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WO2025191053A1 - Microbiocidal pyrazole derivatives - Google Patents

Microbiocidal pyrazole derivatives

Info

Publication number
WO2025191053A1
WO2025191053A1 PCT/EP2025/056837 EP2025056837W WO2025191053A1 WO 2025191053 A1 WO2025191053 A1 WO 2025191053A1 EP 2025056837 W EP2025056837 W EP 2025056837W WO 2025191053 A1 WO2025191053 A1 WO 2025191053A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
alkyl
compounds
compound
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/056837
Other languages
French (fr)
Inventor
Andrew Edmunds
Christopher Charles SCARBOROUGH
Atul Mahajan
Matthias Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of WO2025191053A1 publication Critical patent/WO2025191053A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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.
  • R 1 is selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C3-C6-cycloalkyl;
  • R 2 is selected from cyano, hydroxy, amino, C1-C4-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C3-C6- cycloalkyloxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylamino, di(Ci - C4-alkyl)amino, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, or C1-C4-haloalkylsulfanyl;
  • R 3 is selected from hydrogen, halogen, or C1-C4-alkyl
  • R 4 is selected from hydrogen, halogen, cyano, or C1-C4-alkyl
  • R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl
  • 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;
  • R 7 , R 8 , and R 9 are independently selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C1-C4- haloalkyl;
  • Q is selected from a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or up to the possible number of substituents independently selected from R 10 , wherein R 10 is independently selected from halogen, hydroxy, cyano, carboxy, amino, 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, trifluoromethylsulfonyloxy, C1-C4-alkoxy-C1
  • Z 1 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 contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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-alkyn
  • 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 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 practiced on the human or animal body.
  • the compounds of formula (I) or the intermediate compounds of formula (III) according to the invention 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, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4-alkanecarboxylic 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
  • the compounds of formula (I) or the intermediate compounds of formula (III) according to the invention 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 ethy
  • 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. Also, atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I) according to the invention.
  • a compound of formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of formula (I) according to the invention.
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable oragrochemically acceptable 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 .
  • N-oxides can be prepared by reacting a compound of formula (I) with a suitable oxidizing agent, for example the H2 ⁇ D2/urea adduct, in the presence of an acid anhydride, e.g., trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H2 ⁇ D2/urea adduct
  • an acid anhydride e.g., trifluoroacetic anhydride.
  • the compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
  • halogen 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 haloalky I, 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 -
  • 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-1 -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.
  • C2-Cn-alkynyloxy refers to a radical of the formula -OR a where R a is a C2-Cn-alkynyl radical as generally defined above.
  • C1-Cn-alkoxy-C1-Cn-alkyl refers to an alkyl radical C1-Cn-alkyl (as defined above) substituted with a C1-Cn-alkoxy group as defined above. Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxy methyl.
  • This term can be used interchangeably with the term “C1-Cn-alkyl-C1-Cn- alkoxy” which refers to a radical of the formula -R a -ORb, where R a is a C1-Cn-alkyl group as defined above, and Rb refers to an C1-Cn-alkyl group as defined above.
  • C1-Cn-alkoxy-C1-Cn-alkoxy refers to a radical of the formula -OR a -ORb, wherein R a is a Ci-Cn-alkyl group as defined above, and Rb is a C1-Cn-alkyl group as defined above.
  • C1-Cn-alkyl-C1-Cn-alkoxy-C1-Cn-alkoxy refers to a radical of the formula -R a -ORb- ORc, where R a is a C1-Cn-alkyl group as defined above, and Rb and R c refer to an C1-Cn-alkyl group as defined above.
  • R a is a C1-Cn-alkyl group as defined above
  • Rb and R c refer to an C1-Cn-alkyl group as defined above.
  • C3-C n -cycloalkyl-C1-Cn-alkyl refers to an alkyl radical (as mentioned above) substituted with a C3-Cn-cycloalkyl group. Examples are cyclopropylmethyl, cyclopropylethyl.
  • C3-Cn-halocycloalkyl-Ci-Cn-alkyl refers to an alkyl radical substituted with cycloalkyl group, wherein the cycloalkyl group is substituted by one or more of the same or different halogen atoms. Examples are 3,3- difluorobutylmethyl and 1 -chlorocyclopropylmethyl.
  • Ci-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-Cn-alkylthio“ or “C1-Cn-alkylsulfanyl“ refers to a C1-Cn-alkyl group linked through a sulfur atom. Examples are for example methylthio, ethylthio, isopropylthio-.
  • C1-Cn-haloalkylthio“ or “C1-Cn-haloalkylsulfanyl“ refers to a C1-Cn-haloalkyl group linked through a sulfur atom. Examples are for example trifluoromethylsulfanyl, difluoromethylsulfanyl, and 2,2- difluoroethylsulfanyl.
  • C1-Cn-alkylsulfonyl-C1-Cn-alkyl refers to an a C1-Cn-alkyl radical substituted with a Ci-Cn-alkylsulfonyl group.
  • N-C1-Cn alkylamino refers to a radical of the formula -NH-R a where R a is a Ci-Cn- alkyl radical as defined above.
  • N,N-di(C1-Cn-alkyl)amino refers to a radical of the formula -N(R a )R a where each R a is a Ci-Cn-alkyl radical, which may be the same or different, as defined above.
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms independently 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.
  • 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. 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 and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
  • room temperature or “RT” or “rt” or “ambient temperature” 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.
  • R 1 is selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C3-C6-cycloalkyl. In another embodiment of the invention, R 1 is C1-C4-alkyl. Preferably R 1 is C1-C3-alkyl. More preferably, R 1 is methyl, ethyl, or isopropyl. Even more preferably, R 1 is methyl.
  • R 2 is selected from cyano, hydroxy, amino, C1-C4-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C3-C6-cycloalkyloxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, or C1-C4- haloalkylsulfanyl.
  • R 2 is cyano, hydroxy, C1-C3-alkoxy, C3-C6-cycloalkyloxy, C1-C2-haloalkoxy, C1- C4-alkoxy-C1-C2-alkyl, C1-C2-alkylsulfanyl, C1-C2-alkylsulfinyl, or C1-C2-alkylsulfonyl. More preferably, R 2 is C1- Cs-alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl.
  • R 2 is C1- Cs-alkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl. Still even more preferably, R 2 is methoxy, ethoxy, methoxymethyl, or methylsulfanyl.
  • R 3 is selected from hydrogen, halogen, or C1-C4-alkyl. In another embodiment R 3 is selected from hydrogen, halogen, or C1-C3-alkyl. Preferably R 3 is hydrogen, fluorine, chlorine or methyl. More preferably R 3 is hydrogen or methyl. Even more preferably R 3 is hydrogen. In another embodiment, R 3 is hydrogen or C1-C3-alkyl. In one embodiment of the invention, R 4 is selected from hydrogen, halogen, cyano, or C1-C4-alkyl. Preferably R 4 is hydrogen, fluorine, chlorine, cyano, or C1-C3-alkyl. More preferably, R 4 is hydrogen, fluorine, chlorine, or C1-C3-alkyl. Even more preferably R 4 is hydrogen or methyl. In one embodiment R 4 is hydrogen. In another embodiment R 4 is methyl.
  • R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl.
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl. More preferably R 5 and R 6 are independently selected from hydrogen or methyl. Even more preferably R 5 and R 6 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. More preferably A 1 , A 2 , and A 3 are N.
  • a 1 and A 2 are N, and A 3 is CR 9 .
  • a 1 is CR 7 ; A 2 is CR 8 , and A 3 is N.
  • a 1 is N; A 2 is CR 8 , and A 3 is CR 9 .
  • a 1 is CR 7 ; A 2 is N; and A 3 is CR 9
  • R 7 , R 8 , and R 9 are independently selected from hydrogen, C1-C4-alkyl, C2- C4-alkenyl, C2-C4-alkynyl, or C1-C4-haloalky.
  • R 7 , R 8 , and R 9 are independently selected from hydrogen, halogen, methyl, or trifluoromethyl. More preferably R 7 , R 8 , and R 9 are hydrogen.
  • Q is selected from a 6-membered heteroaryl, wherein any of said 6- membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or up to the possible number of substituents independently selected from R 10 , wherein R 10 is independently selected from halogen, hydroxy, cyano, carboxy, amino, 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, trifluoromethylsulfonyloxy, C1-C4-
  • Q is selected from a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, amino, C1-C3-alkyl, C1-C3-alkoxy, phenyl, 5- or 6-membered heteroaryl, or C3- C6-cycloalkyl, wherein any of 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 C1-C4-alkyl.
  • Q is selected from a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
  • Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is as defined above.
  • Q is selected from Q1 , Q2, Q3, or Q4; wherein Q1 , Q2, Q3 and Q4 are unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
  • Q is selected from Q1 , Q2, or Q3 wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is as defined above.
  • Q is selected from Q1 , Q2, orQ3; wherein Q1 , Q2 and Q3 are unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
  • Q is Q1 : wherein the staggered line denotes the bond to the rest of the molecule, wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is as defined above.
  • Q is Q1 ; wherein Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl. More preferably, Q is Q1 ; wherein Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , and wherein R 10 is selected from halogen, cyano, or amino.
  • R 10 is selected from halogen, hydroxy, cyano, carboxy, amino, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylsulfanyl, Ci- C4-alkylsulfinyl, C1-C4-alkylsulfonyl, trifluoromethylsulfonyloxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4- alkoxy, N-C1-C4-alkylamino, N,N-di(C1-C4)-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-
  • R 10 is selected from halogen, hydroxy, cyano, carboxy, amino, C1-C3- alkyl, C1-C2-haloalkyl, C1-C3-haloalkoxy, C1-C4-alkoxy, C2-C3-alkenyloxy, C2-C3-alkynyloxy, C1-C2- alkylsulfanyl, C1-C2-alkylsulfinyl, C1-C2-alkylsulfonyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C2-alkoxy-C1-C4-alkoxy, C1- Cs-alkoxycarbonyl, C1-C2-alkylcarbonyl, N-C1-C2-alkoxy-C-C1-C2-alkyl-carbonimidoyl, N-hydroxy-C1-C2-alkyl- carbonimidoyl, trifluoromethyl
  • R 10 is selected from halogen, hydroxy, cyano, carboxy, amino, C1-C3-alkyl, C1-C2- haloalkyl, C1-C3-haloalkoxy, C1-C4-alkoxy, C2-C3-alkenyloxy, C2-C3-alkynyloxy, C1-C2-alkylsulfanyl, C1-C2- alkylsulfinyl, C1-C2-alkylsulfonyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C2-alkoxy-C1-C4-alkoxy, C1-C3-alkoxycarbonyl, C1-C2-alkylcarbonyl, N-C1-C2-alkoxy-C-C1-C2-alkyl-carbonimidoyl, N-hydroxy-C1-C2-alkyl-carbonimidoyl, trifluoromethylsulfanyl,
  • R 10 is selected from 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, or 1- cyanocyclopropyl.
  • R 10 is selected from halogen, cyano, amino, C1-C3-alkyl, C1-C3- alkoxy, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein any of 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 is selected from chloro, bromo, methyl, 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 is selected from chloro, bromo, cyano, or amino.
  • R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl, wherein any of said C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl.
  • R 10 is selected from halogen, cyano, C1- C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl. More preferably, R 10 is selected from cyano, chloro, bromo, methyl, methoxy or cyclopropyl.
  • Z 1 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 contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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 C
  • Z 1 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 contains 1 or 2 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, C1-C2- alkylsulfanyl, C1-C2-alkylsulfinyl, C1-C2-alkylsulfonyl, or C2-C4-alkynyl.
  • Z 1 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 contains 1 heteroatom selected from N, O and 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-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, or C2-C4-alkynyl.
  • Z 1 is selected from 1 -methylcyclopropyl, 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3- difluoro-4-pyridyl, 2,3-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluoro-3-pyridyl, 2,4-difluorophenyl, 2,4- difluoropyrimidin-5-yl, 2,5-difluoro-3-pyridyl, 2,5-difluoro-4-pyridyl, 2,5-difluorophenyl, 2,5-difluoropyrimidin-4- yl, 2,6-difluoro-3-pyridyl, 2,6-difluoro-4-pyridyl, 2,6-difluoropyrimidin-4-yl, 2-chlorophenyl, 2-fluoro-3-pyridyl, 2- fluoryl,
  • Z 1 is 1- methylcyclopropyl, cyclobutyl, cyclopropyl, methyl, n-propyl, phenyl, 4-fluorophenyl, 2,4-difluorophenyl, 5- fluoro-2-furyl, 3,5-difluoro-2-furyl, 5-fluoro-2-thienyl, 3,5-difluoro-2-thienyl, 2-fluoro-3-pyridyl, 3-fluoro-2-pyridyl,
  • 3-fluoro-4-pyridyl 4-fluoro-3-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2- pyridyl, 3,5-difluoro-2-pyridy I, or 4,6-difluoro-3-pyridyl.
  • Z 1 is selected from phenyl, 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 5- or 6-membered heteroaryl 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, Ci- C4-alkylsulfonyl, or C2-C4-alkynyl.
  • Z 1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 or 2 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from O or S; and wherein any of said phenyl, and 5- or 6- membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, C1-C2-alkylsulfanyl, C1-C2- alkylsulfinyl, C1-C2-alkylsulfonyl, or C2-C4-alkynyl.
  • Z 1 is selected from phenyl, or 5- or 6- membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2- alkoxy, C1-C2-haloalkoxy, or C2-C4-alkynyl.
  • Z 1 is selected from phenyl, thienyl, furyl, pyridyl, pyridazin, or pyrimidin; and wherein any of said phenyl, thienyl, furyl, pyridyl, pyridazin, and pyrimidin are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C2- alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, or C2-C4-alkynyl.
  • Z 1 is selected from phenyl, thienyl, furyl, pyridyl, pyridazin, or pyrimidin; and wherein any of said phenyl, thienyl, furyl, pyridyl, pyridazin, and pyrimidin are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2-alkoxy, or C2-C4-alkynyl.
  • Z 1 is selected from 1- methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluoro-4-pyridyl, 2,3-difluorophenyl,2,4,6-trifluorophenyl, 2,4- difluoro-3-pyridyl, 2,4-difluorophenyl, 2,4-difluoropyrimidin-5-yl, 2,5-difluoro-3-pyridyl,2,5-difluoro-4-pyridyl, 2,5-difluorophenyl, 2,5-difluoropyrimidin-4-yl , 2,6-difluoro-3-pyridy 1, 2,6-difluoro-4-pyridy 1, 2,6-difluoropyrimidin-
  • Z 1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 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.
  • Z 1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2-alkoxy, or C2-C4-alkynyl.
  • Z 1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro or fluoro.
  • Z 1 is selected from phenyl, 2-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 5-fluoro-2-furyl, 3,5- difluoro-2-furyl, 5-fluoro-2-thienyl, 3,5-difluoro-2-thienyl, 2-fluoro-3-pyridyl, 3-fluoro-2-pyridyl, 3-fluoro-4-pyridyl, 4-fluoro-3-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, 3,5- difluoro-2-pyridyl, or 4,6-difluoro-3-pyridy I.
  • Z 1 is 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridy I, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-py ridyl.
  • Z 1 is selected from phenyl, or 6-membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6- membered heteroaryl are unsubstituted or substituted by 1 or 2 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.
  • Z 1 is selected from phenyl, or 6-membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen.
  • Z 1 is selected from phenyl, 2-fluorophenyl, 4- fluorophenyl, 2,4-difluorophenyl, 2-fluoro-3-pyridyl, 3-fluoro-2-pyridyl, 3-fluoro-4-pyridyl, 4-fluoro-3-pyridyl, 5- fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, or 4,6- difluoro-3-pyridyl.
  • Z 1 is 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5- fluoro-2-pyridy I, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-pyridyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, R 10 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 A8, and R 7 , R 8 and R 9 are independently selected from hydrogen, halogen, methyl, or trifluoromethyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, R 10 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 A8, and R 7 , R 8 and R 9 are hydrogen.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, R 10 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 8 and R 9 are independently selected from hydrogen, halogen, methyl, or trifluoromethyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, R 10 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 8 and R 9 are hydrogen.
  • A is selected from A1 , or A2; and Q is selected from Q1 , Q2, Q3, or Q4.
  • A is selected from A1 , or A2; and Q is selected from Q1 , Q2, or Q3.
  • A is selected from A1 , or A2; and Q is Q1 .
  • A is selected from A1
  • Q is selected from Q1 , Q2, Q3, or Q4.
  • the present invention accordingly, makes available a compound of formula (l-A) having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , Q, A and Z 1 as defined above in all combinations / each permutation.
  • Embodiments according to the invention are provided as set out below.
  • R 1 is C1-C3-alkyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; and wherein R 7 , R
  • R 1 is C1-C3-alkyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; wherein R 7 , R 8
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl;
  • a 1 is
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl;
  • a 1 is
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl;
  • a 1 is
  • the compound of formula (l-A) may be a compound of formula (I-A1), wherein Q is Q1 : wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and Z 1 are as defined for the compounds of formula (I), and wherein A is defined for the compounds of formula (l-A) according to the present invention.
  • R 1 is C1-C3-alkyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl
  • R 2 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloal
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloal
  • R 1 is C1-C3-alkyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl
  • R 2 and Z 1 are as defined for the compounds of formula (I) according to the present invention.
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloal
  • R 1 is C1-C3-alkyl
  • R 2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl
  • R 3 is hydrogen or C1-C3-alkyl
  • R 4 is hydrogen or methyl
  • R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl
  • Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R 10 , wherein R 10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloal
  • any of the compounds of formula (I), (l-A), and (I-A1) 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-56, or compounds listed in Table P.
  • the compound of formula (I) according to the invention is selected from N-[2-(6-cyano-2- pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide, N-[2- (6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl]-1-(3,5-difluoro-2-pyridyl)triazole-4- carboxamide, or N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-methyl
  • 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 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).
  • compounds of formula (Ila), where G° 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-di methylformamide (DMF) in inert solvents such as dichloromethane (DCM) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C.
  • DMF dichloromethane
  • THF tetrahydrofuran
  • 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]-1 H-1 ,2,3-triazolo[4,5- b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (Ila), wherein G° 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]-1 H-1 ,2,3-triazolo[4,5- b]pyridinium
  • 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 (Ila), wherein G° 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 (Ila), wherein G° is G 04 as set forth below, as described for example in Synthesis 2013, 45, 1569.
  • Compounds of formula (II) can be prepared from compounds of formula (lib), wherein A 1 , A 2 , A 3 are N and Z 1 are as described in formula (I), and R° is C1-C4-alkyl, by ester hydrolysis.
  • a variety of conditions can be used, as for example aqueous NaOH or LiOH and an organic water miscible solvent like THF, dimethoxyethane, methanol, or ethanol.
  • ester hydrolyses are well known to those skilled in the art.
  • 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, or cyclopentyl methyl ether in the presence of a Lewis acid such as Ti(O J Pr)4 (see Synlett 2007, (4), 652-654) (Scheme 3).
  • compounds of formula (IV), wherein R 1 , R 2 , R 3 , R 4 , R 10 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 THF, followed by addition of a suitable alkylating agent R 4 -X°, wherein X° is halogen, for example iodomethane.
  • Compounds of formula (IVa), wherein R 4 is hydrogen and R 1 , R 2 , R 3 , R 10 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 DCM 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), (Vlb), (Vic), (Vid) or (Vie), as shown in Scheme 5.
  • Such metal insertions into C-X 01 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 THF and the like.
  • Solutions of the metalated species (Vila) are then treated with compounds of formula (VI), respectively (Via), (Vlb), (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. Let. 2017, 27(17), 4044-4050 (X 01 is Br, n- butyl lithium) and Angew. Chem. Inf. Ed.
  • 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 THF, 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) (Scheme 6).
  • a base such as sodium hydride or n-butyl lithium
  • an inert solvent such as THF
  • R 2 is C1-C4-alkoxy, C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4- haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-haloalkoxy, C3-C6-cycloalkyloxy, or C1-C4-alkylsulfanyl, can also be prepared as shown prepared as shown in Scheme 11 .
  • compounds of formula (II ba), 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 (XXI): wherein R° is Ci-Ce-alkyl, and Ar 1 is phenyl or p-tolyl, with compounds of formula (XVIII), in the presence of a base, e.g., pyridine at temperatures from -50°C to 50°C to yield compounds of formula (llba).
  • a base e.g., pyridine at temperatures from -50°C to 50°C to yield compounds of formula (llba).
  • 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 (XXI)
  • compounds of formula (llba), wherein A 1 , A 2 and A 3 are N and Z 1 is as defined in formula (I) can be obtained by coupling compounds of formula (XXII), wherein A 1 , A 2 and A 3 are N, and R° is as described vide supra, with a boronic acid derivative of formula (XXIII),
  • the coupling product of this reaction 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 (llba).
  • this Chan-Lam coupling is a general method for preparation of compounds of formula (lib). Examples have been shown in the literature for compounds of formula (llbb) wherein Z 1 , R z and R° are as previously defined (see J. Med. Chem.
  • sequence begins with diazotation of compounds of formula (XX) as previously described vide supra and then treatment of the diazionium salt with a compound of formula (XXIV), wherein R° is Ci-Cealkyl, in the presence of a mild base, for example sodium acetate to yield compounds of formula (XXV).
