WO2024256433A1 - Compositions fongicides - Google Patents

Compositions fongicides Download PDF

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Publication number
WO2024256433A1
WO2024256433A1 PCT/EP2024/066165 EP2024066165W WO2024256433A1 WO 2024256433 A1 WO2024256433 A1 WO 2024256433A1 EP 2024066165 W EP2024066165 W EP 2024066165W WO 2024256433 A1 WO2024256433 A1 WO 2024256433A1
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WO
WIPO (PCT)
Prior art keywords
methyl
carboxamide
difluoro
pyridyl
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.)
Ceased
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PCT/EP2024/066165
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English (en)
Inventor
Andrew Edmunds
Christopher Charles SCARBOROUGH
Hanno Christian Wolf
Valeria Grasso
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Priority to CN202480039774.7A priority Critical patent/CN121311114A/zh
Priority to AU2024302452A priority patent/AU2024302452A1/en
Priority to KR1020267000542A priority patent/KR20260023011A/ko
Priority to EP24732900.6A priority patent/EP4727359A1/fr
Publication of WO2024256433A1 publication Critical patent/WO2024256433A1/fr
Anticipated expiration legal-status Critical
Priority to CONC2026/0000206A priority patent/CO2026000206A2/es
Ceased legal-status Critical Current

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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
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00—Botany in general
    • A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to novel fungicidal compositions, to their use in agriculture or horticulture for controlling diseases caused by phytopathogens, especially phytopathogenic fungi, and to methods of controlling diseases on useful plants.
  • fungicidal compounds and compositions belonging to various different chemical classes, have and are being developed for use as fungicides in crops of useful plants, crop tolerance and activity against particular phytopathogenic fungi do not always satisfy the needs of agricultural practice in many respects. Therefore, there is a continuing need to find new compounds and compositions having superior biological properties for use in controlling or preventing infestation of plants by phytopathogenic fungi. For example, compounds possessing a greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, increased biodegradability.
  • compositions comprising mixtures of different fungicidal compounds possessing different modes of action can address some of these needs (e.g., by combining fungicides with differing spectrums of activity).
  • fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I): wherein
  • R 1 is selected from hydrogen, Ci-Cs-alkyl, or Cs-Ce-cycloalkyl;
  • R 2 is selected from hydrogen, halogen, Ci-Cs-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl;
  • R 3 is hydrogen
  • R 4 is selected from hydrogen, or Ci-Cs-alkyl
  • R 5 and R 6 are hydrogen
  • R 7 is selected from hydrogen, Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, or C-i-Cs-alkoxycarbonyl;
  • Z 1 is selected from phenyl, or 5- or 6-membered heteroaryl, wherein any of said 5- or 6-membered heteroaryl contains 1 , 2, or 3 heteroatoms individually selected from N, O or S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-Ca-alkyl, Ci-C2-haloalkyl, or C1-C3- alkoxy;
  • X 1 , X 2 and X 3 are independently selected from CH, N or S, with the proviso that one of X 1 , X 2 and X 3 is S; and A 1 , A 2 and A 3 are independently selected from CH, N, 0 or S, with the proviso that at least one of A 1 , A 2 and A 3 is selected from N, O or S, and that no more than one of A 1 , A 2 and A 3 is O or S; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof; and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, is
  • 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).
  • 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. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • 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.
  • Ci-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
  • Cs-Cn-cycloalkyl refers to three (3) to n membered cycloalkyl radical such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Ci-C n -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.
  • Ci-Cn-haloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2- bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, 0 or S.
  • heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
  • controlling refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
  • pest refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain, and timber); and those pests associated with the damage of man-made structures.
  • the term pest encompasses all stages in the life cycle of the pest.
  • the term "effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
  • fungicide means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • an effective amount is readily determined by the skilled person in the art, using known techniques and by observing results obtained under analogous circumstances. In determining the effective amount, a number of factors are considered including, but not limited to the type of plant or derived product to be applied; the pest to be controlled and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.
  • locus as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • 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 symbol ha is the metric unit of area that equals a square with 100 m side (1 hm 2 ) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.
  • composition stands for the various mixtures or combinations of components (A) and (B) (including the above-defined embodiments), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the components (A) and (B) is not essential for working the present invention.
  • room temperature or “RT” or “rt” or “ambient temperature” refer to a temperature of about 15° C to about 35° C.
  • rt can refer to a temperature of about 20° C to about 30° C.
  • R 1 is selected from hydrogen, Ci-Cs-alkyl, or Cs-Cs-cycloalkyl.
  • R 1 is Ci-Cs-alkyl, or Cs-Ce-cycloalkyl. More preferably R 1 is methyl, ethyl, or cyclopropyl. Even more preferably R 1 is methyl.
