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WO2025210096A1 - Compositions fongicides - Google Patents

Compositions fongicides

Info

Publication number
WO2025210096A1
WO2025210096A1 PCT/EP2025/059013 EP2025059013W WO2025210096A1 WO 2025210096 A1 WO2025210096 A1 WO 2025210096A1 EP 2025059013 W EP2025059013 W EP 2025059013W WO 2025210096 A1 WO2025210096 A1 WO 2025210096A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
carboxamide
pyridyl
difluoro
thiazole
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/EP2025/059013
Other languages
English (en)
Inventor
Andrew Edmunds
Christopher Charles SCARBOROUGH
Hanno Christian Wolf
Valeria Grasso
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 WO2025210096A1 publication Critical patent/WO2025210096A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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

Definitions

  • compositions possessing a greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, increased biodegradability can be used.
  • the term “compounds of formula (I)” refers to component A.
  • the weight ratio of component (A) to component (B) may preferably be from 100:1 to 1:100, from 50:1 to 1:50, from 20:1 to 1:40, from 15:1 to 1:30, from 12:1 to 1:25, from 10:1 to 1:20, from 5:1 to 1:15, from 3:1 to 1:10 or from 2:1 to 1:5.
  • a method of controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, on useful plants or on propagation material thereof which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition according to the invention.
  • fungicidal mixture compositions according to the invention may also include, 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, improved physico-chemical properties, or increased biodegradability).
  • 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, improved physico-chemical properties, or increased biodegradability.
  • the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in optically isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond.
  • the present invention includes all those possible isomeric forms (e.g., geometric isomers) and mixtures thereof for a compound of formula (I).
  • the present invention includes all possible tautomeric forms for a compound of formula (I), and also a racemic compound, i.e., a mixture of at least two enantiomers in a ratio of substantially 50:50.
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g., an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds.
  • 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 haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.
  • amino means a -NH2 group.
  • cyano means a -CN group.
  • 109812_FF 83045) 4
  • hydroxyl or “hydroxy” an -OH group.
  • carboxylic acid means a -COOH group.
  • C1-Cn-alkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n- pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,
  • 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.
  • 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.
  • R 1 is selected from hydrogen, halogen, or C1-C3-alkyl.
  • R 1 is hydrogen, chloro, or methyl.
  • R 2 is hydrogen, or C1-C3-alkyl.
  • R 2 is hydrogen, or methyl.
  • R 3 is selected from hydrogen, or C1-C3-alkyl.
  • R 3 is hydrogen, or methyl.
  • R 4 is selected from hydrogen, cyano, or C1-C3-alkyl.
  • R 4 is hydrogen, or C1-C3-alkyl. More preferably, R 4 is hydrogen, or methyl.
  • R 5 and R 6 are independently selected from hydrogen, halogen, cyano, C1-C3-alkyl, or C1-C3-alkoxy. More preferably, R 5 and R 6 are independently selected from hydrogen, C1-C3- alkyl, or C1-C3-alkoxy. Even more preferably, R 5 and R 6 are independently selected from hydrogen, or C1-C3- alkoxy.
  • A is selected from group and the star the position attached to the carbonyl-group and the star the position from A1 or A2, wherein the staggered line denotes the position attached to the carbonyl-group and the star the position attached to Z 1 .
  • Z 1 is selected from phenyl or pyridyl, wherein said phenyl and said pyridyl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, C1-C3-alkyl, or C1-C3-alkoxy.
  • Z 1 is selected from phenyl or pyridyl, wherein said phenyl and said pyridyl are unsubstituted or substituted by 1 or 2 substituents independently selected from chloro, fluoro, methyl, or methoxy. More preferably, Z 1 is selected from phenyl or pyridyl, wherein said phenyl and said pyridyl are unsubstituted or substituted by 1 or 2 substituents selected from fluoro.
  • the present invention accordingly, makes available a compound of formula (I) having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A and Z 1 as defined above in all combinations / each permutation.
  • fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I): 109812_FF (83045) 6 (I) wherein R 1 is selected from from hydrogen, or methyl; R 3 is selected from hydrogen, or methyl; R 4 is C3-alkyl; R 5 and R 6 are independently selected from hydrogen, cyano, C1-C3-alkyl, or C1-C3-alkoxy; A is selected from A1 or A2, wherein the staggered line denotes carbonyl-group and the star the position attached to Z 1 ; and Z 1 is selected from phenyl and said pyridyl are unsubstituted or substituted by 1 or 2 substituents selected from fluoro; and component (B) is a compound selected from a compound selected from a compound selected from 109812_FF (83045) 6 (I) wherein R 1 is selected from from hydrogen, or methyl; R 3 is selected from hydrogen, or
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I): (I) wherein R 1 is selected from from hydrogen, or methyl; R 3 is selected from hydrogen, or methyl; R 4 is C3-alkyl; R 5 and R 6 are independently selected from hydrogen, cyano, C1-C3-alkyl, or C1-C3-alkoxy; A is selected from A1 or A2, 109812_FF (83045) 8 wherein the staggered line denotes carbonyl-group and the star the position attached to Z 1 ; and Z 1 is selected from phenyl and said pyridyl are unsubstituted or substituted by 1 or 2 substituents selected from fluoro; and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, iso
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I): 109812_FF (83045) 9 (I) wherein R 1 is selected from from hydrogen, or methyl; R 3 is selected from hydrogen, or methyl; R 4 is C3-alkyl; R 5 and R 6 are independently selected from hydrogen, cyano, C1-C3-alkyl, or C1-C3-alkoxy; A is selected from A1 or A2, wherein the staggered line denotes carbonyl-group and the star the position attached to Z 1 ; and Z 1 is selected from phenyl and said pyridyl are unsubstituted or substituted by 1 or 2 substituents selected from fluoro; and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin,
  • component (A) is a compound selected from [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H- isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (X.03), [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5- dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (X.04), [6-methoxy-1-methyl-4-(1- methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (X.07), [(1S,4S)-6- methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-iso
  • Table X Component (A) Entry IUPAC name Structure (1-phenyltriazol-4-yl)-[4-(1,3,5- X.01 trimethylpyrazol-4-yl)-3,4-dihydro-1H- isoquinolin-2-yl]methanone [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H- X.02 isoquinolin-2-yl]-(1-phenyltriazol-4- yl)methanone [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H- X.03 isoquinolin-2-yl]-(2-phenyltetrazol-5- yl)methanone [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5- X.04 dimethylpyrazol-4-yl)-3,4-dihydro-1H- isoquinolin
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, 109812_FF (83045) 16 flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propanecar
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propenamide, or methyl (Z
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propenamide, or methyl (Z)-2
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propenamide, or methyl (
  • Methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate this compound may be prepared from the methods described in WO2020/193387. N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]- 8-fluoro-quinoline-3-carboxamide, these compounds may be prepared from the methods described in WO2017/153380.
  • WO 2018/102345 discloses use of Aureobasidin A as an agricultural fungicide to treat, 10 prevent or control fungal infections in plants and seeds.
  • Enantiomerically pure final compounds may be obtained from racemic starting materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, e.g., by using chiral starting materials.
  • component A refers to the compound of formula (I).