  • a mild base for example sodium acetate
  • Compounds of formula (XXV), wherein Z 1 and R° are as previously defined are then treated with aqueous ammonia in a miscible organic solvent, for example THF or 2-methyl tetra hydrofuran, at temperatures between 0°C to 30°C, to give compounds of formula (XXVI).
  • a miscible organic solvent for example THF or 2-methyl tetra hydrofuran
  • Compounds of formula (lib) may also be prepared by alkylation of compounds of formula (XXII) with compounds of formula (XXVII)
  • Z — X (XXVII) wherein Z 1 is as previously described under formula I, and X° 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 (lib) as described for example in WO14/168221 ; W010/043000; and WO14/32498.
  • compounds according to the invention can be prepared by derivatization at a later stage in the synthesis using a key central intermediate.
  • compounds of formula (I) wherein Q is Q1 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , 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 (la) (below) allow further chemistry to be carried out 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.
  • the reaction is catalyzed by a palladium-based catalyst, for example tefrak/s(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 THF and water, preferably under inert atmosphere.
  • the reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture.
  • 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.
  • compounds offormula (Ic) can be prepared by a Stille reaction of compounds of formula (XXVI 11 b), wherein Yb2 is a trialkyl tin derivative, preferably tri-n-butyl tin, with compounds of formula (la).
  • Such Stille reactions are carried out in the presence of a palladium catalyst, for example tefrak/s(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 catalyst, for example copper(l) iodide.
  • a palladium catalyst for example tefrak/s(triphenylphosphine)palladium(0) or (1 ,1 '-bis(diphenylphosphino)-ferrocene)dichloropalladium- dichloromethane (1 :1 complex
  • an inert solvent such as DMF, acetonitrile, or dioxan
  • compounds of formula (la) can be carbonylated to give compounds of formula (I), namely compounds of formula (Ig) with R 14 C1-C4-alkyl, wherein Q is Q1 , and R 1 , R 2 , R 3 , R 4 , R 5 , R s , R 10 , A 1 , A 2 , A 3 and Z 1 are as defined above for the compound of formula (I),
  • compounds of formula (la) are reacted with carbon monoxide, usually under pressure, in the presence of metal catalyst such as a palladium catalyst (for example, palladium(ll) acetate, [1 ,1 '-bis(diphenylphosphino)ferrocene] palladium(ll) dichloride (Pd(dppf)Cl2), bis(triphenylphosphine)palladium(ll) dichloride (PdCh(PPh3)2) or bis(diphenylphosphino)prop
  • a palladium catalyst for example, pal
  • ester compounds of formula (li) with halide anions, preferably chloride anions, originating from, for example, lithium chloride (or alternatively, sodium or potassium chloride), in solvents such as DMF, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, may also generate the carboxylic acid compounds of formula (Ih).
  • halide anions preferably chloride anions, originating from, for example, lithium chloride (or alternatively, sodium or potassium chloride), in solvents such as DMF, N,N-dimethylacetamide or N-methyl-2-pyrrolidone
  • solvents such as DMF, N,N-dimethylacetamide or N-methyl-2-pyrrolidone
  • Curtius rearrangement compounds of formula (li) 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 examples include TMSNa, 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 (Ij).
  • the reactions can be carried out in alcohols, e.g., t-butyl alcohol, allowing the t-butyl carbamates to be isolated.
  • a compound of formula (I) as defined in any of the embodiments of the present invention can be converted in a manner known perse into another compound as defined in any of the embodiments of the present invention 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.
  • Salts of compounds of formula (I) may be prepared in a manner known perse.
  • 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 a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I) 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.
  • 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 complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • 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 at least three asymmetric carbon atoms.
  • the relationship between enantiomers and diastereomers of compounds of formula (I) is shown below.
  • the compounds of formula (I) have at least two chiral carbon atoms, (stereocenters, wherein the star (*) indicates the chiral carbon atom), such there are four stereoisomers available. These four stereoisomers consist of two sets of enantiomers.
  • 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.
  • 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 or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time also protecting 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. 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.
  • These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Altemaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A.
  • Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. contributing 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, Corynespora spp. including Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp.
  • Diaporthe miriciae also known as Diaporthe ueckeri or Diaporthe ueckerae
  • Didymella spp. Drechslera spp.
  • Elsinoe spp. Elsinoe 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.
  • 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, 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, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya 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 synthesizing 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 CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a Cryl II B(b1 ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryl II B(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(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 synthesizing 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 delta-endotoxins, e.g., CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as delta-endotoxins, e.g., CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insectici
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid- UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • delta-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins, and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, W002/15701).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see W02003/018810).
  • toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93/07278, WO95/34656, EP0427529, EP0451878 and W003/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO95/34656, EP0367474, EP0401979 and WO90/13651 .
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and 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 Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in W02003/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • the compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants.
  • phytopathogenic diseases especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants.
  • soybean plants are genetically modified soybean plants.
  • the genetically modified plants are soybean plants.
  • Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), lntacta®2 XtendTM, Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM.
  • Transgenic soybean plants expressing toxins for example insecticidal proteins such as delta-endotoxins, e.g., CrylAc (CrylAc Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652), event MON87701 x MON89788 (disclosed in WO2014/170327, e.g.
  • event MON87751 (disclosed in WO2014/201235)
  • event DAS-44406-6 e.g., commercially available as Enlist E3 TM , DAS-44406-6, disclosed in WO2012/075426
  • event DAS-81419-2 (described in WO2013/016527, e.g., commercially available as ConkestaTM soybean); event DAS-81419-2 x DAS-44406-6 (e.g., commercially available as ConkestaTM Enlist E3TM Soybean).
  • the compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Altemaria spp.
  • 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 solanaceous crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymoseptoria spp. in cereals.
  • the compounds of formula (I) and compositions comprising said compounds are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C. truncatum or C.
  • Diaporthe spp. e.g., Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn.
  • phaseoli root and stem rot
  • Microsphaera diffusa prowdery mildew
  • Peronospora spp. downy mildew
  • Phialophora spp. e.g., P. g reg ata', stem rot
  • Phomopsis spp. e.g., stem rot: P. phaseoli (teleomorph: Diaporthe phaseolorum)’, Pythium spp. (damping-off); Phytophthora spp.
  • locus 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.
  • vegetative material such as cuttings or tubers, for example potatoes.
  • seeds in the strict sense
  • roots in the strict sense
  • fruits in the tubers
  • bulbs rhizomes
  • parts of plants may also be mentioned.
  • 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.
  • 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 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 WO1997/33890.
  • 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, 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 sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate 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
  • 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.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions 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.
  • Pressurized sprayers wherein the active ingredient is dispersed in finely divided form as a result of vaporization 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- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenz
  • 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 sulfate; 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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, imidazole fungicides, mercury fungicides, morpholine fung
  • TX means one compound selected from compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds listed in Table P (below), and a compound selected from the group of substances consisting of (4E,10Z)-tetradeca-4, 10-dienyl acetate + TX; (7E,9Z)- dodeca-7,9-dien-1-yl acetate + TX; (E)-6-methylhept-2-en-4-ol + TX; (E)-dec-5-en-1-yl acetate with (E)-dec-5- en-1-ol + TX; (E)-tridec-4-en-1-yl acetate + TX; (S)-bioallethrin + TX; (Z)-dodec-7-en-1-yl acetate + TX; (Z)-
  • the active ingredient mixture of the compound selected from compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds 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 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 compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds 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, nematoc
  • 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.
  • 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 plants
  • 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 I kg 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 symbol ha 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.
  • 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.
  • 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 (EG), an emulsion, oil in water (EW), a microemulsion (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),
  • 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, CD, SE, EW, EC 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 sulfonate, an alkyl aryl sulfonate, a lignin sulfonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
  • surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g., the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate, a lignin sulfonate,
  • 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 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.
  • 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 adjuvants), 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 to 80%, preferably between about 5 to 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.
  • 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.
  • compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %)
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Table A This table discloses 20 substituent definitions G of the formula (I) w ere n s o ormu a as defined below:
  • Table B This table discloses 14 substituent definitions Q of the formula (I)
  • Tables C-1 to C-56 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 is OCHs, R 4 is CH3, R 3 , R 5 , and R 6 are H, Q is Q-1 as defined in Table B, and G is as defined in Table A.
  • R 2 is OCHs
  • R 4 is CH3
  • R 3 , R 5 , and R 6 are H
  • Q is Q-1 as defined in Table B
  • G is as defined in Table A.
  • Table C-2 This table provides 20 compounds C-2.01 to C-2.20 of formula (I), wherein R 2 is OCH3, R 4 is CH3, R 3 , R 5 , and R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • compound C-2.04 has the following structure:
  • Table C-3 This table provides 20 compounds C-3.01 to C-3.20 of formula (I), wherein R 2 is OCHs, R 4 is CH3,
  • R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-4 This table provides 20 compounds C-4.01 to C-4.20 of formula (I), wherein R 2 is OCH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-4 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 is OCH3 R 4 is CH 3 ,
  • R 3 , R 5 , R 6 are H, Q is Q-5 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 is OCH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-6 as defined in Table B, and G is as defined in Table A.
  • Table C-7 This table provides 20 compounds C-7.01 to C-7.20 of formula (I), wherein R 2 is OCH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-7 as defined in Table B, and G is as defined in Table A.
  • Table C-8 This table provides 20 compounds C-8.01 to C-8.20 of formula (I), wherein R 2 is OCH3 R 4 is CH 3 ,
  • R 3 , R 5 , R 6 are H, Q is Q-8 as defined in Table B, and G is as defined in Table A.
  • Table C-9 This table provides 20 compounds C-9.01 to C-9.20 of formula (I), wherein R 2 is OCH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-9 as defined in Table B, and G is as defined in Table A.
  • compound C- 9.02 has the following structure: Compound C-9.02
  • Table C-10 This table provides 20 compounds C-10.01 to C-10.20 of formula (I), wherein R 2 is OCH3 R 4 is
  • Table C-11 This table provides 20 compounds C-11 .01 to C-11 .20 of formula (I), wherein R 2 is OCH3, R 4 is
  • Table C-12 This table provides 20 compounds C-12.01 to C-12.20 of formula (I), wherein R 2 is OCH3
  • Table C-14 This table provides 20 compounds C-14.01 to C-14.20 of formula (I), wherein R 2 is OCHs, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-14 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 is OCHs R 3 , R 4 ,
  • R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-16 This table provides 20 compounds C-16.01 to C-16.20 of formula (I), wherein R 2 is OCHs, R 3 , R 4 ,
  • R 5 , R 6 are H, Q is Q-5 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 CH3, R 2 is OCHs, R 3 and R 4 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • compound C-17.04 has the following structure: Compound C-17.04
  • Table C-18 This table provides 20 compounds C-18.01 to C-18.20 of formula (I), wherein R 5 R 6 are CH 3 , R 2 is OCHs R 3 and R 4 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • Table C-19 This table provides 20 compounds C-19.01 to C-19.20 of formula (I), wherein R 3 is H R 4 , R 5 , R 6 are CH3, R 2 is OCHs, 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 3 is H R 4 , R 5 , R 6 are CH3, R 2 is OCHs, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • R 3 is H
  • R 4 is H
  • R 5 is CH3
  • R 2 is OCHs
  • Q is Q-5 as defined in Table B
  • G is as defined in Table A.
  • C-20.18 has the following structure: Compound C-20.18
  • Table C-21 This table provides 20 compounds C-21 .01 to C-21 .20 of formula (I), wherein R 2 is SCH3, R 4 is
  • Table C-22 This table provides 20 compounds C-22.01 to C-22.20 of formula (I), wherein R 2 is SCH3
  • Table C-23 This table provides 20 compounds C-23.01 to C-23.20 of formula (I), wherein R 2 is SCHs, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-24 This table provides 20 compounds C-24.01 to C-24.20 of formula (I), wherein R 2 is SCH3 R 4 is
  • Table C-25 This table provides 20 compounds C-25.01 to C-25.20 of formula (I), wherein R 2 is SO2CH3 R 4 is
  • Table C-26 This table provides 20 compounds C-26.01 to C-26.20 of formula (I), wherein R 2 is SO2CH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-27 This table provides 20 compounds C-27.01 to C-27.20 of formula (I), wherein R 2 is SO2CH3 R 4 is
  • Table C-28 This table provides 20 compounds C-28.01 to C-28.20 of formula (I), wherein R 2 is SO2CH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • Table C-29 This table provides 20 compounds C-29.01 to C-29.20 of formula (I), wherein R 2 is NHCH3, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-30 This table provides 20 compounds C-30.01 to C-30.20 of formula (I), wherein R 2 is NHCH3 R 4 is
  • compound C-30.14 has the following structure: Compound C-30.14
  • Table C-31 This table provides 20 compounds C-31 .01 to C-31 .20 of formula (I), wherein R 2 is NHCH3, R 4 is
  • Table C-32 This table provides 20 compounds C-32.01 to C-32.20 of formula (I), wherein R 2 is NHCHs, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • Table C-33 This table provides 20 compounds C-33.01 to C-33.20 of formula (I), wherein R 2 is N(CH3)2, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-34 This table provides 20 compounds C-34.01 to C-34.20 of formula (I), wherein R 2 is N(CH3)2, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-35 This table provides 20 compounds C-35.01 to C-35.20 of formula (I), wherein R 2 is N(CH3)2, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-36 This table provides 20 compounds C-36.01 to C-36.20 of formula (I), wherein R 2 is N(CH3)2, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • Table C-37 This table provides 20 compounds C-37.01 to C-37.20 of formula (I), wherein R 2 is OH, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-38 This table provides 20 compounds C-38.01 to C-38.20 of formula (I), wherein R 2 is OH, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-39 This table provides 20 compounds C-39.01 to C-39.20 of formula (I), wherein R 2 is OH, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-40 This table provides 20 compounds C-40.01 to C-40.20 of formula (I), wherein R 2 is OH, R 4 is CHs, R 3 , R 5 , R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • Table C-41 This table provides 20 compounds C-41 .01 to C-41 .20 of formula (I), wherein R 2 is NH2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-42 This table provides 20 compounds C-42.01 to C-42.20 of formula (I), wherein R 2 is NH2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-43 This table provides 20 compounds C-43.01 to C-43.20 of formula (I), wherein R 2 is NH2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-44 This table provides 20 compounds C-44.01 to C-44.20 of formula (I), wherein R 2 is NH2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • Table C-45 This table provides 20 compounds C-45.01 to C-45.20 of formula (I), wherein R 2 is CN, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-46 This table provides 20 compounds C-46.01 to C-46.20 of formula (I), wherein R 2 is CN, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-47 This table provides 20 compounds C-47.01 to C-47.20 of formula (I), wherein R 2 is CN, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-48 This table provides 20 compounds C-48.01 to C-48.20 of formula (I), wherein R 2 is CN R 4 is
  • Table C-49 This table provides 20 compounds C-49.01 to C-49.20 of formula (I), wherein R 2 is OCH2CHF2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-50 This table provides 20 compounds C-50.01 to C-50.20 of formula (I), wherein R 2 is OCH2CHF2,
  • R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
  • Table C-51 This table provides 20 compounds C-51 .01 to C-51 .20 of formula (I), wherein R 2 is OCH2CHF2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
  • Table C-52 This table provides 20 compounds C-52.01 to C-52.20 of formula (I), wherein R 2 is OCH2CHF2, R 4 is CH3, R 3 , R 5 , R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • compound C-52.01 has the following structure: Compound C-52.01
  • Table C-53 This table provides 20 compounds C-53.01 to C-53.20 of formula (I), wherein R 2 is OCH3, R 3 and R 4 are CH3, R 5 , and R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-54 This table provides 20 compounds C-54.01 to C-54.20 of formula (I), wherein R 2 is OCH3 R 3 and
  • compound C-54.01 has the following structure: Compound C-54.01
  • Table C-55 This table provides 20 compounds C-55.01 to C-55.20 of formula (I), wherein R 2 is OCH3 R 3 is
  • CHs, R 4 , R 5 , and R 6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
  • Table C-56 This table provides 20 compounds C-56.01 to C-56.20 of formula (I), wherein R 2 is OCH3
  • R 4 , R 5 , and R 6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
  • 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).
  • 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 %
  • 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 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
  • 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)
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • Suspension concentrates active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment.
  • solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment.
  • dilutions living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • 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.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo-emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • EG
  • DABCO 1 ,4-diazabicyclo[2.2.2]octane also known as triethylenediamine or TEDA
  • the compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.
  • LC-MS Method A 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, 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.
  • LC-MS Method B Spectra were recorded on a Mass Spectrometer from Agilent Technologies (MSD-IQ mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, MS2 Scan, Capillary: 3.5 kV, Fragmentor: 110 V, Desolvation Temperature: 325°C, Gas Flow: 13 L/min, Nebulizer Gas: 55 psi, Mass range: 110 to 850 Da) and a 1290 Series HPLC from Agilent: quaternary pump, heated column compartment and diode-array detector.
  • Example Prep-1 Preparation of A/-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl1-1-(2,4- difluorophenyl)triazole-4-carboxamide (compound P-2, Table P) compound P-2, Table P
  • Step 4 Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propanenitrile
  • Step 6 Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propan-1 -amine
  • Step 7 Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate
  • Step 8 Preparation of 1-(2,4-difluorophenyl)tnazole-4-carboxyhc acid
  • Step 9 Preparation of A/-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl1-1-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-2, Table P)
  • reaction mixture was diluted with water (10 mL) and extracted with EtOAc (20 mL X3). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, filtered and concentrated in vacuo io obtain the crude product. This was purified using reverse phase combi flash chromatography eluting with 60-80 % water in CHsCN to afford the title compound as a white solid.
  • Step 1 Preparation of 5-chloro-1 ,3-dimethyl-pyrazole-4-carbaldehvde
  • Step 4 Preparation of 2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl) propanenitrile
  • Step 5 Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propanenitrile
  • Step 6 Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propan-1 -amine
  • Step 7 Preparation of tert-butyl A/-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- vDpropyllcarbamate
  • Step 8 Preparation of tert-butyl A/-[2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- vDpropyllcarbamate
  • Step 9 Preparation of [2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- yl)propyl1ammonium;chloride
  • Step 10 Preparation of ethyl (2E)-2-(p-tolylsulfonylhydrazono)acetate
  • Step 11 Preparation of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate
  • Step 13 Preparation of A/-[2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl1-2-(2,4- difluorophenyl)tetrazole-5-carboxamide (Compound P-1 , table P)
  • reaction mixture was diluted with water (10 mL) and extracted with EtOAc (20 mL X3). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, filtered and concentrated in vacuo to obtain the crude product. This was purified using reverse phase combi flash chromatography eluting with 40-60 % water in CHsCN to afford the title compound as a colourless solid.
  • Example B1 Alternaria solani / tomato / (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 to 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-2, P-3, P-4
  • Example B2 Blumeria qraminis f. sp. tritici (Erysiphe qraminis f. sp. tritici) / wheat / (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 to 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-3, P-4
  • Example B3 Phaeosphaeria nodorum (Septoria nodorum) / wheat / (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 to 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-2, P-3, P-4
  • Example B4 Pyrenophora teres / barley / (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 to 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-2, P-3, P-4
  • Example B5 Mycosphaerella qraminicola (Septoria tritici) / (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 to 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-2, P-3, P-4
  • Example B6 Botryotinia fuckeliana (Botrytis cinerea) / (Gray mould)
  • Example B7 Mycosphaerella arachidis (Cercospora arachidicola) / (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 to 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-2, P-3, P-4

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Abstract

A compound of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, or N-oxides of those compounds, which can be used as fungicides.

Description

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
R1 is selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C3-C6-cycloalkyl;
R2 is selected from cyano, hydroxy, amino, C1-C4-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C3-C6- cycloalkyloxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylamino, di(Ci - C4-alkyl)amino, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, or C1-C4-haloalkylsulfanyl;
R3 is selected from hydrogen, halogen, or C1-C4-alkyl;
R4 is selected from hydrogen, halogen, cyano, or C1-C4-alkyl;
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 a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or up to the possible number of substituents independently selected from R10, wherein R10 is independently selected from halogen, hydroxy, cyano, carboxy, amino, 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, trifluoromethylsulfonyloxy, C1-C4-alkoxy-C1-C4-alkyl, C1- C4-alkoxy-C1-C4-alkoxy, N-C1-C4-alkylamino, N,N-di(C1-C4)-alkylamino, C1-C4-alkoxycarbonyl, C1-C4- alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbonimidoyl, N-hydroxy-C1-C4-alkyl-carbonimidoyl, phenyl, 5- ore- 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, with the proviso that only one is selected from 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-C4-alkoxy; and
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 contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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, 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 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 practiced on the human or animal body.
The compounds of formula (I) or the intermediate compounds of formula (III) according to the invention, which have at least one basic center, 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, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4-alkanecarboxylic 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. The compounds of formula (I) or the intermediate compounds of formula (III) according to the invention, which have at least one acidic group, can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
The 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. Also, atropisomers may occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I) according to the invention. Likewise, a compound of formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of formula (I) according to the invention.