  • R 2 is selected from hydrogen, halogen, Ci-Cs-alkyl, Ci-C4-haloalkyl, or Cs-Ce-cycloalkyl.
  • R 2 is hydrogen, halogen, or Ci-Cs-alkyl. More preferably R 2 is hydrogen, or C1-C3- alkyl. Even more preferably R 2 is hydrogen, methyl, or ethyl. Still even more preferably R 2 is hydrogen, or methyl.
  • R 3 is hydrogen
  • R 4 is selected from hydrogen, or Ci-Cs-alkyl.
  • R 4 is hydrogen, methyl, or ethyl. More preferably R 4 is hydrogen, or methyl.
  • R 7 is selected from hydrogen, Ci-Cs-alkyl, Ci-Cs-alkylcarbonyl, or C1-C3- alkoxycarbonyl.
  • R 7 is hydrogen, Ci-Cs-alkyl, or Ci-Cs-alkoxycarbonyl. More preferably R 7 is hydrogen, or Ci-Cs-alkyl. Even more preferably R 7 is hydrogen, or methyl.
  • Z 1 is selected from phenyl, or 5- or 6-membered heteroaryl, wherein any of said 5- or 6-membered heteroaryl contains 1 , 2, or 3 heteroatoms individually selected from N, O or S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 5- or 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-Cs-alkyl, Ci-C2-haloalkyl, or Ci-Ca-alkoxy.
  • Z 1 is phenyl, or 6-membered heteroaryl, wherein any of said 6-membered heteroaryl contains 1 , or 2 heteroatoms individually selected from N, O or S, with the proviso that only one is selected from O or S; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-Cs-alkyl, Ci-Cz-alkoxy, or Ci-Cz-haloalkyl.
  • Z 1 is phenyl, or 6-membered heteroaryl, wherein any of said 6-membered heteroaryl contains one heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from halogen, Ci-Cs-alkyl, Ci-C2-alkoxy, or Ci-C2-haloalkyl.
  • Z 1 is phenyl, or 6- membered heteroaryl, wherein any of said 6-membered heteroaryl contains one heteroatom selected from N; and wherein any of said phenyl and 6-membered heteroaryl are unsubstituted or substituted by 1 , 2 or 3 substituents independently selected from chlorine, fluorine, methyl, methoxy, or trifluoromethyl.
  • Z 1 is selected from phenyl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6- trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2- pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-fluoro-2- methoxy-phenyl.
  • Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2- fluorophenyl, 4-fluorophenyl or phenyl. Most preferably Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2- pyridyl, 2-fluorophenyl, or 4-fluorophenyl.
  • X 1 , X 2 and X 3 are independently selected CH, N or S, with the proviso that nor more than one of X 1 , X 2 and X 3 is S.
  • X 1 is CH or S
  • X 2 is C or N
  • X 3 is CH, N or S, with the proviso that no more than one of X 1 , X 2 and X 3 is S.
  • More preferably X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N.
  • a 1 , A 2 and A 3 are independently selected from CH, N, O or S, with the proviso that at least one of A 1 , A 2 and A 3 is selected from N, O or S, and that no more than one of A 1 , A 2 and A 3 is O or S.
  • the compound of formula (I) may be a compound of formula (l-A): wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 , X 3 and Z 1 are as defined for the compounds of formula (I) according to the present invention, and A is selected from A1 to A10;
  • the arrow denotes the bond to the Z 1 group.
  • the present invention accordingly, makes available a compound of formula (I) having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 , X 3 , A 1 , A 2 , A 3 and Z 1 as defined above in all combinations I each permutation.
  • the term “compound of formula (I)” refers to component A.
  • the present invention accordingly, makes available a compound of formula (l-A) having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 , X 3 , A and Z 1 as defined above in all combinations / each permutation.
  • the term “compound of formula (l-A)” refers to component A.
  • component (A) is a compound of formula (I), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and A 1 , A 2 and A 3 are independently selected from CH, N,
  • component (A) is a compound of formula (l-A): wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and A is selected from A1 , A2, A3, A4, A
  • the arrow denotes the bond to the Z 1 group; or salt or N-oxide thereof.
  • component (A) is a compound of formula (l-A), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or
  • Ci-Cs-alkyl is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl;
  • X 1 is CH, X 2 is CH, and X 3 is S; or
  • X 1 is S, X 2 is CH, and X 3 is CH; or
  • X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and
  • A is selected from A2, A9, or A10;
  • the arrow denotes the bond to the Z 1 group; or salt or N-oxide thereof.
