  • Example 1 Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-1, Table P) 82714_FF 83 (Compound P-1, Table P) 4-yl)propane nitrile 4-yl)acetonitrile (10.00 g, 78.42 mmol) was dissolved in THF (314 mL) under argon and the pale-yellow solution was cooled to -78°C.
  • Step 2 Preparation of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propanenitrile 4-yl)propanenitrile (2.00 g, 14.80 mmol) was dissolved in THF (59.18 mL) under argon to give a pale-yellow solution. The solution was cooled to -78°C and then treated dropwise with n-butyl lithium (5.90 mL, 14.80 mmol). The resulting pale brown suspension was stirred at this temperature for 10 min. before adding 2,6-dichloropyridine (2.23 g, 14.80 mmol) portion wise.
  • the resulting brown suspension was stirred at -78°C for 5 minutes, let to reach room temperature and stirred for 30 minutes at rt under argon to give a light brown solution.
  • the reaction mixture was poured into water and extracted twice with ethyl acetate. The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, filtered, and 82714_FF 84 concentrated in vacuo at 60°C to give 3.68 g of a dark brown liquid.
  • Step 3 Preparation of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine -2-(1-methylpyrazol-4-yl)propanenitrile (2.71 g, 11.0 mmol) in THF (33.0 mL) was treated dropwise with borane methyl sulfide complex (2.50 g, 3.13 mL, 33.0 mmol) at room temperature under argon and the resulting pale-yellow solution was stirred for 4 hours at 65°C. The reaction mixture was cooled to 0°C before adding dropwise concentrated hydrochloric acid (HCl) (7.36 mL, 44.2 mmol).
  • HCl dropwise concentrated hydrochloric acid
  • reaction mixture was stirred for 1 hour at 50°C.
  • the reaction mixture was cooled to rt and water was added.
  • aq. sodium hydroxide (6N NaOH) was added until pH of 12 and the resulting reaction mixture extracted three times with ethyl acetate.
  • the combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to give 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4- yl)propan-1-amine as a pale-yellow oil, that could be used in the next step without further purification.
  • Step 4 Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate benzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was treated successively with copper(II)sulfate anhydrous (0.053 g, 0.33 mmol), sodium ascorbate (0.46 g, 2.3 mmol) in water (3.6 mL), and then methyl prop-2-ynoate (0.14 g, 0.14 mL, 1.7 mmol) The reddish reaction mixture was stirred for 2 days at rt (monitoring by LCMS). The reaction mixture was then concentrated in vacuo, and the residue taken up in water and EtOAc.
  • the organic layer was separated, washed with brine, and the separated organic layer dried 82714_FF 85 over MgSO4, filtered, and concentrated in vacuo.
  • the crude product was adsorbed onto ISOLUTE® and purified over a silica gel cartridge (Rf200), eluting with cyclohexane/EtOAc, to give the title compound as a white solid.
  • Step 2 Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4- triazole-3-carboxamide (Compound P-4, Table P) 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (0.031 g, 0.12 mmol) was added to a solution of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate (0.025 g, 0.10 mmol) in toluene (0
  • This reaction mixture was stirred under argon atmosphere for 5 minutes and then bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.041 g, 0.16 mmol) was added and the resulting reaction mixture was stirred at 70 °C in microwave. After reaction completion, the reaction mixture was diluted with water, extracted with EtOAc and the organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo.
  • Step 2 Preparation of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate was solubilized in aqueous 6M hydrochloric acid (deionized water) (6 mL, 36 mmol) and ethanol (5 mL) and was cooled to 0 °C.
  • Example 5 Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-3, Table P). (Compound P-3, Table P). hydrazono]-3-oxo-propanoate 82714_FF 90 flask, equipped with a nitrogen inlet, was added 2,4-difluoroaniline (4.00 g, 30.9 mmol) in water (32 mL) and conc. HCl (12 mL, 35%) at room temperature.
  • reaction mixture was cooled to 0 °C and to this solution was added a cold solution of sodium nitrite (2.56 g, 37.1 mmol) in water (32 mL) and the resulting mixture stirred it at 0 °C for 5 min.
  • a solution of ethyl 3- (dimethylamino)prop-2-enoate (12.0 g, 23.4 mmol) and potassium acetate (4.61 g, 46.4 mmol) in ethanol (40 mL) was stirred and cooled to 0 °C. To this was added the above diazotized solution at 0°C dropwise, and the reaction mixture allowed to warm to room temperature and stirred for 18 hrs.
  • reaction mixture was then stirred at 140 °C for 1 h.
  • the reaction was monitored by LC-MS and after completion the reaction mixture was cooled and quenched with ice and cold brine.
  • the reaction mixture was extracted with EtOAc (3x25 mL) and the combined organic layers dried over Na2SO4, and concentrated in vacuo, to yield the crude product. This was purified by combiflash using EtOAc/cyclohexane as eluent (5:95) to afford the title compound as a brown solid.
  • Lithium;2-(2,4-difluorophenyl)triazole-4-carboxylate (70.0 mg, 0.30 mmol) and 2-(6-chloro-2-pyridyl)-2-(1- methylpyrazol-4-yl)propan-1-amine (91.0 mg, 0.36 mmol) were suspended in ethyl acetate (5 mL) and treated with triethyl amine (97.7 ⁇ L, 0.66 mmol) and T3P (50 mass%) in EtOAc (2 mL) at 0 °C. The reaction was stirred at room temperature for 2 hrs after which time TLC and LCMS showed reaction completion.
  • the reaction mixture was diluted with water and extracted with EtOAc (2x25 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo.
  • the crude product was purified by combiflash by using 0-70% EtOAc/cyclohexane as an eluent to obtain the product as a yellow gummy mass.
  • Example B1 Alternaria solani / tomato / leaf disc (early blight) Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf disks are incubated at 23 °C / 21°C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).
  • test plates are incubated at 24 °C and the inhibition of growth is measured photometrically 3-4 days after application.
  • the following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8
  • Example B4 Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) / wheat / leaf disc preventative (Powdery mildew on wheat) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).
  • the following compounds gave at least 80% control of Blumeria graminis f. sp.
  • Example B5 Fusarium culmorum / liquid culture (Head blight) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
  • DMSO DMSO
  • Example B6 Fusarium culmorum / wheat / spikelet preventative (Head blight) Wheat spikelets cv. placed on agar in multiwell plates (24-well format) and sprayed with the formulated test water. The spikelets are inoculated with a spore suspension of the fungus 82714_FF 96 1 day after application.
  • the inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 - 8 days after application).
  • the following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-6
  • Example B7 Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch) Wheat leaf segments cv.
  • Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated test leaf disks are incubated at 20 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
  • the following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8, P-9
  • Example B9 Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth).
  • Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segments are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 20 °C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).
  • test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
  • the following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-5, P-6
  • Example B12 Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added.
  • DMSO DMSO
  • test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
  • the following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-8, P-7, P-9
  • Example B13 Gibberella zeae (Fusarium graminearum) / wheat / spikelet preventative (Head blight) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the spikelets are inoculated with a spore suspension of the fungus.
  • the inoculated test leaf disks are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber, the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 - 8 days after application).
  • the inoculated leaf disks are incubated at 16 °C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • the inoculated leaf disks are incubated at 19 °C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).

Abstract

A compound 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, which can be used as fungicides.

Description

82714_FF 1 MICROBIOCIDAL PYRAZOLE DERIVATIVES The present invention relates to microbiocidal pyrazole derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these pyrazole derivatives, to intermediates useful in the preparation of these pyrazole derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to the use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi. According to a first aspect of the present invention, there is provided a compound of formula (I): wherein
Figure imgf000002_0001
R1 is selected from hydrogen, C1-C4 alkyl, C2-C4alkenyl, C2-C4 alkynyl, or C3-C6cycloalkyl; R2 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4haloalkyl, C3- C6cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl- carbonimidoyl, or C1-C4 alkoxycarbonyl; R3 is selected from hydrogen, halogen, or C1-C4 alkyl; R4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R5 and R6 are independently selected from hydrogen, or C1-C4 alkyl; A1 is selected from CR7 or N, A2 is selected from CR8 or N; A3 is selected from CR9 or N; R7, R8, and R9 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl; Q is selected from Q1, Q2, Q3, Q4, or Q5; 82714_FF 2 wherein;
Figure imgf000003_0001
R10, R11, R12 and R13 are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-4alkylamino, N,N-diC1-4alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S; and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4alkoxy; Z1 is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein any of said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S; and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof. Surprisingly, it has been found that the compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi. According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the invention. Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier. According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of 82714_FF 3 formula (I) according to the invention, or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof. According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) according to the invention as a fungicide. According to this particular aspect of the invention, the use may exclude methods for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body. 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- C4 alkane- 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 dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. 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. 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. Where substituents are indicated as being “optionally substituted”, this means that they may or may not carry one or more identical or different substituents, e.g., one, two or three Rx substituents. For example, C1-C6alkyl substituted by 1, 2 or 3 halogens, may include, but not be limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, - CF3, -CH2CF3 or -CF2CH3 groups. As another example, C1-C6alkoxy substituted by 1, 2 or 3 halogens, may include, but not be limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups. Further the term “optionally substituted” as used herein, means that the referred group is unsubstituted or substituted. As used herein, the term "halogen" or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl. 82714_FF 4 As used herein, amino means a -NH2 group. As used herein, cyano means a -CN group. As used herein, the term “hydroxyl” or “hydroxy” means an -OH group. As used herein, the term “carboxylic acid” means a -COOH group. As used herein, the term "C1-Cn-alkyl” refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n- pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 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. As used herein, the term “C2-Cn-alkenyl” refers to a straight or branched alkenyl chain moiety having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-l -enyl, but-2-enyl. As used herein, the term “C2-Cn-alkynyl” refers to a straight or branched alkynyl chain moiety having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl, As used herein, the term “C3-Cn-cycloalkyl” refers to three (3) to n membered cycloalkyl radical such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. As used herein, the term "C1-Cn-alkoxy" refers to a straight-chain or branched saturated alkyl radical having one (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 and 1,1-dimethylethoxy. The term “C2-Cn-alkenyloxy” as used herein refers to a straight-chain or branched alkenyl chain having two (2) to n carbon atoms (as mentioned above) which is attached via an oxygen atom. As used herein, the term "C1-Cn-haloalkyl" refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-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, a term "C1-C2fluoroalkyl" would refer to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. Similarly, the term 82714_FF 5 “C2-Cn-haloalkenyl” or “C2-Cn-haloalkynyl” as used herein refers to a C2-Cn-alkenyl or C2-Cn-alkynyl radical respectively substituted with one or more halogen atoms which may be the same or different. Similarly, the term “C3-Cn-halocycloalkyl” or “C1-Cn-haloalkoxy” as used herein refers to a C3-Cn-cycloalkyl radical or C1-Cn- alkoxyl radical respectively substituted with one or more halo atoms which may be the same or different. As used herein, the term “C1-Cn-alkylthio“ or “C1-Cn-alkylsulfanyl“refers to a C1-Cn-alkyl group linked through a sulfur atom. As used herein, the term “C1-Cn-alkylsulfinyl“ refers to a C1-Cnalkyl group linked through the sulfur atom of a sulfinyl (or S(=O)-) group. As used herein, the term “C1-Cn-alkylsulfonyl“ refers to a C1-Cnalkyl group linked through the sulfur atom of a sulfonyl (or S(=O)2-) group. As used herein, the term “C1-Cn-alkylcarbonyl” refers to a C1-Cn-alkyl group linked through the carbon atom of a carbonyl (C=O) group. As used herein, the term “C1-Cn-alkoxycarbonyl” refers to a C1-Cn-alkoxy moiety linked through a carbon atom of a carbonyl (or C=O) group. As used herein, the term “C1-Cn-alkoxycarbonyl-C1-C6-alkyl” refers to a C1-Cn-alkyl radical substituted by a “C1- Cn-alkoxycarbonyl group. As used herein, the term “benzoyl” refers to a phenyl group linked through the carbon atom of a carbonyl (C=O) group. As used herein, the term “ C 1 -C n-alkylaminocarbonyl” refers to a C1 -C n -alkylamino group (or R a NHC(=O)-, wherein Ra is a C1-Cn-alkyl group) linked through the carbon atom of a carbonyl (C=O) group. As used herein, the term “N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl” refers to a radical of the formula - C(Ra)=NO(Rb) where Ra is a C1-C4 alkyl radical as generally defined above, and Rb is a C1-C4 alkyl radical as generally defined above. As used herein the term “N-hydroxy-C-C1-C4 alkyl-carbonimidoyl” refers to a radical of the formula -C(Ra)=NOH where Ra is a C1-C4 alkyl radical as generally defined above. As used herein, the term “heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl. The term “heteroaryl-C1-Cn-alkyl” or “heteroaryl- C3-Cn-cycloalkyl” refers to an C1-Cn-alkyl or C3-Cn-cycloalkyl radical respectively substituted by a heteroaryl group. The heteroaryl-C1-Cn-alkyl or heteroaryl-C3-Cn-cycloalkyl radical may be substituted on heteroaryl, alkyl and/or cycloalkyl group as appropriate. 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. 82714_FF 6 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. 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. An effective amount is readily determined by the skilled person in the art, using 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. As used herein, the term “room temperature” or “RT” or “rt” refer to a temperature of about 15° C to about 35° C. For example, rt can refer to a temperature of about 20° C to about 30° C. The following list provides definitions, including preferred definitions, for substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, A1, A2, A3, Q (Q1, Q2, Q3, Q4, and Q5) and Z1 with reference to the compounds of formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document. In an embodiment of the invention R1 is selected from C1-C4 alkyl. Preferably R1 is methyl, ethyl or isopropyl. More preferably R1 is methyl. In an embodiment of the invention R2 is selected from hydrogen, halogen, C1-C6 alkyl, C3-C6cycloalkyl, C1-C2 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C2 alkyl-carbonimidoyl, or N-hydroxy-C-C1-C2 alkyl-carbonimidoyl. Preferably R2 is selected from hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2-alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, or N-hydroxy-C1-C2 alkyl-carbonimidoyl. More preferably R2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, – C(CH3)=NOCH2CH3, or –C(CH3)=NOH. Even more preferably R2 is selected from hydrogen, fluorine, chlorine, or methyl. In an embodiment of the invention, R3 is selected from hydrogen, halogen, or C1-C2 alky. Preferably R3 is hydrogen, fluorine, chlorine, or methyl. More preferably R3 is hydrogen or methyl. Even more preferably R3 is hydrogen. In an embodiment of the invention, R4 is hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4-alkylcarbonyl, or C1-C4- alkoxycarbonyl. Preferably R4 is hydrogen, chlorine, fluorine, C1-C3-alkyl, cyano, or CO2Me. More preferably R4 is hydrogen, methyl, ethyl, isopropyl, or cyano. Even more preferably R4 is hydrogen or methyl. In one embodiment R4 is hydrogen. In another embodiment R4 is methyl. 82714_FF 7 In an embodiment of the invention, R5 and R6 are independently selected from hydrogen or C1-C2-alkyl. Preferably R5 and R6 are independently selected from hydrogen or methyl. More preferably R5 and R6 are hydrogen. In an embodiment of the invention, Q is selected from Q1, Q2, Q3 or Q4:
Figure imgf000008_0001
Preferably, Q is selected from Q1, Q2, or Q3:
Figure imgf000008_0002
More preferably, Q is Q1:
Figure imgf000008_0003