In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable oragrochemically acceptable 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 . N-oxides can be prepared by reacting a compound of formula (I) with a suitable oxidizing agent, for example the H2<D2/urea adduct, in the presence of an acid anhydride, e.g., trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem. 1989, 32 (12), 2561- 73, or W02000/15615. The compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
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 haloalky I, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.
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-1 -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 "C2-Cn-alkynyloxy" refers to a radical of the formula -ORa where Ra is a C2-Cn-alkynyl radical as generally defined above.
As used herein, the term “C1-Cn-alkoxy-C1-Cn-alkyl” refers to an alkyl radical C1-Cn-alkyl (as defined above) substituted with a C1-Cn-alkoxy group as defined above. Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxy methyl. This term can be used interchangeably with the term “C1-Cn-alkyl-C1-Cn- alkoxy” which refers to a radical of the formula -Ra-ORb, where Ra is a C1-Cn-alkyl group as defined above, and Rb refers to an C1-Cn-alkyl group as defined above.
As used herein, the term “C1-Cn-alkoxy-C1-Cn-alkoxy” refers to a radical of the formula -ORa-ORb, wherein Ra is a Ci-Cn-alkyl group as defined above, and Rb is a C1-Cn-alkyl group as defined above.
As used herein, the term “C1-Cn-alkyl-C1-Cn-alkoxy-C1-Cn-alkoxy” refers to a radical of the formula -Ra-ORb- ORc, where Ra is a C1-Cn-alkyl group as defined above, and Rb and Rc refer to an C1-Cn-alkyl group as defined above.As used herein, the term “C3-Cn-cycloalkyl-C1-Cn-alkyl” refers to an alkyl radical (as mentioned above) substituted with a C3-Cn-cycloalkyl group. Examples are cyclopropylmethyl, cyclopropylethyl. Similarly, the term “ C3-Cn-halocycloalkyl-Ci-Cn-alkyl” refers to an alkyl radical substituted with cycloalkyl group, wherein the cycloalkyl group is substituted by one or more of the same or different halogen atoms. Examples are 3,3- difluorobutylmethyl and 1 -chlorocyclopropylmethyl.
As used herein, the term "Ci-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-fluoroethy 1, 2,2,2-trichloroethyl. Similarly, the term “C1-Cn-haloalkoxy” as used herein refers to a C1-Cn-alkoxyl radical respectively substituted with one or more halogen 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. Examples are for example methylthio, ethylthio, isopropylthio-.
As used herein, the term “C1-Cn-haloalkylthio“ or “C1-Cn-haloalkylsulfanyl“refers to a C1-Cn-haloalkyl group linked through a sulfur atom. Examples are for example trifluoromethylsulfanyl, difluoromethylsulfanyl, and 2,2- difluoroethylsulfanyl.As used herein, the term “Ci -Cn-alky Isulfinyl" refers to a C1-Cn-alkyl 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-Cn-alkyl group linked through the sulfur atom of a sulfonyl (or S(=O)2-) group.
As used herein, the term “C1-Cn-alkylsulfonyl-C1-Cn-alkyl” refers to an a C1-Cn-alkyl radical substituted with a Ci-Cn-alkylsulfonyl 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-alkylaminocarbonyl” refers to a C1-Cn-alkylamino group (or RaNHC(=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-Cn alkylamino” refers to a radical of the formula -NH-Ra where Ra is a Ci-Cn- alkyl radical as defined above.
As used herein, the term "N,N-di(C1-Cn-alkyl)amino" refers to a radical of the formula -N(Ra)Ra where each Ra is a Ci-Cn-alkyl radical, which may be the same or different, as defined above.
As used herein, the term “N-C1-Cn-alkoxy-C-C1-Cn-alkyl-carbonimidoyl” refers to a radical of the formula - C(Ra)=NO(Rb) where Ra is a C1-Cn-alkyl radical as generally defined above, and Rb is a C1-Cn-alkyl radical as generally defined above.
As used herein the term “N-hydroxy-C-C1-Cn-alkyl-carbonimidoyl” refers to a radical of the formula -C(Ra)=NOH where Ra is a C1-Cn-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 independently 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.
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 and 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” or “ambient temperature” 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, A1, A2, A3, Q 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 one embodiment of the invention, R1 is selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C3-C6-cycloalkyl. In another embodiment of the invention, R1 is C1-C4-alkyl. Preferably R1 is C1-C3-alkyl. More preferably, R1 is methyl, ethyl, or isopropyl. Even more preferably, R1 is methyl.
In one embodiment ofthe invention, R2 is selected from cyano, hydroxy, amino, C1-C4-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C3-C6-cycloalkyloxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, or C1-C4- haloalkylsulfanyl. Preferably, R2 is cyano, hydroxy, C1-C3-alkoxy, C3-C6-cycloalkyloxy, C1-C2-haloalkoxy, C1- C4-alkoxy-C1-C2-alkyl, C1-C2-alkylsulfanyl, C1-C2-alkylsulfinyl, or C1-C2-alkylsulfonyl. More preferably, R2 is C1- Cs-alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl. Even more preferably, R2 is C1- Cs-alkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl. Still even more preferably, R2 is methoxy, ethoxy, methoxymethyl, or methylsulfanyl.
In one embodiment of the invention, R3 is selected from hydrogen, halogen, or C1-C4-alkyl. In another embodiment R3 is selected from hydrogen, halogen, or C1-C3-alkyl. Preferably R3 is hydrogen, fluorine, chlorine or methyl. More preferably R3 is hydrogen or methyl. Even more preferably R3 is hydrogen. In another embodiment, R3 is hydrogen or C1-C3-alkyl. In one embodiment of the invention, R4 is selected from hydrogen, halogen, cyano, or C1-C4-alkyl. Preferably R4 is hydrogen, fluorine, chlorine, cyano, or C1-C3-alkyl. More preferably, R4 is hydrogen, fluorine, chlorine, or C1-C3-alkyl. Even more preferably R4 is hydrogen or methyl. In one embodiment R4 is hydrogen. In another embodiment R4 is methyl.
In one embodiment of the invention, R5 and R6 are independently selected from hydrogen, or C1-C4-alkyl. Preferably R5 and R6 are independently selected from hydrogen or C1-C3-alkyl. More preferably R5 and R6 are independently selected from hydrogen or methyl. Even more preferably R5 and R6 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 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, C2-C4-alkynyl, or C1-C4-haloalky. Preferably R7, R8, and R9 are independently selected from hydrogen, halogen, methyl, or trifluoromethyl. More preferably R7, R8, and R9 are hydrogen.
In one embodiment of the invention, Q is selected from a 6-membered heteroaryl, wherein any of said 6- membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or up to the possible number of substituents independently selected from R10, wherein R10 is independently selected from halogen, hydroxy, cyano, carboxy, amino, 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, trifluoromethylsulfonyloxy, C1-C4-alkoxy-C1-C4-alkyl, C1- C4-alkoxy-C1-C4-alkoxy, N-C1-C4-alkylamino, N,N-di(C1-C4)-alkylamino, C1-C4-alkoxycarbonyl, C1-C4- alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbonimidoyl, N-hydroxy-C1-C4-alkyl-carbonimidoyl, phenyl, 5- ore- 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, with the proviso that only one is selected from 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-C4-alkoxy. Preferably, Q is selected from a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, amino, C1-C3-alkyl, C1-C3-alkoxy, phenyl, 5- or 6-membered heteroaryl, or C3- C6-cycloalkyl, wherein any of 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 C1-C4-alkyl.
More preferably, Q is selected from a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
In another embodiment of the invention, Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is as defined above. Preferably, Q is selected from Q1 , Q2, Q3, or Q4; wherein Q1 , Q2, Q3 and Q4 are unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
Preferably, Q is selected from Q1 , Q2, or Q3 wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is as defined above. Preferably, Q is selected from Q1 , Q2, orQ3; wherein Q1 , Q2 and Q3 are unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
More preferably, Q is Q1 : wherein the staggered line denotes the bond to the rest of the molecule, wherein any of said 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is as defined above. Preferably, Q is Q1 ; wherein Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl. More preferably, Q is Q1 ; wherein Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, and wherein R10 is selected from halogen, cyano, or amino.
In an embodiment of the invention, R10 is selected from halogen, hydroxy, cyano, carboxy, amino, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylsulfanyl, Ci- C4-alkylsulfinyl, C1-C4-alkylsulfonyl, trifluoromethylsulfonyloxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4- alkoxy, N-C1-C4-alkylamino, N,N-di(C1-C4)-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4- alkoxy-C1-C4-alkyl-carbonimidoyl, N-hydroxy-C1-C4-alkyl-carbonimidoyl, 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, with the proviso that only one is selected from 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-C4-alkoxy. In another embodiment of the invention, R10 is selected from halogen, hydroxy, cyano, carboxy, amino, C1-C3- alkyl, C1-C2-haloalkyl, C1-C3-haloalkoxy, C1-C4-alkoxy, C2-C3-alkenyloxy, C2-C3-alkynyloxy, C1-C2- alkylsulfanyl, C1-C2-alkylsulfinyl, C1-C2-alkylsulfonyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C2-alkoxy-C1-C4-alkoxy, C1- Cs-alkoxycarbonyl, C1-C2-alkylcarbonyl, N-C1-C2-alkoxy-C-C1-C2-alkyl-carbonimidoyl, N-hydroxy-C1-C2-alkyl- carbonimidoyl, trifluoromethylsulfonyloxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein any of 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 is selected from halogen, hydroxy, cyano, carboxy, amino, C1-C3-alkyl, C1-C2- haloalkyl, C1-C3-haloalkoxy, C1-C4-alkoxy, C2-C3-alkenyloxy, C2-C3-alkynyloxy, C1-C2-alkylsulfanyl, C1-C2- alkylsulfinyl, C1-C2-alkylsulfonyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C2-alkoxy-C1-C4-alkoxy, C1-C3-alkoxycarbonyl, C1-C2-alkylcarbonyl, N-C1-C2-alkoxy-C-C1-C2-alkyl-carbonimidoyl, N-hydroxy-C1-C2-alkyl-carbonimidoyl, trifluoromethylsulfonyloxy, 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 is selected from cyano, carboxy, chloro, fluoro, bromo, methyl, ethyl, trifluoromethyl, ethoxy, ethoxy, propoxy, allyloxy, prop-2-noxy, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, methylsulfanyl, methylsulfinyl, methyl-sulfonyl, methoxymethyl, ethoxymethyl, 2-methoxy- ethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, - C(CH3)=NOCH2CH3, -C(CH3)=NOH, trifluoromethylsulfonyloxy, 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 is selected from chloro, fluoro, bromo, cyano, carboxy, methyl, trifluoromethyl, methoxy, propoxy, allyloxy, prop-2-ynoxy, difluoromethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2- methoxy-ethoxymethyl, methoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3,-C(CH3)=NOCH2CH3,- C(CH3)=NOH, trifluoromethyl-sulfonyloxy, 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 is selected from 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, or 1- cyanocyclopropyl.
In still another embodiment of the invention, R10 is selected from halogen, cyano, amino, C1-C3-alkyl, C1-C3- alkoxy, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein any of 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 is selected from chloro, bromo, methyl, 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 is selected from chloro, bromo, cyano, or amino. In still another embodiment of the invention, R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl, wherein any of said C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl. Preferably, R10 is selected from halogen, cyano, C1- C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl. More preferably, R10 is selected from cyano, chloro, bromo, methyl, methoxy or cyclopropyl.
In one embodiment of the invention, 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 contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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.
Preferably, 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 contains 1 or 2 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, C1-C2- alkylsulfanyl, C1-C2-alkylsulfinyl, C1-C2-alkylsulfonyl, or C2-C4-alkynyl. More preferably, 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 contains 1 heteroatom selected from N, O and 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-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, or C2-C4-alkynyl. Even more preferably, Z1 is selected from 1 -methylcyclopropyl, 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3- difluoro-4-pyridyl, 2,3-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluoro-3-pyridyl, 2,4-difluorophenyl, 2,4- difluoropyrimidin-5-yl, 2,5-difluoro-3-pyridyl, 2,5-difluoro-4-pyridyl, 2,5-difluorophenyl, 2,5-difluoropyrimidin-4- yl, 2,6-difluoro-3-pyridyl, 2,6-difluoro-4-pyridyl, 2,6-difluoropyrimidin-4-yl, 2-chlorophenyl, 2-fluoro-3-pyridyl, 2- fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluoro-4-pyridyl, 2-fluorophenyl, 2- fluoropyrimidin-4-yl, 2-fluoropyrimidin-5-yl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluoro-2-pyridyl, 3,4- difluorophenyl, 3,5-difluoro-2-furyl, 3,5-difluoro-2-pyridyl, 3,5-difluoro-2-thienyl, 3,5-difluoro-4-pyridyl, 3,5- difluorophenyl, 3,5-difluoropyridazin-4-yl, 3,6-difluoro-2-pyridyl, 3,6-difluoropyridazin-4-yl, 3-chlorophenyl, 3- fluoro-2-furyl, 3-fluoro-2-pyridyl, 3-fluoro-2-thienyl, 3-fluoro-4-pyridyl, 3-fluorophenyl, 3-fluoropyridazin-4-yl, 3- methoxyphenyl, 3-methylphenyl, 3-thienyl, 4,5-difluoro-2-pyridyl, 4,5-difluoropyridazin-3-yl,4,5- difluoropyrimidin-2-yl, 4,6-difluoro-2-pyridyl, 4,6-difluoro-3-pyridyl, 4,6-difluoropyridazin-3-yl,4,6- difluoropyrimidin-2-yl, 4-chlorophenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, 4-fluoro-2- methoxy-phenyl, 4-fluoro-3-pyridyl, 4-fluorophenyl, 4-fluoropyridazin-3-yl, 4-fluoropyrimidin-2-yl, 4- fluoropyrimidin-5-yl, 4-methylphenyl, 5,6-difluoro-2-pyridyl, 5,6-difluoro-3-pyridyl, 5,6-difluoropyridazin-3-yl, 5,6-difluoropyridazin-4-yl, 5,6-difluoropyrimidin-4-yl, 5-fluoro-2-furyl, 5-fluoro-2-pyridyl, 5-fluoro-2-thienyl, 5- fluoro-3-pyridyl, 5-fluoropyridazin-3-yl, 5-fluoropyridazin-4-yl, 5-fluoropyrimidin-2-yl, 5-fluoropyrimidin-4-yl, 6- fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 6-fluoropyridazin-3-yl, 6-fluoropyridazin-4-yl, 6-fluoropyrimidin-4-yl, cyclobutyl, cyclohexyl, cyclopentyl, cyclopropyl, methyl, or n-propyl. Still even more preferably, Z1 is 1- methylcyclopropyl, cyclobutyl, cyclopropyl, methyl, n-propyl, phenyl, 4-fluorophenyl, 2,4-difluorophenyl, 5- fluoro-2-furyl, 3,5-difluoro-2-furyl, 5-fluoro-2-thienyl, 3,5-difluoro-2-thienyl, 2-fluoro-3-pyridyl, 3-fluoro-2-pyridyl,
3-fluoro-4-pyridyl, 4-fluoro-3-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2- pyridyl, 3,5-difluoro-2-pyridy I, or 4,6-difluoro-3-pyridyl.
In another embodiment of the invention, Z1 is selected from phenyl, 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 5- or 6-membered heteroaryl 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, Ci- C4-alkylsulfonyl, or C2-C4-alkynyl. Preferably, Z1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 or 2 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from O or S; and wherein any of said phenyl, and 5- or 6- membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, C1-C2-alkylsulfanyl, C1-C2- alkylsulfinyl, C1-C2-alkylsulfonyl, or C2-C4-alkynyl. More preferably, Z1 is selected from phenyl, or 5- or 6- membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2- alkoxy, C1-C2-haloalkoxy, or C2-C4-alkynyl. Even more preferably, Z1 is selected from phenyl, thienyl, furyl, pyridyl, pyridazin, or pyrimidin; and wherein any of said phenyl, thienyl, furyl, pyridyl, pyridazin, and pyrimidin are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C2- alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, or C2-C4-alkynyl. Even more preferably, Z1 is selected from phenyl, thienyl, furyl, pyridyl, pyridazin, or pyrimidin; and wherein any of said phenyl, thienyl, furyl, pyridyl, pyridazin, and pyrimidin are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2-alkoxy, or C2-C4-alkynyl. Still even more preferably, Z1 is selected from 1- methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluoro-4-pyridyl, 2,3-difluorophenyl,2,4,6-trifluorophenyl, 2,4- difluoro-3-pyridyl, 2,4-difluorophenyl, 2,4-difluoropyrimidin-5-yl, 2,5-difluoro-3-pyridyl,2,5-difluoro-4-pyridyl, 2,5-difluorophenyl, 2,5-difluoropyrimidin-4-yl , 2,6-difluoro-3-pyridy 1, 2,6-difluoro-4-pyridy 1, 2,6-difluoropyrimidin-
4-yl, 2-chlorophenyl, 2-fluoro-3-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluoro- 4-pyridyl, 2-fluorophenyl, 2-fluoropyrimidin-4-yl, 2-fluoropyrimidin-5-yl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4- difluoro-2-pyridyl, 3,4-difluorophenyl, 3,5-difluoro-2-furyl, 3,5-difluoro-2-pyridyl, 3,5-difluoro-2-thienyl, 3,5- difluoro-4-pyridyl, 3,5-difluorophenyl, 3,5-difluoropyridazin-4-yl, 3,6-difluoro-2-pyridyl, 3,6-difluoropyridazin-4- yl,3-chlorophenyl, 3-fluoro-2-furyl, 3-fluoro-2-pyridyl, 3-fluoro-2-thienyl, 3-fluoro-4-pyridyl, 3-fluorophenyl, 3- fluoropyridazin-4-yl, 3-methoxyphenyl, 3-methylphenyl, 3-thienyl, 4,5-difluoro-2-pyridyl, 4,5-difluoropyridazin- 3-yl,4,5-difluoropyrimidin-2-yl, 4,6-difluoro-2-pyridyl, 4,6-difluoro-3-pyridyl, 4,6-difluoropyridazin-3-yl,4,6- difluoropyrimidin-2-yl, 4-chlorophenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, 4-fluoro-2- methoxy-phenyl, 4-fluoro-3-pyridyl, 4-fluorophenyl, 4-fluoropyridazin-3-yl, 4-fluoropyrimidin-2-yl, 4- fluoropyrimidin-5-yl, 4-methylphenyl, 5,6-difluoro-2-pyridyl, 5,6-difluoro-3-pyridyl, 5,6-difluoropyridazin-3-yl, 5,6-difluoropyridazin-4-yl, 5,6-difluoropyrimidin-4-yl, 5-fluoro-2-furyl, 5-fluoro-2-pyridyl, 5-fluoro-2-thienyl, 5- fluoro-3-pyridyl, 5-fluoropyridazin-3-yl, 5-fluoropyridazin-4-yl, 5-fluoropyrimidin-2-yl, 5-fluoropyrimidin-4-yl, 6- fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 6-fluoropyridazin-3-yl, 6-fluoropyridazin-4-yl, 6-fluoropyrimidin-4-yl.
In another embodiment of the invention, Z1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 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. Preferably, Z1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2-alkoxy, or C2-C4-alkynyl. More preferably, Z1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro or fluoro. Even more preferably, Z1 is selected from phenyl, 2-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 5-fluoro-2-furyl, 3,5- difluoro-2-furyl, 5-fluoro-2-thienyl, 3,5-difluoro-2-thienyl, 2-fluoro-3-pyridyl, 3-fluoro-2-pyridyl, 3-fluoro-4-pyridyl, 4-fluoro-3-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, 3,5- difluoro-2-pyridyl, or 4,6-difluoro-3-pyridy I. Still even more preferably, Z1 is 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridy I, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-py ridyl.
In another embodiment of the invention, Z1 is selected from phenyl, or 6-membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6- membered heteroaryl are unsubstituted or substituted by 1 or 2 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. Preferably, Z1 is selected from phenyl, or 6-membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen. More preferably, Z1 is selected from phenyl, 2-fluorophenyl, 4- fluorophenyl, 2,4-difluorophenyl, 2-fluoro-3-pyridyl, 3-fluoro-2-pyridyl, 3-fluoro-4-pyridyl, 4-fluoro-3-pyridyl, 5- fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, or 4,6- difluoro-3-pyridyl. Still even more preferably, Z1 is 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5- fluoro-2-pyridy I, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-pyridyl.
In one embodiment of the invention, the compound of formula (I) may be a compound of formula (l-A): wherein R1 , R2, R3, R4, R5, R6, R10, Q and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R7, R8 and R9 are independently selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2- C4-alkynyl, or C1-C4-haloalkyl.
Preferably, in the compound of formula (l-A) R1 , R2, R3, R4, R5, R6, Q, R10 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 A8, and R7, R8 and R9 are independently selected from hydrogen, halogen, methyl, or trifluoromethyl.
More preferably, in the compound of formula (l-A) R1 , R2, R3, R4, R5, R6, Q, R10 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 A8, and R7, R8 and R9 are hydrogen.
In an embodiment of the invention, in the compound of formula (l-A) wherein R1, R2, R3, R4, R5, R6, Q, R10 and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R8 and R9 are independently selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, or C1-C4-haloalkyl. Preferably, in the compound of formula (l-A) R1 , R2, R3, R4, R5, R6, Q, R10 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 R8 and R9 are independently selected from hydrogen, halogen, methyl, or trifluoromethyl.