  • component (A) is a compound of formula (I) with component (B) as active ingredients
  • AX means one component (A) selected from compounds of formula (I), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention): pydiflumetofen + AX, benzovindiflupyr + AX, bixafen + AX, fluxapyroxad + AX, isopyrazam + AX, penflufen + AX, penthiopyrad + AX, sedaxane
  • component (A) is a compound of formula (I) with component (B) as active ingredients
  • AX means one component (A) selected from compounds of formula (I), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention): pydiflumetofen + AX, benzovindiflupyr + AX, bixafen + AX, fluxapyroxad + AX, isopyrazam + AX, penflufen + AX, penthiopyrad + AX,
  • component (A) is a compound of formula (I) with component (B) as active ingredients
  • AX means one component (A) selected from compounds of formula (I), or compounds selected from 109812_FF (83045) 21 (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), , (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaleuca alternifolia oil (an extract of the tea tree plant Melaleuca alternifolia (commercially available as Timorex Gold®
  • component (A) is a compound of formula (I) with component (B) as active ingredients
  • AX means one component (A) selected from compounds of formula (I), or compounds selected from (X.11), (X.12), (X.15), (X.17), (X.20) or (X.21), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaleuca alternifolia oil (an extract of the tea tree plant Melaleuca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)) + AX, Reynoutria sachalinensis extract (commercially available as REGALIA®) + AX, a plant extract based on the extract of Quillaja saponaria Molina (commercially available as BO
  • component (A) is compound no. X.03 [4-(1- methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (X.03), or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxystrobin, metyltetraprole, f
  • component (A) is compound no. X.11 [1-(2,4- difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2- yl]methanone (X.11), or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxy
  • component (A) is compound no. X.16 [(1S,4S)-4- (5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)tetrazol-5- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxystro
  • component (A) is compound no. X.17 [2-(2,4- difluorophenyl)tetrazol-5-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxystrobin, met
  • component (A) is compound no. X.18 [1-(3,5- difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxystrobin,
  • component (A) is compound no. X.19 [1-(3,5- difluoro-2-pyridyl)triazol-4-yl]-[rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H- isoquinolin-2-yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin,
  • component (A) is compound no. X.20 [(1S,4S)-4- (5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(3,5-difluoro-2-pyridyl)triazol-4- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, tri
  • component (A) is compound no. X.21 [1-(2,4- difluorophenyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxystrobin, metyltetraprole, fen
  • component (A) is compound no. X.03 [4-(1- methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N-[[4-(1- methylpyra
  • component (A) is compound no. X.04 [2-(2,4- difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, 109812_FF (83045) 33 mefentrifluconazole, flufenoxadiazam, fludioxon
  • component (A) is compound no. X.07 [6-methoxy- 1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-meth
  • component (A) is compound no. X.17 [2-(2,4- difluorophenyl)tetrazol-5-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cypro
  • component (A) is compound no. X.19 [1-(3,5- difluoro-2-pyridyl)triazol-4-yl]-[rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H- isoquinolin-2-yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufe
  • component (A) is compound no. X.03 [4-(1- methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N-[[4
  • component (A) is compound no. X.04 [2-(2,4- difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, or a 109812_FF (83045) 47 salt, enantiomer, tautomer or N-oxide thereof, and (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil,
  • component (A) is compound no. X.07 [6-methoxy- 1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-meth
  • component (A) is compound no. X.09 [(1S,4S)-6- methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5- yl)methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludio
  • component (A) is compound no. X.11 [1-(2,4- difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cypro
  • component (A) is compound no. X.12 [1-(3,5- difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam,
  • component (A) is compound no. X.15 [(1S,4S)-4- (5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam,
  • component (A) is compound no. X.16 [(1S,4S)-4- (5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)tetrazol-5- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam,
  • component (A) is compound no. X.17 [2-(2,4- difluorophenyl)tetrazol-5-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, 109812_FF (83045) 49 prothioconazole, mefentrifluconazole, c
  • component (A) is compound no. X.18 [1-(3,5- difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cy
  • component (A) is compound no. X.19 [1-(3,5- difluoro-2-pyridyl)triazol-4-yl]-[rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H- isoquinolin-2-yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufe
  • component (A) is compound no. X.20 [(1S,4S)-4- (5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(3,5-difluoro-2-pyridyl)triazol-4- yl]methanone, or a salt, enantiomer, tautomer or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenox
  • component (A) is compound no. X.21 [1-(2,4- difluorophenyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, or a salt, 109812_FF (83045) 50 enantiomer, tautomer or N-oxide thereof, and (B) is a compound selected from pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil,
  • the composition may comprise an additional active ingredient component (C), which is different to component (B), and is selected from the group consisting of pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, isofetamid, fluindapyr, cyclobutrifluram, fluoxastrobin, fenamidone, mandestrobin, picoxystrobin, pyraclostrobin, famoxadone, kresoxim-methyl, trifloxystrobin, azoxystrobin, metyltetraprole, amisulbrom, cyazofamid, fenpicoxamid, florylpicoxamid, metaryl
  • component (C), which is different to component (B), is a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyraclostrobin, trifloxystrobin, azoxystrobin, metyltetraprole, fenpicoxamid, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, tetraconazole, prothiocon
  • component (C), which is different to component (B), is a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N- [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclo
  • component (C), which is different to component (B), is a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, mefentrifluconazole, flufenoxadiazam, cyprodinil, fludioxonil, N-methoxy-N- [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl
  • a fungicidal composition comprising a mixture of component (A) and a component (B) and a component (C) as active ingredients, wherein component (A) is a compound of formula (I) selected from compounds (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention, and wherein component (C), and component (B), are a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penthiopyrad,
  • a fungicidal composition comprising a mixture of component (A) and a component (B) and a component (C) as active ingredients, wherein component (A) is a compound of formula (I) selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention, and wherein component (C), and component (B), are a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, sedaxane, boscalid
  • a fungicidal composition comprising a mixture of component (A) and a component (B) and a component (C) as active ingredients, wherein component (A) is a compound of formula (I) selected from compounds (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention, and wherein component (C), and component (B), are a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpicoxa
  • a fungicidal composition comprising a mixture of component (A) and a component (B) and a component (C) as active ingredients, wherein component (A) is a compound of formula (I) selected from compounds (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), listed in table X according to the present invention, and wherein component (C), and component (B), are a compound selected from the group consisting of pydiflumetofen, benzovindiflupyr, cyclobutrifluram, pyraclostrobin, azoxystrobin, metyltetraprole, florylpico
  • the weight ratio of component (A) to the mixture of components (B) and (C) may be from 100:1 to 1:100, or 50:1 to 1:50, or 20:1 to 1:20, or 10:1 to 1:10, or 5:1 and 1:5.
  • the weight ratio of component (A) to the mixture of components (B) and (C) may be from 2:1 to 1:2, or 4:1 to 2:1, or 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, 109812_FF (83045) 55 or 1:1500, or 1:350, or 2:350, or 4:350, or 2:750, or 4:750.
  • 109812_FF 83045) 55 or 1:1500, or 1:350, or 2:350, or 4:350, or 2:750, or 4:750.
  • the weight ratio of component (A) to the sum of component (B) and component (C) may be from 100:1 to 1:100, preferably from 50:1 to 1:50, more preferably from 20:1 to 1:40, even more preferably from 15:1 to 1:30, still more preferably from 12:1 to 1:25, or from 10:1 to 1:20, or from 10:1 to 1:10, or from 5:1 to 1:15, or from 5:1 to 1:5, or from 4:1 to 1:4, or from 3:1 to 1:10, or from 3:1 to 1:3, or from 2:1 to 1:5, or 1:1.
  • the compounds of formula (I) according to the present invention can be made as shown in the following Schemes 1 to 19, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
  • the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
  • Compounds of formula (I) may be prepared by a person skilled in the art following known methods.
  • 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 and R 6 are as defined above for the compound of formula (I) by reaction with a compound of formula (II), wherein A and Z 1 are as defined above for the compound of formula (I) (Scheme 1).
  • A are as formula (I), are activated to compounds of formula (IIa) by methods known to a person skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852.
  • compounds of formula (IIa), where X 0 is halogen are formed by treatment of compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic quantities of N,N-dimethylformamide (DMF) in inert solvents such as dichloromethane (DCM) or tetrahydrofuran (THF) at temperatures between 20°C to 100°C, preferably 25°C.
  • DMF N,N-dimethylformamide
  • DCM dichloromethane
  • THF tetrahydrofuran
  • nitriles of formula (XII) can also be reduced to the primary amines with hydrogen in the presence of a catalyst, such as a Platinum salt, or Raney-Nickel in the 109812_FF (83045) 62 presence of a hydrogen donor, for example or methanol.
  • a catalyst such as a Platinum salt, or Raney-Nickel in the 109812_FF (83045) 62 presence of a hydrogen donor, for example or methanol.