wherein R10, R11, R12 and R13 are as defined above. In an embodiment of the invention R12 and R13 are independently selected from hydrogen, halogen, cyano, C1- C4 alkyl, or C1-C4 alkoxy. Preferably R12 and R13 are independently selected from hydrogen, chlorine, bromine, fluorine, or methyl. More preferably R12 and R13 are hydrogen. In an embodiment of the invention R10 and R11 are independently selected from hydrogen, halogen, hydroxy, cyano, amino, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4alkenyloxy, C2-C4 alkynyloxy, 82714_FF 8 C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-4alkylamino, N,N-diC1- 4alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy- C1-C4 alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, carboxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O, or S; and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C 4haloalkyl, or C1-C4 alkoxy. In another embodiment of the invention R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3alkenyloxy, C2-C3 alkynyloxy, C1- C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1- C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, N-hydroxy-C1-C2 alkyl- carbonimidoyl, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, carboxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 or 2 heteroatoms individually selected from N and O, and wherein any of said phenyl, 5- or 6- membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, or methyl. In a preferred embodiment R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1- C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3alkenyloxy, C2-C3 alkynyloxy, C1- C2 alkylsulfanyl, C1-C2 alkylsulfnyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1- C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, N-hydroxy-C1-C2 alkyl-carbonimidoyl, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, carboxy, phenyl, 2- cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4- (trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5- chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3- methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably R10 and R11 are independently selected from hydrogen, chloro, fluoro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methyl- sulfonyl, methoxymethyl, ethoxymethyl, 2-methoxy-ethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert- butoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, –C(CH3)=NOCH2CH3, –C(CH3)=NOH, methyl- aminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1- yl], [3-(trifluoromethyl) pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4- chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably R10 and R11 are independently selected from 82714_FF 9 hydrogen, chloro, fluoro, bromo, methyl, trifluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, methoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2-, methoxy ethoxymethyl, methoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, – C(CH3)=NOCH2CH3, –C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethyl- sulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl) pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1- yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol- 1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol- 1-yl, cyclopropyl, or 1-cyanocyclopropyl. Still even more preferably R10 and R11 are independently selected from hydrogen, chloro, fluoro, bromo, methoxy, cyano, amino, carboxy, 2-cyanophenyl, 3-cyanophenyl, 4- cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3- chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1- yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1- cyanocyclopropyl. In still another embodiment of the invention R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein said 5- or 6- membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6- membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl. More preferably R10 and R11 are independently selected from hydrogen, chloro, bromo, methoxy, cyano, amino, 2-cyanophenyl, 3-cyanophenyl, 4- cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1-cyanocyclopropyl. Even more preferably R10 and R11 are independently selected from hydrogen, chloro, bromo, cyano, or amino. In an embodiment of the invention, Q is selected from Q1, Q2, Q3, or Q4:
Figure imgf000010_0001
R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R12 and R13 are hydrogen. 82714_FF 10 In another embodiment of the invention, Q is selected from Q1, Q2, Q3, or Q4; wherein R10 and R11 are independently selected from hydrogen, halogen, cyano, or amino; and R12 and R13 are hydrogen. Preferably Q is selected from Q1, Q2, or Q3:
Figure imgf000011_0001
R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R12 and R13 are hydrogen. In another embodiment of the invention, Q is selected from Q1, Q2, or Q3; wherein R10 and R11 are independently selected from hydrogen, halogen, cyano, or amino; and R12 and R13 are hydrogen. More preferably Q is Q1
Figure imgf000011_0002
R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R12 and R13 are hydrogen. In another embodiment of the invention, Q is Q1; wherein R10 and R11 are independently selected from hydrogen, halogen, cyano, or amino; and R12 and R13 are hydrogen. In an embodiment of the invention A1 is selected from CR7 or N; A2 is selected from CR8 or N; A3 is selected from CR9 or N; wherein at least two of A1, A2 and A3 are selected from N. Preferably in one embodiment of the 82714_FF 11 invention A1 is selected from CR7; and A2 and A3 are N. Preferably in another embodiment A1 and A2 are N; and A3 is selected from CR9. Preferably in another embodiment A1 is N; A2 is CR8, and A3 is N. More preferably A1, A2, and A3 are N. In another embodiment of the invention A1 and A2 are N, and A3 is CR9. In still another embodiment of the invention A1 is CR7; A2 is CR8, and A3 is N. In still another embodiment of the invention A1 is N; A2 is CR8, and A3 is CR9. In still another embodiment of the invention A1 is CR7; A2 is N; and A3 is CR9 In an embodiment of the invention R7, R8, and R9 are independently selected from hydrogen, C1-C4 alkyl, C2- C4 alkenyl, C1-C4 haloalkyl, or C2-C4 alkynyl. Preferably R7, R8, and R9 are independently selected from hydrogen, halogen, methyl, ortrifluoromethyl. More preferably R7, R8, and R9 are hydrogen. In an embodiment of the invention Z1 is selected from C1-C4 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6-cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S, and wherein any of said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C2-C4-alkynyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy. In another embodiment Z1 is selected from C1-C3 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6- cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1, 2 or 3 heteroatoms individually selected from N, O or S, and wherein any of said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl. In another embodiment Z1 is selected from C1-C3 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6- cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, O or S, and wherein any of said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl. Preferably Z1 is selected from 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro- 2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4- fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5- fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4- chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1- methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, or phenyl. More preferably Z1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2- chlorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3- 82714_FF 12 fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, or phenyl. Even more preferably Z1 is selected from 1-methylpyrazol-4-yl, 2,4,6- trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4- difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl. Still even more preferably Z1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl. In another embodiment of the invention Z1 is selected from C1-C4 alkyl, phenyl, a 5- to 6- membered heteroaryl, or C3-C6-cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1, 2 or 3 heteroatoms individually selected from N, O or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl. Preferably Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and -5 to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4alkyl, or C1-C4alkoxy. More preferably Z1 is selected from 1- methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro- 2-pyridyl, 2-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2- thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2- methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or methyl. Still more preferably Z1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 3,5-difluoro-2- furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2- fluorophenyl, 4-fluorophenyl, or phenyl. In another embodiment of the invention Z1 is selected from phenyl, a 5- to 6- membered heteroaryl, or C3-C6- cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl. Preferably Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6- membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. The present invention, accordingly, makes available a compound of formula (I) having R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, A1, A2, A3, Q (Q-1, Q2, Q3, Q4, and Q5) and Z1 with reference to formula (I) as defined above in all combinations / each permutation. Embodiments according to the invention are provided as set out below. In one embodiment there is provided a compound of formula (I) wherein R1 is selected from hydrogen, C1-C6 alkyl, C2-C6alkenyl, C2-C6 alkynyl, or C3-C6cycloalkyl; 82714_FF 13 R2 is selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3- C6cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl- carbonimidoyl, or C1-C6 alkoxycarbonyl; R3 is selected from hydrogen, halogen or C1-C4 alkyl; R4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R5 and R6 are independently selected from hydrogen or C1-C4 alkyl; A1 is selected from CR7 or N, A2 is selected from CR8 or N; A3 is selected from CR9 or N; R7, R8, and R9 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl; Q is selected from Q1, Q2, Q3, Q4, or Q5; wherein;
Figure imgf000014_0001
R10, R11, R12 and R13 are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-4alkylamino, N,N-diC1-4alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S, and wherein any of said phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4alkoxy; and Z1 is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein said 5- or 6- membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 82714_FF 14 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof. In an embodiment of the invention, the compound of formula (I) may be a compound of formula (Ia):
Figure imgf000015_0001
Q3, Q4 and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, and A is selected from the group consisting of: and R7, R8 and
Figure imgf000015_0002
C4 haloalkyl. Preferably, in the compound of formula (Ia) R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4 and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A9, and R7, R8 and R9 are hydrogen, halogen, methyl, or trifluoromethyl. More preferably, in the compound of formula (Ia) R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A9, and R7, R8 and R9 are hydrogen. 82714_FF 15 In an embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from arrow the bond to the Z1 group, and R7 is
Figure imgf000016_0001
C1-C4 haloalkyl. Preferably, in the compound of formula (Ia) R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3, and R7 is hydrogen, halogen, methyl, or trifluoromethyl. More preferably, in the compound of formula (Ia) R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3, and R7 is hydrogen. In another embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from C(=O) group, and the arrow the bond to the Z1 group.
Figure imgf000016_0002
R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2. More preferably, in the compound of formula (Ia) R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2. 82714_FF 16 In still another embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2; R7 is hydrogen; and Q is selected from Q1, Q2, Q3, or Q4. In still another embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2; R7 is hydrogen; and Q is selected from Q1, Q2, or Q3. In still another embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2; R7 is hydrogen; and Q is Q1. In an embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13,and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from
Figure imgf000017_0001
wherein indicates the bond to the C(=O) group and the arrow the bond to the Z1 group. In of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, and Q is selected from Q1, Q2, Q3, or Q4. In still another embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, and Q is selected from Q1, Q2, or Q3. In still another embodiment of the invention, in the compound of formula (Ia) wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1, and Q is Q1. Preferably, in the compound of formula (Ia) of the invention R1 is C1-C4-alkyl, 82714_FF 17 R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; A is A1, or A2; R7 is hydrogen; Q is Q1, Q2 or Q3; R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; R12 and R13 are independently selected from hydrogen; and Z1 is selected from phenyl, a 5- to 6- membered heteroaryl, or C3-C6-cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl. Preferably, in the compound of formula (Ia) of the invention R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; A is A1, or A2; R7 is hydrogen; Q is Q1; R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano or methyl; R12 and R13 are selected from hydrogen; and Z1 is selected from phenyl, a 5- to 6- membered heteroaryl, or C3-C6-cycloalkyl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl. In an embodiment of the invention, the compound of formula (Ia) may be a compound of formula (Ia-A), wherein A is A1: 82714_FF 18
Figure imgf000019_0001
wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4, and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention. Preferably, in the compound of formula (Ia-A) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; and Q, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention. In another embodiment, in the compound of formula (Ia-A) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; Q is Q1, Q2, or Q3, R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; R12 and R13 are independently selected from hydrogen; and Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. In still another embodiment, in the compound of formula (Ia-A) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; 82714_FF 19 R5 and R6 are independently selected from hydrogen or methyl; Q is Q1, R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano or methyl; R12 and R13 are independently selected from hydrogen; and Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. In an embodiment of the invention, the compound of formula (Ia) may be a compound of formula (Ia-B), wherein A is A2:
Figure imgf000020_0001
wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4 and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention. Preferably, in the compound of formula (Ia-B) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; and Q, R10, R11, R12, R13 and Z1 are as defined for the compounds of formula (I) according to the present invention. In another embodiment, in the compound of formula (Ia-B) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; Q is Q1, Q2, or Q3, 82714_FF 20 R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; R12 and R13 are hydrogen; and Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. In still another embodiment, in the compound of formula (Ia-B) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; Q is Q1; R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; R12 and R13 are hydrogen; and Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. In an embodiment of the invention, the compound of formula (Ia) may be a compound of formula (Ia-C), wherein A is A3, and wherein R7 is hydrogen:
Figure imgf000021_0001
wherein R1, R2, R3, R4, R5, R6, Q (Q1, Q2, Q3, Q4 and Q5), R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (I) according to the present invention. Preferably, in the compound of formula (Ia-C) of the invention, 82714_FF 21 R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; and Q, R10, R11, R12, R13, and Z1 are as defined for the compounds of formula (II) according to the present invention. In another embodiment, in the compound of formula (Ia-C) of the invention, R1 is C1-C4-alkyl R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; Q is Q1, Q2 or Q3; R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; R12 and R13 are hydrogen; and Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. In still another embodiment, in the compound of formula (Ia-C) of the invention, R1 is C1-C4-alkyl, R2 is hydrogen, fluorine, chlorine, or methyl; R3 is hydrogen or methyl, R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or methyl; Q is Q1; R10 and R11 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6- membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; R12 and R13 are hydrogen; and Z1 is selected from phenyl or a 5- to 6- membered heteroaryl; wherein said 5- or 6-membered heteroaryl comprises 1 heteroatom selected from N or S, and wherein said phenyl and 5- to 6- membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. 82714_FF 22 The presence of one or more possible asymmetric carbon atoms in any of the compounds of formula (I), (Ia), (Ia-A), (Ia-B) and (Ia-C) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Preferably, the compound of formula (I) according to the invention is selected from compounds listed in any one of Tables C-1 to C-21 or compounds listed in Table P. More preferably the compound of formula (I) according to the invention is selected from compounds listed in Table P. In one embodiment of the invention, the compound of formula (I) is selected from N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(3,5-difluoro-2-pyridyl)triazole-4-carboxamide, N-[2-(6-bromo-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, or N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide. In one embodiment of the invention, the compound of formula (I) is selected from N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide, or N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide. The below intermediates are novel and as such form a further aspect of the invention. According to a fifth aspect of the invention, there is provided an intermediate compound of formula (III) or a salt thereof:
Figure imgf000023_0001
R6 and Q correspond to the same definitions as for the compounds of formula (I) according to the present invention. 82714_FF 23 The intermediate compounds of formula (III) possess the same definitions for R1, R2, R3, R4, R5, R6 and Q as for the compounds of formula (I) according to the invention and their corresponding preferences. According to a sixth aspect of the invention, there is provided an intermediate compound of formula (IIb) or a salt thereof:
Figure imgf000024_0001
wherein A1, A2, A3 and Z1 are defined as for the compounds of formula (I) according to the present invention. The intermediate compounds of formula (IIb) possess the same definitions for A1, A2, A3 and Z1 as for the compounds of formula (I) according to the invention and their corresponding preferences. In one embodiment the compound of formula (IIb) may be a compound of formula (IIba), wherein R7 is hydrogen, R0 is C1-C6 alkyl, A1, A2, A3 are N, and Z1 is as defined for the compounds of formula (I) according to the present invention.