More preferably, in the compound of formula (l-A) R1 , R2, R3, R4, R5, R6, Q, R10 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 R8 and R9 are hydrogen.
In another embodiment of the invention, in the compound of formula (l-A) wherein R1 , R2, R3, R4, R5, R6, Q, R10 and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group.
Preferably, in the compound of formula (l-A) R1, R2, R3, R4, R5, R6, Q (Q1 , Q2, Q3, Q4, and Q5), R10 and Z1 are as defined for the compounds of formula (I) according to the present invention, and A is selected from A1 , or A2.
In still another embodiment of the invention, in the compound of formula (l-A) wherein R1 , R2, R3, R4, R5, R6, R10 and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1 , or A2; and Q is selected from Q1 , Q2, Q3, or Q4.
In still another embodiment of the invention, in the compound of formula (l-A) wherein R1 , R2, R3, R4, R5, R6, R10 and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1 , or A2; and Q is selected from Q1 , Q2, or Q3.
In still another embodiment of the invention, in the compound of formula (l-A) wherein R1 , R2, R3, R4, R5, R6, R10 and Z1 are as defined for the compounds of formula (I) according to the present invention, A is selected from A1 , or A2; and Q is Q1 .
In another embodiment of the invention, in the compound of formula (l-A) wherein R1 , R2, R3, R4, R5, R6, R10 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 (l-A) wherein R1 , R2, R3, R4, R5, R6, R10 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 (l-A) wherein R1 , R2, R3, R4, R5, R6, R10 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 . The present invention, accordingly, makes available a compound of formula (I) having R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, Q, A1, A2, A3 and Z1 as defined above in all combinations / each permutation.
The present invention, accordingly, makes available a compound of formula (l-A) having R1 , R2, R3, R4, R5, R6, R7, R8, R9, R10, Q, A and Z1 as defined above in all combinations / each permutation.
Embodiments according to the invention are provided as set out below.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; and wherein R7, R8, and R9 are hydrogen; and R2 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; wherein R7, R8, and R9 are hydrogen; Z1 is selected from phenyl, or 5- or 6- membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2-alkoxy, or C2-C4-alkynyl; and R2 is as defined for the compounds of formula (I) according to the present invention. Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; wherein R7, R8, and R9 are hydrogen; and Z1 is selected from phenyl, or 5- or 6-membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2-alkoxy, or C2-C4-alkynyl.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; wherein R7, R8, and R9 are hydrogen; and Z1 is selected from phenyl, or 6- membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6-membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; 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; and wherein R7, R8, and R9 are hydrogen; and Z1 is selected from 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5- difluoro-2-pyridyl.
In an embodiment of the invention, the compound of formula (l-A) may be a compound of formula (I-A1), wherein Q is Q1 : wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and Z1 are as defined for the compounds of formula (I), and wherein A is defined for the compounds of formula (l-A) according to the present invention.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R8 and R9 are hydrogen; Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; and R2 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R8 and R9 are hydrogen; Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; and Z1 is selected from phenyl, or 6-membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R8 and R9 are hydrogen; Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; and Z1 is selected from 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5-fluoro-2- pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-pyridyl.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group; Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; and R2 and Z1 are as defined for the compounds of formula (I) according to the present invention.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R8 and R9 are hydrogen; Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; and Z1 is selected from phenyl, or 6-membered heteroaryl; wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen.
Preferably, in the compound of formula (I) according to the present invention, R1 is C1-C3-alkyl; R2 is C1-C3- alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl,or C1-C2-alkylsulfanyl; R3 is hydrogen or C1-C3-alkyl; R4 is hydrogen or methyl; R5 and R6 are independently selected from hydrogen or C1-C3-alkyl; A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R8 and R9 are hydrogen; Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl; and Z1 is selected from 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2-pyridyl, 5-fluoro-2- pyridyl, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-pyridyl.
The presence of one or more possible asymmetric carbon atoms in any of the compounds of formula (I), (l-A), and (I-A1) 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-56, 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.
More preferably the compound of formula (I) according to the invention is selected from N-[2-(6-cyano-2- pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide, N-[2- (6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl]-1-(3,5-difluoro-2-pyridyl)triazole-4- carboxamide, or N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl]-2-(2,4- difluorophenyl)tetrazole-5-carboxamide.
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 17, 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 17 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 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 .
Scheme 1
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 (Ila) 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 (Ila), where G° 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-di methylformamide (DMF) in inert solvents such as dichloromethane (DCM) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C. Treatment of compounds of formula (Ila) 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]-1 H-1 ,2,3-triazolo[4,5- b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (Ila), wherein G° is G01, G02 or G03 as set forth below (Scheme 2), in an inert solvent, e.g. pyridine, DMF, acetonitrile, DCM2 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 (Ila), wherein G° 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).
Scheme 2
Compounds of formula (II) can be prepared from compounds of formula (lib), wherein A1, A2, A3 are N and Z1 are as described in formula (I), and R° is C1-C4-alkyl, by ester hydrolysis. A variety of conditions can be used, as for example aqueous NaOH or LiOH and an organic water miscible solvent like THF, dimethoxyethane, methanol, or ethanol. Such ester hydrolyses are well known to those skilled in the art. Compounds of formula (lib) can also be directly converted to compounds of formula (I) by reacting compounds of formula (lib) with compounds of formula (III) in the presence of trimethyl aluminium, or trimethyl aluminium-DABCO complex in an inert solvent such as toluene or DCM. 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 (lib) 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 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 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 THF, 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, or cyclopentyl methyl ether in the presence of a Lewis acid such as Ti(OJPr)4 (see Synlett 2007, (4), 652-654) (Scheme 3).
Scheme 3
Compounds of formula (IV), wherein R1, R2, R3, R4, R10 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.
For example, compounds of formula (IV), wherein R1, R2, R3, R4, R10 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 THF, followed by addition of a suitable alkylating agent R4-X°, wherein X° is halogen, for example iodomethane. Compounds of formula (IVa), wherein R4 is hydrogen and R1, R2, R3, R10 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 DCM 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 (Scheme 4).
Compounds of formula (V) may be prepared from compounds of formula (VI), respectively from any of compounds of formula (Via), (Vlb), (Vic), (Vid) or (Vie), as shown in Scheme 5.
Scheme 5
As shown in Scheme 5, compounds of formula (VII), wherein R1 , R2, R3, R10 (R10 refers to R10a, R10b, R10C and R10d) 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 THF and the like. Solutions of the metalated species (Vila) are then treated with compounds of formula (VI), respectively (Via), (Vlb), (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. Let. 2017, 27(17), 4044-4050 (X01 is Br, n- butyl lithium) and Angew. Chem. Inf. Ed. 2016, 55(17), 5332-5336, US2014/0349990, W02002/004424, W02021/009068 (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 THF, 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) (Scheme 6).
Scheme 6
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 THF or tert-butyl methyl ether, at temperatures between -78°C to rt, followed by addition of a compound of formula (XI), respectively any of compounds of formula (Xia), (Xlb), (Xlc), (Xld) or (Xie), wherein R10 is 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) (Scheme 7).
Scheme 7 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 (la), wherein R1, R2, R3, R5, Q, R10, 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), (Vlb), (Vic), (Vid) or (Vie), with 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 DCM, in the presence of a base, for example triethyl amine. This reaction is shown in Scheme 8.
(Via) (Vlb) (Vic) (Vid) (Vie)
Scheme 8
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 (Vila) (see Scheme 5) in an inert solvent such as THF, known to a person skilled in the art as Michael reaction of organometallics to nitro alkenes (Scheme 9).
Scheme 9 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 (Illa), wherein R1 , R2, R3, R5, R10 and Q are as defined above for the compound of formula (I) 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 (Scheme 10).
Scheme 10
Compounds of formula (Illa) are converted into compounds of formula (la) by the methods described in Schemes 1 and 2.
Certain compounds of formula (V), wherein R2 is C1-C4-alkoxy, C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4- haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-haloalkoxy, C3-C6-cycloalkyloxy, or C1-C4-alkylsulfanyl, can also be prepared as shown prepared as shown in Scheme 11 .
Scheme 11
As shown in Scheme 11 , Vilsmeier reaction of compounds of formula (XVI) leads to compounds of formula (XVIIa), which when treated with compounds H-R2, wherein R2 C1-C4-alkoxy, C1-C4-alkylamino, di(C1-C4- alkyl)amino, C1-C4-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-haloalkoxy, C3-C6-cycloalkyloxy, or C1-C4-alkylsulfanyl, and a base such as K2CO3 or sodium tert-butoxide, leads to compounds of formula (XVIIb). Vilsmeier reactions to compounds of formula (XVIIb) have been reported (see W02008059370 and W02017004674, Synthesis 2013, 45(23), 3211-3227, Tetrahedron Lett. 2014, 55(33), 4568-4571 , Sulfur Lett. 1986, 4(5), 175-83). Compounds of formula (VIII) can be prepared by reaction of compounds of formula (XVIIb) with tosylmethyl isocyanide (TOSMIC) in the presence of a base (scheme 12).
Such TOSMIC reactions have been reported for example in Synth. Comm. 1988, 18 (18), 2331-5. Compounds of formula II are either commercially available or can be synthesized as described vide infra.
Compounds of formula (lib) wherein A1 , A2, A3 are N and Z1 is as described in for formula (I), namely compounds of formula (llba) can be obtained by reacting a diazonium salt of formula (XVIII)
Z1— N=N Y
(XVIII) 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 (XIX), wherein R° is Ci-Ce-alkyl. This 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 Tetrahedron 2020, 76(14), 131063. Compounds of formula (XVIII) as defined just before, can be prepared from primary amines of formula (XX) 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 II), the diazotation step and the cycloaddition steps can be performed sequentially, without the need of isolating (XVIII). This variant is also described in Tetrahedron 2020, 76(14), 131063. The chemistry is summarized in scheme 13: the two steps can also be performed sequencially in one pot
Scheme 13
Compounds of formula (XX) are commercially available, as are compounds of formula (XIX) (e.g., R° is methyl,
CAS [6832-16-2]).
Very similarly, compounds of formula (II ba), wherein A1, A2, A3 are N, and Z1 is as described in for formula (I), can be prepared by reacting a compound of formula (XXI): wherein R° is Ci-Ce-alkyl, and Ar1 is phenyl or p-tolyl, with compounds of formula (XVIII), in the presence of a base, e.g., pyridine at temperatures from -50°C to 50°C to yield compounds of formula (llba). 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 (XXI) are prepared as described in the literature cited vide supra and exemplified in the preparation examples of the application.
Alternatively, compounds of formula (llba), wherein A1 , A2 and A3 are N and Z1 is as defined in formula (I) can be obtained by coupling compounds of formula (XXII), wherein A1 , A2 and A3 are N, and R° is as described vide supra, with a boronic acid derivative of formula (XXIII),
O H
T- - B
O H
(XXIII) wherein Z1 is as defined 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 (XXII), wherein A1, A2 and A3 are N, exist in tautomeric forms.
Persons skilled in the art will envisage that the coupling product of this reaction 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 (llba). Those skilled in the art will realize that this Chan-Lam coupling is a general method for preparation of compounds of formula (lib). Examples have been shown in the literature for compounds of formula (llbb) wherein Z1 , Rz and R° are as previously defined (see J. Med. Chem. 2018, 61 , 8, 3370-3388 and WO14/041106), compounds of formula (llbc) and (llbd) w re as defined under formula (I), and R° is Ci-Ce-alkyl (see WO15/155626, EP2390252) and compounds of formula (II be) wherein Z1 , R7, R8 and R9 are as defined under formula (I), and R° is Ci-Ce-alkyl (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 (llba), wherein A1, A2 and A3 are N, and Z1 is as defined in formula (I), is shown in Scheme 14.
Scheme 14
As shown in Scheme 14, sequence begins with diazotation of compounds of formula (XX) as previously described vide supra and then treatment of the diazionium salt with a compound of formula (XXIV), wherein R° is Ci-Cealkyl, in the presence of a mild base, for example sodium acetate to yield compounds of formula (XXV). Compounds of formula (XXV), wherein Z1 and R° are as previously defined, are then treated with aqueous ammonia in a miscible organic solvent, for example THF or 2-methyl tetra hydrofuran, at temperatures between 0°C to 30°C, to give compounds of formula (XXVI). Finally, diazotation of compounds of formula (XXVI) 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 (II ba). The sequence of reactions has been previously described in W013/087805.
Compounds of formula (lib) may also be prepared by alkylation of compounds of formula (XXII) with compounds of formula (XXVII)
Z — X (XXVII) wherein Z1 is as previously described under formula I, and X° 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 (lib) as described for example in WO14/168221 ; W010/043000; 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 (lib) (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, 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 (la) (below) allow further chemistry to be carried out 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 15. As shown in Scheme 15, compounds of formula (I), wherein Q is Q1 , and R1, R2, R3, R4, R5, R6, R10, A1, A2, A3 and Z1 are as defined above for the compound of formula (I), and R10a is cyano, namely compounds of formula (lb), can be obtained from compound of formula (la) by treatment with an inorganic cyanide source, such as CuCN, in an inert solvent, such as 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, e.g., Sci. Synth. 2004, 19, 173-195.
Compounds of formula (I), wherein Q is Q1 , and R1, R2, R3, R4, R5, R6, R10, A1 , A2, A3 and Z1 are as defined above for the compound of formula (I), and R10a is 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, with the proviso that only one is selected from 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 15) by a Suzuki reaction, which involves, for example, reacting compounds of formula (la), wherein X04 is a leaving group like, for example, chlorine, bromine or iodine, with compounds of formula (XXVIlla), wherein Ybi can be a boron-derived functional group, as for example B(OH)2 or B(ORt>i)2, wherein RM can be a C1-C4-alkyl group or the two groups ORM 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 tefrak/s(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 THF 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 offormula (Ic) can be prepared by a Stille reaction of compounds of formula (XXVI 11 b), wherein Yb2 is a trialkyl tin derivative, preferably tri-n-butyl tin, with compounds of formula (la). Such Stille reactions are carried out in the presence of a palladium catalyst, for example tefrak/s(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 catalyst, for example copper(l) 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 (XXVIlla) and (XXVIlIb) are commercially available or can be prepared by those skilled in the art. Further compounds available from compounds of formula (la) are shown in Scheme 16.
Scheme 16
As shown in Scheme 16, compounds of formula (I), wherein Q is Q1 , and R1, R2, R3, R4, R5, R6, R10, 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 (la), can be treated with compounds of formula (XXIX) under Stille reactions conditions to give compounds of formula (Id). Compounds of formula (Id) can be isolated or directly hydrolysed under aqueous acidic conditions to give compounds of formula (le). 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 (le) can be converted to compound of formula (If), wherein Q is Q1 , and R1 , R2, R3, R4, R5, R6, R10, 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 (le) with compounds of formula (XXX) (or a salt thereof), wherein R13 is hydrogen or C1-C4-alkyl, in an inert solvent such as methanol, ethanol, THF, 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 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, 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 (la) (Scheme 17).
Scheme 17
As shown in Scheme 17, compounds of formula (la) can be carbonylated to give compounds of formula (I), namely compounds of formula (Ig) with R14 C1-C4-alkyl, wherein Q is Q1 , and R1, R2, R3, R4, R5, Rs, R10, A1 , A2, A3 and Z1 are as defined above for the compound of formula (I), In such alkoxycarbonylations, compounds of formula (la) are reacted with carbon monoxide, usually under pressure, in the presence of metal catalyst such as a palladium catalyst (for example, palladium(ll) acetate, [1 ,1 '-bis(diphenylphosphino)ferrocene] palladium(ll) dichloride (Pd(dppf)Cl2), bis(triphenylphosphine)palladium(ll) dichloride (PdCh(PPh3)2) or bis(diphenylphosphino)propane]palladium(ll) dichloride (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 cosolvent (e.g. toluene, dioxane or DMF), and preferably in the presence of a base, such as for example trimethylamine, at temperatures between 20°C and 200°C, preferably between 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 (Ig) can be easily saponified to compounds of formula (Ih) under conditions known to those skilled in the art, for example conditions such as aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, THF or dioxane at rt, or up to refluxing conditions. Alternatively, treating ester compounds of formula (li) with halide anions, preferably chloride anions, originating from, for example, lithium chloride (or alternatively, sodium or potassium chloride), in solvents such as DMF, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, may also generate the carboxylic acid compounds of formula (Ih). The reaction temperatures for such an O-demethylation range preferably from 20°C to the boiling point of the reaction mixture, orthe reaction may be performed under microwave irradiation. Compounds of formula (Ih) can be converted to amides of formula (I), namely compounds of formula (li) with R15 and R16 are independently hydrogen or C1-C4-alkyl, wherein Q is Q1 , and R1 , R2, R3, R4, R5, R6, R10, 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 R15R1SNH. These methods have been discussed vide supra in Schemes 1 and 2.
Further compounds of formula (li) can be converted to compounds of formula (I), namely compounds of formula (Ij) wherein R9 is amino; Q is Q1 ; and R1, R2, R3, R4, R5, R6, R10, 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 (li) 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 TMSNa, 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 (Ij). 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 (Ij). 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 (Ij) so obtained can be amidated to compounds of formula (Ik), wherein Q is Q1 , and R1 , R2, R3, R4, R5, R6, R10, 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 (XXXI) 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. , R10) 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 perse into another compound as defined in any of the embodiments of the present invention 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 perse. 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 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.
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.
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 complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, 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 at least three asymmetric carbon atoms. The relationship between enantiomers and diastereomers of compounds of formula (I) is shown below.
A person skilled in the art is well aware that above diastereomers and enantiomers of formula (I), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, A1, A2, A3, Q and Z1 are as defined for formula (I) are within the scope of the invention.
The compounds of formula (I) have at least two chiral carbon atoms, (stereocenters, wherein the star (*) indicates the chiral carbon atom), such there are four stereoisomers available. These four stereoisomers consist of two sets of enantiomers.
For compounds of formula (I), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, A1 , A2, A3, Q and Z1 are as defined for the compounds of formula (I), wherein R4 is not hydrogen, and wherein R5 and R6 are not hydrogen, the relationship between enantiomers and diastereomers is illustrated below.
A person skilled in the art is well aware that above diastereomers and enantiomers of formula (I), wherein R1 , R2, R3, R4, R5, R6, R7, R8, R9, R10, A1, A2, A3, Q 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 (l-A), and (I-A1), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, Q and Z1 are as defined for formula (I), and wherein A is as defined for compounds of formula (l-A), 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 or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time also protecting 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. 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, Altemaria 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 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, Corynespora spp. including Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp. including Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), 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, 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 synthesizing 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 CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a Cryl II B(b1 ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryl II B(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA 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 synthesizing 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 delta-endotoxins, e.g., CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid- UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
Further, in the context of the present invention there are to be understood by delta-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, W002/15701). Truncated toxins, for example a truncated CrylAb, 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 W02003/018810).
Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93/07278, WO95/34656, EP0427529, EP0451878 and W003/052073.
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. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO95/34656, EP0367474, EP0401979 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 Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylActoxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb 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:
1 . Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. 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 I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb 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 I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in W02003/018810.
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 Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants. In one embodiment such soybean plants are genetically modified soybean plants.
In one embodiment the genetically modified plants are soybean plants. Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™.
Transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g., CrylAc (CrylAc Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652), event MON87701 x MON89788 (disclosed in WO2014/170327, e.g. commercially available as Intacta RR2 PRO® soybean), event MON87751 (disclosed in WO2014/201235), event DAS-44406-6 (e.g., commercially available as Enlist E3TM, DAS-44406-6, disclosed in WO2012/075426), or event DAS-81419-2 (described in WO2013/016527, e.g., commercially available as Conkesta™ soybean); event DAS-81419-2 x DAS-44406-6 (e.g., commercially available as Conkesta™ Enlist E3™ Soybean).
Furthermore, such a list of transgenic events is provided by the United States Department of Agriculture's (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the World Wide Web at aphis.usda.gov. The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Altemaria spp. 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 solanaceous crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymoseptoria spp. in cereals.
The compounds of formula (I) and compositions comprising said compounds, are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C. truncatum or C. gloeosporioides)', Corynespora cassiicola (leaf spots); Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot); Diaporthe spp., e.g., Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn. phaseoli) (root and stem rot); Microsphaera diffusa (powdery mildew); Peronospora spp. (downy mildew), e.g., P. manshurica; Phakopsora pachyrhizi and P. meibomiae (soybean rust); Phialophora spp., e.g., P. g reg ata', stem rot; Phomopsis spp., e.g., stem rot: P. phaseoli (teleomorph: Diaporthe phaseolorum)’, Pythium spp. (damping-off); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g., P. megasperma, syn. P. sojae)', Rhizoctonia spp., e.g., R. solani (root and stem rot); Sclerotinia spp. (stem rot or white mold); Septoria spp., e.g., S. glycines (brown spot); S. rolfsii (syn. Athelia rolfsii); Thielaviopsis spp. (black root rot).
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 WO1997/33890.