  • a catalyst such as a Platinum salt, or Raney-Nickel in the 109812_FF (83045) 62 presence of a hydrogen donor, for example or methanol.
  • a hydrogen donor for example or methanol.
  • This reaction is shown in Scheme 13.
  • Compounds of , R 1 , R 2 , R 3 , R 5 R 6 are as compound of formula (I), may be prepared by a person skilled in the art following known methods. More specifically, compounds of formula (XII), and intermediates thereof, may be prepared from compounds of formula
  • Salts of compounds of formula (I) may be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger 109812_FF (83045) 70 reagent and salts with bases, for example, by with a suitable acid or with a suitable ion exchanger reagent.
  • Enantiomeric mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities,
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • 109812_FF 83045) 71 It is advantageous to isolate or synthesize in 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.
  • g a.i./ha refers to the application rate given in gramm [g ] of active ingredient [a.i.] per unit of surface [ha].
  • the unit hectare is the metric unit of area that equals a square with 100 m side (1 hm 2 ) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.
  • 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.
  • effective amount refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect. An effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • pathogens may include:Oomycetes, including Phytophthora species such as Phytophthora cactorum, Phytophthora capsici, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythroseptica, Phytophthora fragariae, Phytophthora infestans, Phytophthora nicotianae, Phytophthora porri, and Phytophthora sojae; Pythium species such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; other Peronosporales such as Bremia lactucae, Hyaloperonospora parasitica, Sclerophthora macrospora, Sclerospora graminicola; Peronospora species including Peronospora de
  • Plasmopara species including Plasmopara halstedii and Plasmopara viticola; Pseudoperonospora species including Pseudoperonospora cubensis and Pseudoperonospora humili; Peronosclerospora species including Peronosclerospora maydis, Peronosclerospora philippinensis and Peronosclerospora sorghi; Albuginales such as Albugo candida, Albugo occidentalis, and Albugo tragopogonis; and Saprolegniales such as Aphanomyces species, including Aphanomyces cochliodes; Ascomycetes, including Mycosphaerellales such as Actinothyrium graminis, Asperisporium caricae, Cercospora species including Cercospor
  • Neocosmospora phaseoli Neocosmospora solani, Neonectria candida, Paramyrothecium roridum, Sarocladium oryzae, Trichoderma spp.
  • Sordariomycetes such as Wongia garrettii and Wongia griffinii
  • Taphrinales such as Taphrina bullata and Taphrina deformans
  • Onygenales such as Ajellomyces capsulatus, Blastomyces dermatitidis, Coccidioides species including 109812_FF (83045) 76 Coccidioides immitis
  • Basidiomycetes including Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Cronartium ribicola,
  • Puccinia striiformis f.sp. tritici and Puccinia triticina Pucciniastrum coryli, Tranzschelia discolor, Uromyces species including Uromyces betae, Uromyces pisi and Uromyces viciae- fabae; Tilletiales such as Neovossia moliniae, and Tilletia species including Tilletia caries and Tilletia controversa; Ustilaginales such as Sporisorium reilianum and Ustilago species including Ustilago maydis, Ustilago segetum var. nuda, Ustilago segetum var.
  • Urocystidales such as Urocystis species including Urocystis agropyri
  • Agaricales such as Marasmiellus inoderma, Mycena spp., Moniliophthora roreri and Moniliophthora perniciosa
  • Cantharellales such as Sclerotium spp.
  • Typhula species including Typhula incarnata and Typhula ishikariensis
  • Ceratobasidiales such as Waitea circinata, and Rhizoctonia species including Rhizoctonia cerealis, Rhizoctonia solani and Rhizoctonia theobromae
  • Atheliales such as Athelia rolfsii
  • Corticiales such as Corticium invisum and Laetisaria fuciformis
  • Cystodilobasidiales such as Itersonilia perplexans
  • Entylomatales such as Entyloma calendulae f.sp.
  • Exobasidiales such as Exobasidium vexans
  • Hymenochaetales such as Phellinus igniarius
  • Russulales such as Stereum hirsutum
  • Tremellales such as Cryptococcus species including Cryptococcus neoformans
  • Zygomycetes including Mucorales such as Choanephora cucurbitarum, Mucor spp., Rhizopus oryzae, Absidia corymbifera and Rhizomucor pusillus
  • Blastocladiomycetes including Physoderma maydis; as well as diseases caused by other species and genera closely related to those listed above.
  • compositions may also have activity against diseases caused by Actinobacteria such as Streptomyces scabiei; Proteobacteria such as Erwinia amylovora, Pectobacterium carotovorum, Xanthomonas species including Xanthomonas axonopodis, Xanthomonas campestris, Xanthomonas oryzae and Xanthomonas vesicatoria; and Pseudomonas species including Pseudomonas syringae; Cercozoa such as Polymyxa betae, Polymyxa graminis and Spongospora subterranea; and Bigyra such as Labyrinthula zosterae; as well as diseases caused by other species and genera closely related to those listed above.
  • Actinobacteria such as Streptomyces scabiei
  • Proteobacteria such as Erwinia am
  • compositions may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
  • bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
  • composition according to the invention is effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g., Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g., the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g., Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g., Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosc
  • Crops of useful plants in which the composition according to the invention can be used include 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), mille
  • 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
  • Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g., improved storage stability, higher nutritional value and improved flavour). Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors.
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g., imazamox, by conventional methods of breeding is Clearfield® summer canola.
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g., glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®. Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin- producing bacteria.
  • toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi. 109812_FF (83045) 78
  • An example of a crop that has been modified the Bacillus thuringiensis toxin is the Bt maize KnockOut ⁇ (Syngenta Seeds).
  • An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot ⁇ (Syngenta Seeds).
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I ⁇ (Dow AgroSciences, Pioneer Hi-Bred International).
  • herbicide tolerant for example Herculex I ⁇ (Dow AgroSciences, Pioneer Hi-Bred International).
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard ⁇ (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm ⁇ (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus ⁇ (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink ⁇ (maize variety that expresses a Cry9(c) toxin); Herculex I ⁇ (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ⁇ (cotton variety that expresses a CryIA(c) toxin); Bollgard I ⁇ (cotton variety that expresses a CryIA(c) toxin); Bollgard II® (cotton variety
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ -endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C
  • 109812_FF 83045) 79
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, EP-A-451878 and WO 03/052073.
  • YieldGard ⁇ (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm ⁇ (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus ⁇ (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink ⁇ (maize variety that expresses a Cry9C toxin); Herculex I ⁇ (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ⁇ (cotton variety that expresses a Cry1Ac toxin); Bollgard I ⁇ (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a
  • transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 109812_FF (83045) 80 2. Bt176 Maize from Syngenta Seeds SAS, de l'Hobit 27, F-31790 St.
  • composition comprising a mixture of components (A) and (B) and any fungicidal solutions used to control phytopathogenic fungi such as Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. including P. maydis, P.
  • sdhC T79N, T79I, W80S, W80A, A84F, N86S, N86A, P127A, R151M/S/T/G, R151S, R151T, H152R/Y, V166M, T168R.
  • sdhD I50F, M114V, D129G, T20P+K186R; Pyrenophora teres:
  • sdhB S66P, N235I, H277Y.
  • sdhC K49E, R64K, N75S, G79R, H134R, S135R.
  • sdhD D124E, H134R, G138V, D145G
  • Ramularia collo-cygni In sdhB: N224T, T267I.
  • sdhC N87S, G91R, H146R/L, G171D, H153R; Phakopsora pachyrhizi: C-I86F; Sclerotinia sclerotiorum: In sdhB: H273Y.
  • sdhC G91R, H146R.
  • sdhD T108K, H132R, G150R.
  • compositions according to the present invention comprising a mixture of components (A) and (B), are used to control fungal strains which are resistant to one or more fungicides from any of the following fungicidal MoA classes: quinone-outside-inhibitors (QoI), quinone-inside-inhibitors (QiI), succinate dehydrogenase inhibitors (SDHI) and sterol demethylation-inhibitors (DMI).