Figure imgf000024_0002
possible asymmetric carbon atoms in a compound of formula (III) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. The compounds of formula (I) as defined in any of the embodiments of the present invention can be made as shown in the following Schemes 1 to 15, in which, unless otherwise stated, the definition of each variable is as defined above in any of the embodiments according to the invention. In any of the Schemes 1 to 15 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. More specifically, compounds of formula (I) may be prepared from compounds of formula (III) or a salt thereof, wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I) by reaction with a compound of formula (II), wherein A1, A2, A3, and Z1 are as defined above for the compound of formula (I). This reaction is shown in Scheme 1. 82714_FF 24
Figure imgf000025_0001
In Scheme 1, compounds of formula (II), wherein A1, A2, A3 and Z1 are as defined above for the compound of formula (I), are activated to compounds of formula (IIa) by methods known to a person skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852. For example, compounds of formula (IIa), where G0 is halogen, are formed by treatment of compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic quantities of N,N-dimethylformamide (DMF) in inert solvents such as methylene dichloride (CH2Cl2) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C. Treatment of compounds of formula (IIa) with compounds of formula (III), wherein R1, R2, R3, R4, R5, R6 and Q are as defined above for the compound of formula (I), optionally in the presence of a base, e.g. triethylamine or pyridine, leads to compounds of formula (I). Alternatively, compounds of formula (I) may be prepared by treatment of compounds of formula (II) with dicyclohexyl carbodiimide (DCC), 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5- b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (IIa), wherein G0 is G01, G02 or G03 as set forth below (Scheme 2), in an inert solvent, e.g. pyridine, DMF, acetonitrile, CH2Cl2 or THF, optionally in the presence of a base, e.g. triethylamine, at temperatures between 30°C and 180°C. Finally, a compound of formula (II) can also be activated by reaction with a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (IIa), wherein G0 is G04 as set forth below, as described for example in Synthesis 2013, 45, 1569. Further reaction with an amine (or a salt thereof) of the compound of formula (III) leads to compounds of formula (I). 82714_FF 25
Figure imgf000026_0001
Compounds of formula (II) can be prepared from compounds of formula (IIb), wherein A1, A2, A3 are N and Z1 are as described in formula (I), and R0 is C1-C4alkyl, by ester hydrolysis. A variety of conditions can be used, as for example aqueous sodium hydroxide or lithium hydroxide and an organic water miscible solvent like THF or dimethoxyethane or methanol or ethanol. Such ester hydrolyses are well known to those skilled in the art. Compounds of formula (IIb) can also be directly converted to compounds of formula (I) by reacting compounds of formula (IIb) with compounds of formula (III) in the presence of trimethyl aluminium, or trimethyl aluminium- DABCO complex in an inert solvent such as toluene or methylene chloride. Such reactions have been reported in the literature (see Tetrahedron Lett. 1977, 4171-4174, and Tetrahedron Lett. 2006, 5767-5769, and references cited therein). Compounds of formula (II) and (IIb) are commercially available or can be synthesized as described vide infra. Compounds of formula (III), or salts thereof, wherein R1, R2, R3, R4, R5, R6, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I), may be prepared by a person skilled in the art by a reaction between nitriles of formula (IV), wherein R1, R2, R3, R4, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I), and a suitable nucleophile such as (dimethyl sulfide)dihydroboron (BMS) in a suitable aprotic solvent such as tetrahydrofuran, for example as described in J. Org. Chem. 1981, 47, 3153. Alternatively, Grignard reagents R5MgBr or R6MgBr, wherein R5 and R6 are as defined above for the compound of formula (I), may be added as nucleophiles to compounds of formula (IV), sequentially or simultaneously, to allow more highly substituted amines of formula (III) to be prepared. Such Grignard additions to nitriles are carried out in an inert solvent such as diethyl ether, tert-butylmethyl ether, and cyclopentyl methyl ether in the presence of a Lewis acid such as Ti(O-iPr)4 (see Synlett 2007, (4), 652-654). This reaction is shown in Scheme 3. 82714_FF 26
Figure imgf000027_0001
Compounds of formula (IV), wherein R1, R2, R3, R4, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I), may be prepared by a person skilled in the art following known methods. More specifically, compounds of formula (IV), and intermediates thereof, may be prepared from compounds of formula (V) as shown in Scheme 4.
Figure imgf000027_0002
For example, compounds of formula (IV), wherein R1, R2, R3, R4, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I) and R4 is different from hydrogen, may be prepared by a person skilled in the art by deprotonation of compound of formula (IVa), wherein R4 is hydrogen and R1, R2, R3 and Q are as defined above for the compound of formula (I), using a strong base such as n-butyl lithium or sodium hydride at cryogenic temperatures in an inert solvent such as tetrahydrofuran, followed by addition of a suitable alkylating agent R4-X0, wherein X0 is halogen, for example iodomethane. Compounds of formula (IVa), wherein R4 is hydrogen and R1, R2, R3, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I), may be prepared from alcohols of formula (V) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a nonpolar solvent such as dichloromethane at temperatures between 0°C and the boiling point of the reaction mixture. Such transformations are well known in the literature under a variety of conditions, for example as described in Org. Lett.2008, 10, 4570 and references therein. This reaction is shown in Scheme 4. Compounds of formula (V) may be prepared from compounds of formula (VI), respectively from any of compounds of formula (VIa), (VIb), (VIc), (VId) or (VIe), as shown in Scheme 5. 82714_FF 27
Figure imgf000028_0001
As shown in Scheme 5, compounds of formula (VII), wherein R1, R2,R3, R10, R11, R12, R13, are as defined above for the compound of formula (I) and X01 is bromo or iodo, are metalated with an appropriate reagent such as turbo Grignard (isopropylmagnesium chloride-lithium chloride complex), or an alkyl lithium, such as n-butyl lithium to give an intermediate Grignard or alkyl lithium reagent (M is MgX01 or Lithium). Such metal insertions into C-X01 bonds are well known to those skilled in the art and are generally carried out at temperatures between -78°C to rt, in inert solvents such as ethers, e.g., tert-butyl methyl ether or tetrahydrofuran and the like. Solutions of the metalated species (VIIa) are then treated with compounds of formula (VI), respectively (VIa), (VIb), (VIc), (VId), or (VIe) to give compounds of formula (V). Similar reactions of these type have been described in for example WO 2012/102297 and Bio. Med. Chem. Lett.2017, 27(17), 4044-4050 (X01 is Br, n-butyl lithium) and Angew. Chem. Int. Ed.2016, 55(17), 5332-5336, US2014/0349990, WO2002/004424, WO2021/009068 (X01 is iodo, turbo Grignard (isopropylmagnesium chloride-lithium chloride complex)). Compounds of formula (VI) and (VII) are either commercially available or are readily prepared by methods known by those skilled in the art. A further synthesis of compounds of formula (I) involves treatment of compounds of formula (VIII) with a base, such as sodium hydride or n-butyl lithium, in an inert solvent, such as tetrahydrofuran, and subsequent alkylation with compounds of formula (IX), wherein R4 is as described under formula (I) and X02 is a leaving group such as halogen, mesylate or tosylate, to yield compounds of formula (X). This reaction is shown in Scheme 6. 82714_FF 28
Figure imgf000029_0001
Compounds of formula (X), wherein R1, R2, R3, and R4 are as defined above for the compound of formula (I), are then treated with a strong base such as sodium hydride or an alkyl lithium base such as n-butyl lithium in an inert solvent, such as tetrahydrofuran or tert-butyl methyl ether, at temperatures between -78°C to room temperature, followed by addition of a compound of formula (XI), respectively any of compounds of formula (XIa), (XIb), (XIc), (XId) or (XIe), wherein R9, R10, R11, and R12 are as defined above for the compound of formula (I), and X03 is a leaving group such as halogen, preferably F, Cl or Br to give compounds of formula (IV). This reaction is shown in Scheme 7.
Figure imgf000029_0002
Compounds of formula (IV) are converted into compounds of formula (I) as previously described in Schemes 1, 2 and 3. Those skilled in the art will recognize that conversion of compounds (VIII) into compounds of formula (IV) can be carried out sequentially or in the same reaction vessel, enabling a streamlined conversion of compounds of formula (VIII) to compounds of formula (IV). This is described in more details in the preparative examples. Compounds of formula (Ia), wherein R1, R2, R3, R5, Q, R10, R11, R12, R13, A1, A2, A3 and Z1 are as described above for compounds of formula (I) and R4 and R6 are hydrogen, can also be prepared by treatment of compounds of formula (VI), respectively any of compounds of formula (VIa), (VIb), (VIc), (VId) or (VIe), with 82714_FF 29 compounds of formula (XII), wherein R5 is as described above for compounds of formula (I) in the presence of a base, such as triethyl amine, optionally in an inert solvent, such as ethanol or methanol, to give compounds of formula (XIII). These compounds may be isolated and converted to compounds of formula (XIV) by treatment with an anhydride, such as trifluoroacetic acid anhydride, in an inert solvent, such as methylene chloride, in the presence of a base, for example triethyl amine. This reaction is shown in Scheme 8.
Figure imgf000030_0001
Those skilled in the art will appreciate that compounds of formula (VI) can be converted into compounds of formula (XIV) without isolation of the intermediates of formula (XIII). Such reactions, known as the Henry reactions, are well described in the literature, as evidenced in Tetrahedron 2001, 57(6), 915–945, and references cited therein. Compounds of formula (XIV) can be converted into compounds of formula (XV) by treatment with compounds of formula (VIIa) (see Scheme 5) in an inert solvent such as tetrahydrofuran, known to a person skilled in the art as Michael reaction of organometallics to nitro alkenes. This reaction is shown in Scheme 9.
Figure imgf000030_0002
Similar Michael additions of organometallics to nitro alkenes have been reported for example in Org. Lett.2007, 9, 85-87. Reduction of the nitro group in compounds of formula (XV) to the amine to give compounds of formula (IIIa), wherein R1, R2, R3, R5, R10, R11, R12, R13, and Q are as defined above for the compound of formula (I) 82714_FF 30 and R4 and R6 are hydrogen, can be achieved by a multitude of methods generally known to those skilled in the art, such as Bechamp reduction, or reduction with hydrogen in the presence of a metal catalyst. This reaction is shown in Scheme 10.
Figure imgf000031_0001
Scheme 10 Compounds of formula (IIIa) are converted into compounds of formula (Ia) by the methods described in Schemes 1 and 2. Compounds of formula II are either commercially available or can be synthesized as described vide infra. Compounds of formula (IIb) wherein A1, A2, A3 are N and Z1 is as described in for formula (I), namely compounds of formula (IIba)
Figure imgf000031_0002
a diazonium salt of formula (XVI) (XVI) wherein Z1 is as defined under formula I above and Y- being the counter ion depending on the conditions in which the diazotation step is performed, for example Cl- or BF4-, and compounds of formula (XVII),
Figure imgf000031_0003
reaction can be catalyzed with various silver salts, a preferred one being silver acetate, and performed in a variety of solvents, for example THF, DMF or toluene or a mixture thereof, usually at temperatures between 0°C and 25°C, in presence of at least one equivalent of a base, for example sodium carbonate. These dipolar [3 + 2] cycloadditions are highly regioselective and are described, for example in 82714_FF 31 Tetrahedron 2020, 76(14), 131063. Compounds of formula (XVI) as defined just before, can be prepared from primary amines of formula (XVIII) by reaction with a diazotation reagent, for example a salt of nitrous acid, for example sodium nitrite. The solvent can be an aqueous solution of an acid, for example diluted hydrochloric acid or tetrafluoroboric acid. The counter ion Y- is defined by the acid used. Diazotation reactions are commonly used in organic synthesis, even on industrial scale, and are known by the person skilled in the art. In order to reduce the risk of decomposition of the intermediates of formula (XVI), the diazotation step and the cycloaddition steps can be performed sequentially, without the need of isolating (XVI). This variant is also described in Tetrahedron 2020, 76(14), 131063. The chemistry is summarized in scheme 11:
Figure imgf000032_0001
Figure imgf000032_0002
Scheme 11
Figure imgf000032_0003
Compounds of formula (XVII) are commercially available, as are compounds of formula (XVII) (e.g., R0 is methyl, CAS [6832-16-2]). Very similarly, compounds of formula (IIba), wherein A1, A2, A3 are N and Z1 is as described in for formula (I), can be prepared by reacting a compound of formula (XIX):
Figure imgf000032_0004
is phenyl or p-tolyl, with compounds of formula (XVI), in the presence of a base, e.g., pyridine at temperatures from -50°C to 50°C to yield compounds of formula (IIba). Such reactions have good precedence in the literature, for example Chem. Comm.2017, 53(69), 9620-9623, Angew. Chem. Int. Ed. 2017, 56(47), 15044-15048, and J. Am. Chem. Soc. 2016, 138(44), 14609-14615. Compounds of formula (XXVIII) are prepared as described in the literature cited vide supra and exemplified in the preparation examples of the application. 82714_FF 32 Alternatively, compounds of formula (IIba), wherein A1, A2 and A3 are N and Z1 is as defined in formula (I) can be obtained by coupling compounds of formula (XX), N, and R0 is as described vide supra, with a boronic acid derivative of formula (XXI),
Figure imgf000033_0001
in formula I. This Chan-Lam type coupling reaction is usually performed in a solvent like dichloromethane, in presence of a catalytic amount of a copper-based catalyst under mild reaction temperatures, in presence of a base, such as potassium carbonate, under atmospheric air or oxygen. It is to be noted that compounds of formula (XX), wherein A1, A2 and A3 are N, exist in tautomeric forms.; Persons skilled in the art
Figure imgf000033_0002
could be either one of the regioisomers or a mixture thereof, but when the reaction conditions are chosen as described in J. Org. Chem. 2014, 79, 6703−6707, the reaction shows an excellent regioselectivity for compounds of the formula (IIba). Those skilled in the art will realize that this Chan-Lam coupling is a general method for preparation of compounds of formula (IIb). Examples have been shown in the literature for compounds of formula (IIbb)
Figure imgf000033_0003
as previously defined (see J. Med. Chem.2018, 61, 8, 3370–3388 and WO14/041106), compounds of formula (IIbc) and (IIbd) 82714_FF 33
Figure imgf000034_0001
(see WO15/155626, EP2390252) and compounds of formula (IIbe)
Figure imgf000034_0002
are as defined under formula (I) (see J. Med. Chem.2017, 60(14), 6166- 6190, Org. Lett.2008, 10(8), 1653-1655, and Bio. Med. Chem. Lett.2009, 19(5), 1451-1456), as representative examples. A further method for the preparation of compounds of formula (IIba), wherein A1, A2 and A3 are N and Z1 are as defined in formula (I), is shown in Scheme 12.