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, 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 sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate 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. Pressurized sprayers, wherein the active ingredient is dispersed in finely divided form as a result of vaporization 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- 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, gammabutyrolactone, 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 sulfate; 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 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 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
The following mixtures of the compounds of formula (I) with active ingredients are preferred. The abbreviation “TX” means one compound selected from compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds listed in Table P (below), and a compound selected from the group of substances consisting of (4E,10Z)-tetradeca-4, 10-dienyl acetate + TX; (7E,9Z)- dodeca-7,9-dien-1-yl acetate + TX; (E)-6-methylhept-2-en-4-ol + TX; (E)-dec-5-en-1-yl acetate with (E)-dec-5- en-1-ol + TX; (E)-tridec-4-en-1-yl acetate + TX; (S)-bioallethrin + TX; (Z)-dodec-7-en-1-yl acetate + TX; (Z)- hexadec-11-en-1-yl acetate + TX; (Z)-hexadec-11-enal + TX; (Z)-hexadec-13-en-11-yn-1-yl acetate + TX; (Z)- icos-13-en-10-one + TX; (Z)-tetradec-7-en-1-al + TX; (Z)-tetradec-9-en-1-ol + TX; (Z)-tetradec-9-en-1-yl acetate + TX; 1 ,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX; 1-(2-chlorophenyl)-3,3-dimethyl-2-(1 ,2,4-triazol- 1-ylmethyl)butan-2-ol + TX; 1-(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1 , 1 -difluoro-3-(1 ,2,4-triazol-1 - yl)propan-2-ol + TX; 1 -hydroxy-1 H-pyridine-2-thione + TX; 1 -methylcyclopropene + TX; 1- naphthaleneacetamide + TX; 1 -naphthylacetic acid + TX; 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX; 2,4-D + TX; 2,4-DB + TX; 2,6-dichloro-N-(4-trifluormethylbenzyl)benzamide + TX; 2-(1 ,3- dithiolan-2-yl)phenyl dimethylcarbamate + TX; 2-(2-butoxyethoxy)ethyl piperonylate + TX; 2-(4,5-dimethyl-1 ,3- dioxolan-2-yl)phenyl methylcarbamate + TX; 2-(difluoromethyl)-N-((3R)-1 ,1 ,3-trimethylindan-4-yl) pyridine-3- carboxamide + TX; 2-(octylthio)-ethanol + TX; 2-bromo-2-bromomethyl-pentanedinitrile + TX; 2-chlorovinyl diethyl phosphate + TX; 2-imidazolidone + TX; 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX; 2- thiocyanatoethyl laurate + TX; 3-(4-chlorophenyl)-5-methylrhodanine + TX; 3-(difluoromethyl)-1-methyl-N- [1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX; 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl- indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX; 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4- yl)-1-methyl-pyrazole-4-carboxamide + TX; 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX; 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate + TX; 3-phenylphenol + TX; 4,5-dichlorodithiol-3-one + TX; 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX; 4-(2-bromo-4-fluoro-phenyl)-N-(2- chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX; 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX; 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX; 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX; 4-CPA + TX; 4- methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX; 4-methylnonan-5-ol with 4-methylnonan-5-one + TX; 4-phenylphenol + TX; 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX; 5-amino-1 ,3,4-thiadiazole- 2-thiol + TX; 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine + TX; 5-hydroxy-6-methyl-4-(((E)-pyridin-3- ylmethylene)amino)-4,5-dihydro-1 ,2,4-triazin-3(2H)-one + TX; 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX; 8-hydroxyquinoline sulfate + TX; 11 -ethyl-10,12-dioxo-2,5,8-trithia-4, 11 - diazatricyclo[7.3.0.03,7]dodeca-1 (9),3,6-triene-6-carbonitrile + TX; 14-methyloctadec-1-ene + TX; [(9Z,11 E)- tetradeca-9,11-dienyl] acetate + TX; [(Z)-dodec-9-enyl] acetate + TX; abamectin + TX; acephate + TX; acequinocyl + TX; acetamiprid + TX; acethion + TX; acetoprole + TX; acibenzolar + TX; acibenzolar-S-methyl + TX; acrinathrin + TX; Adoxophyes orana GV + TX; Agrobacterium radiobacter + TX; alanycarb + TX; albendazole + TX; aldicarb + TX; allethrin + TX; allosamidin + TX; allyl alcohol + TX; allyxycarb + TX; alphaecdysone + TX; alpha-multistriatin + TX; Amblyseius spp. + TX; ametoctradin + TX; amidithion + TX; amidoflumet + TX; amidothioate + TX; aminocarb + TX; amisulbrom + TX; amiton + TX; amiton hydrogen oxalate + TX; amitraz + TX; anabasine + TX; Anagrapha falcifera NPV + TX; Anagrus atomus + TX; ancymidol + TX; anilazine + TX; anisiflupurin + TX; anthraquinone + TX; antu + TX; Aphelinus abdominalis + TX; Aphidius colemani + TX; Aphidoletes aphidimyza + TX; athidathion + TX; aureofungin + TX; Autographa californica NPV + TX; avermectin B1 a + TX; azaconazole + TX; azadirachtin A + TX; azafenidin + TX; azamethiphos + TX; azinphos-ethyl + TX; azinphos-methyl + TX; azithiram + TX; azoxystrobin + TX; Bacillus sphaericus (Neide) + TX; Bacillus thuringiensis + TX; Bacillus thuringiensis delta endotoxin + TX; Bacillus thuringiensis ssp. aizawai + TX; baculovirus + TX; barthrin + TX; Beauveria brongniartii + TX; benalaxyl + TX; benalaxyl-M + TX; benazepril + TX; benclothiaz + TX; benfuracarb + TX; benomyl + TX; bensultap + TX; benthiavalicarb + TX; benzalkonium chloride + TX; benzamorf + TX; benzothiostrobin + TX; benzovindiflupyr + TX; beta-cyfluthrin + TX; beta-cypermethrin + TX; bethoxazin + TX; bifemetstrobin + TX; bifenazate + TX; bifenthrin + TX; binapacryl + TX; bioallethrin + TX; bioethanomethrin + TX; biopermethrin + TX; bioresmethrin + TX; bisthiosemi + TX; bistrifluron + TX; bitertanol + TX; bixafen + TX; blasticidin-S + TX; borax + TX; bordeaux mixture + TX; boscalid + TX; brodifacoum + TX; brofenvalerate + TX; brofl uthrin ate + TX; bromadiolone + TX; bromfenvinfos + TX; bromophos + TX; bromophos-ethyl + TX; bromuconazole + TX; bufencarb + TX; bupirimate + TX; buprofezin + TX; buserelin + TX; busulfan + TX; but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX; butacarb + TX; butathiofos + TX; butocarboxim + TX; butonate + TX; butopyronoxyl + TX; butoxy(polypropylene glycol) + TX; butoxycarboxim + TX; butylamine + TX; cadusafos + TX; calciferol + TX; calcium phosphate + TX; calcium polysulfide + TX; cambendazole + TX; captafol + TX; captan + TX; carbanolate + TX; carbaryl + TX; carbendazim + TX; carbendazim hydrochloride + TX; carbofuran + TX; carbosulfan + TX; carboxin + TX; carprofen + TX; carpropamid + TX; cartap + TX; cartap hydrochloride + TX; cefalexin + TX; cefovecin + TX; cefquinome + TX; ceftiour + TX; cestex + TX; cevadine + TX; chinomethionat + TX; chitosan + TX; chlobenthiazone + TX; chloralose + TX; chlorantraniliprole + TX; chlorbenside + TX; chlordimeform + TX; chlorethephon + TX; chlorethoxyfos + TX; chlorfenapyr + TX; chlorfenazole + TX; chlorfentazine + TX; chlorfenvinphos + TX; chlorfluazuron + TX; chlormephos + TX; chlormequat + TX; chlorodimeform hydrochloride + TX; chloroinconazide + TX; chloromebuform + TX; chloromethiuron + TX; chloroneb + TX; chlorothalonil + TX; chlorphoxim + TX; chlorprazophos + TX; chlorpyrifos + TX; chlorpyrifos-methyl + TX; chlortetracycline + TX; chlorthiophos + TX; chlozolinate + TX; cholecalciferol + TX; chromafenozide + TX; Chrysoperla carnea + TX; cinerin + TX; cinerin I + TX; cinerin II + TX; cis-jasmone + TX; cis-resmethrin + TX; cismethrin + TX; clenbuterol + TX; climbazole + TX; cloethocarb + TX; clofencet + TX; clorsulon + TX; clothianidin + TX; clozylacon (acetamide) + TX; codlelure + TX; copper acetate + TX; copper hydroxide + TX; copper naphthenate + TX; copper octanoate + TX; copper oleate + TX; copper oxide + TX; copper oxychloride + TX; copper silicate + TX; copper sulfate + TX; copper(ll) carbonate + TX; coumachlor + TX; coumafene + TX; coumafuryl + TX; Coumatetralyl + TX; coumethoxystrobin (jiaxiangjunzhi) + TX; coumithoate + TX; coumoxystrobin + TX; cryolite + TX; Cryptolaemus montrouzieri + TX; cuelure + TX; cufraneb + TX; cuprous(l) oxide + TX; cyanofenphos + TX; cyanthoate + TX; cyazofamid + TX; cybutryne + TX; cyclafuramid + TX; cyclethrin + TX; cyclobutrifluram + TX; Cydia pomonella GV + TX; cyenopyrafen + TX; cyflufenamid + TX; cyflumetofen + TX; cyfluthrin + TX; cyhalothrin + TX; cymiazole + TX; cymoxanil + TX; cypermethrin (alphametrin) + TX; cyphenothrin + TX; cyproconazole + TX; cyprodinil + TX; cyprodinil + TX; cyromazine + TX; cytokinins + TX; D-tetramethrin + TX; Dacnusa sibirica + TX; DAEP + TX; dazomet + TX; DCPM + TX; debacarb + TX; decarbofuran + TX; deltamethrin + TX; demephion-0 + TX; demephion-S + TX; demeton-0 + TX; demeton-S + TX; demeton-S-methyl + TX; demeton-S-methylsulphon + TX; diafenthiuron + TX; dialifos + TX; diazinon + TX; dibutyl adipate + TX; dibutyl phthalate + TX; dibutyl succinate + TX; dicapthon + TX; dichlobentiazox + TX; dichlofluanid + TX; dichlone + TX; dichlorprop + TX; dichlorvos + TX; dichlozoline + TX; diclocymet + TX; diclomezine + TX; dicloran + TX; dicofol + TX; dicresyl + TX; dicrotophos + TX; dicyclanil + TX; dicyclopentadiene + TX; diethofencarb + TX; diethyltoluamide + TX; difenacoum + TX; difenoconazole + TX; difenzoquat + TX; difethialone + TX; diflovidazin + TX; diflubenzuron + TX; diflumetorim + TX; Diglyphus isaea + TX; dimatif + TX; dimefluthrin + TX; dimetan + TX; dimethachlon + TX; dimethipin + TX; dimethirimol + TX; dimethoate + TX; dimethomorph + TX; dimethrin + TX; dimethyl disulfide + TX; dimethyl phthalate + TX; dimetilan + TX; dimoxystrobin + TX; dinactin + TX; diniconazole + TX; diniconazole-M + TX; dinobuton + TX; dinocap + TX; dinocton + TX; dinoseb + TX; dinotefuran + TX; diofenolan + TX; dioxabenzofos + TX; diphenylamine + TX; dipyrithione + TX; disparlure + TX; disulfiram + TX; disulfoton + TX; ditalimfos + TX; dithianon + TX; dithicrofos + TX; dithiocarbamate + TX; dodec-8-en-1-yl acetate + TX; dodemorph + TX; dodicin + TX; dodine + TX; dofenapyn + TX; dominicalure + TX; doramectin + TX; drazoxolon + TX; DSP + TX; ecdysterone + TX; edifenphos + TX; emamectin benzoate + TX; EMPC + TX; empenthrin + TX; Encarsia formosa + TX; endosulfan + TX; endothal + TX; endothion + TX; enestroburin (enoxastrobin) + TX; enrofloxacin + TX; entomopathogenic bacteria + TX; entomopathogenic fungi + TX; entomopathogenic virus + TX; EPBP + TX; epoxiconazole + TX; eprinomectin + TX; Eretmocerus eremicus + TX; esfenvalerate + TX; etaconazole + TX; ethaboxam + TX; ethiofencarb + TX; ethion + TX; ethiprole + TX; ethirimol + TX; ethoate- methyl + TX; ethoprophos + TX; ethoxyquin + TX; ethyl 4-methyloctanoate + TX; ethyl formate + TX; ethyl hexanediol + TX; etofenprox + TX; etoxazole + TX; etridiazole + TX; etrimfos + TX; eugenol + TX; eurax + TX; EXD + TX; exo-brevicomin + TX; famoxadone + TX; famphur + TX; farnesol with nerolidol + TX; febantel + TX; fenamidone + TX; fenaminstrobin + TX; fenamiphos + TX; fenarimol + TX; fenazaquin + TX; fenbendazole + TX; fenbuconazole + TX; fenbutatin oxide + TX; feneptamidoquin + TX; fenethacarb + TX; fenfluthrin + TX; fenfuram + TX; fenhexamid + TX; fenitrothion + TX; fenobucarb + TX; fenopyramid + TX; fenothiocarb + TX; fenoxacrim + TX; fenoxanil + TX; fenoxycarb + TX; fenpiclonil + TX; fenpicoxamid + TX; fenpirithrin + TX; fenpropathrin + TX; fenpropidin + TX; fenpropimorph + TX; fenpyrazamine + TX; fenpyroximate + TX; fensulfothion + TX; fenthion + TX; fenthion-ethyl + TX; fentin + TX; fentin acetate + TX; fentin chloride + TX; fentin hydroxide + TX; fenvalerate + TX; ferbam + TX; ferimzone + TX; ferric phosphate + TX; fipronil + TX; flocoumafen + TX; flonicamid + TX; florfenicol + TX; florylpicoxamid + TX; fluacrypyrim + TX; fluazinam + TX; fluazuron + TX; flubendazole + TX; flubendiamide + TX; flubeneteram + TX; flubenzimin + TX; flucycloxuron + TX; flucycloxuron + TX; flucythrinate + TX; fludioxonil + TX; fluenetil + TX; flufenerim + TX; flufenoxuron + TX; flufenoxystrobin + TX; flufenprox + TX; fluindapyr + TX; flumetralin + TX; flumetylsulforim + TX; flumorph + TX; fluopicolide + TX; fluopimomide + TX; fluopyram + TX; fluoroimide + TX; fluoxapiprolin + TX; fluoxastrobin + TX; fluoxytioconazole + TX; flupyrazofos + TX; fluquinconazole + TX; flusilazole + TX; flusulfamide + TX; flutianil + TX; flutolanil + TX; flutriafol + TX; fluxapyroxad + TX; folpet + TX; fonofos + TX; forchlorfenuron + TX; formaldehyde + TX; formetanate + TX; formetanate hydrochloride + TX; formothion + TX; formparanate + TX; fosetyl + TX; fosetyl-aluminium + TX; fosmethilan + TX; fosthiazate + TX; fosthietan + TX; frontalin + TX; fuberidazole + TX; furalaxyl + TX; furametpyr + TX; furathiocarb + TX; furethrin + TX; furfural + TX; gibberellic acid + TX; glyodin + TX; glyphosate + TX; grandlure I + TX; grandlure II + TX; grandlure III + TX; grandlure IV + TX; guazatine triacetate + TX; halfenprox + TX; halofenozide + TX; hemel + TX; heptenophos + TX; Heterorhabditis bacteriophora and H. megidis + TX; hexaconazole + TX; hexadecyl cyclopropanecarboxylate + TX; hexaflumuron + TX; hexalure + TX; hexamide + TX; hexythiazox + TX; Hippodamia convergens + TX; huanjunzuo (rac-(1 S,2S)-1-(4-chlorophenyl)-2-(1 ,2,4-triazol-1-yl)cycloheptanol) + TX; hydramethylnon + TX; hydrated lime (calcium hydroxide) + TX; hymexazol + TX; hyquincarb + TX; icaridin + TX; imanin (hypericin) + TX; imazalil + TX; imazalil sulfate + TX; imibenconazole + TX; imidacloprid + TX; iminoctadine + TX; indoxacarb + TX; inpyrfluxam + TX; iodocarb + TX; ipconazole + TX; ipfentrifluconazole + TX; ipflufenoquin + TX; iprobenfos (IBP) + TX; iprodione + TX; iprovalicarb + TX; ipsdienol + TX; ipsenol + TX; IPSP + TX; isamidofos + TX; isazofos + TX; isocarbophos + TX; isofetamid + TX; isoflucypram + TX; isolan + TX; isoprocarb + TX; isoprothiolane + TX; isopyrazam + TX; isothioate + TX; isotianil + TX; isoxathion + TX; ivermectin + TX; japonilure + TX; jasmolin I + TX; jasmolin II + TX; juvenile hormone I + TX; juvenile hormone II + TX; juvenile hormone III + TX; kadethrin + TX; kanamycin + TX; kasugamycin + TX; kasugamycin hydrochloride hydrate + TX; kinetin + TX; kinoprene + TX; kresoxim-methyl + TX; kurstaki + TX; lambda-cyhalothrin + TX; Leptomastix dactylopii + TX; leptophos + TX; levamisole + TX; lineatin + TX; lirimfos + TX; looplure + TX; lufenuron + TX; Ivbenmixianan + TX; lythidathion + TX; m-cumenyl methylcarbamate + TX; Macrolophus caliginosus + TX; magnesium phosphide + TX; malathion + TX; maleic hydrazide + TX; malonoben + TX; Mamestra brassicae NPV + TX; mancopper + TX; mancozeb + TX; mandestrobin + TX; mandipropamid + TX; maneb + TX; mazidox + TX; mebendazole + TX; mecarbam + TX; mecarphon + TX; medlure + TX; mefentrifluconazole + TX; megatomoic acid + TX; meloxicam + TX; menazon + TX; mepanipyrim + TX; meperfluthrin + TX; mephosfolan + TX; mepiquat + TX; mepronil + TX; meptyldinocap + TX; mesulfenfos + TX; metaflumizone + TX; metalaxyl + TX; metalaxyl-M + TX; metaldehyde + TX; metam + TX; metam-potassium + TX; metam-sodium + TX; Metaphycus helvolus + TX; Metarhizium anisopliae var. acridum + TX; Metarhizium anisopliae var. anisopliae + TX; metarylpicoxamid + TX; metconazole + TX; methacrifos + TX; methamidophos + TX; methasulfocarb + TX; methidathion + TX; methiocarb + TX; methiotepa + TX; methocrotophos + TX; methomyl + TX; methoprene + TX; methoquin-butyl + TX; methothrin + TX; methoxyfenozide + TX; methyl apholate + TX; methyl eugenol + TX; methyl iodide + TX; methyl neodecanamide + TX; metiram + TX; metofluthrin + TX; metolcarb + TX; metominostrobin + TX; metoxadiazone + TX; metrafenone + TX; metyltetraprole + TX; mevinphos + TX; mexacarbate + TX; MGK 264 + TX; milbemycin + TX; milbemycin oxime + TX; monocrotophos + TX; morantel tartrate + TX; morzid + TX; moxidectin + TX; muscalure + TX; myclobutanil + TX; myclozolin + TX; Myrothecium verrucaria composition + TX; N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4- carboxamide + TX; N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropy Ipheny I) methyl] - 1 -methyl-py razole- 4-carboxamide + TX; nabam + TX; naled + TX; NC-170 + TX; nemadectin + TX; Neodiprion sertifer NPV and N. lecontei NPV + TX; niclosamide-olamine + TX; nicotine + TX; nicotine sulfate + TX; nikkomycins + TX; nitenpyram + TX; nithiazine + TX; nitrapyrin + TX; nitrilacarb + TX; nitrothal-isopropyl + TX; norbormide + TX; nornicotine + TX; novaluron + TX; noviflumuron + TX; nuarimol + TX; O,O,O',O'-tetrapropyl dithiopyrophosphate + TX; octadeca-2,13-dien-1-yl acetate + TX; octadeca-2,13-dien-1-yl acetate + TX; octhilinone + TX; ofurace + TX; oleic acid + TX; omethoate + TX; orfralure + TX; Orius spp. + TX; orysastrobin + TX; osthol + TX; ostramone + TX; oxadixyl + TX; oxamate + TX; oxamyl + TX; oxantel pamoate + TX; oxasulfuron + TX; oxathiapiprolin + TX; oxfendazole + TX; oxibendazole + TX; oxine copper + TX; oxolinic acid + TX; oxpoconazole + TX; oxycarboxin + TX; oxydemeton-methyl + TX; oxydeprofos + TX; oxydisulfoton + TX; oxytetracycline + TX; oxytetracycline dihydrate + TX; paclobutrazol + TX; Paecilomyces fumosoroseus + TX; paraoxon + TX; parathion + TX; parathion-methyl + TX; parbendazole + TX; pefurazoate + TX; penconazole + TX; pencycuron + TX; penethamate + TX; penflufen + TX; penthiopyrad + TX; permethrin + TX; petroleum oils + TX; PH 60-38 + TX; phenamacril + TX; phenthoate + TX; phorate + TX; phosacetim + TX; phosalone + TX; phosfolan + TX; phosglycin + TX; phosmet + TX; phosnichlor + TX; phosphamidon + TX; phosphocarb + TX; phosphonic acid + TX; phosphorus + TX; phoxim + TX; phoxim-methyl + TX; phthalide + TX; Phytoseiulus persimilis + TX; picarbutrazox + TX; picoxystrobin + TX; pimobendan + TX; pindone + TX; piperalin + TX; piperonyl butoxide + TX; piprotal + TX; pirimetaphos + TX; pirimicarb + TX; pirimiphos-methyl + TX; polycarbamate + TX; polynactin + TX; polyoxin B + TX; polyoxin d + TX; potassium ethylxanthate + TX; potassium hydroxyquinoline sulfate + TX; praziquantel + TX; precocene I + TX; precocene II + TX; precocene III + TX; primidophos + TX; probenazole + TX; prochloraz + TX; procymidone + TX; profenofos + TX; profluthrin + TX; prohexadione + TX; prohexadione-calcium + TX; promacyl + TX; promecarb + TX; propamidine + TX; propamocarb + TX; propaphos + TX; propargite + TX; propetamphos + TX; propiconazole + TX; propineb + TX; propionic acid + TX; propoxur + TX; propyl isomer + TX; proquinazid + TX; prothidathion + TX; prothioconazole + TX; prothiofos + TX; prothoate + TX; protrifenbute + TX; pydiflumetofen + TX; pymetrozine + TX; pyraclofos + TX; pyraclostrobin + TX; pyrafluprole + TX; pyrametostrobin + TX; pyrantel pamoate + TX; pyraoxystrobin + TX; pyrapropoyne + TX; pyraziflumid + TX; pyrazophos + TX; pyrazoxone + TX; pyresmethrin + TX; pyrethrin I + TX; pyrethrin II + TX; pyrethrins (natural products) + TX; pyrethroids (natural products) + TX; pyribencarb + TX; pyridaben + TX; pyridachlometyl + TX; pyridalyl + TX; pyridaphenthion + TX; pyridin-4-amine + TX; pyrifenox + TX; pyrifluquinazon + TX; pyrimethanil + TX; pyrimidifen + TX; pyrimorph + TX; pyriofenone + TX; pyriprole + TX; pyriproxyfen + TX; pyrisoxazole + TX; pyroquilon + TX; quassia + TX; quinalphos + TX; quinalphos-methyl + TX; quinoclamine + TX; quinofumelin + TX; quinonamid + TX; quinothion + TX; quinoxyfen + TX; quintozene + TX; R-1492 + TX; R-metalaxyl + TX; Reynoutria sachalinensis extract + TX; ribavirin + TX; rotenone + TX; ryanodine (ryania) + TX; sabadilla + TX; schradan + TX; scilliroside + TX; seboctylamine + TX; sedaxane + TX; selamectin + TX; sesamex + TX; sesamolin + TX; siglure + TX; silafluofen + TX; silthiofam + TX; simeconazole + TX; sodium tetrathiocarbonate + TX; sophamide + TX; sordidin + TX; spinetoram + TX; spinosad + TX; spirodiclofen + TX; spiromesifen + TX; spirotetramat + TX; spiroxamine + TX; Steinernema bibionis + TX; Steinernema carpocapsae + TX; Steinernema feltiae + TX; Steinernema glaseri + TX; Steinernema riobrave + TX; Steinernema riobravis + TX; Steinernema scapterisci + TX; Steinernema spp. + TX; streptomycin + TX; streptomycin sesquisulfate + TX; sulcatol + TX; sulcofuron + TX; sulfiram + TX; sulfur + TX; sulprofos + TX; tar oils + TX; tau-fluvalinate + TX; TCMTB + TX; TDE + TX; tebuconazole + TX; tebufenozide + TX; tebufenpyrad + TX; tebufloquin + TX; tebupirimfos + TX; tecnazene + TX; teflubenzuron + TX; tefluthrin + TX; temephos + TX; terallethrin + TX; terbam + TX; terbufos + TX; tetrachlorvinphos + TX; tetraconazole + TX; tetradec-11-en-1-yl acetate + TX; tetradifon + TX; tetramethrin + TX; tetramethylfluthrin + TX; tetranactin + TX; thiabendazole + TX; thiacloprid + TX; thiadiazole copper + TX; thiamethoxam + TX; thiapronil + TX; thicrofos + TX; thicyofen + TX; thidiazuron + TX; thifluzamide + TX; thiocarboxime + TX; thiocyclam + TX; thiocyclam hydrogen oxalate + TX; thiodicarb + TX; thiofanox + TX; thiometon + TX; thiophanate + TX; thiophanate-methyl + TX; thioquinox + TX; thiosultap + TX; thiosultap-disodium + TX; thiram + TX; thuringiensin + TX; tiadinil + TX; tiamulin + TX; tioxymid + TX; tolclofos-methyl + TX; tolfenpyrad + TX; tolprocarb + TX; tolylfluanid + TX; tralomethrin + TX; transpermethrin + TX; tretamine + TX; triadimefon + TX; triadimenol + TX; triarathene + TX; triazamate + TX; triazophos + TX; triazoxide + TX; tribufos + TX; trichlorfon + TX; trichlormetaphos-3 + TX; trichloronat + TX; Trichogramma spp. + TX; triclabendazole + TX; triclopyricarb + TX; tricyclazole + TX; tridemorph + TX; trifenmorph + TX; trifloxystrobin + TX; triflumizole + TX; triflumuron + TX; triforine + TX; trimedlure + TX; trimedlure A + TX; trimedlure B1 + TX; trimedlure B2 + TX; trimedlure C + TX; trimethacarb + TX; trinactin + TX; trinexapac + TX; trinexapac-ethyl + TX; triprene + TX; triticonazole + TX; trunc-call + TX; tulathromycin + TX; Typhlodromus occidentalis + TX; uniconazole + TX; uredepa + TX; validamycin + TX; valifenalate + TX; vamidothion + TX; vaniliprole + TX; veratridine + TX; veratrine + TX; verbutin + TX; Verticillium lecanii + TX; vinclozolin + TX; XMC + TX; xylenols + TX; zeatin + TX; zeta- cypermethrin + TX; zhongshengmycin + TX; zinc naphthenate + TX; zinc thiazole + TX; zineb + TX; ziram + TX; zolaprofos + TX; zoxamide + TX; 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3- carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX; methyl