  • QoI quinone-outside-inhibitors
  • QiI quinone-inside-inhibitors
  • SDHI succinate dehydrogenase inhibitors
  • DI sterol demethylation-inhibitors
  • compositions of this invention can be mixed with one or more further pesticides including further fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • further pesticides including further fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • Fungicides such as etridiazole, fluazinam, benalaxyl, benalaxyl-M (kiralaxyl), furalaxyl, metalaxyl, metalaxyl- M (mefenoxam), dodicin, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5- dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, N'-[4-[[3-[(4- 109812_FF (83045) 83 chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]- phenyl]-N-ethyl-N-methyl-formamidine, ethirimol,
  • TX represents a compound (according to the definition of component (A) of the compositions of the present invention) selected from compounds of formula (I), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), as defined in the Table X above): 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-
  • 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, +
  • the mixtures of compounds of formula (I) (selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), as listed in Table X (above) with active ingredients described above comprise a compound selected from Table X (above) and an active ingredient as described above 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, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred,
  • mixture compositions 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.
  • component (A) is a compound of formula (I) selected from selected from compounds of formula (I), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), (X.11), (X.12), (X.13), (X.14), (X.15), (X.16), (X.17), (X.18), (X.19), (X.20), or (X.21), as listed in Table X (above), 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 109812_FF (83045) 95 ingredients when applied in a sequential manner, one after the other with a reasonably short period, such as a few hours
  • compositions of the present invention may also be used in crop enhancement.
  • crop enhancement means an improvement in plant vigour, an improvement in plant quality, improved tolerance to stress factors, and/or improved input use efficiency.
  • an ‘improvement in plant vigour’ means that certain traits are improved qualitatively or quantitatively when compared with the same trait in a control plant which has been grown under the same conditions in the absence of the method of the invention.
  • Such traits include, but are not limited to, early and/or improved germination, improved emergence, the ability to use less seeds, increased root growth, a more developed root system, increased root nodulation, increased shoot growth, increased tillering, stronger tillers, more productive tillers, increased or improved plant stand, less plant verse (lodging), an increase and/or improvement in plant height, an increase in plant weight (fresh or dry), bigger leaf blades, greener leaf colour, increased pigment content, increased photosynthetic activity, earlier flowering, longer panicles, early grain maturity, increased seed, fruit or pod size, increased pod or ear number, increased seed number per pod or ear, increased seed mass, enhanced seed filling, less dead basal leaves, delay of senescence, improved vitality of the plant, increased levels of amino acids in storage tissues and/or less inputs needed (e.g., less fertiliser, water and/or labour needed).
  • a plant with improved vigour may have an increase in any of the aforementioned traits or any combination or two or more of the aforementioned traits.
  • an ‘improvement in plant quality’ means that certain traits are improved qualitatively or quantitatively when compared with the same trait in a control plant which has been grown under the same conditions in the absence of the method of the invention.
  • Such traits include, but are not limited to, improved visual appearance of the plant, reduced ethylene (reduced production and/or inhibition of reception), improved quality of harvested material, e.g., seeds, fruits, leaves, vegetables (such improved quality may manifest as improved visual appearance of the harvested material), improved carbohydrate content (e.g., increased quantities of sugar and/or starch, improved sugar acid ratio, reduction of reducing sugars, increased rate of development of sugar), improved protein content, improved oil content and composition, improved nutritional value, reduction in anti-nutritional compounds, improved organoleptic properties (e.g., improved taste) and/or improved consumer health benefits (e.g., increased levels of vitamins and anti-oxidants), improved post-harvest characteristics (e.g., enhanced shelf-life and/or storage stability, easier processability, easier extraction of compounds), more homogenous crop development (e.g., synchronised germination, flowering and/or fruiting of plants), and/or improved seed quality (e.g., for use in following seasons).
  • improved quality of harvested material e
  • a plant with improved quality may have an increase in any of the aforementioned traits or any combination or two or more of the aforementioned traits.
  • an ‘improved tolerance to stress factors’ means that certain traits are improved qualitatively or quantitatively when compared with the same trait in a control plant which has been grown under the same conditions in the absence of the method of the invention.
  • Such traits include, but are 109812_FF (83045) 96 not limited to, an increased tolerance and/or to abiotic stress factors which cause sub-optimal growing conditions such as drought (e.g., any stress which leads to a lack of water content in plants, a lack of water uptake potential or a reduction in the water supply to plants), cold exposure, heat exposure, osmotic stress, UV stress, flooding, increased salinity (e.g., in the soil), increased mineral exposure, ozone exposure, high light exposure and/or limited availability of nutrients (e.g., nitrogen and/or phosphorus nutrients).
  • a plant with improved tolerance to stress factors may have an increase in any of the aforementioned traits or any combination or two or more of the aforementioned traits.
  • an ‘improved input use efficiency’ means that the plants are able to grow more effectively using given levels of inputs compared to the grown of control plants which are grown under the same conditions in the absence of the method of the invention.
  • the inputs include, but are not limited to fertiliser (such as nitrogen, phosphorous, potassium, micronutrients), light and water.
  • a plant with improved input use efficiency may have an improved use of any of the aforementioned inputs or any combination of two or more of the aforementioned inputs.
  • crop enhancements of the present invention include a decrease in plant height, or reduction in tillering, which are beneficial features in crops or conditions where it is desirable to have less biomass and fewer tillers. Any or all of the above crop enhancements may lead to an improved yield by improving e.g., plant physiology, plant growth and development and/or plant architecture.
  • ‘yield’ includes, but is not limited to, (i) an increase in biomass production, grain yield, starch content, oil content and/or protein content, which may result from (a) an increase in the amount produced by the plant per se or (b) an improved ability to harvest plant matter, (ii) an improvement in the composition of the harvested material (e.g., improved sugar acid ratios, improved oil composition, increased nutritional value, reduction of anti-nutritional compounds, increased consumer health benefits) and/or (iii) an increased/facilitated ability to harvest the crop, improved processability of the crop and/or better storage stability/shelf life.
  • an increase in biomass production, grain yield, starch content, oil content and/or protein content which may result from (a) an increase in the amount produced by the plant per se or (b) an improved ability to harvest plant matter, (ii) an improvement in the composition of the harvested material (e.g., improved sugar acid ratios, improved oil composition, increased nutritional value, reduction of anti-nutritional compounds, increased consumer health benefits) and/or (i
  • Increased yield of an agricultural plant means that, where it is possible to take a quantitative measurement, the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without application of the present invention. According to the present invention, it is preferred that the yield be increased by at least 0.5%, more preferred at least 1%, even more preferred at least 2%, still more preferred at least 4%, preferably 5% or even more. Any or all of the above crop enhancements may also lead to an improved utilisation of land, i.e. land which was previously unavailable or sub-optimal for cultivation may become available.
  • plants which show an increased ability to survive in drought conditions may be able to be cultivated in areas of sub-optimal rainfall, e.g., perhaps on the fringe of a desert or even the desert itself.
  • crop enhancements are made in the substantial absence of pressure from pests and/or diseases and/or abiotic stress.
  • improvements in plant vigour, stress tolerance, quality and/or yield are made in the substantial absence of pressure from pests 109812_FF (83045) 97 and/or diseases.
  • pests and/or may be controlled by a pesticidal treatment that is applied prior to, or at the same time as, the method of the present invention.
  • compositions of the present invention may also be used in the field of protecting storage goods against attack of fungi.
  • storage goods is understood to denote natural substances of vegetable and/or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Storage goods of vegetable origin such as plants or parts thereof, for example stalks, leaves, tubers, seeds, fruits, or grains
  • timber also falling under the definition of storage goods is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Storage goods of animal origin are hides, leather, furs, hairs, and the like.
  • the composition according to the present invention can prevent disadvantageous effects such as decay, discoloration, or mold.
  • storage goods is understood to denote natural substances of vegetable origin and/or their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • “storage goods” is understood to denote wood. Therefore, a further aspect of the present invention is a method of protecting storage goods, which comprises applying to the storage goods a composition according to the invention.
  • the composition of the present invention may also be used in the field of protecting technical material against attack of fungi.