Figure imgf000034_0003
As shown in scheme 12, sequence begins with diazotation of compounds of formula (XVIII) as previously described vide supra and then treatment of the diazionium salt with a compound of formula (XXII), wherein R0 is C1-C6alkyl, in the presence of in the presence of a mild base, for example sodium acetate to yield compounds of formula (XXIII). Compounds of formula (XXIII), wherein Z1 and R0 are as previously defined, are then treated 82714_FF 34 with aqueous ammonia in a miscible organic solvent, for example tetrahydrofuran or 2-methyl tetrahydrofuran, at temperatures between 0°C to 30°C, to give compounds of formula (XXIV). Finally, diazotation of compounds of formula (XXIV) with a salt of nitrous acid, for example sodium nitrite, in a slightly acidic medium, for example acetic acid or aqueous hydrochloric acid at temperatures between -20°C to 0°C leads to spontaneous cyclization of the diazonium salt formed to the tetrazole compounds of formula (IIba). The sequence of reactions has been previously described in WO13/087805. Compounds of formula (IIb) may also be prepared by alkylation of compounds of formula (XX)
Figure imgf000035_0001
(XXIV) (XXIV) wherein Z1 is as previously described under formula I and X0 is halogen, preferably chlorine, bromine or iodine in the presence of a base, for example and alkaline earth metal base such as NaOH, KOH, LiOH, Cs2CO3, K2CO3 and the like, in inert aprotic or protic solvents. Such alkylation’s are well known to those skilled in the art and have been used in this context to prepare compounds of formula (IIb) as described for example in WO14/168221; WO10/043000; and WO14/32498. Those skilled in the art will relize this can lead to mixtures of regiosomeric compounds that can be separted by chromatographic techniques, or pure isomers can be obtained by the judicous choice of condtitions and additives (for example palladium catalysts for so called Buchwald aminations). For cases where Z1 is heteroaryl or aryl, SnAr reactions (with or without copper catalysis) may be used to prepare compounds of formula (IIb) (see for example, Polyhedron 2019, 165, 22-30; US2018/0170909; Org. Lett.2022, 24(20), 3620-3625, J.Org. Chem.2017, 82(14), 7420-7427, Chem. Comm. 2021, 57(57), 7047-7050, ACS Catalysis 2019, 9(12), 10674-10679, Synthesis 2017, 49(23), 5120-5130, J.Org. Chem.2019, 84(12), 8160-8167, and references cited therein). Further compounds according to the invention can be prepared by derivatization at a later stage in the synthesis using a key central intermediate. For example, compounds of formula (I), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compounds of formula (I), and X04 is halogen, preferably bromine or chlorine, e.g., compounds of formula (Ia): 82714_FF 35
Figure imgf000036_0001
such as palladium catalysed carbonylations, Suzuki reactions, Stille couplings, copper catalysed introduction of sulphonyl groups, haloalkyl groups, and cyano moieties, as well as SnAr reactions with a variety of nucleophiles. Examples of such reactions are shown in Scheme 13.
Figure imgf000036_0003
Scheme 13
Figure imgf000036_0002
82714_FF 36 As shown in Scheme 13, compounds of formula (I), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and R9 is cyano, namely compounds of formula (Ib), can be obtained from compound of formula (Ia) by treatment with an inorganic cyanide source such as CuCN an inert solvent such as dimethylformamide (DMF) or N-methyl-2-pyrrolidone at temperatures between 0°C and 150°C. Such reactions are well known in the literature, for example, in J. Het. Chem.1987, 24(2), 373-6, Liebigs Ann. Chem.1994, (10), 1049-53, and Org. Prep. Proc. Int.1985, 17(6), 391-9. Other methods for introduction of the cyano group by substitution of a halogen atom are known in the art. See, for example, Science of Synthesis 2004, 19, 173-195. Compounds of formula (I), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and R9a is C1-C4 haloalkyl, namely compounds of formula (Ic), can be prepared by treating compounds of formula (Ia) wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and X04 is halogen, preferably bromine, with compounds of formula (XXV), wherein R9a is C1-C4 haloalkyl, in an inert solvent such as DMF or N-methyl-2-pyrrolidone at temperatures between room temperature and 150°C. Such reactions are known in the literature (Org. Lett.2014, 16(6), 1744-1747). Compounds of formula (I), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and R9b is phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6 cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy, namely compounds of formula (Id), can prepared (as shown in Scheme 13) by a Suzuki reaction, which involves, for example, reacting compounds of formula (Ia), wherein X04 is a leaving group like, for example, chlorine, bromine or iodine, with compounds of formula (XXVIa), wherein Yb1 can be a boron-derived functional group, as for example B(OH)2 or B(ORb1)2, wherein Rb1 can be a C1-C4 alkyl group or the two groups ORb1 can form, together with the boron atom, a five membered ring, as for example a pinacol boronic ester. The reaction is catalyzed by a palladium-based catalyst, for example tetrakis(triphenylphosphine)-palladium or (1,1'-bis(diphenylphosphino)- ferrocene)dichloropalladium-dichloromethane (1:1 complex), in presence of a base, like sodium carbonate or cesium fluoride, in a solvent or a solvent mixture, like, for example, a mixture of 1,2-dimethoxyethane and water, or dioxane and water, or methyl tetrahydrofuran and water, preferably under inert atmosphere. The reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture. Such Suzuki reactions are well known to those skilled in the art and have been reviewed, for example, in J. Organomet. Chem.1999, 576, 147–168. Alternatively, compounds of formula (Ic) can be prepared by a Stille reaction of compounds of formula (XXVIb), wherein Yb2 is a trialkyl tin derivative, preferably tri-n-butyl tin, with compounds of formula (Ia). Such Stille reactions are carried out in the presence of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium(0) or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium- dichloromethane (1:1 complex), in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive, such as cesium fluoride, or lithium chloride, and optionally in the presence of a further 82714_FF 37 catalyst, for example copper(I) iodide. Such Stille couplings are also well known to those skilled in the art, and have been described, for example, in J. Org. Chem.2005, 70, 8601-8604, J. Org. Chem.2009, 74, 5599-5602, and Angew. Chem. Int. Ed, 2004, 43, 1132-1136. A large number of compounds of formula (XXVIa) and (XXVIb) are commercially available or can be prepared by those skilled in the art. Further compounds available from compounds of formula (Ia) are shown in Scheme 14.
Figure imgf000038_0001
As shown in Scheme 14, compounds of formula (I), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and X04 is a leaving group like, for example, chlorine, bromine or iodine, namely compounds of formula (Ia), can be treated with compounds of formula (XXVII) under Stille reactions conditions to give compounds of formula (Ie). Compounds of formula (Ie) can be isolated, or directly hydrolysed under aqueous acidic conditions to give compounds of formula (If). Such reactions are known in the literature and have been described, for example, in Synthesis 2001, (10), 1551- 1555, and Tetrahedron 2001, 57(13), 2507-2514. Compounds of formula (If) can be converted to compound of formula (Ig), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and R13 is hydrogen or C1-C4 alkyl by treatment of compounds of formula (If) with compounds of formula (XXVIII) (or a salt thereof), wherein R13 is hydrogen or C1-C4 alkyl, in an inert solvent such as methanol, ethanol, tetrahydrofuran, methyl, optionally in the presence of an inorganic base such as sodium or potassium carbonate, or organic bases such as triethylamine and the like. Many examples for the 82714_FF 38 preparation of such oximes are known in the literature (see, for example, Molecules 2019, 24, 2470 and references cited therein) and are well known to those skilled in the art. Further compounds that can be prepared from compounds of formula (I), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and X04 is a leaving group like, for example, chlorine, bromine or iodine, namely compounds of formula (Ia), are shown in Scheme 15.
Figure imgf000039_0001
As shown in Scheme 15, compounds of formula (Ia) can be carbonylated to give compounds of formula (I), namely compounds of formula (Ih) with R14 C1-C4 alkyl, wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), In such alkoxycarbonylations, compounds of formula (Ia) are reacted with carbon monoxide, usually under pressure, in the presence of metal catalyst such as a palladium catalyst (for example, palladium(II) acetate, [1,1'- bis(diphenylphosphino)ferrocene] palladium(II) dichloride (Pd(dppf)Cl2), bis(triphenylphosphine)palladium(II) dichloride (PdCl2(PPh3)2) or bis(diphenylphosphino)propane]palladium(II) (PdCl2(dippp)), optionally in the presence of a phosphine ligand such as triphenylphosphine or 1,1'-bis(diphenylphosphino)ferrocene, in the presence of an alcohol (R14OH) (typically methanol or ethanol), wherein R14 is C1-C4 alkyl, optionally in the presence of a co-solvent (e.g. toluene, dioxane or N,N-dimethylformamide), and preferably in the presence of a base, such as for example trimethylamine, at temperatures between 20°C and 200°C, preferably between 82714_FF 39 50°C and 180°C. Such carbonylation reactions are well known to those skilled in the art and also in the literature (see J. Org. Chem.2008, 73, 7102–7107, and references cited therein). Such compounds of formula (Ih) can be easily saponified to compounds of formula (Ii) under conditions known to those skilled in the art, for example conditions such as aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature, or up to refluxing conditions. Alternatively, treating ester compounds of formula (Ih) with halide anions, preferably chloride anions, originating from, for example, lithium chloride (or alternatively, sodium or potassium chloride), in solvents such as N,N-dimethylformamide, N,N- dimethylacetamide or N-methyl-2-pyrrolidone, may also generate the carboxylic acid compounds of formula (Ii). The reaction temperatures for such an O-demethylation range preferably from 20°C to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation. Compounds of formula (Ii) can be converted to amides of formula (I), namely compounds of formula (Ij) with R15 and R16 are independently hydrogen or C1-C4 alkyl, wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined for the compound of formula (I). Such reactions usually involve activating the carboxyl group, followed by treatment with a compound R15R16NH or using coupling agents to perform the direct conversion of the acids to the amides upon treatment with compounds of formula R15R16NH. These methods have been discussed vide supra in Schemes 1 and 2. Further compounds of formula (Ij) can be converted to compounds of formula (I), namely compounds of formula (Ik) with R9 amino, wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), by a so called Curtius rearrangement. In the Curtius rearrangement compounds of formula (Ij) are treated with an organo-azide in the presence of a suitable base and optionally in the presence or absence of Lewis acids, in an inert solvent at temperatures between 50°C and 200°C. Examples of organo-azide include TMSN3, sodium azide, diphenyl phosphoryl azide or tosyl azide and suitable solvent may be toluene, xylene, THF or acetonitrile. Example of suitable Lewis acids may include Zn(OTf)2 amongst others. The isocyanates formed in the rearrangement react with water to form carbamates which decarboxylate under the reaction conditions to the corresponding amines of formula (lk). Alternatively, the reactions can be carried out in alcohols, e.g., t-butyl alcohol, allowing the t-butyl carbamates to be isolated. These in turn can be cleaved in a separate step by methods known to those skilled in the art with acids (such as trifluoroacetic acid) to yield compounds of formula (Ik). Examples of such Curtius reactions have been reported, for example, in Org. Lett.2005, 7, 4107-4110, J. Med.Chem. 2006, 49(12), 3614-3627, and Tetrahedron 1974, 30, 2151-2157. Compounds of formula (Ik) so obtained can be amidated to compounds of formula (Im), wherein Q is Q1, and R1, R2, R3, R4, R5, R6, R10, R11, R12, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and R18 is C1-C4 alkyl by treatment with compounds of formula (XIX) according to the amidation methods described vide supra. Those skilled in the art will recognize that such chemistry can be applied to any of the compounds of formula (I), where Q is Q1, Q2, Q3, Q4, or Q5 at any positions of the heterocycles of formula Q (i.e., R9, R10, R11 or R12) when the later groups are a leaving group such as a halogen atom. A compound of formula (I) as defined in any of the embodiments of the present invention can be converted in a manner known per se into another compound as defined in any of the embodiments of the present invention 82714_FF 40 by replacing one or more substituents of the starting compound in the customary manner by (an)other substituent(s) according to the invention. Those skilled in the art will also appreciate that compounds of formula (I) can be further transformed to further derivatives of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C-C-bond forming reactions in the presence of metal catalysts, heteroatom-carbon bond formation in the presence of metal catalysts, oxidation, and reduction. 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. Salts of compounds of formula (I) may 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. Depending on the procedure or the reaction conditions, the compounds of formula (I), which have salt-forming properties, can be obtained in free form or in the form of salts. The compounds of formula (I) and, where appropriate, the tautomer’s 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 herein below, even when stereochemical details are not mentioned specifically in each case. The compounds of formula (I) of the present invention exhibit an asymmetric carbon atom at the bis-benzylic position: A skilled person would be well aware that both enantiomers are within the scope of the invention. 82714_FF 41 Diastereomeric mixtures or racemic 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. Enantiomeric 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 com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents. 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. 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. As an example, compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns. Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention. The compounds of formula (I) of the present invention exhibit two asymmetric carbon atoms. The relationship between enantiomers and diastereomers of compounds of formula (I) is shown below.