3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1 ,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522) + TX; methyl (2R)-2-[2-chloro-
4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6- difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; aminopyrifen (this compound may be prepared from the methods described in WO 2014/006945) + TX; dipymetitrone (this compound may be prepared from the methods described in WO 2011/138281) + TX; 1-[6-(difluoromethyl)-5-methyl-3-pyridyl]-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX; 1-[4-(difluoromethoxy)-2- methyl-phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX; 1-[2-chloro-4-(difluoromethoxy)phenyl]-2-(1 ,2,4-triazol- 1-yl)-1-[1-(triflu°romethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX; 1-(5,6-dimethyl-3-pyridyl)-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzenecarbothioamide (this compound may be prepared from the methods described in WO 2015/185485) + TX; 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2017/178245) + TX; flufenoxadiazam + TX; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (this compound may be prepared from the methods described in WO 2015/185485) + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX; (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3- enamide (this compound may be prepared from the methods described in WO 2013/092224) + TX; methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl] phenyl] acetate (this compound may be prepared from the methods described in WO 2022/033906) + TX; (2E)-2- methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl] acetamide (this compound may be prepared from the methods described in WO 2022/033906) + TX; (2E)-2- [2-[[(E)-[3-(4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N- methyl-acetamide (this compound may be prepared from the methods described in WO 2021/249928) + TX; methyl (2E)-2-[2-[[(E)-[3-(4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2- methoxyimino-acetate (this compound may be prepared from the methods described in WO 2021/249928) + TX; 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX; 3-[2-(1-chlorocyclopropyl)- 3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX; 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4- triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2- yl]-N-[1-(2-fluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin- 2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; N-[1-(2- fluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]- N-[1-(2,6-difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 2-(difluoromethyl)-5-[2-[1-(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-1 ,3,4- oxadiazole (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[5- (difluoromethyl)-l ,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[(4-bromo-2-methyl-phenyl)methyl]-3- [3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX; 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6- methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX; N-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]oxazole-4-carboxamide (this compound may be prepared from the methods described in WO 2022/133114) + TX; ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenoxy]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2022/133114) + TX; ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-4- carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX; ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-4- carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX; methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX; methyl N-[[5-[1-(2,6- difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX; methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro- phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX; methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4- triazol-1-yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX; 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline + TX; 5-fluoro-3,3,4,4-tetramethyl-1-(3- quinolyl)isoquinoline + TX; 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]acetamide (this compound may be prepared from the methods described in WO 2020/256113) + TX; N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl-propanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX; N-[methoxy-[5-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]butanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX; 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4- yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX; 2-(difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX; 2-(difluoromethyl)-N-(1 ,1 ,3-trimethylindan-4- yl)pyridine-3-carboxamide + TX; (5R)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4- methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX; (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX; 3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX; methyl (Z)-3-methoxy-2-(2-methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251) + TX; 2-[(2,6-difluoro-4-pyridyl)-(2-methylpropanoyl)amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2-[(2,6-difluoro-4-pyridyl)-(tetrahydropyran-4-carbonyl)amino]-N- (2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5- methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1); 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4- carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1); 2-[(2,6-difluoro- 4-pyridyl)-(2-methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511 A1 , WO2021244952A1); 2-[acetyl-(2,6-difluoro-4- pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473) + TX; methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate (this compound may be prepared from the methods described in W02020/193387) + TX; methyl (Z)-2- (5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (this compound may be prepared from the methods described in W02020/193387) + TX; N-[(1 R)-1-benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3- carboxamide (this compound may be prepared from the methods described in WO2017/153380) + TX; N-[(1 S)- 1-benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380) + TX; 2-[(2,6-difluoro-4-pyridyl)-(oxetane-3-carbonyl)amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (/?) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methyl-thiazole-4-carboxamide + TX; or the (/?) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX; or the (/?) or (S) enantiomer or mixtures thereof + TX (this compound may be prepared from the methods described in WO 2017/055473).
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 lUPAC/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 compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds 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 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 compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds 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 compounds of formula (I), (l-A), or (I-A1), or compounds selected from compounds listed in Tables C-1 to C-56, or compounds listed in Table P (below), and the active ingredients) 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.
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 I kg 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 (EG), an emulsion, oil in water (EW), a microemulsion (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) 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, CD, SE, EW, EC 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 sulfonate, an alkyl aryl sulfonate, a lignin sulfonate, 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 adjuvants), 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 to 80%, preferably between about 5 to 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: 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-56 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-56 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.
Table A: This table discloses 20 substituent definitions G of the formula (I) w ere n s o ormu a as defined below:
Table B: This table discloses 14 substituent definitions Q of the formula (I) Tables C-1 to C-56 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 is OCHs, R4 is CH3, R3, R5, and 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
Table C-2: This table provides 20 compounds C-2.01 to C-2.20 of formula (I), wherein R2 is OCH3, R4 is CH3, R3, R5, and R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
For example, compound C-2.04 has the following structure:
Compound C-2.04
Table C-3: This table provides 20 compounds C-3.01 to C-3.20 of formula (I), wherein R2 is OCHs, R4 is CH3,
R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-4: This table provides 20 compounds C-4.01 to C-4.20 of formula (I), wherein R2 is OCH3, R4 is CH3, R3, R5, R6 are H, Q is Q-4 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 is OCH3 R4 is CH3,
R3, R5, R6 are H, Q is Q-5 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 is OCH3, R4 is CH3, R3, R5, R6 are H, Q is Q-6 as defined in Table B, and G is as defined in Table A.
Table C-7: This table provides 20 compounds C-7.01 to C-7.20 of formula (I), wherein R2 is OCH3, R4 is CH3, R3, R5, R6 are H, Q is Q-7 as defined in Table B, and G is as defined in Table A.
Table C-8 This table provides 20 compounds C-8.01 to C-8.20 of formula (I), wherein R2 is OCH3 R4 is CH3,
R3, R5, R6 are H, Q is Q-8 as defined in Table B, and G is as defined in Table A.
Table C-9: This table provides 20 compounds C-9.01 to C-9.20 of formula (I), wherein R2 is OCH3, R4 is CH3, R3, R5, R6 are H, Q is Q-9 as defined in Table B, and G is as defined in Table A. For example, compound C- 9.02 has the following structure: Compound C-9.02
Table C-10 This table provides 20 compounds C-10.01 to C-10.20 of formula (I), wherein R2 is OCH3 R4 is
CH3, R3, R5, R6 are H, Q is Q-10 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 is OCH3, R4 is
CH3, R3, R5, R6 are H, Q is Q-11 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 is OCH3
CH3, R3, R5, R6 are H, Q is Q-12 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 is OCHs R4 is
CH3, R3, R5, R6 are H, Q is Q-13 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 is OCHs, R4 is CH3, R3, R5, R6 are H, Q is Q-14 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 is OCHs R3, R4,
R5, R6 are H, Q is Q-2 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
Table C-16: This table provides 20 compounds C-16.01 to C-16.20 of formula (I), wherein R2 is OCHs, R3, R4,
R5, R6 are H, Q is Q-5 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 CH3, R2 is OCHs, R3 and R4 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A. For example, compound C-17.04 has the following structure: Compound C-17.04
Table C-18 This table provides 20 compounds C-18.01 to C-18.20 of formula (I), wherein R5 R6 are CH3, R2 is OCHs R3 and R4 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-19 This table provides 20 compounds C-19.01 to C-19.20 of formula (I), wherein R3 is H R4, R5, R6 are CH3, R2 is OCHs, 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 R3 is H R4, R5, R6 are CH3, R2 is OCHs, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound
C-20.18 has the following structure: Compound C-20.18
Table C-21 : This table provides 20 compounds C-21 .01 to C-21 .20 of formula (I), wherein R2 is SCH3, R4 is
CH3, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-22 This table provides 20 compounds C-22.01 to C-22.20 of formula (I), wherein R2 is SCH3
CH3, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-23: This table provides 20 compounds C-23.01 to C-23.20 of formula (I), wherein R2 is SCHs, R4 is CHs, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
Table C-24 This table provides 20 compounds C-24.01 to C-24.20 of formula (I), wherein R2 is SCH3 R4 is
CH3, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-25 This table provides 20 compounds C-25.01 to C-25.20 of formula (I), wherein R2 is SO2CH3 R4 is
CH3, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-26: This table provides 20 compounds C-26.01 to C-26.20 of formula (I), wherein R2 is SO2CH3, R4 is CH3, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-27 This table provides 20 compounds C-27.01 to C-27.20 of formula (I), wherein R2 is SO2CH3 R4 is
CH3, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
Table C-28: This table provides 20 compounds C-28.01 to C-28.20 of formula (I), wherein R2 is SO2CH3, R4 is CH3, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-29: This table provides 20 compounds C-29.01 to C-29.20 of formula (I), wherein R2 is NHCH3, R4 is CH3, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-30 This table provides 20 compounds C-30.01 to C-30.20 of formula (I), wherein R2 is NHCH3 R4 is
CH3, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A. For example, compound C-30.14 has the following structure: Compound C-30.14
Table C-31 This table provides 20 compounds C-31 .01 to C-31 .20 of formula (I), wherein R2 is NHCH3, R4 is
CH3, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A. Table C-32: This table provides 20 compounds C-32.01 to C-32.20 of formula (I), wherein R2 is NHCHs, R4 is CHs, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-33: This table provides 20 compounds C-33.01 to C-33.20 of formula (I), wherein R2 is N(CH3)2, R4 is CHs, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-34: This table provides 20 compounds C-34.01 to C-34.20 of formula (I), wherein R2 is N(CH3)2, R4 is CHs, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-35: This table provides 20 compounds C-35.01 to C-35.20 of formula (I), wherein R2 is N(CH3)2, R4 is CHs, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
Table C-36: This table provides 20 compounds C-36.01 to C-36.20 of formula (I), wherein R2 is N(CH3)2, R4 is CHs, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-37: This table provides 20 compounds C-37.01 to C-37.20 of formula (I), wherein R2 is OH, R4 is CHs, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-38: This table provides 20 compounds C-38.01 to C-38.20 of formula (I), wherein R2 is OH, R4 is CHs, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-39: This table provides 20 compounds C-39.01 to C-39.20 of formula (I), wherein R2 is OH, R4 is CHs, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
Table C-40: This table provides 20 compounds C-40.01 to C-40.20 of formula (I), wherein R2 is OH, R4 is CHs, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-41 : This table provides 20 compounds C-41 .01 to C-41 .20 of formula (I), wherein R2 is NH2, R4 is CH3, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-42: This table provides 20 compounds C-42.01 to C-42.20 of formula (I), wherein R2 is NH2, R4 is CH3, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-43: This table provides 20 compounds C-43.01 to C-43.20 of formula (I), wherein R2 is NH2, R4 is CH3, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
Table C-44: This table provides 20 compounds C-44.01 to C-44.20 of formula (I), wherein R2 is NH2, R4 is CH3, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-45: This table provides 20 compounds C-45.01 to C-45.20 of formula (I), wherein R2 is CN, R4 is CH3, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-46: This table provides 20 compounds C-46.01 to C-46.20 of formula (I), wherein R2 is CN, R4 is CH3, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-47: This table provides 20 compounds C-47.01 to C-47.20 of formula (I), wherein R2 is CN, R4 is CH3, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A. Table C-48 This table provides 20 compounds C-48.01 to C-48.20 of formula (I), wherein R2 is CN R4 is
CH3, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
Table C-49: This table provides 20 compounds C-49.01 to C-49.20 of formula (I), wherein R2 is OCH2CHF2, R4 is CH3, R3, R5, R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-50 This table provides 20 compounds C-50.01 to C-50.20 of formula (I), wherein R2 is OCH2CHF2,
R4 is CH3, R3, R5, R6 are H, Q is Q-3 as defined in Table B, and G is as defined in Table A.
Table C-51 : This table provides 20 compounds C-51 .01 to C-51 .20 of formula (I), wherein R2 is OCH2CHF2, R4 is CH3, R3, R5, R6 are H, Q is Q-4 as defined in Table B, and G is as defined in Table A.
Table C-52: This table provides 20 compounds C-52.01 to C-52.20 of formula (I), wherein R2 is OCH2CHF2, R4 is CH3, R3, R5, R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound C-52.01 has the following structure: Compound C-52.01
Table C-53: This table provides 20 compounds C-53.01 to C-53.20 of formula (I), wherein R2 is OCH3, R3 and R4 are CH3, R5, and R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-54 This table provides 20 compounds C-54.01 to C-54.20 of formula (I), wherein R2 is OCH3 R3 and
R4 are CH3, R5, and R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound C-54.01 has the following structure: Compound C-54.01
Table C-55 This table provides 20 compounds C-55.01 to C-55.20 of formula (I), wherein R2 is OCH3 R3 is
CHs, R4, R5, and R6 are H, Q is Q-2 as defined in Table B, and G is as defined in Table A.
Table C-56 This table provides 20 compounds C-56.01 to C-56.20 of formula (I), wherein R2 is OCH3
CH3, R4, R5, and R6 are H, Q is Q-5 as defined in Table B, and G is as defined in Table A.
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).
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 % 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 dusts 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 concentrates 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 %
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 flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment. 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
CDCI3 deuterated chloroform
DABCO 1 ,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA
DCC dicyclohexyl carbodiimide
DCM dichloromethane
DMF dimethylformamide
DMSO dimethyl sulfoxide
DMSO-d6 deuterated Dimethyl sulfoxide
EtOAc ethyl acetate
HCI hydrochloric acid h/hrs hour/hours
LC-MS Liquid Chromatography Mass Spectrometry (LC-MS, LCMS or LC/MS) MgSO4 magnesium sulphate
Na2SO4 sodium sulphate rh relative humidity rt room temperature
Rt retention time sat. saturated ssp. subspecies
TLC thin layer chromatography
THF tetrahydrofuran
PREPARATION EXAMPLES
The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.
Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point.
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 CFCh (19F) standard. Spectra measured in deuterated solvents as indicated. Either one of the LC-MS methods below was used to characterize the compounds. The characteristic LC-MS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H)+ or (M-H)-.
LC-MS Method A: 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, 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 pm, 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.
LC-MS Method B: Spectra were recorded on a Mass Spectrometer from Agilent Technologies (MSD-IQ mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, MS2 Scan, Capillary: 3.5 kV, Fragmentor: 110 V, Desolvation Temperature: 325°C, Gas Flow: 13 L/min, Nebulizer Gas: 55 psi, Mass range: 110 to 850 Da) and a 1290 Series HPLC from Agilent: quaternary pump, heated column compartment and diode-array detector. Column: AGILENT POROSHELL 120 EC-C18, 1.9 pm, 50 x 2.1 mm, Temp: 40°C, DAD Wavelength range (nm): 190 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.1 % HCOOH: gradient: 0-0.5 min 10% B, 90%A; 1.2-1.5 min 95% B, 05 %A; 1.8-2.5 min 10%B, 90%A; Flow (mL/min) 0.8 LC-MS Method C: Spectra were recorded on a Mass Spectrometer from Agilent Technologies (6410 Triple Quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, MS2 Scan, Capillary: 4.00 kV, Fragmentor: 100 V, Desolvation Temperature: 350°C, Gas Flow: 11 L/min, Nebulizer Gas: 45 psi, Mass range: 110 to 1000 Da) and a 1200 Series HPLC from Agilent: quaternary pump, heated column compartment and VWD detector. Column: KINETEX EVO C18, 2.6 pm, 50 x 4.6 mm, Temp: 40°C, Detector VWD Wavelength: 254 nm, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.1 % HCOOH: gradient: 0 min 10% B, 90%A; 0.9-1 .8 min 100% B; 1.8-2.2 min 100-10% B; 2.2- 2.5 min 10%B; Flow (mL/min) 1.8.