  • the term “technical material” includes paper; carpets; constructions; cooling and heating systems; wallboards; ventilation and air conditioning systems and the like; preferably “technical material” is understood to denote wallboards.
  • the composition according to the present invention can prevent disadvantageous effects such as decay, discoloration, or mold.
  • the composition according to the invention is generally formulated in various ways using formulation adjuvants, such as carriers, solvents, and surface-active substances.
  • the formulations can be in various physical forms, e.g., in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g., from the Manual on Development and Use of FAO and WHO Specific
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • 109812_FF 83045) 98
  • the formulations can be prepared e.g., by mixing active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g., slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane, or chemically modified polymers and starch xanthates, or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • the formulation adjuvants that are suitable for the preparation of the formulations according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxi
  • Suitable solid carriers are, for example, talc, dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecyl- benzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • the formulations according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the formulation according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the formulations generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of component (A) and component (B) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • compositions or compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Certain mixture compositions comprising a component (A), wherein said component (A) is a compound of formula (I) described above may show a synergistic effect.
  • synergism corresponds to a positive value for the difference of (O-E). In the case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.
  • composition according to the invention may also have further surprising advantageous properties.
  • advantageous properties are: more advantageous degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.
  • component (A) When applied to the useful plants component (A) is typically applied at a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, e.g., 50, 75, 100 or 200 g a.i./ha, typically in association with 1 to 5000 g a.i./ha, particularly 2 to 2000 g a.i./ha, e.g., 100, 250, 500, 800, 1000, 1500 g a.i./ha of component (B).
  • the application rates of the composition according to the invention depend on the type of effect desired, and typically range from 20 to 4000 g of total composition per hectare.
  • composition according to the invention When the composition according to the invention is used for treating seed, rates of 0.001 to 50 g of a compound of component (A) per kg of seed, preferably from 0.01 to 10 g per kg of seed, and 0.001 to 50 g of a compound of component (B), per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient.
  • a literary reference, patent application, or patent is cited within the text of this application, the entire text of said citation is herein incorporated by reference.
  • 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 % Kaolin 62 % 27 % - 109812_FF (83045) 102 The combination is thoroughly mixed with the 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.
  • Coated granules Active ingredients 8% 109812_FF (83045) 103 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.
  • 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.
  • 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 suspensions of any desired dilution can be obtained by dilution with water.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 109812_FF (83045) 104 28% of the active ingredients.
  • the medium 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
  • LC-MS Method A Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment, diode- array detector and ELSD.
  • LC-MS Method G Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector.
  • LC-MS method H Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source ⁇ (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, ⁇ Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector.
  • Example P1 Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4- yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound X.04, Table P)
  • Step 1 Preparation of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline suspension of 4-bromoisoquinoline (2.0 g, 9.4204 mmol), 1,5-dimethyl-4-(4,4,5,5- 2-yl)-1H-pyrazole (2.3484 g, 10.362 mmol) and potassium carbonate (1.4322 g, 10.362 mmol) in a toluene/methanol mixture (30mL, 5:1) was degassed with argon for several minutes, and then tetrakis(triphenylphosphaniumyl)palladium (0.545 g
  • reaction mixture was heated at 100°C and stirred for 1 hr under microwave irradiation. After cooling down to rt, the reaction mixture was poured into water, extracted with EtOAc, the organic layer separated, dried over Na2SO4, filtered, and 109812_FF (83045) 108 concentrated in vacuo. Purification of the crude by flash chromatography over silica gel (eluting with EtOAc /30% methanol) afforded the title compound.
  • Step 2 Preparation of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline methanol (90 mL) was added g, . was at rt (room temperature), and then hydrochloric acid (1.25 M in methanol) was added until the pH reached 2-3. After 30 minutes of stirring at rt, the reaction mixture was diluted with water and basified with 2 N sodium hydroxide, and the mixture extracted with EtOAc (3x25 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The resulting yellow oil was used without further purification.
  • Step 4 Preparation of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate 109812_FF (83045) 109 a solution of 6M hydrochloric acid in deionized water (6 mL, 36 mmol) and ethanol (5 mL) was cooled to 0°C.
  • Step 5 Preparation of [[2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H- isoquinolin-2-yl]methanone (Compound X.04, Table P) To a solution of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate (0.1 g, 0.39 mmol) in toluene (2 mL), was added 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline-hydrochloride (0.
  • Example P2 Preparation of [1-(2,4-difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl- 3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound X.11, Table P) Step 1: Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate difluoro-benzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was added successively copper (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).
  • Step 2 Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid difluorophenyl)triazole-4-carboxylate (0.31 g, 1.3 mmol) was dissolved in water (3.2 mL) under argon to give a pale brown solution. To this was added lithium hydroxide monohydrate (0.047 g, 1.9 mmol), and the mixture was stirred at room temperature.
  • LCMS shows desired mass and consumption of starting material.
  • the tetrahydrofuran was evaporated in vacuo, and then aqueous HCl 2N (ca.0.5 mL) was added to leave the aqueous phase with a pH 3-4.
  • the resulting lightly red suspension was filtered, the white cake washed with water and cyclohexane and dried in vacuo at 55°C to give 1-(2,4-difluorophenyl)triazole-4-carboxylic acid as white solid.
  • Step 3 Preparation of (1,5-dimethylpyrazol-4-yl)-phenyl-methanol 4-carbaldehyde (25 g, 201.39 mmol) in THF (400 mL) was added phenyl magnesium bromide 1 molar in THF (228 mL, 227.57 mmol) dropwise at 0-5°C under argon atmosphere over 15 min. After the addition, the ice-bath was removed, and the white suspension was stirred at rt for 3hr. The reaction mixture was poured into sat. ammonium chloride solution and extracted with EtOAc.
  • borane dimethyl sulfide complex (12.62 g, 15.8 mL, 156.2 mmol) was added dropwise at rt under argon atmosphere and the resulting colorless reaction mixture was stirred at 65°C for 2 hrs.
  • the reaction mixture was cooled to 0°C before adding HCl (23 g, 34.71 mL, 208.2 mmol) dropwise (strong gas evolution) and the mixture was stirred at 65°C for 1 hr and allowed to stand overnight at rt.
  • the mixture was diluted with water and treated with NaOH 6M (to pH 12).
  • Step 3 Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine -2-(1-methylpyrazol-4-yl)acetonitrile (3.2 g, 14 mmol) in tetrahydrofuran (42 was with borane dimethyl sulfide complex (4.0 mL, 42 mmol) at rt under argon.
  • Step 4 Preparation of rac- Preparation of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4- tetrahydroisoquinoline flask, equipped with a magnetic stirrer bar, was charged with 2-(3-methoxyphenyl)-2- yl)ethanamine (80 mg, 0.34 mmol), HCl 37 % (1.7mL) and acetaldehyde (0.19 mL, 3.46 mmol). The reaction mixture was stirred at rt for 3 hrs and then slowly poured into water and neutralized with saturated aqueous NaHCO3 (strong gas evolution) until pH 8.
  • Racemic mixture was further purified by Column: Chiral pak-IG (250 x 20mm; 5 ⁇ m), Mobile Phase A : TBME (80%), Mobile phase B: EtOH (20%) Isocratic, Flow rate:17 mL/min, DAD Detection: DAD, Run Time: 45min, Sample preparation: 580 mg in 10mL EtOH+4mL THF+1mL TBME, to give syn enatiomers in rotameric form.
  • Example I-1 Preparation of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline
  • Step 1 Preparation of 4-(1-methylpyrazol-4-yl)isoquinoline to example P1, step 1 LCMS (Method A): m/z 210 (M+H), retention time 0.41 min.
  • Example I-2 Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline 109812_FF (83045) 118 methanol flask, equipped with a magnetic stirrer bar, was charged with 1-methyl-1H- pyrazole-4-carbaldehyde (2.20 g, 19.2 mmol) and tetrahydrofuran (40 mL). To the colorless solution, phenylmagnesium bromide 1 molar in THF (21 mL, 21.1 mmol) was added dropwise at 0-5°C under argon atmosphere for 15 min.