82714_FF 42 A
Figure imgf000043_0001
R1, R2, R3, R4, R5, R6, R7, R8, R9, A1, A2, A3, Q, R10, R11, R12, R13, and Z1 are as defined for formula (I) are within the scope of the invention. Further a person skilled in the art is well aware that above diastereomers and enantiomers are applicable to compounds of formula (Ia), (Ia-A), (Ia-B) and (Ia-C), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, A1, A2, A3, Q, R10, R11, R12, R13, and Z1 are as defined for formula (I) and are within the scope of the invention. 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. As already indicated, surprisingly, it has now been found that the compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi. The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants. The compounds of formula (I) can be used to inhibit or destroy the pests that occur on plants 82714_FF 43 or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms. The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) according to the invention is applied to the plants, to parts thereof or the locus thereof. As used herein, the term "controlling" when used in context of infestation of plants or plant propagation material and /or harvest food crops refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced. The term "preventing" when used in context of infestation of plants or plant propagation material and /or harvest food crops refers to the avoidance of a symptom due to microbial attack or fungal infections (growth of fungi). It is also possible to use a compound of formula (I) according to the invention as a fungicide. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection. It may also be possible to use compounds of formula (I) according to the invention as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown. The active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated. Furthermore, the compounds of formula (I) according to the invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management. In addition, the invention could be used to protect non-living materials from fungal attack, e.g., lumber, wall boards and paint. The compounds of formula (I) according to the invention are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia 82714_FF 44 lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp., Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp., Didymella spp., Drechslera spp., Elsinoe spp.,Epidermophyton spp., Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp., Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp., Sclerotium spp., Septoria spp., including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp., Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp. including V. inaequalis, Verticillium spp., and Xanthomonas spp. The compounds of formula (I) according to the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees, or evergreens, for example conifers, as well as for tree injection, pest management and the like. Within the scope of present invention, target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, 82714_FF 45 rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes. The term "useful plants" is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g., imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®. The term "useful plants" is to be understood as also including useful 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. Examples of such plants are: YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Bollgard I® (cotton variety that expresses a CryIA(c) toxin); Bollgard II® (cotton variety that expresses a CryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate- tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®. The term "crops" is to be understood as including also crop plants which have been so transformed using recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as -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 82714_FF 46 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. Further, in the context of the present invention there are to be understood by delta-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, WO2002/015701). 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 WO2003/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO2003/052073. The processes for the preparation of such transgenic plants are generally known to a 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 WO95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO90/13651. 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 butterflies (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 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); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®. Further examples of such transgenic crops are: 82714_FF 47 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 2003/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 6.1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 × MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Alternaria species in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solani in potatoes and vegetables; Uncinula necator in grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium in cucurbits; Leveillula taurica in cucurbits and solanacious crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymospetoria spp. in cereals. 82714_FF 48 The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation. The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term “plant propagation material” is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds. The compounds of formula (I) according to the invention may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g., in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects. Suitable carriers and adjuvants, e.g., for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO97/33890. Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate. Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent. Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, 82714_FF 49 these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate. Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins. Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers. Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates. Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein said active ingredient is dispersed in finely divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used. Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art. Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2- butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 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- 82714_FF 50 dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma- butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, 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, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N- methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates. Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin. A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, 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 lauryl trimethylammonium 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 dialkyl phosphate esters. Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, and sticking agents. In addition, further, other biocidal active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidal 82714_FF 51 active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators. Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009. In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar- S-methyl. The compounds of formula (I) according to the invention are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation. The compounds of formula (I) according to the invention may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemical usable salt form, and at least one of the above-mentioned adjuvants. The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the invention, an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I). The compound of formula (I) according to the invention may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities. Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorous 82714_FF 52 fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides. Examples of suitable additional active ingredients include the following: petroleum oils, 1,1-bis(4-chlorophenyl)- 2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4- chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carbophenothion, cymiazole, chinomethionat, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorfenethol, chlorfenson, chlorfensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyphos, cufraneb, cyanthoate, DCPM, DDT, demephion, demephion-O, demephion-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfon, dichlofluanid, dichlorvos, dicliphos, dienochlor, dimefox, dinex, dinex-diclexine, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenyl sulfone, disulfiram, DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethoate-methyl, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenetil, fluorbenside, FMC 1137, formetanate, formetanate hydrochloride, formparanate, gamma-HCH, glyodin, halfenprox, hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolin II, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, mesulfen, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycins, nitrilacarb, nitrilacarb 1:1 zinc chloride complex, omethoate, oxydeprofos, oxydisulfoton, pp'-DDT, parathion, permethrin, phenkapton, phosalone, phosfolan, phosphamidon, polychloroterpenes, polynactins, proclonol, promacyl, propoxur, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quintiofos, R-1492, phosglycin, rotenone, schradan, sebufos, selamectin, sophamide, SSI-121, sulfiram, sulfluramid, sulfotep, sulfur, diflovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxime, thiofanox, thiometon, thioquinox, thuringiensin, triamiphos, triarathene, triazophos, triazuron, trifenofos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, cybutryne, dichlone, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8- hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodicin, fenaminosulf, formaldehyde, hydrargaphen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline 82714_FF 53 sulfate, probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en- 1-yl acetate with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradeca- 4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)- hexadec-13-en-11-yn-1-yl acetate, (Z)-icos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)- tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol with 4-methylnonan- 5-one, alpha-multistriatin, brevicomin, codlelure, codlemone, cuelure, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8, 10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acid, methyl eugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol, tetradec- 11-en-1-yl acetate, trimedlure, trimedlure A, trimedlure B1, trimedlure B2, trimedlure C, trunc-call, 2- (octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin- butyl, methylneodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4- ethylphenyl)ethane, 1,2-dichloropropane with 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1- (3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2- yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2- isovalerylindan-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3- bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl(prop-2-ynyl)amino- 3,5-xylyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acethion, acrylonitrile, aldrin, allosamidin, allyxycarb, alpha-ecdysone, aluminium phosphide, aminocarb, anabasine, athidathion, azamethiphos, Bacillus thuringiensis delta endotoxins, barium hexafluorosilicate, barium polysulfide, barthrin, Bayer 22/190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2- chloroethyl) ether, borax, bromfenvinfos, bromo-DDT, bufencarb, butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadine, 82714_FF 54 chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, clocythrin, copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, cyanofenphos, cyanophos, cyclethrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, dicapthon, dichlofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilor, dimefluthrin, dimetan, dimethrin, dimethylvinphos, dimetilan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzofos, dithicrofos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenethacarb, fenitrothion, fenoxacrim, fenpirithrin, fensulfothion, fenthion-ethyl, flucofuron, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, guazatine, guazatine acetates, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hyquincarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lead arsenate, leptophos, lirimfos, lythidathion, m-cumenyl methylcarbamate, magnesium phosphide, mazidox, mecarphon, menazon, mercurous chloride, mesulfenfos, metam, metam-potassium, metam-sodium, methanesulfonyl fluoride, methocrotophos, methoprene, methothrin, methoxychlor, methyl isothiocyanate, methylchloroform, methylene chloride, metoxadiazone, mirex, naftalofos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion- methyl, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, phenkapton, phosnichlor, phosphine, phoxim-methyl, pirimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiofos, pyrazophos, pyresmethrin, quassia, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadilla, schradan, sebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar oils, tazimcarb, TDE, tebupirimfos, temephos, terallethrin, tetrachloroethane, thicrofos, thiocyclam, thiocyclam hydrogen oxalate, thionazin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronat, trimethacarb, tolprocarb, triclopyricarb, triprene, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprofos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, trifenmorph, 1,2-dibromo-3-chloropropane, 1,3- dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5- methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anisiflupurin, benclothiaz, cytokinins, DCIP, furfural, isamidofos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenols, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, norbormide, phosacetim, phosphorus, pindone, pyrinuron, scilliroside, sodium fluoroacetate, thallium sulfate, 82714_FF 55 warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propyl isomer, S421, sesamex, sesasmolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanid, bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrothal-isopropyl, edifenphos, iprobenphos, phosdiphen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim,fluopicolide, fluoxytioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetylaluminium, hymexazol, iprovalicarb, cyazofamid, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'- trifluoro-biphenyl-2-yl)-amide, isoflucypram, isotianil, dipymetitrone, 6-ethyl-5,7-dioxo- pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4- yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3- (difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)- N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4- (2- bromo- 4- fluorophenyl)-N-(2-chloro-6- fluorophenyl)-1,3-dimethyl-1H-pyrazol- 5- amine, fluindapyr, coumethoxystrobin (jiaxiangjunzhi), lvbenmixianan, dichlobentiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1- yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiprolin, tert-butyl N- [6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1- dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [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- 82714_FF 56 phenyl] methanesulfonate, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3- chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N- [1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl- phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1- yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, ametoctradin, amisulbrom, penflufen, (Z,2E)-5-[1-(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide, florylpicoxamid, fenpicoxamid, metarylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3- dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO2020/056090), 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 WO2020/056090), 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 WO2020/097012), 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 WO2020/097012), 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 WO2020/109391), 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 WO2020/109391), 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 WO2020/109391),N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1- methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1- methyl-pyrazole-4-carboxamide, benzothiostrobin, phenamacril, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoyne, picarbutrazox, 2-(difluoromethyl)-N- (3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4- yl)pyridine- 3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3- pyridyl]oxy]benzonitrile, metyltetraprole, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3- carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy) [1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol, fluoxapiprolin, enoxastrobin, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop- 2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate, methyl (Z)-2-[5-(3- isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3- propylpyrazol-1-yl)phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1- yl]phenoxy]prop-2-enoate (these compounds may be prepared from the methods described in WO2020/079111), methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, methyl (Z)-2-(5- cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020/193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1- yl)propyl]-3-pyridyl]oxy] benzonitrile, 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, 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, trinexapac, coumoxystrobin, zhongshengmycin, 82714_FF 57 thiodiazole copper, zinc thiazole, amectotractin, iprodione, seboctylamine, N'-[5-bromo-2-methyl-6-[(1S)-1- methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2- propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy- ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3- pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N- isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2015/155075); 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); N-isopropyl-N’-[5-methoxy- 2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, 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); N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019/110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro- quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3- trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro- quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro- N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3- fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8- fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N- ((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1- methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017/153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl- isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro- 3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7- methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro- 3,3-dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5- dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4- methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl- isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N- 82714_FF 58 [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol- 3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole-4-carboxylate, 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 WO2017/055473, WO2017/055469, WO 2017/093348 and WO2017/118689); 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 WO2017/029179); 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 WO2017/029179); 3-[2-(1- chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro- phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO2016/156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound may be prepared from the methods described in WO2014/006945); 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 WO2011/138281) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (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 WO2018/153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'- [2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO2016/202742); 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 WO2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (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 WO2017/220485); 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 WO2018/065414); 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 WO2018/158365); 2,2-difluoro-N-methyl-2- [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzamide, N-[N-methoxy-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). The compounds of the invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP0357460, EP0444964 and EP0594291. Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US5,015,630, WO94/15944 and WO95/22552. Additional anthelmintic agents include the benzimidazoles such 82714_FF 59 as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel. The compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US5,478,855, US4,639,771 and DE-19520936. The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO96/11945, WO93/19053, WO 93/25543, EP0626375, EP0382173, WO94/19334, EP0382173, and EP0503538. The compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like. The compounds of the invention may be used in combination with terpene alkaloids, for example those described in WO95/19363 or WO04/72086, particularly the compounds disclosed therein. Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following: Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion. Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717. Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan- 3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, beta- cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, 82714_FF 60 cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin. Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen. Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1111, R-195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301. Biological agents: Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi. Bactericides: chlortetracycline, oxytetracycline, streptomycin. Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole. The following mixtures of the compounds of Formula (I) with active ingredients are preferred. The abbreviation “TX” means one compound selected from the group consisting of compounds of formula (I), (Ia), (Ia-A), (Ia-B) or (Ia-C), or one compound selected from the group consisting of the compounds as represented in Tables C- 1 to C-21 or a compound as listed in Table P (below): a compound selected from the group of substances consisting of petroleum oils + TX, 1,1-bis(4-chlorophenyl)- 2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, 82714_FF 61 carbophenothion + TX, cymiazole + TX, chinomethionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, cufraneb + TX, cyanthoate + TX, DCPM + TX, DDT + 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, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dienochlor + TX, dimefox + TX, dinex + TX, dinex-diclexine + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinosulfon + TX, dinoterbon + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate-methyl + TX, etrimfos + TX, fenazaflor + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpyrad + TX, fenpyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, flubenzimine + TX, flucycloxuron + TX, fluenetil + TX, fluorbenside + TX, FMC 1137 + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, gamma-HCH + TX, glyodin + TX, halfenprox + TX, hexadecyl cyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, lindane + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, mesulfen + TX, methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2- chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifluridide + TX, nikkomycins + TX, nitrilacarb + TX, nitrilacarb 1:1 zinc chloride complex + TX, omethoate + TX, oxydeprofos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phenkapton + TX, phosalone + TX, phosfolan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, proclonol + TX, promacyl + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pyrimitate + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, phosglycin + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, sophamide + TX, SSI-121 + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, diflovidazin + TX, tau-fluvalinate + TX, TEPP + TX, terbam + TX, tetradifon + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trifenofos + TX, trinactin + TX, vamidothion + TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichlone + TX, dichlorophen + TX, endothal + TX, fentin + TX, hydrated lime + TX, nabam + TX, quinoclamine + TX, quinonamid + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, crufomate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1- hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodicin + TX, fenaminosulf + TX, formaldehyde + TX, hydrargaphen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + 82714_FF 62 TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, apholate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + 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)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + 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, (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, 14-methyloctadec-1- ene + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, alpha-multistriatin + TX, brevicomin + TX, codlelure + TX, codlemone + TX, cuelure + TX, disparlure + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1- yl acetate + TX, dodeca-8 + TX, 10-dien-1-yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, frontalin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure + TX, looplure + TX, medlure + TX, megatomoic acid + TX, methyl eugenol + TX, muscalure + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methylneodecanamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1- bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2- ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + 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-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2- isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4- methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl 82714_FF 63 dimethylcarbamate + TX, acethion + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, anabasine + TX, athidathion + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiofos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidafos + TX, dicapthon + TX, dichlofenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dilor + TX, dimefluthrin + TX, dimetan + TX, dimethrin + TX, dimethylvinphos + TX, dimetilan + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, diofenolan + TX, dioxabenzofos + TX, dithicrofos + TX, DSP + TX, ecdysterone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, etaphos + TX, ethiofencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, fenchlorphos + TX, fenethacarb + TX, fenitrothion + TX, fenoxacrim + TX, fenpirithrin + TX, fensulfothion + TX, fenthion-ethyl + TX, flucofuron + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, furathiocarb + TX, furethrin + TX, guazatine + TX, guazatine acetates + TX, sodium tetrathiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hyquincarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprothiolane + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kelevan + TX, kinoprene + TX, lead arsenate + TX, leptophos + TX, lirimfos + TX, lythidathion + TX, m-cumenyl methylcarbamate + TX, magnesium phosphide + TX, mazidox + TX, mecarphon + TX, menazon + TX, mercurous chloride + TX, mesulfenfos + TX, metam + TX, metam- potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methocrotophos + TX, methoprene + TX, methothrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methylchloroform + TX, methylene chloride + TX, metoxadiazone + TX, mirex + TX, naftalofos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O- diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, phenkapton + TX, phosnichlor + TX, phosphine + TX, phoxim- methyl + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + TX, quassia + TX, quinalphos-methyl + TX, quinothion + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, kadethrin + TX, ryania + TX, ryanodine + TX, sabadilla) + TX, schradan + TX, sebufos + TX, SI-0009 + TX, thiapronil + TX, 82714_FF 64 sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron- sodium + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tazimcarb + TX, TDE + TX, tebupirimfos + TX, temephos + TX, terallethrin + TX, tetrachloroethane + TX, thicrofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thionazin + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronat + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triprene + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, and meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, trifenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo- 1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H- purin-6-amine + TX, benclothiaz + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + TX, potassium ethylxanthate + TX,acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, alpha-chlorohydrin + TX, antu + TX, barium carbonate + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbormide + TX, phosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, scilliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5- (1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, verbutin + TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, mercuric oxide + TX, thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazole + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, - simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropidine + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl -+ TX, Rmetalaxyl + TX, ofurace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + 82714_FF 65 TX, dimoxystrobin + TX, enestroburin + TX, fenaminstrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim-methyl + TX, metominostrobin + TX, trifloxystrobin + TX, orysastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid + TX, bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothal-isopropyl + TX, edifenphos + TX, iprobenphos + TX, phosdiphen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, cyclobutrifluram + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminium + TX, hymexazol + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamid + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl- 2-yl)-amide + TX, isoflucypram + TX, isotianil + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo- pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan- 4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)- 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro- phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1, 3- dimethyl- 1H- pyrazol- 5- amine + TX, fluindapyr + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, lvbenmixianan + TX, dichlobentiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4- dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiprolin + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole+ TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4- yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'- [4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + 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, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3- (difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2- [[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctradin + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamid + TX, fenpicoxamid + TX, tebufloquin + TX, 82714_FF 66 ipflufenoquin + TX, quinofumelin + TX, isofetamid + 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, benzothiostrobin + TX, phenamacril + TX, 5-amino-1,3,4-thiadiazole- 2-thiol zinc salt (2:1) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + 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, metyltetraprole + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, α- (1, 1- dimethylethyl) - α- [4'- (trifluoromethoxy) [1, 1'- biphenyl] - 4- yl] -5- pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + 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, trinexapac + TX, coumoxystrobin + TX, zhongshengmycin + TX, thiodiazole copper + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, N-octyl-N'-[2-(octylamino)ethyl]ethane- 1,2-diamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl- formamidine + 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-(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'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl- formamidine + TX (these compounds may be prepared from the methods described in WO2015/155075); N'- [5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-4- (2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine+ TX, N’-[4-(1-cyclopropyl-2,2,2- trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N’-[5-methoxy-2- methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N’-[5-methoxy-2-methyl- 4-[2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2019/110427); 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-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1- benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]- 7,8-difluoro-quinoline-3-carboxamide + 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, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1- benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + 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 (these compounds may be prepared from the methods described 82714_FF 67 in WO2017/153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 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, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4- difluoro-3,3-dimethyl-isoquinoline + TX (these compounds may be prepared from the methods described in WO2017/025510); 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, 6-chloro-4,4-difluoro-3,3-dimethyl-1- (4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3- dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H- cyclopenta[e]benzimidazole + TX (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph may be prepared from the methods described in WO2017/055473, WO2017/055469, WO2017/093348 and WO2017/118689; 2-[6-(4- chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO2016/156290); 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO2016/156290); (4-phenoxyphenyl)methyl 2-amino-6- methyl-pyridine-3-carboxylate + TX (this compound may be prepared from the methods described in WO2014/006945); 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound may be prepared from the methods described in WO2011/138281); N-methyl-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3- dimethyl-pent-3-enamide + TX (this compound may be prepared from the methods described in WO2018/153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro- 4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in WO2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4- 82714_FF 68 yl]pyridine-3-carboxamide + TX (this compound may be prepared from the methods described in WO2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3- methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds may be prepared from the methods described in WO2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound may be prepared from the methods described in WO2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4- carboxylate + TX (this compound may be prepared from the methods described in WO2018/158365) ; 2,2- difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + 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-[N-methoxy-C-methyl-carbonimidoyl]-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds may be prepared from the methods described in WO2018/202428), chloroinconazide + TX, flumetylsulforim + TX, fluoxytioconazole + TX, flufenoxadiazam +TX, metarylpicoxamid +TX. The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html. 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. The active ingredient mixture of the compound selected from the group consisting of compounds of formula (I), (Ia), (Ia-A), (Ia-B) or (Ia-C), or one compound selected from the group consisting of the compounds as represented in Tables C-1 to C-21 or a compound as listed in Table P (below):is preferably in a mixing ratio of from 100:1 to 1:100, 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, and still more especially from 5:1 to 1:5 Those mixing ratios are by weight. The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of 82714_FF 69 a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body. The mixtures comprising a compound selected from the compounds of formula (I),) (Ia), (Ia-A), (Ia-B), (Ia-C), or one compound selected from the group consisting of the compounds as represented in Tables C-1 to C-21 or a compound as listed in Table P (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying a compound selected from the compounds of formula (I),) (Ia), (Ia-A), (Ia-B), (Ia-C), or one compound selected from the group consisting of the compounds as represented in Tables C-1 to C-21 or a compound as listed in Table P (below): and the active ingredient(s) as described above, is not essential for working the present invention. 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. 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. Another aspect of the invention is related to the use of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms. A further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials. 82714_FF 70 Controlling or preventing means reducing infestation by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated. A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I) according to the invention, or an agrochemical composition which contains at least one compound of formula (I), is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula (I) according to the invention can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g., in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation. A formulation, e.g., a composition containing the compound of formula (I) according to the invention and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants). Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds. The term “g a.i./ha” as used herein refer to the application rate given in gram [g ] of active ingredient [a.i.] per unit of surface [ha]. The unit hectare (symbol ha) is the metric unit of area that equals a square with 100 m side (1 hm2) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system. When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of formula (I) per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient. Suitably, a composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development. The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro- emulsion (ME), an oil 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 82714_FF 71 (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. Such compositions may be produced in conventional manner, e.g., by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers, and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol. A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g., as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g., as slow-release capsules or microcapsules. In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts, and adjuvant(s), the active agent consisting of at least the compound of formula (I) according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline, compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha. Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts: 82714_FF 72 active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 % The disclosure in the present application makes available each and every combination of embodiments disclosed herein. The compounds according to the following Tables C-1 to C-21 may 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 any of Tables C-1 to C-21 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. The disclosure in the present application makes available each and every combination of embodiments disclosed herein. The compounds according to the following Tables C-1 to C-21 may 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). Table A: This table discloses 20 substituent definitions G of the formula (I)
Figure imgf000073_0001
82714_FF 73 wherein G is of formula defined below: Index G
Figure imgf000074_0001
Index G l] l]
Figure imgf000074_0003
Table B: This table discloses 14 substituent definitions Q of the Formula (I)
Figure imgf000074_0002
Index Q
Figure imgf000074_0004
82714_FF 74 Tables C-1 to C-21 disclose specific compounds of the invention of formula (I), wherein Q and G substituents are as defined in tables A and B. Table C-1: This table provides 20 compounds C-1.01 to C-1.20 of formula (I) wherein R2, R4, R5, R6 are H, Q is Q-1 as defined in Table B, and G is as defined in Table A. For example, compound C-1.01 has the following structure: Compound C-1.01
Figure imgf000075_0001
C-2.01 to C-2.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-1 as defined in Table B, and G is as defined in Table A. For example, compound C-2.05 has the following structure: Compound C-2.05
Figure imgf000075_0002
C-3.01 to C-3.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A. For example, compound C-3.11 has the following structure; Compound C-3.11
Figure imgf000075_0003
C-4.01 to C-4.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A. Table C-5: This table provides 20 compounds C-5.01 to C-5.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-4 as defined in Table B, and G is as defined in Table A. Table C-6: This table provides 20 compounds C-6.01 to C-6.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A. 82714_FF 75 Table C-7: This table provides 20 compounds C7.01 to C-7.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-6 as defined in Table B, and G is as defined in Table A. Table C-8: This table provides 20 compounds C8.01 to C-8.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-7 as defined in Table B, and G is as defined in Table A. Table C-9: This table provides 12 compounds C-9.01 to C-9.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-8 as defined in Table B, and G is as defined in Table A. For example, compound C-9.03 has the following structure: Compound C-9.03
Figure imgf000076_0001