Example Prep-1 : Preparation of A/-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl1-1-(2,4- difluorophenyl)triazole-4-carboxamide (compound P-2, Table P) compound P-2, Table P
Step 1 : Preparation of 5-methoxy-1-methyl-pyrazole-4-carbaldehvde
To a solution of 5-chloro-1-methyl-pyrazole-4-carbaldehyde (CAS [117007-77-9], 6.25 g, 41.1 mmol) in methanol (62.5 mL), sodium methoxide (18.3 mL, 17.8 g, 82.1 mmol) was added at rt under argon. The resulting reaction mixture was stirred at 60°C for 6h whereupon LCMS and TLC showed reaction completion. The reaction mixture was diluted with water (50 mL) and sat. aqueous ammonium chloride and extracted with EtOAc (150 mL X3). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to obtain the crude product. The crude product was absorbed on celite and purified using combi flash chromatography (eluting with 30-60 % EtOAC/Cyclohexane) to obtain the title compound.
1H NMR (400 MHz, CDCb) δ ppm 9.74 (s, 1 H) 7.78 (s, 1 H) 4.30 (s, 3 H) 3.67 (s, 3 H)
Step 2: Preparation of 2-(5-methoxy-1-methyl-pyrazol-4-yl)acetonitrile
A sample of potassium tert-butoxide (2.11 g, 18.35 mmol).) in 1 ,2-dimethoxyethane (DME, 200 mL) was cooled to -65°C and treated with tosyl-methyl isocyanide (2.09 g, 10.49 mmol.) in DME (5 mL) under argon. The reaction mixture was stirred at -65 to -60 C for about 1-2 hr. To this mixture was added 5-methoxy-1-methyl- pyrazole-4-carbaldehyde (1 .05 g, 7.5 mmol) in DME (8 mL) at -65 to -60°C over 1 hr. Stirring was continued at this temperature for 2 hr. Methanol (0.8 mL) was added at -65°C to give a clear solution and the reaction mixture was then heated to 80°C for 2 h. After completion of the reaction (monitored by LCMS and TLC), it was cooled to 0°C and quenched 5% acetic acid in water (until the pH became slightly acidic), stirred for 5 min, and diluted with EtOAc (50 mL). Both aqueous and organic layers were separated, and the aqueous layer back extracted with EtOAc (60 mL), The combined organic layers, were washed with brine solution (10 mL), dried over Na2SO4, and concentrated in vacuo. The crude product was absorbed on celite and purified using combi flash chromatography (eluting with 20-50 % EtOAc) to afford pure title compound as a brown liquid.
LC-MS (Method A): ret. time 0.19 min, m/z = 152 (M+H). 1H NMR (400 MHz, CDCb) δ ppm: 7.32 (s, 1 H); 3.98 (s, 3 H); 3.69 (s, 3 H); 3.52 (s, 2 H).
Step 3: Preparation of 2-(5-methoxy-1-methyl-pyrazol-4-yl)propanenitrile
A solution of potassium tert-butoxide (151 mg, 1.32 mmol) and 2-(5-methoxy-1-methyl-pyrazol-4-yl)acetonitrile ((200 mg, 1 .32mmol) in THF (4 mL) was cooled to 0°C allowed to stir at rt and then treated with iodomethane (210 mg, 1 .45 mmol). The reaction mixture was allowed to warm to rt and stirred at this temperature monitoring by LCMS and TLC. After reaction completion, the mixture was diluted with water (20 ml) and saturated aqueous ammonium chloride solution (10 ml). The mixture was extracted with EtOAc (60 ml X3), and the combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to obtain the crude compound. This was absorbed on celite and purified using combi flash chromatography (eluting with 50-60 % EtOAc in cyclohexane) to afford the pure title compound.
LCMS (Method A): ret. time; 0.91 min, m\z = 166 (M+H). 1H NMR (400 MHz, CDCb): 6 ppm 7.34 (s, 1 H); 3.97 (s, 3 H); 3.78-3.84 (m, 1 H); 3.71 (s, 3 H); 1 .60 - 1 .65 (m, 3 H).
Step 4: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propanenitrile
A solution of 2-(5-methoxy-1-methyl-pyrazol-4-yl)propanenitrile (400 mg, 2.42 mmol) in THF (8 mL) was cooled to -10°C to -15°C and treated with potassium tert-butoxide (277 mg, 2.42 mmol). To this solution was added 2,6-dichloropyridine (376 mg, 2.54 mmol) in THF (1 .5 mL). The reaction mixture was allowed to warm to rt and stirred under N2. After reaction completion (monitoring by LCMS) the mixture was diluted with cold water (10 mL) and extracted with EtOAc (30 mL, X3). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to obtain the crude compound. This was absorbed on celite and purified using combi flash chromatography (eluting with 40-50 % EtOAc in cyclohexane) to obtain the title compound as a yellow gum.
LC-MS (Method A): ret. time 1.01 min, m/z = 277 (M+H). 1H NMR (400 MHz, CDCb) δ ppm 7.61 (t, J=7.82 Hz, 1 H) 7.39 (dd, J=7.63, 0.63 Hz, 1 H) 7.26 (s, 1 H) 7.19 - 7.23 (m, 1 H) 3.90 (s, 3 H) 3.63 (m, 3 H) 2.03 (s, 3 H)
Step 6: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propan-1 -amine
To a solution of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propanenitrile (0.65 mmol, 360 mg) in THF (2 mL) was added borane dimethylsulfide complex (3.3 mL, 6.5 mmol) at rt under nitrogen. The resulting reaction mixture was stirred for 1 h at 60°C, monitoring by LCMS. Upon completion, the solution was cooled and then carefully treated dropwise with 6N HCI (0.44 mL, 2.61 mmol, strong gas evolution!) and stirred at 60°C for 1 h. After allowing it to cool to rt, it was basified with 6N NaOH to pH 12 and extracted with EtOAc (50 mL X3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. This afforded the title compound as yellow oil, which was used without further purification in the next steps.
LC-MS (Method A): ret. time 0.27 min, m/z = 281/283 (M+H)
Step 7: Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate
A solution of 1-azido-2,4-difluoro-benzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was treated successively with copper(ll)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 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); ret. time 0.79 min, m/z=240 [M+H], 1H NMR (400 MHz, CDCI3) 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 8: Preparation of 1-(2,4-difluorophenyl)tnazole-4-carboxyhc acid
A sample of methyl 1-(2,4-difluorophenyl)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. Then UOH.H2O (0.047 g, 1.9 mmol) was then added and the mixture was stirred at rt. After 3 hrs LC/MS (desired mass at rt=0.63 min and consumption of starting material. The sample was concentrated in vacuo and the residue taken up in water and EtOAc, and the mixture acidified with HCI 2N. 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): ret. time 0.63 min, m/z=226 [M+H], 1H NMR (400 MHz, DMSO) δ ppm 121 - 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 9: Preparation of A/-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl1-1-(2,4- difluorophenyl)triazole-4-carboxamide (Compound P-2, Table P)
A solution of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid (44 mg, 0.185 mmol) and 2-(6-chloro-2-pyridyl)-2- (5-methoxy-1-methyl-pyrazol-4-yl)propan-1 -amine (130 mg, 0.185 mmol) in EtOAc (4 mL) was treated with DIPEA (98 mg, 0.74 mmol) and 1-propanephosphonic anhydride (300 mg, 0.27 mL, 0.463 mmol) at 0°C and the reaction mixture was stirred at rt monitoring by LCMS. Upon reaction completion, the reaction mixture was diluted with water (10 mL) and extracted with EtOAc (20 mL X3). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, filtered and concentrated in vacuo io obtain the crude product. This was purified using reverse phase combi flash chromatography eluting with 60-80 % water in CHsCN to afford the title compound as a white solid.
LCMS (Method A) ret. time: 1 .09; m/z = 488 (M+H). 1H NMR (400 MHz, CDCI3) δ ppm 8.50 (d, J=2.63 Hz, 1 H) 8.18 (t, J=6.30 Hz, 1 H) 7.88-7.94 (dd, J=8.76, 5.75 Hz, 1 H) 7.57-7.61 (t, J=7.82 Hz, 1 H) 121 (s, 1 H) 7.21- 7.23 (d, J=7.75 Hz, 1 H) 7.18-7.16 (d, J=7.75 Hz, 1 H) 7.07-7.12 (t, J=8.60 Hz, 2 H) 4.10 - 4.24 (m, 2 H) 3.70 (s, 3 H) 3.59 (s, 3 H) 1 .74 (s, 3 H). 19F NMR (377 MHz, CDCb) δ ppm -106.38 (s, 1 F) -118.48 (s, 1 F)
Example Prep-2: Preparation of A/-[2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl1-2-
(2,4-difluorophenyl)tetrazole-5-carboxamide (Example P-1 , Table P)
Example P-1 , Table P
Step 1 : Preparation of 5-chloro-1 ,3-dimethyl-pyrazole-4-carbaldehvde
A solution of 2,5-dimethylpyrazol-3-ol (10 g, 44.6 mmol) and phosphorus(V) oxychloride (21 .2 mL) was stirred at 90°C for 1 h. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was concentrated in vacuo and the residue treated with sat. aqueous sodium bicarbonate solution (until the pH was basic), The aqueous layer was extracted with EtOAc (50 mL X3), and the combined organic layers were then washed with brine and dried over sodium sulphate and concentrated in vacuo to obtain the crude product. The crude product was purified by combi flash using 20-30% EtOAc in cyclohexane to obtain 5-chloro-1 ,3-dimethyl- pyrazole-4-carbaldehyde as a white solid.
LCMS (Method B): ret. time 1 .0 min, m/z = 159 (M+H)
Step 2: Preparation of 5-methoxy-1 ,3-dimethyl-pyrazole-4-carbaldehvde
To a solution of 5-chloro-1 ,3-dimethyl-pyrazole-4-carbaldehyde (8.3 g, 52 mmol) in methanol (83 mL), was added sodium methanolate (23 mL, 100 mmol) at rt under argon. The resulting reaction mixture was stirred at 60°C for 6h whereupon LCMS and TLC showed reaction completion. The reaction mixture was diluted with water (50 mL) and sat. aqueous ammonium chloride and extracted with EtOAc (150 mL X3). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to obtain the crude product. This was purified by combi flash using 30-40% EtOAc in cyclohexane to afford the title compound as a white solid.
LC-MS (Method A): ret. time 0.34 min, m/z = 155 (M+H)
Step 3: Preparation of 2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)acetonitrile
A sample of potassium tert-butoxide (11 g, 95 mmol).) in 1 ,2-Dimethoxyethane (130 mL) was cooled to -65°C and treated with tosyl-methyl isocyanide (11 g, 54 mmol.) in DME (5 mL) under argon. The reaction mixture was stirred at -65 to -60°C for about 1 to 2 hr. To this mixture was added 5-methoxy-1 ,3-dimethyl-pyrazole-4- carbaldehyde (6.3 g, 39 mmol) in DME (5 mL) was added at -65 to -60°C over 1 hr. Stiring was continued at this temperature for 2 h (Note: thick mass observed). Methanol (4.1 mL) was added at -65°C to give clear solution. The reaction mixture was then heated to 80°C for 2 h. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was cooled to 0°C and quenched 5% acetic acid in water (until the pH became slightly acidic), stirred for 5 min, and diluted with EtOAc (10 mL). Both aqueous and organic layers were separated, and the aqueous layer extracted with EtOAc (60 mL), The combined organic layers, were washed with brine solution (10 mL), dried over Na2SO4, and concentrated in vacuo. The crude compound was purified by combi flash using 50-70% EtOAc in cyclohexane to afford the title compound as a brown liquid.
LC-MS (Method B): ret. time 0.74 min, m/z = 166 (M+H)
Step 4: Preparation of 2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl) propanenitrile
A solution of potassium tert-butoxide (83 mg, 0.72 mmol) and 2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- yl)acetonitrile (100 mg, 0.60 mmol) in DMSO (1 mL) was allowed to stir at rt. After 10 min, iodomethane (0.042 mL, 0.66 mmol) was added, and the reaction mixture was stirred under nitrogen at rtfor 30 min. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was diluted with cold water (20 mL) and sat. aqueous ammonium chloride and extracted with EtOAc (40 mL X3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude compound was purified by combi flash using 50-60% EtOAc in cyclohexane to afford the title compound as a colorless liquid.
LC-MS (Method B): ret. time 1.31 min, m/z = 180 (M+H)
Step 5: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propanenitrile
A solution of 2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propanenitrile (1.5 g, 6.7 mmol) in DMSO (15 mL) and potassium tert-butoxide (1.2 g,11 mmol) was stirred at rt., and after 10 min, 2,6-dichloropyridine (1.1 g, 7.4 mmol) in DMSO (5 mL) was added dropwise. The reaction mixture was stirred under nitrogen at rt for 30 min After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was diluted with cold water (20 mL) and sat. ammonium chloride and extracted with EtOAc (40 mL X3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product was purified by combi flash using 50-70% EtOAc in cyclohexane to afford the title compound as a yellow oil.
LC-MS (Method A): ret. time 1 .06 min, m/z = 291 (M+H)
Step 6: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propan-1 -amine
To a solution of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propanenitrile (1.53 g, 4.21 mmol) in THF (12.6 mL) was added borane dimethylsulfide complex (21 mL, 42.1 mmol) at rt under nitrogen. The resulting reaction mixture was stirred for 1 h at 70°C, monitoring by LCMS. Upon completion, the solution was then carefully treated dropwise with 6N HCI (0.95 mL, 5.75 mmol, strong gas evolution!) and stirred at 60°C for 1 h. After allowing it to cool to rt, it was basified with 6N NaOH to pH 12 and extracted with EtOAc (50 mL X3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. This afforded the title compound as yellow oil, which was used without further purification in the next steps.
LC-MS (Method A): ret. time, 0.13 min, m/z = 295 (M+H).
Step 7: Preparation of tert-butyl A/-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- vDpropyllcarbamate
A solution of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propan-1 -amine (1.5 g, 4.3 mmol) in THF (23 mL,) and water (15 mL,) stirred at 0°C, sodium hydrogen carbonate (1.7 g, 19 mmol.) and di-tert- butyl dicarbonate (1 .1 mL, 4.3 mmol) were added at 0°C. The resultant reaction mixture was stirred at rt for 2 h. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with water, aqueous layer was extracted with EtOAc (X3). The combined organic layer was washed with brine and dried over sodium sulphate and concentrated in vacuo to obtain the crude product. Crude compound was purified by combi flash using 60-80% EtOAc in cyclohexane to afford tert-butyl N-[2-(6-chloro-2-pyridyl)-2-(5- methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]carbamate (1 .4 g, 74 %) as yellow oil.
LCMS (Method A): ret. time 1.11 min, m/z = 395 (M+H)
Step 8: Preparation of tert-butyl A/-[2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- vDpropyllcarbamate
A solution of tert-butyl N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]carbamate (1.4 g, 3.2 mmol) in toluene (7.0 mL) and water (7.0 mL) stirred at rt. To this reaction mixture, potassium acetate (0.89 g, 8.9 mmol), potassium ferrocyanide (4.9 g, 13 mmol) were added, and the reaction mixture further degassed with nitrogen for 10 min. Under nitrogen (2-Dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1 '- biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium(ll) methanesulfonate (1.4 g, 1.6 mmol.) was added and the reaction mixture was heated for 4 hr at 90°C. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with water, aqueous layer was extracted with EtOAc (X3). The combined organic layer was washed with brine and dried over sodium sulphate and concentrated in vacuo to obtain the crude product. Crude compound was purified by combi flash using 80% EtOAc in cyclohexane to afford tertbutyl N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]carbamate (1 .0 g, 69 %) as brown oil.
LCMS (Method B): ret. time 1.76 min, m/z = 386 (M+H)
Step 9: Preparation of [2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4- yl)propyl1ammonium;chloride
To a solution of tert-butyl N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]carbamate (320 mg, 0.74 mmol) in diethyl ether (3.2 mL) 2 M HCI in diethyl ether (1.49 mL, 2.98 mmol.) was added drop wise at 0°C. The reaction mixture was warmed to rt and stirred at rt for 6 h, monitored by LCMS. The reaction mixture was concentrated under vacuum at 30°C to afford [2-(6-cyano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl- pyrazol-4-yl)propyl]ammonium;chloride (290 mg, 96 %) was as yellow solid. The crude product was taken to next step as such.
LCMS (Method A): ret. time 0.39 min, m/z = 286 (M+H)
Step 10: Preparation of ethyl (2E)-2-(p-tolylsulfonylhydrazono)acetate
A solution of 4-methylbenzenesulfonohydrazide (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 rt. The reaction mixture was stirred for 1 hr and the ethanol was 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): ret. time 1 .04 min, m/z = 271 [M+H], 1H NMR (400 MHz, CDCI3) 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) 2.44 (s, 3 H) 1 .23 - 1 .37 (m, 3 H).
Step 11 : Preparation of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate
A sample of 2,4-difluoroaniline (1 g, 7.74 mmol) was solubilized in aqueous 6M HCI (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 reaction mixture was stirred for 1 hr at 0°C and then added dropwise to a solution of ethyl (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 rt and then stirred for 5 hrs. The resulting reaction mixture was diluted with 1 N HCI and the aqueous layer was extracted with EtOAc (20 mL X3). 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, CDCI3) δ ppm 7.86 -
7.94 (m, 1 H) 7.11 - 7.21 (m, 2 H) 4.60 (q, J=7.21 Hz, 2 H) 1 .51 (t, J=7.13 Hz, 3 H)
Step 12: Preparation of 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid
To a stirred solution of methyl 5-methylisoxazole-3-carboxylate (300 mg, 1 .18 mmol) in THF (3 mL) and water (1 .5 mL) was added UOH.H2O (0.113 mg, 4.72) at rt and the reaction mixture was stirred at rt for 30 min. The organic solvent was removed by concentration in vacuo, and the aqueous residue diluted with 2N HCI, and 81 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): ret. time = 0.87-1 .11 min, 227 [M+H]; 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 13: Preparation of A/-[2-(6-cvano-2-pyridyl)-2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl1-2-(2,4- difluorophenyl)tetrazole-5-carboxamide (Compound P-1 , table P)
A solution of 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid (61 mg, 0.21 mmol) and [2-(6-cyano-2-pyridyl)- 2-(5-methoxy-1 ,3-dimethyl-pyrazol-4-yl)propyl]ammonium;chloride (80 mg, 0.19 mmol) in EtOAc (20 mL) was treated with DIPEA (0.15 mL, 0.79 mmol) and 1-propanephosphonic anhydride (379 mg, 0.35 mL, 0.59 mmol) at 0°C and the reaction mixture was stirred at rt monitoring by LCMS. Upon reaction completion, the reaction mixture was diluted with water (10 mL) and extracted with EtOAc (20 mL X3). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, filtered and concentrated in vacuo to obtain the crude product. This was purified using reverse phase combi flash chromatography eluting with 40-60 % water in CHsCN to afford the title compound as a colourless solid.
LCMS (Method A) Ret Time: 1 .02; m/z = 494 (M+H); 1H NMR (400 MHz, CDCI3) δ ppm 8.33-8.36 (br t, J=6.44 Hz, 1 H), 7.89 - 7.94 (m, 1 H), 7.75 - 7.77 (m, 1 H), 7.62-7.64 (d, J=7.63 Hz, 1 H), 7.46-7.48 (d, J=8.25 Hz, 1 H), 7.10 - 7.14 (m, 2 H), 4.16-4.18 (br d, J=6.63 Hz, 2 H), 3.86 (s, 3 H), 3.67 (s, 3 H), 1 .79 (s, 3 H),1 .65 (s, 3 H) 19F NMR (376 MHz, CDCb) δ ppm -103.80 (s, 1 F) -114.75 (s, 1 F)
Examples of synthesized compounds are shown in Table P.