  • Step 2 Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile with a magnetic stirrer bar and condenser, was charged with (1-methylpyrazol- - g, 15.6 mmol) and DCM (156 mL).
  • Step 4 Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine equipped with a magnetic stirrer bar, was charged with 2-(1-methylpyrazol-4-yl)-2- phenyl-propanenitrile (2.82 g, 13.3 mmol) and THF (40 mL).
  • borane dimethyl sulfide complex (4.0 mL, 40.0 mmol) was added dropwise at rt under argon atmosphere and the resulting colorless mixture was stirred at 65°C for 2 hrs.
  • the reaction mixture was cooled to 0°C before adding HCl (8.9 mL, 53.7 mmol) dropwise (strong gas evolution) and the mixture was stirred at 65°C for 1 hr and allowed to stand overnight at rt.
  • the mixture was diluted with water (80mL), basified with 13 mL NaOH 6M (pH 12) and the mixture extracted twice with EtOAc.
  • Step 6 Preparation of methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate flask, equipped with a magnetic stirrer bar, was charged with methyl N-[2-(1- 4- -2- propyl] carbamate (422 mg, 1.54 mmol), HCl (5.00 mL/mmol, 9.26 g, 7.72 mL, 94.0 mmol) and paraformaldehyde (93 mg, 0.97 mmol). The reaction mixture was stirred at rt for 40 min, where LCMS analysis showed reaction completion.
  • Step 7 Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline bottom flask, equipped with a magnetic stirrer bar, was charged methyl 4-methyl-4-(1- -1,3-dihydroisoquinoline-2-carboxylate (3.86 g, 13.5 mmol), 1,2-dichloroethane (5.00 ml/mmol, 68 mL) and iodotrimethylsilane (8.37 g, 5.69 mL, 40.6 mmol). The reaction mixture was stirred at 60°C under argon atmosphere for 45 min (LCMS analysis showed reaction completion).
  • Example I-3 Preparation of rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-1,2,3,4- tetrahydroisoquinoline analogously to the method described for rac-(1S,4S)-4-(1,5-dimethylpyrazol-4- - in example P2.
  • Step 1 Preparation of (5-chloro-1-methyl-pyrazol-4-yl)-phenyl-methanol G), m/z 223 [M+H], retention time: 1.03 min.
  • Step 2 Preparation of 2-(5-chloro-1-methyl-pyrazol-4-yl)-2-phenyl-acetonitrile G): m/z 232 [M+H], retention time: 1.06 min.
  • Step 3 Preparation of 2-(5-chloro-1-methyl-pyrazol-4-yl)-2-phenyl-ethanamine G): m/z 236 [M+H], retention time: 0.28 min. 109812_FF (83045) 122
  • Step 4 Preparation of methyl N-[2-(5-chloro-1- pyrazol-4-yl)-2-phenyl-ethyl]carbamate 294 [M+H], retention time: 0.96 min.
  • Step 5 Preparation of methyl rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H- isoquinoline-2-carboxylate m/z 320 [M+H], retention time: 1.29 min.
  • Step 6 of rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline m/z 262 [M+H], retention time: 0.92 min.
  • Example I-4 Preparation of methyl 1-(3,5-difluoro-2-pyridyl)triazole-4-carboxylate difluoro-pyridine and methyl prop-2-ynoate as analogously described in example had the following characterization data: LCMS (Method A): m/z 241 [M+H], retention time: 0.79 min.
  • Example I-5 Preparation of 1-(3,5-difluoro-2-pyridyl)triazole-4-carboxylic acid 109812_FF (83045) 123 Prepared from methyl 1-(3,5-difluoro-2-pyridyl)triazole-4-carboxylate as analogously described in example P2, step 2.
  • 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 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 109812_FF (83045) 127 fuckeliana at 20 ppm when compared to under the same conditions, which showed extensive disease development: X.03, X.04, X.07, X.09, X.11, X.12, X.15, X.16, X.17, X.18, X.19, X.020, and X.021
  • Example B3 Glomerella lagenarium (Colletotrichum lagenarium) /(Anthracnose) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth).
  • test compound After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3 to 4 days after application.
  • DMSO DMSO
  • 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.
  • Example B5 Fusarium culmorum / (Head blight) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application.
  • DMSO DMSO
  • the inoculated test leaf disks are incubated at 20°C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber, the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 to 8 days after application).
  • the following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.20 109812_FF (83045) 128
  • Example B7 Phaeosphaeria nodorum (Septoria / 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).
  • test compound 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.
  • DMSO DMSO
  • test compound 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.
  • DMSO DMSO
  • a X.21 Metarylpicoxamid 1:3 2:6 DMSO solution of the test compounds was placed X.21 Flufenoxadiazam 1:1 20:20 X.21 Flufenoxadiazam 3.3:1 20:6 into a microtiter plate (96-well format) and the X.21 Flufenoxadiazam 1:10 2:20 nutrient broth containing the fungal spores was X.21 Flufenoxadiazam 1:3 2:6 X.21 Methyl (Z)-2-(5-cyclohexyl-2- 1:1 20:20 added to it.
  • test plates were incubated at 24°C methyl-phenoxy)-3-methoxy- prop-2-enoate 10 and the inhibition of growth was determined 109812_FF (83045) 148 visually and/or photometrically at 620nm after X.11 Methyl (Z)-2-(5-cyclohexyl-2- 3.3:1 20:6 methyl-phenoxy)-3-methoxy- days.
  • a DMSO solution of the test cyclopropane-carboxamide compounds was placed into a microtiter plate (96- X.20 N,2-dimethoxy-N-[[4-[5-(tri- 1:1 20:20 fluoromethyl)-1,2,4-oxadiazol- well format) and the nutrient broth containing the 3-yl]phenyl]methyl]- propanamide fungal spores was added to it.
  • test plates were X.20 N,2-dimethoxy-N-[[4-[5-(tri- 3.3:1 20:6 incubated at 24°C and the inhibition of growth was fluoromethyl)-1,2,4-oxadiazol- 3-yl]phenyl]methyl]- 10 determined visually and/or photometrically at propanamide

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Abstract

L'invention concerne une composition fongicide comprenant un mélange de composants (A) et (B), les composants (A) et (B) étant tels que définis dans la revendication 1, et l'utilisation des compositions dans l'agriculture ou l'horticulture pour lutter contre ou prévenir l'infestation de plantes par des micro-organismes phytopathogènes, de préférence des champignons.