C-10.01 to C-10.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-9 as defined in Table B, and G is as defined in Table A. Table C-11: This table provides 20 compounds C-11.01 to C-11.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-10 as defined in Table B, and G is as defined in Table A. Table C-12: This table provides 20 compounds C-12.01 to C-12.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-11 as defined in Table B, and G is as defined in Table A. Table C-13: This table provides 20 compounds C-13.01 to C-13.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-12 as defined in Table B, and G is as defined in Table A. Table C-14: This table provides 20 compounds C-14.01 to C-14.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-13 as defined in Table B, and G is as defined in Table A. Table C-15: This table provides 20 compounds C-15.01 to C-15.20 of formula (I) wherein R2, R5, R6 are H, R4 is CH3, Q is Q-14 as defined in Table B, and G is as defined in Table A. For example, compound C-15.12 has the following structure: Compound C-15.12
Figure imgf000076_0002
82714_FF 76 Table C-16: This table provides 20 compounds C-16.01 to C-16.20 of formula (I) wherein R5, R6 are H, R2 and R4 are CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A. Table C-17: This table provides 20 compounds C-17.01 to C-17.20 of formula (I) wherein R5, R6 are H, R2 and R4 are CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A. Table C-18: This table provides 20 compounds C-18.01 to C-18.20 of formula (I) wherein R5, R6 are H, R2 and R4 are CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound C-18.01 has the following structure: Table C-19: This table provides 20 compounds C-19.01 to C-19.20 of formula (I) wherein R5, R6 are H, R2 is Cl, R4 is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A. Table C-20: This table provides 20 compounds C-20.01 to C-20.20 of formula (I) wherein R5, R6 are H, R2 is Cl, R4 is CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A. Table C-21: This table provides 20 compounds C-21.01 to C-21.20 of formula (I) wherein R5, R6 are H, R2 is Cl, R4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound C-21.01 has the following structure: Compound C-21.04
Figure imgf000077_0001
EXAMPLES The Examples which follow serve to illustrate the invention and are not meant in any way to limit the invention. The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, if necessary, for example 60 ppm, 20 ppm or 2 ppm. Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability). Throughout this description, temperatures are given in degrees Celsius (°C) and “m.p.” means melting point. LC/MS or LC-MS or LCMS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows. 82714_FF 77 1H NMR and 19F NMR measurements were recorded on a Bruker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS (1H) and CFCl3 (19F) 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)-. LCMS Method A: Spectra were recorded on a Mass Spectrometer from Waters Corp. (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350- 600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and 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. LCMS Method B: Spectra were recorded on a Mass Spectrometer from Waters Corp. (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source. Optimized Mass Parameter: Ionisation method: Electrospray (ESI), Polarity: Positive and Negative Polarity Switch, Scan Type: Full Scan, Capillary (kV): 0.8, Cone Voltage (V): 23, Source Temperature (°C): 120, Desolvation Gas Flow (L/Hr): 1000, Desolvation Temperature (°C): 600, Gas Flow @ Cone (L/Hr): 50, Mass range : 110 to 1200 Da; Gradient conditions: solvent A: water with 0.1% formic acid: acetonitrile: 95 : 5 v/v, solvent B: acetonitrile with 0.05% formic acid Time (minutes) A (%) B (%) Flow rate (ml/min) 09 0 10 0.6 0.2 90 10 0.6 0.3 50 50 0.6 0.6 0 100 0.6 1.3 0 100 0.6 1.4 90 10 0.6 1.6 90 10 0.6 PDA Wavelength range: 200 to 400 nm Column: Acquity UPLC HSS T3 C18, Column length: 30 mm, Internal diameter of column: 2.1 mm, Particle Size: 1.8 μ, Column oven temperature: 40°C. LCMS Method C: Spectra were recorded on a Mass Spectrometer from Waters Corp. (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source. 82714_FF 78 Optimized Mass Parameter: Ionisation method: Electrospray (ESI); Polarity: Positive and Negative Polarity Switch; Scan Type: Full Scan; Capillary (kV): 3.00; Cone Voltage (V): 41.00; Source Temperature (°C): 150; Desolvation Gas Flow (L/Hr): 1000; Desolvation Temperature (°C): 500; Gas Flow @ Cone (L/Hr): 50; Mass range: 110 to 1000 Da Gradient conditions: Solvent A: water with 0.1% formic acid: acetonitrile: 95: 5 v/v; Solvent B: acetonitrile with 0.05% formic acid Time (minutes) A (%) B (%) Flow rate (ml/min) 0 90 10 0.6 0.2 90 10 0.6 0.3 50 50 0.6 0.6 0 100 0.6 1.3 0 100 0.6 1.4 90 10 0.6 1.6 90 10 0.6 PDA Wavelength range: 200 to 400 nm; Column: Acquity UPLC HSS T3 C18; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 μ; Column oven temperature: 40°C. LCMS Method D: Spectra were recorded on a 6410 Triple Quadruple Mass Spectrometer from Agilent Technologies (HPLC: Agilent 1200 Series HPLC) Optimized Mass Parameter: Ionisation method: Electrospray (ESI); Polarity: Positive and Negative Polarity Switch; Scan Type: MS2 Scan; Capillary (kV): 4.00; Fragmentor (V): 100.00; Gas Temperature (°C): 350; Gas Flow (L/min): 11; Nebulizer Gas (psi): 40; Mass range: 110 to 1000 Da; Detection(VWD): 254 nm. Gradient conditions: Solvent A: water with 0.1% formic acid : acetonitrile: 95 : 5 v/v; Solvent B: acetonitrile with 0.1% formic acid Time (minutes) A (%) B (%) Flow rate (ml/min) 0 90 10 1.8 0.9 0 100 1.8 1.8 0 100 1.8 2.2 90 10 1.8 2.5 90 10 1.8 Column: KINETEX EVO C18; Column length: 50 mm; Internal diameter of column: 4.6 mm; Particle Size: 2.6 µ; Column oven temperature: 40°C LCMS Method E: Spectra were recorded on a Mass Spectrometer from Waters (Acquity QDa Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8 kV, Cone range: 25 V, Extractor: V (No extractor voltage for Qda detector) Source Temperature: 120°C, 82714_FF 79 Desolvation Temperature: 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. LCMS Method F: Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C,  Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1% formic acid, B= Acetonitrile + 0.1% formic acid, gradient: 0-100% B in 3.0 min; Flow (ml/min) 0.75. Formulation Examples Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration. Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - - 20 % The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment. Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % 82714_FF 80 calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c) Active ingredients 5 % 6 % 4 % Talcum 95 % - - Kaolin - 94 % - mineral filler - - 96 % Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruder granules Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % Kaolin 82 % 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 % 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 % 82714_FF 81 The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. 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 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose. Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. Abbreviations CDCl3 deuterated chloroform conc. concentrated 82714_FF 82 DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA DCC dicyclohexyl carbodiimide DIPEA Diisopropylethylamine (N,N-Diisopropylethylamine) DMF dimethylformamide (N,N-dimethylformamide) DMSO dimethyl sulfoxide DMSO-d6 deuterated Dimethyl sulfoxide equiv. equivalent EtOAc ethyl acetate HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate HCl hydrochloric acid h/hrs hour (s) LCMS Liquid Chromatography Mass Spectrometry rh relative humidity rt room temperature RT retention time ssp. subspecies TBME methyl tert-butyl ether or tert-butyl methyl ether THF tetrahydrofuran TLC thin layer chromatography TMS tetramethylsilan T3P propylphosphonic anhydride, a reactive n-propyl phosphonic acid cyclic anhydride Preparation Examples: The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below. “Mp” means melting point in °C (grad Celsius). Free radicals represent methyl groups. 1H NMR and 19F NMR measurements were recorded on a Bruker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS (1H) and CFCl3 (19F) 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)-. Example 1: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-1, Table P) 82714_FF 83 (Compound P-1, Table P)
Figure imgf000084_0001
4-yl)propane nitrile
Figure imgf000084_0002
4-yl)acetonitrile (10.00 g, 78.42 mmol) was dissolved in THF (314 mL) under argon and the pale-yellow solution was cooled to -78°C. To this solution was added dropwise n-butyl lithium (31 mL, 78.42 mmol) and the resulting pale brown suspension was stirred at this temperature for 25 minutes. After this time, iodomethane (11.24 g, 4.93 mL, 78.42 mmol) was added dropwise. The resulting brown solution was stirred at -78°C for 5 minutes, allowed to warm to room temperature (rt) and stirred for 30 minutes at rt under argon. The reaction mixture was poured into water, and then extracted twice with EtOAc. The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to give 2-(1-methylpyrazol-4-yl)propanenitrile as a light brown liquid. LC/MS (Method A); 136 [M+H]+; retention time: 0.43 min, 0.44 min, 0.55 min. 1H NMR (400 MHz, CDCl3) δ ppm 1.64 (d, J=6.90 Hz, 3 H) 3.86 - 3.93 (m, 4 H) 7.40 (s, 1 H) 7.46 (s, 1 H). Step 2: Preparation of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propanenitrile
Figure imgf000084_0003
4-yl)propanenitrile (2.00 g, 14.80 mmol) was dissolved in THF (59.18 mL) under argon to give a pale-yellow solution. The solution was cooled to -78°C and then treated dropwise with n-butyl lithium (5.90 mL, 14.80 mmol). The resulting pale brown suspension was stirred at this temperature for 10 min. before adding 2,6-dichloropyridine (2.23 g, 14.80 mmol) portion wise. The resulting brown suspension was stirred at -78°C for 5 minutes, let to reach room temperature and stirred for 30 minutes at rt under argon to give a light brown solution. The reaction mixture was poured into water and extracted twice with ethyl acetate. The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, filtered, and 82714_FF 84 concentrated in vacuo at 60°C to give 3.68 g of a dark brown liquid. The crude brown liquid was purified by flash chromatography with an eluent of ethyl acetate in cyclohexane to yield 2-(6-chloro-2-pyridyl)-2-(1- methylpyrazol-4-yl)propanenitrile (2.71 g, 74.2 yield) as a pale-yellow oil. LC/MS (Method A); 247 [M+H]+; retention time: 0.82 min. 1H NMR (400 MHz, CDCl3) δ ppm 2.12 (s, 3 H) 3.90 (s, 3 H) 7.27 - 7.32 (m, 1 H) 7.45 (s, 1 H) 7.46 - 7.54 (m, 2 H) 7.62 - 7.74 (m, 1 H). Step 3: Preparation of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine
Figure imgf000085_0001
-2-(1-methylpyrazol-4-yl)propanenitrile (2.71 g, 11.0 mmol) in THF (33.0 mL) was treated dropwise with borane methyl sulfide complex (2.50 g, 3.13 mL, 33.0 mmol) at room temperature under argon and the resulting pale-yellow solution was stirred for 4 hours at 65°C. The reaction mixture was cooled to 0°C before adding dropwise concentrated hydrochloric acid (HCl) (7.36 mL, 44.2 mmol). The reaction mixture was stirred for 1 hour at 50°C. The reaction mixture was cooled to rt and water was added. To this reaction mixture aq. sodium hydroxide (6N NaOH) was added until pH of 12 and the resulting reaction mixture extracted three times with ethyl acetate. The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to give 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4- yl)propan-1-amine as a pale-yellow oil, that could be used in the next step without further purification. 1H NMR (400 MHz, DMSO d6) δ ppm 1.57 (s, 3 H) 2.98 (d, J=12.72 Hz, 1 H) 3.16 (d, J=12.72 Hz, 1 H) 3.77 (s, 3 H) 7.20 - 7.35 (m, 3 H) 7.50 (s, 1 H) 7.75 (t, J=7.81 Hz, 1 H). Step 4: Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate
Figure imgf000085_0002
benzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was treated successively with copper(II)sulfate anhydrous (0.053 g, 0.33 mmol), sodium ascorbate (0.46 g, 2.3 mmol) in water (3.6 mL), and then methyl prop-2-ynoate (0.14 g, 0.14 mL, 1.7 mmol) The reddish reaction mixture was stirred for 2 days at rt (monitoring by LCMS). The reaction mixture was then concentrated in vacuo, and the residue taken up in water and EtOAc. The organic layer was separated, washed with brine, and the separated organic layer dried 82714_FF 85 over MgSO4, filtered, and concentrated in vacuo. The crude product was adsorbed onto ISOLUTE® and purified over a silica gel cartridge (Rf200), eluting with cyclohexane/EtOAc, to give the title compound as a white solid. LC/MS (Method A) m/z=240 [M+H]+; retention time =0.79 min; 1H NMR (400 MHz, CDCl3) δ ppm 4.02 (s, 3 H) 7.09 - 7.17 (m, 2 H) 7.96 - 8.05 (m, 1 H) 8.59 (d, J=2.57 Hz, 1 H) Step 5: Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid
Figure imgf000086_0001
triazole-4-carboxylate (0.31 g, 1.3 mmol) was dissolved in THF (6.5 mL) and water (3.2 mL) under argon to give a pale brown solution. To this solution LiOH.H2O (0.047 g, 1.9 mmol) was added and the mixture was stirred at rt. After 3 hours LC/MS analysis (desired mass at rt=0.63 min) showed complete consumption of starting material. The sample was concentrated in vacuo and the residue taken up in water and EtOAc, and the resulting mixture acidified with 2N HCl. The organic layer was separated, dried over Na2SO4, filtered, and concentrated in vacuo to give the title compound as a white solid. LC/MS (Method A): m/z=226 [M+H]+; retention time =0.63 min; 1H NMR (400 MHz, DMSO) δ ppm 7.27 - 7.52 (m, 1 H) 7.73 (ddd, J=11.10, 8.71, 2.57 Hz, 1 H) 7.95 (td, J=8.80, 5.87 Hz, 1 H) 9.15 (d, J=1.47 Hz, 1 H) 13.26 - 13.60 (m, 1 H) Step 6: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole- 4-carboxamide (Compound P-1, Table P) 1-(2,4-difluorophenyl)triazole-4-carboxylic acid (0.225g, 1.0 mmol) and 2-(6-chloro-2-pyridyl)-2-(1- methylpyrazol-4-yl)propan-1-amine (0.25 g, 1 mmol) was suspended in EtOAc (6 mL). To this mixture was added diisopropylethylamine (DIPEA) (0.65g, 5 mmol) and 1-propanephosphonic anhydride (T3P, 50 mass% in EtOAc, 2mL) at 0 °C and the reaction mixture was stirred at rt for 2 hours (LCMS analysis showed reaction completion). The reaction mixture was diluted with water and the resulting mixture extracted with l EtOAc (2x20 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under in vacuo. The crude product was absorbed on silica gel and purified by combiflash eluting with 0-80% cyclohexane/EtOAc to give the title compound as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 8.50 (d, J=2.57 Hz, 1 H) 8.05 (br t, J=6.36 Hz, 1 H) 7.91 (td, J=8.71, 5.69 Hz, 1 H) 7.58 (t, J=7.82 Hz, 1 H) 7.35 (s, 1 H) 7.29 (s, 1 H) 7.23 (d, J=7.82 Hz, 1 H) 7.12 (dd, J=8.86, 8.01 Hz, 2 H) 7.06 - 7.10 (m, 1 H) 4.11 (dd, J=16.75, 6.60 Hz, 2 H) 3.88 (s, 3 H) 1.74 (s, 3 H); LC/MS (Method B): m/z=458 [M+H]+; retention time =1.09 min 82714_FF 86 Example 2: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)- 1,2,4-triazole-3-carboxamide (Compound P-4, Table P). (Compound P-4, Table P)
Figure imgf000087_0001
-1,2,4-triazole-3-carboxylate
Figure imgf000087_0002
in Org. Lett. 2018, 20, 6930−6933. Thus, a solution of 2,4- difluorobenzenediazonium.tetrafluoroborate (prepared as described in J. Am. Chem. Soc. (1956), 78, 2593-6, 500 mg, 0.5 g, 2.1939 mmol) in THF (8.8 mL) was cooled to 0°C and lithium acetate dihydrate (0.44765 g, 4.3879 mmol), Cu(OAc)2 (0.10 equiv., 0.03985 g, 0.21939 mmol) and methyl 2-isocyanoacetate (1.20 equiv., 0.2609 g, 0.239 mL, 2.6327 mmol) were added at 0°C and the mixture was stirred at this temperature for 4 hours. LCMS analysis showed reaction completion after this time. The reaction mixture was poured into water (25mL) and the resulting mixture was extracted with EtOAc (2X20mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude material was purified by column chromatographie (24g SiO2, eluting with an EtOAc/cyclohexane gradient) to give the title compound as an oil. 1H NMR (400 MHz, CDCl3) δ ppm 8.68 (d, J=2.81 Hz, 1 H) 7.93 - 8.00 (m, 1 H) 7.08 - 7.14 (m, 2 H) 4.08 (s, 3 H) 1.27 (s, 1 H) Step 2: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4- triazole-3-carboxamide (Compound P-4, Table P) 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (0.031 g, 0.12 mmol) was added to a solution of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate (0.025 g, 0.10 mmol) in toluene (0.75 mL) in a microwave vial. This reaction mixture was stirred under argon atmosphere for 5 minutes and then bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.041 g, 0.16 mmol) was added and the resulting reaction mixture was stirred at 70 °C in microwave. After reaction completion, the reaction mixture was diluted with water, extracted with EtOAc and the organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. The resultant crude residue was purified by chromatography on silica gel, using a cyclohexane/ethyl acetate eluent system, to afford N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-1- (2,4-difluorophenyl)-1,2,4-triazole-3-carboxamide as a gummy mass. 82714_FF 87 LCMS (Method C): 458 [M+H]+; retention time = 1.03 min; 1H NMR (400 MHz, CDCl3) δ ppm 8.52 (d, 1 H), 8.27 (br t, 1 H), 7.94 (td, 1 H), 7.51 (t, 1 H), 7.23 - 7.20 (m, 2 H), 7.14-7.18 (m, 1 H), 6.98 - 7.10 (m, 3 H), 4.01 (dd, 2 H), 3.80 (s, 3 H), 1.66 (s, 3H) Example 3: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4- difluorophenyl)tetrazole-5-carboxamide (Compound P-6, Table P) (Compound P-6, Table P).
Figure imgf000088_0001
tolylsulfonylhydrazono)acetate
Figure imgf000088_0002
(CAS [1576-35-8], 2 g, 10.73 mmol) in ethanol (40 mL) was treated with ethyl 2-oxoacetate (2.63 g, 12.88 mmol) at room temperature. The reaction mixture was stirred for 1 hour and the ethanol removed by concentration in vacuo. The residue obtained was diluted with water and extracted with EtOAc. The organic phase was separated, and the solvent was evaporated in vacuo to afford ethyl (2E)-2-(p-tolylsulfonylhydrazono)acetate, which was used as such for the next step (step 2). LCMS (Method C): 271 [M+H]+; retention time = 1.04 min; 1H NMR (400 MHz, CDCl3) δ ppm 9.31 (s, 1 H) 7.85 (d, J=8.31 Hz, 2 H) 7.34 (d, J=8.07 Hz, 2 H) 7.23 (s, 1 H) 4.27 (q, J=7.09 Hz, 2 H) 4.14 (q,J=7.09 Hz, 1 H) 2.44 (s, 3 H) 2.07 (s, 2 H) 1.23 - 1.37 (m, 7 H). Step 2: Preparation of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate
Figure imgf000088_0003
was solubilized in aqueous 6M hydrochloric acid (deionized water) (6 mL, 36 mmol) and ethanol (5 mL) and was cooled to 0 °C. To that solution was added sodium nitrite (0.64 g, 9.29 mmol) and the resulting solution was stirred for 1 hour at 0°C, and then added dropwise to a solution of ethyl 82714_FF 88 (2E)-2-(p-tolylsulfonylhydrazono)acetate (2.3g, 8.51 mmol) in pyridine (20 mL) at -20 °C. The reaction mixture was slowly allowed to warm to room temperature and then stirred for 5 hours. The resulting mixture was diluted with 1N HCl and the aqueous layer was extracted with EtOAc (3x20 mL). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to give the crude product which was purified by column chromatography eluting with 30% EtOAc in hexane to give ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate as a reddish oil. LCMS (Method B): [M+H+] not detected; retention time = 1.10 min; 1H NMR (400 MHz, CDCl3δ ppm 7.86 - 7.94 (m, 1 H) 7.11 - 7.21 (m, 2 H) 4.60 (q, J=7.21 Hz, 2 H) 2.03 (s, 1 H) 1.51 (t, J=7.13 Hz, 3 H) Step 3: Preparation of 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid
Figure imgf000089_0001
5-methylisoxazole-3-carboxylate (300 mg, 1.18 mmol) in THF (3 mL) and water (1.5 mL) was added LiOH.H2O (0.113 mg, 4.72) at rt and the reaction mixture was stirred at room temperature for 30 min. The organic solvent was removed by concentration in vacuo, and the aqueous residue diluted with 2N HCl, and then extracted with EtOAc (3x20 mL). The combined organic phases were dried over Na2SO4, filtered, and concentrated in vacuo to afford reddish solid 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid. LCMS (Method C): 227 [M+H]+; retention time = 0.87-1.11 min; 1H NMR (400 MHz, DMSO-d6) δ ppm 8.10 (td, J=8.69, 5.75 Hz, 1 H) 7.73 - 7.88 (m, 1 H) 7.40 - 7.50 (m, 1 H) 3.36 - 3.63 (m, 3 H) 3.07 - 3.35 (m, 3 H) 1.99 (s, 1 H) 1.91 (s, 1 H) 1.24 (s, 1 H) Step 4: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole- 5-carboxamide (Compound P-6, Table X). A mixture of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (6.37 g, 22.9 mmol, prepared as previously described), 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid (6.32 g, 25.2 mmol), N,N- diisopropylethylamine (DIPEA) (9.33 g, 68.6 mmol) and T3P (50 mass% in EtOAc) (40 mL) was stirred in EtOAc (114 mL) at room temperature for 1 hour. LCMS showed completion of reaction after this time. The reaction mixture was diluted with water and EtOAc, the organic layer separated and the aqueous layer back- extracted three times with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and evaporated in vacuo. The crude product was purified by column chromatography eluting with EtOAc/cycloheaxane to give N- [2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide as off white solid. LCMS (Method B): 459 [M+H]+; retention time = 1.14 min; 82714_FF 89 1H NMR (400 MHz, DMSO-d6) δ ppm 8.75 (t, J=6.38 Hz, 1 H), 8.07 (td, J=8.76, 5.75 Hz, 1 H), 7.76 - 7.83 (m, 2 H), 7.62 (s, 1 H), 7.45 (t, J=8.38 Hz, 1 H), 7.38 (d, J=7.38 Hz, 1 H), 7.35 (d, J=0.75 Hz, 1 H), 7.29 (d, J=7.25 Hz, 1 H), 4.08 (dd, J=13.26, 6.25 Hz, 1 H), 3.91 (dd, J=13.32, 6.57 Hz, 1 H), 3.78 (s, 3 H), 1.66 (s, 3 H) Example 4: Preparation of N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4- difluorophenyl)tetrazole-5-carboxamide (Compound P-5, Table P). (Compound P-5, Table P).