Table P: Synthesized compounds and spectral and physical chemical data
BIOLOGICAL EXAMPLES
Example B1 : Alternaria solani / tomato / (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 to 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-2, P-3, P-4
Example B2: Blumeria qraminis f. sp. tritici (Erysiphe qraminis f. sp. tritici) / wheat / (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 to 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-3, P-4
Example B3: Phaeosphaeria nodorum (Septoria nodorum) / wheat / (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 to 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-2, P-3, P-4
Example B4: Pyrenophora teres / barley / (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 to 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-2, P-3, P-4
Example B5: Mycosphaerella qraminicola (Septoria tritici) / (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 to 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-2, P-3, P-4
Example B6: Botryotinia fuckeliana (Botrytis cinerea) / (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 to 4 days after application. 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-2, P-4
Example B7: Mycosphaerella arachidis (Cercospora arachidicola) / (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 to 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-2, P-3, P-4

Claims

1 . A compound of formula (I) wherein
R1 is selected from hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C3-C6-cycloalkyl;
R2 is selected from cyano, hydroxy, amino, C1-C4-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C3-C6- cycloalkyloxy, C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4- alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, or C1-C4- haloalkylsulfanyl;
R3 is selected from hydrogen, halogen, or C1-C4-alkyl;
R4 is selected from hydrogen, halogen, cyano, or C1-C4-alkyl;
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 a 6-membered heteroaryl, wherein any of said 6-membered heteroaryl is selected from wherein the staggered line denotes the bond to the rest of the molecule; and wherein any of said 6- membered heteroaryl is unsubstituted or substituted by 1 or up to the possible number of substituents independently selected from R10, wherein
R10 is independently selected from halogen, hydroxy, cyano, carboxy, amino, 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, trifluoromethylsulfonyloxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy- C1-C4-alkoxy, N-C1-C4-alkylamino, N,N-di(C1-C4)-alkylamino, C1-C4-alkoxycarbonyl, C1-C4- alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbonimidoyl, N-hydroxy-C1-C4-alkyl-carbonimidoyl, 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, with the proviso that only one is selected from 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-C4-alkoxy; and
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 contains 1 , 2, or 3 heteroatoms individually selected from N, O and S, with the proviso that only one is selected from 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, or N-oxide thereof.
2. The compound according to claim 1 , wherein R1 is C1-C3-alkyl; and R5 and R6 are hydrogen.
3. The compound according to claim 1 or claim 2, wherein R3 is hydrogen, or C1-C3-alkyl; and R4 is hydrogen or methyl.
4. The compound according to any one of claims 1 to 3, wherein R2 is C1-C3-alkoxy, C1-C2-haloalkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2-alkylsulfanyl.
5. The compound according to claim 4, wherein R2 is C1-C3-alkoxy, C1-C4-alkoxy-C1-C2-alkyl, or C1-C2- alkylsulfanyl.
6. The compound according to any one of claims 1 to 5, wherein Q is selected from wherein the staggered line denotes the bond to the rest of the molecule; wherein any of said 6- membered heteroaryl Q1 , Q2, Q3 and Q4 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3- alkoxy, or C3-C6-cycloalkyl.
7. The compound according to any one of claims 1 to 6, wherein Q is Q1 , and wherein Q1 is unsubstituted or substituted by 1 or 2 substituents independently selected from R10, wherein R10 is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, or C3-C6-cycloalkyl.
8. The compound according to any one of claims 1 to 7, wherein Z1 is selected from phenyl, or 5- or 6- membered heteroaryl; wherein any of said 5 or 6-membered heteroaryl contains 1 heteroatom selected from N, O and S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro, fluoro, C1-C2-alkyl, C1-C2- alkoxy, or C2-C4-alkynyl
9. The compound according to claim 8, wherein Z1 is 4-fluorophenyl, 2,4-difluorophenyl, 3-fluoro-2- pyridyl, 5-fluoro-2-pyridy I, 2,6-difluoro-3-pyridyl, 3,4-difluoro-2-pyridyl, or 3,5-difluoro-2-pyridyl.
10. The compound of formula (I) according to any one of claims 1 to 9, wherein the compound of formula
(I) is a compound of formula (l-A) wherein R1, R2, R3, R4, R5, R6, R10, Q and Z1 are as defined for the compound of formula (I) according any one of claims 1 to 9; and A is selected from wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group, and wherein R7, R8 and R9 are independently selected from hydrogen, C1-C4-alkyl, C2- C4-alkenyl, C2-C4-alkynyl, or C1-C4-haloalkyl.
11 . The compound according to claim 10, wherein A is selected from A1 or A2 wherein the staggered line denotes the bond to the C(=O) group, and the arrow denotes the bond to the Z1 group.
12. An agrochemical composition comprising a fungicidally effective amount of a compound as defined in any one of claims 1 to 11 .
13. The agrochemical composition according to claim 12, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound as defined in any one of claims 1 to 11 , or a composition comprising said compound, 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 11 as a fungicide.
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Citations (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO1997033890A1 (en) 1996-03-11 1997-09-18 Novartis Ag Pyrimidin-4-one derivatives as pesticide
WO2000015615A1 (en) 1998-09-15 2000-03-23 Syngenta Participations Ag Pyridine ketones useful as herbicides
WO2002004424A1 (en) 2000-07-07 2002-01-17 Pfizer Limited Pyrazole derivatives
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2008059370A2 (en) 2006-11-17 2008-05-22 Pfizer Japan Inc. Substituted bicyclocarboxyamide compounds
WO2009064652A1 (en) 2007-11-15 2009-05-22 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87701 and methods for detection thereof
WO2010043000A1 (en) 2008-10-17 2010-04-22 Akaal Pharma Pty Ltd S1p receptors modulators and their use thereof
WO2011138281A2 (en) 2010-05-06 2011-11-10 Bayer Cropscience Ag Process for the preparation of dithiine tetracarboxydiimides
EP2390252A1 (en) 2010-05-19 2011-11-30 Almirall, S.A. New pyrazole derivatives
WO2012075426A1 (en) 2010-12-03 2012-06-07 Dow Agrosciences Llc Stacked herbicide tolerance event 8264.44.06.1, related transgenic soybean lines, and detection thereof
WO2012102297A1 (en) 2011-01-26 2012-08-02 杏林製薬株式会社 Pyrazolopyridine derivative or pharmacologically acceptable salt thereof
WO2013016527A1 (en) 2011-07-26 2013-01-31 Dow Agrosciences Llc Insect resistant and herbicide tolerant soybean event 9582.814.19.1
WO2013087805A1 (en) 2011-12-14 2013-06-20 Boehringer Ingelheim International Gmbh Piperazine derivatives and their use as positive allosteric modulators of mglu5 receptors
WO2013092224A1 (en) 2011-12-21 2013-06-27 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi resistant to qo inhibitors
WO2014006945A1 (en) 2012-07-04 2014-01-09 アグロカネショウ株式会社 2-aminonicotinic acid ester derivative and bactericide containing same as active ingredient
WO2014032498A1 (en) 2012-09-03 2014-03-06 Crown Bioscience Inc. (Taicang) Highly selective c-met inhibitors as anticancer agents
WO2014041106A1 (en) 2012-09-17 2014-03-20 F. Hoffmann-La Roche Ag Triazole carboxamide derivatives
WO2014095675A1 (en) 2012-12-19 2014-06-26 Bayer Cropscience Ag Difluoromethyl-nicotinic-indanyl carboxamides as fungicides
WO2014168221A1 (en) 2013-04-11 2014-10-16 富士フイルム株式会社 Near-infrared-ray-absorbing composition, near-infrared-ray cut filter using same, manufacturing method therefor, camera module, and manufacturing method therefor
WO2014170327A1 (en) 2013-04-19 2014-10-23 Bayer Cropscience Ag Method for combating pests
US20140349990A1 (en) 2013-05-27 2014-11-27 Novartis Ag Pyrazolopyrrolidine Derivatives and their Use in the Treatment of Disease
WO2014201235A2 (en) 2013-06-14 2014-12-18 Monsanto Technology Llc Soybean transgenic event mon87751 and methods for detection and use thereof
WO2015155626A1 (en) 2014-04-10 2015-10-15 Pfizer Inc. 2-AMINO-6-METHYL-4,4a,5,6-TETRAHYDROPYRANO[3,4-d][1,3]THIAZIN-8a(8H)-YL-1,3-THIAZOL-4-YL AMIDES
WO2015185485A1 (en) 2014-06-06 2015-12-10 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi
WO2016156290A1 (en) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazole derivatives
WO2017004674A1 (en) 2015-07-06 2017-01-12 The University Of Sydney Therapeutic compounds and compositions for treating social disorders and substance use disorders
WO2017016915A1 (en) 2015-07-24 2017-02-02 Basf Se Pyridine compounds useful for combating phytopathogenic fungi
WO2017029179A1 (en) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Triazole derivatives, intermediates thereof and their use as fungicides
WO2017055473A1 (en) 2015-10-02 2017-04-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017153380A1 (en) 2016-03-10 2017-09-14 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2017178245A1 (en) 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017207362A1 (en) 2016-05-30 2017-12-07 Syngenta Participations Ag Microbiocidal thiazole derivatives
US20180170909A1 (en) 2016-12-21 2018-06-21 Janssen Biotech, Inc. Pyrazole derivatives as malt1 inhibitors
WO2018153707A1 (en) 2017-02-22 2018-08-30 Basf Se Crystalline forms of a strobilurin type compound for combating phytopathogenic fungi
WO2019093522A1 (en) 2017-11-13 2019-05-16 株式会社クレハ Azole derivative, intermediate compound, method for producing azole derivative, agent for agricultural and horticultural use, and material protection agent for industrial use
WO2019105933A1 (en) 2017-11-29 2019-06-06 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020056090A1 (en) 2018-09-14 2020-03-19 Fmc Corporation Fungicidal halomethyl ketones and hydrates
WO2020097012A1 (en) 2018-11-06 2020-05-14 Fmc Corporation Substituted tolyl as fungicides
WO2020109511A1 (en) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
WO2020109509A1 (en) 2018-11-30 2020-06-04 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020127780A1 (en) 2018-12-20 2020-06-25 Bayer Aktiengesellschaft Heterocyclyl pyridazine as fungicidal compounds
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020256113A1 (en) 2019-06-21 2020-12-24 日本農薬株式会社 Oxadiazole compound or salts thereof, and agricultural/horticultural bactericide containing said compound, and method for using same
WO2021009068A1 (en) 2019-07-12 2021-01-21 Scenic Immunology B.V. N-substituted-3,4-(fused 5-ring)-5-phenyl-pyrrolidine-2-one compounds as inhibitors of isoqc and/or qc enzyme
WO2021183707A2 (en) 2020-03-11 2021-09-16 Fmc Corporation Fungicidal halomethyl ketones and hydrates and their mixtures
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021249928A1 (en) 2020-06-10 2021-12-16 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors v
WO2021249800A1 (en) 2020-06-10 2021-12-16 Basf Se Substituted [1,2,4]triazole compounds as fungicides
WO2021255093A1 (en) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft Active compound combination
WO2021255070A1 (en) 2020-06-18 2021-12-23 Bayer Aktiengesellschaft Active compound combinations
WO2022033906A1 (en) 2020-08-11 2022-02-17 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii
WO2022133114A1 (en) 2020-12-17 2022-06-23 Fmc Corporation Fungicidal oxadiazoles and their mixtures
WO2023012044A1 (en) * 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
JP2023078251A (en) 2023-03-10 2023-06-06 住友化学株式会社 Method for producing acrylic acid derivative
WO2024156886A1 (en) * 2023-01-27 2024-08-02 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Patent Citations (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO1997033890A1 (en) 1996-03-11 1997-09-18 Novartis Ag Pyrimidin-4-one derivatives as pesticide
WO2000015615A1 (en) 1998-09-15 2000-03-23 Syngenta Participations Ag Pyridine ketones useful as herbicides
WO2002004424A1 (en) 2000-07-07 2002-01-17 Pfizer Limited Pyrazole derivatives
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2008059370A2 (en) 2006-11-17 2008-05-22 Pfizer Japan Inc. Substituted bicyclocarboxyamide compounds
WO2009064652A1 (en) 2007-11-15 2009-05-22 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87701 and methods for detection thereof
WO2010043000A1 (en) 2008-10-17 2010-04-22 Akaal Pharma Pty Ltd S1p receptors modulators and their use thereof
WO2011138281A2 (en) 2010-05-06 2011-11-10 Bayer Cropscience Ag Process for the preparation of dithiine tetracarboxydiimides
EP2390252A1 (en) 2010-05-19 2011-11-30 Almirall, S.A. New pyrazole derivatives
WO2012075426A1 (en) 2010-12-03 2012-06-07 Dow Agrosciences Llc Stacked herbicide tolerance event 8264.44.06.1, related transgenic soybean lines, and detection thereof
WO2012102297A1 (en) 2011-01-26 2012-08-02 杏林製薬株式会社 Pyrazolopyridine derivative or pharmacologically acceptable salt thereof
WO2013016527A1 (en) 2011-07-26 2013-01-31 Dow Agrosciences Llc Insect resistant and herbicide tolerant soybean event 9582.814.19.1
WO2013087805A1 (en) 2011-12-14 2013-06-20 Boehringer Ingelheim International Gmbh Piperazine derivatives and their use as positive allosteric modulators of mglu5 receptors
WO2013092224A1 (en) 2011-12-21 2013-06-27 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi resistant to qo inhibitors
WO2014006945A1 (en) 2012-07-04 2014-01-09 アグロカネショウ株式会社 2-aminonicotinic acid ester derivative and bactericide containing same as active ingredient
WO2014032498A1 (en) 2012-09-03 2014-03-06 Crown Bioscience Inc. (Taicang) Highly selective c-met inhibitors as anticancer agents
WO2014041106A1 (en) 2012-09-17 2014-03-20 F. Hoffmann-La Roche Ag Triazole carboxamide derivatives
WO2014095675A1 (en) 2012-12-19 2014-06-26 Bayer Cropscience Ag Difluoromethyl-nicotinic-indanyl carboxamides as fungicides
WO2014168221A1 (en) 2013-04-11 2014-10-16 富士フイルム株式会社 Near-infrared-ray-absorbing composition, near-infrared-ray cut filter using same, manufacturing method therefor, camera module, and manufacturing method therefor
WO2014170327A1 (en) 2013-04-19 2014-10-23 Bayer Cropscience Ag Method for combating pests
US20140349990A1 (en) 2013-05-27 2014-11-27 Novartis Ag Pyrazolopyrrolidine Derivatives and their Use in the Treatment of Disease
WO2014201235A2 (en) 2013-06-14 2014-12-18 Monsanto Technology Llc Soybean transgenic event mon87751 and methods for detection and use thereof
WO2015155626A1 (en) 2014-04-10 2015-10-15 Pfizer Inc. 2-AMINO-6-METHYL-4,4a,5,6-TETRAHYDROPYRANO[3,4-d][1,3]THIAZIN-8a(8H)-YL-1,3-THIAZOL-4-YL AMIDES
WO2015185485A1 (en) 2014-06-06 2015-12-10 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi
WO2016156290A1 (en) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazole derivatives
WO2017004674A1 (en) 2015-07-06 2017-01-12 The University Of Sydney Therapeutic compounds and compositions for treating social disorders and substance use disorders
WO2017016915A1 (en) 2015-07-24 2017-02-02 Basf Se Pyridine compounds useful for combating phytopathogenic fungi
WO2017029179A1 (en) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Triazole derivatives, intermediates thereof and their use as fungicides
WO2017055473A1 (en) 2015-10-02 2017-04-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017153380A1 (en) 2016-03-10 2017-09-14 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2017178245A1 (en) 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017207362A1 (en) 2016-05-30 2017-12-07 Syngenta Participations Ag Microbiocidal thiazole derivatives
US20180170909A1 (en) 2016-12-21 2018-06-21 Janssen Biotech, Inc. Pyrazole derivatives as malt1 inhibitors
WO2018153707A1 (en) 2017-02-22 2018-08-30 Basf Se Crystalline forms of a strobilurin type compound for combating phytopathogenic fungi
WO2019093522A1 (en) 2017-11-13 2019-05-16 株式会社クレハ Azole derivative, intermediate compound, method for producing azole derivative, agent for agricultural and horticultural use, and material protection agent for industrial use
WO2019105933A1 (en) 2017-11-29 2019-06-06 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020056090A1 (en) 2018-09-14 2020-03-19 Fmc Corporation Fungicidal halomethyl ketones and hydrates
WO2020097012A1 (en) 2018-11-06 2020-05-14 Fmc Corporation Substituted tolyl as fungicides
WO2020109511A1 (en) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
WO2020109509A1 (en) 2018-11-30 2020-06-04 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020127780A1 (en) 2018-12-20 2020-06-25 Bayer Aktiengesellschaft Heterocyclyl pyridazine as fungicidal compounds
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020256113A1 (en) 2019-06-21 2020-12-24 日本農薬株式会社 Oxadiazole compound or salts thereof, and agricultural/horticultural bactericide containing said compound, and method for using same
WO2021009068A1 (en) 2019-07-12 2021-01-21 Scenic Immunology B.V. N-substituted-3,4-(fused 5-ring)-5-phenyl-pyrrolidine-2-one compounds as inhibitors of isoqc and/or qc enzyme
WO2021183707A2 (en) 2020-03-11 2021-09-16 Fmc Corporation Fungicidal halomethyl ketones and hydrates and their mixtures
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021249928A1 (en) 2020-06-10 2021-12-16 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors v
WO2021249800A1 (en) 2020-06-10 2021-12-16 Basf Se Substituted [1,2,4]triazole compounds as fungicides
WO2021255070A1 (en) 2020-06-18 2021-12-23 Bayer Aktiengesellschaft Active compound combinations
WO2021255093A1 (en) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft Active compound combination
WO2022033906A1 (en) 2020-08-11 2022-02-17 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii
WO2022133114A1 (en) 2020-12-17 2022-06-23 Fmc Corporation Fungicidal oxadiazoles and their mixtures
WO2023012044A1 (en) * 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024156886A1 (en) * 2023-01-27 2024-08-02 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
JP2023078251A (en) 2023-03-10 2023-06-06 住友化学株式会社 Method for producing acrylic acid derivative

Non-Patent Citations (46)

* Cited by examiner, † Cited by third party
Title
"The Pesticide Manual", 2009, BRITISH CROP PROTECTION COUNCIL
A. ALBINIS. PIETRA: "Heterocyclic N-oxides", 1991, CRC PRESS
A. WOOD: "The Pesticide Manual - A World Compendium", 1995, THE BRITISH CROP PROTECTION COUNCIL
ACS CATALYSIS, vol. 9, no. 12, 2019, pages 10674 - 10679
ANGEW. CHEM. INT. ED, vol. 43, 2004, pages 1132 - 1136
ANGEW. CHEM. INT. ED., vol. 55, no. 17, 2016, pages 5332 - 5336
ANGEW. CHEM. INT. ED., vol. 56, no. 47, 2017, pages 15044 - 15048
BIO. MED. CHEM. LETT., vol. 19, no. 5, 2009, pages 1451 - 1456
BIO. MED. CHEM. LETT., vol. 27, no. 17, 2017, pages 4044 - 4050
CHEM. COMM., vol. 53, no. 6832-16-2, 2017, pages 9620 - 9623
CHEM. COMM., vol. 57, no. 57, 2021, pages 7047 - 7050
J. AM. CHEM. SOC., vol. 138, no. 44, 2016, pages 14609 - 14615
J. HET. CHEM., vol. 24, no. 2, 1987, pages 373 - 6
J. MED. CHEM., vol. 32, no. 12, 1989, pages 2561 - 73
J. MED. CHEM., vol. 49, no. 12, 2006, pages 3614 - 3627
J. MED. CHEM., vol. 60, no. 14, 2017, pages 6166 - 6190
J. MED. CHEM., vol. 61, no. 8, 2018, pages 3370 - 3388
J. ORG. CHEM., vol. 47, 1981, pages 3153
J. ORG. CHEM., vol. 70, 2005, pages 8601 - 8604
J. ORG. CHEM., vol. 73, 2008, pages 7102 - 7107
J. ORG. CHEM., vol. 74, 2009, pages 5599 - 5602
J. ORG. CHEM., vol. 79, 2014, pages 6703 - 6707
J. ORG. CHEM., vol. 82, no. 14, 2017, pages 7420 - 7427
J. ORGANOMET. CHEM., vol. 576, 1999, pages 147 - 168
J.ORG. CHEM., vol. 84, no. 12, 2019, pages 8160 - 8167
LIEBIGS ANN. CHEM., vol. 10, 1994, pages 1049 - 53
no. 117007-77-9
ORG. LETT., vol. 10, no. 8, 2008, pages 1653 - 1655
ORG. LETT., vol. 24, no. 20, 2022, pages 3620 - 3625
ORG. LETT., vol. 7, 2005, pages 4107 - 4110
ORG. LETT., vol. 9, 2007, pages 85 - 87
ORG. PREP. PROC. INT., vol. 17, no. 6, 1985, pages 391 - 9
POLYHEDRON, vol. 165, 2019, pages 22 - 30
SCI. SYNTH., vol. 19, 2004, pages 173 - 195
SULFUR LETT., vol. 4, no. 5, 1986, pages 175 - 83
SYNTH. COMM., vol. 18, no. 18, 1988, pages 2331 - 5
SYNTHESIS, vol. 10, 2001, pages 1551 - 1555
SYNTHESIS, vol. 45, no. 23, 2013, pages 3211 - 3227
SYNTHESIS, vol. 49, no. 23, 2017, pages 5120 - 5130
TETRAHEDRON LETT., 1977, pages 4171 - 4174
TETRAHEDRON LETT., 2006, pages 5767 - 5769
TETRAHEDRON LETT., vol. 55, no. 33, 2014, pages 4568 - 4571
TETRAHEDRON, vol. 30, 1974, pages 2151 - 2157
TETRAHEDRON, vol. 57, no. 13, 2001, pages 2507 - 2514
TETRAHEDRON, vol. 61, no. 46, 2005, pages 10827 - 10852
TETRAHEDRON, vol. 76, no. 14, 2020, pages 131063

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