PCT/EP2025/059013 2024-04-03 2025-04-02 Compositions fongicides Pending WO2025210096A1 (fr)

Applications Claiming Priority (4)

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Citations (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2010043000A1 (fr) 2008-10-17 2010-04-22 Akaal Pharma Pty Ltd Modulateurs des récepteurs s1p et leur utilisation
WO2011138281A2 (fr) 2010-05-06 2011-11-10 Bayer Cropscience Ag Procédé de production de dithiine-tétracarboxy-diimides
EP2390252A1 (fr) 2010-05-19 2011-11-30 Almirall, S.A. Nouveaux dérivés de pyrazole
WO2013087805A1 (fr) 2011-12-14 2013-06-20 Boehringer Ingelheim International Gmbh Dérivés de pipérazine et leur utilisation à titre de modulateurs allostériques positifs des récepteurs mglur5
WO2013092224A1 (fr) 2011-12-21 2013-06-27 Basf Se Utilisation de composés de type strobilurine pour combattre des champignons phytopathogènes résistants aux inhibiteurs du site qo
WO2014006945A1 (fr) 2012-07-04 2014-01-09 アグロカネショウ株式会社 Dérivé d'ester d'acide 2-aminonicotinique et bactéricide le contenant comme principe actif
WO2014032498A1 (fr) 2012-09-03 2014-03-06 Crown Bioscience Inc. (Taicang) Inhibiteurs hautement sélectifs de c-met utilisés comme agents anticancéreux
CN103772278A (zh) 2014-01-02 2014-05-07 湖南华腾制药有限公司 一种重要四氢异喹啉衍生物中间体及其合成方法
WO2014095675A1 (fr) 2012-12-19 2014-06-26 Bayer Cropscience Ag Utilisation de carboxamides difluorométhyl-nicotinique-indanyle comme fongicides
WO2014168221A1 (fr) 2013-04-11 2014-10-16 富士フイルム株式会社 Composition absorbant les rayons proche infrarouge, filtre de coupure de rayon proche infrarouge l'utilisant, procédé de fabrication de celui-ci, module de caméra, et procédé de fabrication de celui-ci
WO2015155626A1 (fr) 2014-04-10 2015-10-15 Pfizer Inc. Amides 2-amino-6-méthyl-4,4a,5,6-tétrahydropyrano[3,4-d][1,3]thiazin-8a(8h)-yl-1,3-thiazol-4-yle
WO2015185485A1 (fr) 2014-06-06 2015-12-10 Basf Se Utilisation d'oxadiazoles substitués pour lutter contre des fongus phytopathogènes
WO2016156290A1 (fr) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Nouveaux dérivés d'imidazole à substitution en position 5
WO2017016915A1 (fr) 2015-07-24 2017-02-02 Basf Se Composés pyridine utiles pour lutter contre des champignons phytopathogènes
WO2017029179A1 (fr) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Dérivés de triazole, leurs intermédiaires et leur utilisation comme fongicides
WO2017055469A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017055473A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017093348A1 (fr) 2015-12-02 2017-06-08 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017118689A1 (fr) 2016-01-08 2017-07-13 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017153380A1 (fr) 2016-03-10 2017-09-14 Syngenta Participations Ag Dérivés microbiocides de quinoléine (thio)carboxamide
WO2017178245A1 (fr) 2016-04-11 2017-10-19 Basf Se Oxadiazoles substitués pour lutter contre des champignons phytopathogènes
WO2017207362A1 (fr) 2016-05-30 2017-12-07 Syngenta Participations Ag Dérivés de thiazole microbiocides
WO2018102345A1 (fr) 2016-11-30 2018-06-07 Agrobiologics Llc Utilisation de l'auréobasidine antifongique en agriculture
US20180170909A1 (en) 2016-12-21 2018-06-21 Janssen Biotech, Inc. Pyrazole derivatives as malt1 inhibitors
WO2018153707A1 (fr) 2017-02-22 2018-08-30 Basf Se Formes cristallines d'un composé de type strobilurine pour lutter contre des champignons phytopathogènes
WO2019093522A1 (fr) 2017-11-13 2019-05-16 株式会社クレハ Dérivé d'azole, composé intermédiaire, procédé de production d'un dérivé d'azole, agent à usage agricole et horticole, et agent de protection de matériau à usage industriel
WO2019105933A1 (fr) 2017-11-29 2019-06-06 Syngenta Participations Ag Dérivés de thiazole microbiocides
WO2020056090A1 (fr) 2018-09-14 2020-03-19 Fmc Corporation Halométhyl cétones et hydrates fongicides
WO2020097012A1 (fr) 2018-11-06 2020-05-14 Fmc Corporation Tolyles substitués utilisés en tant que fongicides
WO2020109509A1 (fr) 2018-11-30 2020-06-04 Syngenta Participations Ag Dérivés de thiazole microbiocides
WO2020109511A1 (fr) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Dérivés de 2-acylamino-thiazole-4-carboxamide microbiocides
WO2020127780A1 (fr) 2018-12-20 2020-06-25 Bayer Aktiengesellschaft Hétérocyclyl-pyridazine utilisée en tant que composés fongicides
WO2020193387A1 (fr) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Composés fongicides
WO2020256113A1 (fr) 2019-06-21 2020-12-24 日本農薬株式会社 Composé d'oxadiazole ou sels de celui-ci, bactéricide agricole/horticole contenant ledit composé, et procédé d'utilisation associé
WO2021183707A2 (fr) 2020-03-11 2021-09-16 Fmc Corporation Halométhyl cétones et hydrates fongicides et leurs mélanges
WO2021244952A1 (fr) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Dérivés microbiocides
WO2021249928A1 (fr) 2020-06-10 2021-12-16 Basf Se Utilisation de composés de type strobilurine pour lutter contre des champignons phytopathogènes, contenant une substitution d'acides aminés f129l dans la protéine cytochrome b mitochondrial conférant une résistance à des inhibiteurs de qo v
WO2021249800A1 (fr) 2020-06-10 2021-12-16 Basf Se Composés de [1,2,4]triazole substitués utilisés en tant que fongicides
WO2021255093A1 (fr) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft Combinaison de composés actifs
WO2021255070A1 (fr) 2020-06-18 2021-12-23 Bayer Aktiengesellschaft Combinaisons de composés actifs
WO2022033906A1 (fr) 2020-08-11 2022-02-17 Basf Se Utilisation de composés de type strobilurine pour lutter contre des champignons phytopathogènes, contenant une substitution d'acide aminé f129l dans la protéine cytochrome b mitochondriale conférant une résistance à des inhibiteurs qo viii
WO2022133114A1 (fr) 2020-12-17 2022-06-23 Fmc Corporation Oxadiazoles fongicides et leurs mélanges
WO2022253645A1 (fr) * 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Dérivés de tétrahydroisoquinoléine microbiocides
WO2024068950A1 (fr) * 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Dérivés de pyrazole microbiocides
WO2024115546A1 (fr) * 2022-11-30 2024-06-06 Syngenta Crop Protection Ag Compositions fongicides

Patent Citations (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2010043000A1 (fr) 2008-10-17 2010-04-22 Akaal Pharma Pty Ltd Modulateurs des récepteurs s1p et leur utilisation
WO2011138281A2 (fr) 2010-05-06 2011-11-10 Bayer Cropscience Ag Procédé de production de dithiine-tétracarboxy-diimides
EP2390252A1 (fr) 2010-05-19 2011-11-30 Almirall, S.A. Nouveaux dérivés de pyrazole
WO2013087805A1 (fr) 2011-12-14 2013-06-20 Boehringer Ingelheim International Gmbh Dérivés de pipérazine et leur utilisation à titre de modulateurs allostériques positifs des récepteurs mglur5
WO2013092224A1 (fr) 2011-12-21 2013-06-27 Basf Se Utilisation de composés de type strobilurine pour combattre des champignons phytopathogènes résistants aux inhibiteurs du site qo
WO2014006945A1 (fr) 2012-07-04 2014-01-09 アグロカネショウ株式会社 Dérivé d'ester d'acide 2-aminonicotinique et bactéricide le contenant comme principe actif
WO2014032498A1 (fr) 2012-09-03 2014-03-06 Crown Bioscience Inc. (Taicang) Inhibiteurs hautement sélectifs de c-met utilisés comme agents anticancéreux
WO2014095675A1 (fr) 2012-12-19 2014-06-26 Bayer Cropscience Ag Utilisation de carboxamides difluorométhyl-nicotinique-indanyle comme fongicides