Figure imgf000090_0001
4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide (2.40 g, 4.97 mmol, prepared as described in example 3) and zinc cyanide (1.19 g, 9.94 mmol) were dissolved in N,N-dimethylformamide (25 mL) under a nitrogen atmosphere. The resulting reaction mixture was degassed under nitrogen for 10 minutes. Then, tetrakis(triphenylphosphine)palladium(0) (0.58 g, 0.49 mmol) was added, and the resulting pale brown suspension was stirred in microwave at 120°C for 2 hours. The progress of the reaction was monitored by LCMS. After completion of reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was dried over Na2SO4 and concentrated in vacuo. The crude compound was purified by combi flash using EtOAc/cyclohexane as eluent. The resulting compound was further purified by reverse phase column using acetonitrile in water as eluent to give N-[2-(6-cyano-2-pyridyl)- 2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide as a white solid. LCMS (Method B): 450 [M+H]+; retention time = 0.95 min; 1H NMR (400 MHz, DMSO-d6) δ ppm 8.80 (t, J=6.30 Hz, 1 H), 8.07 (td, J=8.74, 5.75 Hz, 1 H), 7.90 - 7.99 (m, 2 H), 7.80 (ddd, J=11.10, 8.83, 2.69 Hz, 1 H), 7.64 (s, 1 H), 7.63 (d, J=8.34 Hz, 1 H), 7.42 - 7.48 (m, 1 H), 7.36 (d, J=0.73 Hz, 1 H), 4.13 (dd, J=13.33, 6.24 Hz, 1 H), 3.94 (dd, J=13.39, 6.66 Hz, 1 H), 3.78 (s, 3 H), 1.69 (s, 3 H). Example 5: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-3, Table P). (Compound P-3, Table P).
Figure imgf000090_0002
hydrazono]-3-oxo-propanoate 82714_FF 90
Figure imgf000091_0001
flask, equipped with a nitrogen inlet, was added 2,4-difluoroaniline (4.00 g, 30.9 mmol) in water (32 mL) and conc. HCl (12 mL, 35%) at room temperature. The reaction mixture was cooled to 0 °C and to this solution was added a cold solution of sodium nitrite (2.56 g, 37.1 mmol) in water (32 mL) and the resulting mixture stirred it at 0 °C for 5 min. In another round bottom flask, a solution of ethyl 3- (dimethylamino)prop-2-enoate (12.0 g, 23.4 mmol) and potassium acetate (4.61 g, 46.4 mmol) in ethanol (40 mL) was stirred and cooled to 0 °C. To this was added the above diazotized solution at 0°C dropwise, and the reaction mixture allowed to warm to room temperature and stirred for 18 hrs. LCMS showed formation of the desired product. The reaction was diluted with water and extracted with EtOAc (3x50 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo to give crude ethyl 2- [(2,4-difluorophenyl)hydrazono]-3-oxo-propanoate as brown solid which was used as such in next step. LCMS (Method B): 257 [M+H]+; retention time = 1.09 min Step 2: Preparation of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxyimino-propanoate
Figure imgf000091_0002
difluorophenyl)hydrazono]-3-oxo-propanoate (3.00 g, 5.85 mmol) in ethanol (30 mL) was added potassium acetate (1.45 g, 14.6 mmol) and hydroxylaminehydrochloride (0.49 g, 7.02 mmol). The reaction mixture was stirred for 2h at 80°C. LCMS showed complete conversion to the desired product. The reaction mixture was cooled to rt and diluted with water and extracted EtOAc (3x50 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to give the title compound as a brown solid which was used as such for the next step. LCMS (Method B): 272 [M+H]+; retention time = 1.16 min; Step 3: Preparation of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate 82714_FF 91
Figure imgf000092_0001
-3-hydroxyimino-propanoate (3.4 g, 6.3 mmol) was treated with acetic anhydride (34 mL, 10mL/g) at room temperature. The reaction mixture was then stirred at 140 °C for 1 h. The reaction was monitored by LC-MS and after completion the reaction mixture was cooled and quenched with ice and cold brine. The reaction mixture was extracted with EtOAc (3x25 mL) and the combined organic layers dried over Na2SO4, and concentrated in vacuo, to yield the crude product. This was purified by combiflash using EtOAc/cyclohexane as eluent (5:95) to afford the title compound as a brown solid. LCMS (Method C): 254 [M+H]+; retention time = 1.19 min Step 4: Preparation of lithium;2-(2,4-difluorophenyl)triazole-4-carboxylate
Figure imgf000092_0002
triazole-4-carboxylate (0.10 g, 0.31 mmol) in THF (0.4 mL) and water (0.1 mL) was added lithium hydroxide (11.0 mg 0.47 mmol) and the reaction was stirred at rt room temperature for 3 hours. After completion of reaction, the reaction mixture was concentrated in vacuo, and the residue triturated with TBME. This yielded lithium;2-(2,4-difluorophenyl)triazole-4-carboxylate which was used as such for the next step. LCMS (Method B): 224[M+H]+; retention time = 0.29 min Step 5: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole- 4-carboxamide (Compound P-3, Table P). Lithium;2-(2,4-difluorophenyl)triazole-4-carboxylate (70.0 mg, 0.30 mmol) and 2-(6-chloro-2-pyridyl)-2-(1- methylpyrazol-4-yl)propan-1-amine (91.0 mg, 0.36 mmol) were suspended in ethyl acetate (5 mL) and treated with triethyl amine (97.7 µL, 0.66 mmol) and T3P (50 mass%) in EtOAc (2 mL) at 0 °C. The reaction was stirred at room temperature for 2 hrs after which time TLC and LCMS showed reaction completion. The reaction mixture was diluted with water and extracted with EtOAc (2x25 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by combiflash by using 0-70% EtOAc/cyclohexane as an eluent to obtain the product as a yellow gummy mass. LCMS (Method C): 458[M+H]+; retention time = 1.19 min; 82714_FF 92 1H NMR (400 MHz, CDCl3) δ ppm 8.28 (s, 1 H), 8.13 - 8.23 (m, 1 H), 7.89-7.95 (m, 1 H), 7.58 (t, J=7.82 Hz, 1 H), 7.32 (s, 1 H), 7.16 - 7.25 (m, 2 H), 6.97 – 7.10 (m, 3 H), 4.03 (d, J=6.36 Hz, 2 H), 3.88 (s, 3 H), 1.72 (s, 3 H) Example 6: Preparation of N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-2, Table P). (Compound P-2, Table P).
Figure imgf000093_0001
pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5- carboxamide (0.1 g, 0.20 mmol) and zinc cyanide (0.049 g, 0.41 mmol) in N,N-Dimethylformamide anhydrous (1 mL) was de-gassed under nitrogen for 10 minutes. Then tetrakis(triphenylphosphine)palladium(0) (0.024 g, 0.020 mmol) was added and the resulting pale brown suspension was stirred in microwave at 120 °C for 3 hours. After the completion of the reaction, the reaction mixture was diluted with ice cold water and extracted with EtOAc (2x25 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude product was absorbed over silica gel and purified by combiflash by using 0- 80% EtOAc/cyclohexane as an eluent to obtain the product as a white gummy solid. LCMS (Method B): 449[M+H]+; retention time = 1.07 min; 1H NMR (400 MHz, CDCl3) δ ppm 8.28 (s, 1 H), 8.07 (brt, 1 H), 7.90- 7.94 (m, 1 H), 7.76 (t, J=7.29 Hz, 1 H), 7.62 (d, J=7.46 Hz, 1 H), 7.43 (d, J=8.07 Hz, 1 H), 7.23 - 7.32 (m, 2 H), 7.02 - 7.11 (m, 2 H), 4.07 (d, J=6.48 Hz, 2 H), 3.89 (s, 3 H), 1.74 (s, 3 H) Further examples of synthesized compounds of formula (I) are shown in Table P. Table P: Synthesized compounds and Spectral and Physical Chemical Data. )d
Figure imgf000093_0002
82714_FF 93 N-[2-(6-chloro-2-pyridyl)-2-(1-
Figure imgf000094_0001
82714_FF 94 N-[2-(6-chloro-2-pyridyl)-2-(1-
Figure imgf000095_0001
BIOLOGICAL EXAMPLES Example B1: Alternaria solani / tomato / leaf disc (early blight) Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23 °C / 21°C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Alternaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-3, P-5, P-6, P-7, P-8 Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. 82714_FF 95 The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8 Example B3: Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (Anthracnose) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is measured photometrically 3-4 days after application. The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8 Example B4: Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) / wheat / leaf disc preventative (Powdery mildew on wheat) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application). The following compounds gave at least 80% control of Blumeria graminis f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-2, P-5, P-6, P-7, P-8, P-9 Example B5: Fusarium culmorum / liquid culture (Head blight) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-6, P-7, P-8 Example B6: Fusarium culmorum / wheat / spikelet preventative (Head blight) Wheat spikelets cv. placed on agar in multiwell plates (24-well format) and sprayed with the
Figure imgf000096_0001
formulated test water. The spikelets are inoculated with a spore suspension of the fungus 82714_FF 96 1 day after application. The inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 - 8 days after application). The following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-6 Example B7: Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8, P-9 Example B8: Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8, P-9 Example B9: Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-7, P-8 82714_FF 97 Example B10: Pyrenophora teres / barley / leaf disc preventative (Net blotch) Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20 °C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-3, P-5, P-6, P-7, P-8, P-9 Example B11: Sclerotinia sclerotiorum / liquid culture (cottony rot) Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-5, P-6 Example B12: Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-5, P-6, P-8, P-7, P-9 Example B13: Gibberella zeae (Fusarium graminearum) / wheat / spikelet preventative (Head blight) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the spikelets are inoculated with a spore suspension of the fungus. The inoculated test leaf disks are incubated at 20 °C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber, the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 - 8 days after application). 82714_FF 98 The following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-7 Example B14: Phytophthora infestans / tomato / leaf disc preventative (late blight) Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 16 °C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Phytophthora infestans at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-2 Example B15: Plasmopara viticola / grape / leaf disc preventative (late blight) Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 19 °C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application). The following compounds gave at least 80% control of Plasmopara viticola at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1, P-2 Example B16: Magnaporthe grisea (Pyricularia oryzae) / liquid culture (Rice Blast) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated

Claims

82714_FF 99 CLAIMS 1. A compound of formula (I): wherein
Figure imgf000100_0001
R1 is selected from hydrogen, C1-C4 alkyl, C2-C4alkenyl, C2-C4 alkynyl, or C3-C6cycloalkyl; R2 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4haloalkyl, C3- C6cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl- carbonimidoyl, or C1-C4 alkoxycarbonyl; R3 is selected from hydrogen, halogen, or C1-C4 alkyl; R4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1- C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R5 and R6 are independently selected from hydrogen, or C1-C4 alkyl; A1 is selected from CR7 or N, A2 is selected from CR8 or N; A3 is selected from CR9 or N; R7, R8, and R9 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl; Q is selected from Q1, Q2, Q3, Q4, or Q5;
82714_FF 100 wherein;
Figure imgf000101_0001
R10, R11, R12 and R13 are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-4alkylamino, N,N-diC1-4alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl- carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S; and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4alkoxy; Z1 is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein any of said 5- or 6-membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O or S; and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof. 2. The compound of formula (I) according to claim 1, wherein A1 is selected from CH or N; A2 is selected from CH or N; A3 is selected from CHor N; and wherein at least two of A1, A2 and A3 are selected from N. 3. The compound of formula (I) according to claim 1 or claim 2, wherein R1 is selected from methyl, ethyl, or isopropyl. 4. The compound of formula (I) according to any one of claims 1 to 3, wherein R2 is selected from hydrogen, fluorine, chlorine, or methyl. 82714_FF 101 5. The compound of formula (I) according to any one of claims 1 to 4, wherein R3 is selected from hydrogen or methyl. 6. The compound of formula (I) according to any one of claims 1 to 5, wherein R4 is selected from hydrogen or methyl. 7. The compound of formula (I) according to any one of claims 1 to 6, wherein R5 and R6 are independently selected from hydrogen or methyl. 8. The compound of formula (I) according to any one of claims 1 to 7, wherein Q is selected from Q1, Q2, or Q3. 9. The compound of formula (I) according to any one of claims 1 to 8, wherein R10 and R11 are independently selected from hydrogen, chloro, bromo, methoxy, cyano, amino, 2-cyanophenyl, 3-cyanophenyl, 4- cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol- 1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl; and R12 and R13 are hydrogen. 10. The compound of formula (I) according to claim 9, wherein R10 and R11 are independently selected from hydrogen, chloro, bromo, cyano, or amino. 11. The compound of formula (I) according to any one of claims 1 to 10, wherein Z1 is selected from 1- methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2- fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4- fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2- thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, or phenyl. 12. The compound of formula (I) according to any one of claims 1 to 11, wherein Z1 is selected from 1- methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2- furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl. 13. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12. 14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 82714_FF 102 12, or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof. 15. Use of a compound according to any one of claims 1 to 12 as a fungicide.
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