WO2014168221A1 (fr) 2013-04-11 2014-10-16 富士フイルム株式会社 Composition absorbant les rayons proche infrarouge, filtre de coupure de rayon proche infrarouge l'utilisant, procédé de fabrication de celui-ci, module de caméra, et procédé de fabrication de celui-ci
CN103772278A (zh) 2014-01-02 2014-05-07 湖南华腾制药有限公司 一种重要四氢异喹啉衍生物中间体及其合成方法
WO2015155626A1 (fr) 2014-04-10 2015-10-15 Pfizer Inc. Amides 2-amino-6-méthyl-4,4a,5,6-tétrahydropyrano[3,4-d][1,3]thiazin-8a(8h)-yl-1,3-thiazol-4-yle
WO2015185485A1 (fr) 2014-06-06 2015-12-10 Basf Se Utilisation d'oxadiazoles substitués pour lutter contre des fongus phytopathogènes
WO2016156290A1 (fr) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Nouveaux dérivés d'imidazole à substitution en position 5
WO2017016915A1 (fr) 2015-07-24 2017-02-02 Basf Se Composés pyridine utiles pour lutter contre des champignons phytopathogènes
WO2017029179A1 (fr) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Dérivés de triazole, leurs intermédiaires et leur utilisation comme fongicides
WO2017055469A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017055473A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017093348A1 (fr) 2015-12-02 2017-06-08 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017118689A1 (fr) 2016-01-08 2017-07-13 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017153380A1 (fr) 2016-03-10 2017-09-14 Syngenta Participations Ag Dérivés microbiocides de quinoléine (thio)carboxamide
WO2017178245A1 (fr) 2016-04-11 2017-10-19 Basf Se Oxadiazoles substitués pour lutter contre des champignons phytopathogènes
WO2017207362A1 (fr) 2016-05-30 2017-12-07 Syngenta Participations Ag Dérivés de thiazole microbiocides
WO2018102345A1 (fr) 2016-11-30 2018-06-07 Agrobiologics Llc Utilisation de l'auréobasidine antifongique en agriculture
US20180170909A1 (en) 2016-12-21 2018-06-21 Janssen Biotech, Inc. Pyrazole derivatives as malt1 inhibitors
WO2018153707A1 (fr) 2017-02-22 2018-08-30 Basf Se Formes cristallines d'un composé de type strobilurine pour lutter contre des champignons phytopathogènes
WO2019093522A1 (fr) 2017-11-13 2019-05-16 株式会社クレハ Dérivé d'azole, composé intermédiaire, procédé de production d'un dérivé d'azole, agent à usage agricole et horticole, et agent de protection de matériau à usage industriel
WO2019105933A1 (fr) 2017-11-29 2019-06-06 Syngenta Participations Ag Dérivés de thiazole microbiocides
WO2020056090A1 (fr) 2018-09-14 2020-03-19 Fmc Corporation Halométhyl cétones et hydrates fongicides
WO2020097012A1 (fr) 2018-11-06 2020-05-14 Fmc Corporation Tolyles substitués utilisés en tant que fongicides
WO2020109509A1 (fr) 2018-11-30 2020-06-04 Syngenta Participations Ag Dérivés de thiazole microbiocides
WO2020109511A1 (fr) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Dérivés de 2-acylamino-thiazole-4-carboxamide microbiocides
WO2020127780A1 (fr) 2018-12-20 2020-06-25 Bayer Aktiengesellschaft Hétérocyclyl-pyridazine utilisée en tant que composés fongicides
WO2020193387A1 (fr) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Composés fongicides
WO2020256113A1 (fr) 2019-06-21 2020-12-24 日本農薬株式会社 Composé d'oxadiazole ou sels de celui-ci, bactéricide agricole/horticole contenant ledit composé, et procédé d'utilisation associé
WO2021183707A2 (fr) 2020-03-11 2021-09-16 Fmc Corporation Halométhyl cétones et hydrates fongicides et leurs mélanges
WO2021244952A1 (fr) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Dérivés microbiocides
WO2021249928A1 (fr) 2020-06-10 2021-12-16 Basf Se Utilisation de composés de type strobilurine pour lutter contre des champignons phytopathogènes, contenant une substitution d'acides aminés f129l dans la protéine cytochrome b mitochondrial conférant une résistance à des inhibiteurs de qo v
WO2021249800A1 (fr) 2020-06-10 2021-12-16 Basf Se Composés de [1,2,4]triazole substitués utilisés en tant que fongicides
WO2021255070A1 (fr) 2020-06-18 2021-12-23 Bayer Aktiengesellschaft Combinaisons de composés actifs
WO2021255093A1 (fr) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft Combinaison de composés actifs
WO2022033906A1 (fr) 2020-08-11 2022-02-17 Basf Se Utilisation de composés de type strobilurine pour lutter contre des champignons phytopathogènes, contenant une substitution d'acide aminé f129l dans la protéine cytochrome b mitochondriale conférant une résistance à des inhibiteurs qo viii
WO2022133114A1 (fr) 2020-12-17 2022-06-23 Fmc Corporation Oxadiazoles fongicides et leurs mélanges
WO2022253645A1 (fr) * 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Dérivés de tétrahydroisoquinoléine microbiocides
WO2024068950A1 (fr) * 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Dérivés de pyrazole microbiocides
WO2024115546A1 (fr) * 2022-11-30 2024-06-06 Syngenta Crop Protection Ag Compositions fongicides

Non-Patent Citations (41)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's Detergents and Emulsifiers Annual", 1981, MC PUBLISHING CORP
ACS CATALYSIS, vol. 9, no. 12, 2019, pages 10674 - 10679
ANG. CHEM. INT. ED., vol. 56, no. 47, 2017, pages 15044 - 15048
CHEM. COMM., vol. 53, no. 69, 2017, pages 9620 - 9623
CHEM. COMM., vol. 57, no. 57, 2021, pages 7047 - 7050
CHEM. SCI., vol. 4, 2013, pages 2374 - 2379
COLBY, S.R.: "Calculating synergistic and antagonistic responses of herbicide combination", WEEDS, vol. 15, 1967, pages 20 - 22, XP001112961
COOLS ET AL., PLANT PATHOL., vol. 62, 2013, pages 36 - 42
DATABASE CHEMCATS [online] Chemical Abstracts Service / STN; 6 April 2023 (2023-04-06), .: "(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin compounds", XP093277191, retrieved from www.stn.org Database accession no. 1383639024, 1323863277, 0777565698, 0668481915 *
FRAAIJE ET AL., PHYTOPATHOL, vol. 95, no. 8, 2005, pages 933 - 41
GISI ET AL., PEST MANAG SCI., vol. 56, 2000, pages 833 - 841
J. AM. CHEM. SOC., vol. 114, 1992, pages 5959
J. AM. CHEM. SOC., vol. 138, no. 44, 2016, pages 14609 - 14615
J. ORG. CHEM., vol. 47, 1981, pages 3153
J. ORG. CHEM., vol. 79, 2014, pages 6703 - 6707
J. ORGANOMET. CHEM., vol. 576, 1999, pages 147 - 168
J.ORG. CHEM., vol. 82, no. 14, 2017, pages 7420 - 7427
J.ORG. CHEM., vol. 84, no. 12, 2019, pages 8160 - 8167
LUCAS, PESTIC OUTLOOK, vol. 14, no. 6, 2003, pages 268 - 70
MEUNIER ET AL., PEST MANAG SCI., vol. 75, 2019, pages 2107 - 2114
ORG. BIOMOL. CHEM., vol. 14, 2016, pages 6853
ORG. LETT, vol. 10, 2008, pages 4570
ORG. LETT., vol. 24, no. 20, 2022, pages 3620 - 3625
PASCHE ET AL., J. CROP PROT., vol. 27, no. 3-5, 2008, pages 427 - 435
POLYHEDRON, vol. 165, 2019, pages 22 - 30
REACT. KINET. CATAL. LETT., vol. 92, 2007, pages 99 - 104
SCHMITZ HK ET AL., PEST MANAG. SCI., vol. 70, 2014, pages 378 - 388
SEMAR ET AL., J. PLANT DIS. PROT., vol. 3, 2007, pages 117 - 119
SIEROTZKI ET AL., PEST MANAG. SCI, vol. 63, no. 3, 2007, pages 225 - 233
SIEROTZKISCALLIET, PHYTOPATHOLOGY, vol. 103, no. 9, 2013, pages 880 - 887
SIMÕES ET AL., J. PLANT DIS. PROT., vol. 125, 2018, pages 21 - 2
SYNTHESIS, vol. 4, 1979, pages 281 - 3
SYNTHESIS, vol. 49, no. 23, 2017, pages 5120 - 5130
TAKESAKO ET AL., J. ANTIBIOT., vol. 44, 1991, pages 919 - 924
TETRAHEDRON LETT., 1977, pages 4171 - 4174
TETRAHEDRON LETT., 2006, pages 5767 - 5769
TETRAHEDRON, vol. 43, 1987, pages 439
TETRAHEDRON, vol. 61, no. 46, 2005, pages 10827 - 10852
TETRAHEDRON, vol. 76, no. 14, 2020, pages 131063
WALKER ET AL., ENVIRON. MICROBIOL., 2021
YOUNG ET AL., PEST MANAG SCI., vol. 74, no. 2, 2018, pages 489 - 498

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