  • component (A) is a compound selected from [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol- 2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (X.01 ); [5- (2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02); [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1- methylpyrazol-4-yl)
  • component (A) is a compound selected from [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol- 2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (X.01 ); [5- (2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02); [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1- methylpyrazol-4-yl)
  • component (B) is a compound selected from 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, metharylpicoxamid, ametoctradin, fluazinam, fent
  • 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, fenpicoxamid, florylpicoxamid, metharylpicoxamid, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, tetraconazole, prothioconazole, mefentri
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide, N-[(1 S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, 2-[cyano-(2,6-difluoro-
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl.
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl.
  • component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja saponaria Molina (commercially available as BOTRISTOP®), or Aureobasidin A.
  • TAEGRO® i.e, Bacillus amyloliquefaciens strain FZB24
  • melaluca alternifolia oil an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)
  • Reynoutria sachalinensis extract commercially available as REGALIA®
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), or Aureobasidin A.
  • TAEGRO® i.e, Bacillus amyloliquefaciens strain FZB24
  • melaluca alternifolia oil an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofung
  • the component (B) compounds are referred to herein and above by a so-called "ISO common name” or another "common name” being used in individual cases or a trademark name.
  • the component (B) compounds are known and are commercially available and/or can be prepared using procedures known in the art and/or procedures reported in the literature.
  • TIMOREX GoldTM or “Timorex Gold®” as used herein refers to melaluca alternifolia oil, which is an extract of the tea tree plant Melaluca alternifolia, commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide.
  • TAEGROTM or TAEGRO® refers to a microorganism-based fungicide formulated as a wettable powder containing 130 g/kg Bacillus amyloliquefaciens strain FZB24, having Accession No. DSM 10271 (13% w/w minimum of 1x10 exp 13 CFU/kg), commercially available as TAEGRO®.
  • BOTRISTOP® refers to a broad spectrum biofungicide, a plant extract based on the extract of Quillaja saponaria Molina
  • REGALIA® refers to a biofungicide, a plant extract based on the extract of Reynoutria sachalinensis extract (commercially available as REGALIA®)
  • Aureobasidin A is an antifungal cyclic depsipeptide antibiotic produced by Aureobasidium pullulans. See, for instance: Takesako et al., J. Antibiot. 1991 , 44, 919-924.
  • WO 2018/102345 discloses the use of Aureobasidin A as an agricultural fungicide to treat, 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), or to a compound of formula (l-A).
  • Embodiments according to the invention are provided as set out below.
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S,
  • component (A) is a compound of
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (I), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl;
  • X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and A 1 , A 2 and A 3 are independently selected from CH, N, O or S, with the proviso that at least one of A 1 , A 2 and A 3 is selected from N, O or S, and that no more than one of A 1 , A 2 and A 3 is O or S; or salt or N-oxide thereof; and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl.
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (l-A): wherein R 1 is selected from Ci-Cs-alkyl, or Ca-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S,
  • component (B) is a compound selected from 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,
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (l-A), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl;
  • X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and A is selected from A1 , A2, A3, A4, A9, or A10;
  • 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, fenpicoxamid, florylpicoxamid, metharylpicoxamid, fluazinam, fenpropidin, fenhexamid, cyproconazole
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A)) is a compound of formula (l-A), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl;
  • X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and A is selected from A1, A2, A3, A4, A9, or A10;
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide, N-[(1 S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, 2-[cyano-(2,6-difluoro- 4-pyridyl)amino]
  • a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a compound of formula (l-A), wherein R 1 is selected from Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; R 2 is selected from hydrogen, or Ci-Cs-alkyl; R 3 is hydrogen; R 4 is selected from hydrogen, or methyl; R 5 and R 6 are hydrogen; R 7 is selected from hydrogen, or Ci-Cs-alkyl; Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl;
  • X 1 is CH, X 2 is CH, and X 3 is S; or X 1 is S, X 2 is CH, and X 3 is CH; or X 1 is CH, X 2 is N, and X 3 is S; or X 1 is S, X 2 is N, and X 3 is N; and A is selected from A1 , A2, A3, A4, A9, or A10;
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl.
  • 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), (l-A), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in table X according to the present invention): pydiflumetofen + AX, benzovindiflupyr + AX, bixafen + AX, fluxapyroxad + AX, isopyrazam + AX, penflufen + AX, penthiopyrad + AX, sedaxane + AX, boscalid + AX, fluopyram + AX, thifluzamide + AX, pyraziflumid + AX, isoflucypram
  • 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), (l-A), or compounds selected from (X.01 ), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in table X according to the present invention): pydiflumetofen + AX, benzovindiflupyr + AX, bixafen + AX, fluxapyroxad + AX, isopyrazam + AX, penflufen + AX, penthiopyrad + AX, sedaxane + AX, boscalid + AX, fluopyram + AX, thifluzamide + AX, pyraziflumid + 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), (l-A), or compounds selected from (X.01 ), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)) + AX, Reynoutria sachalinensis extract (commercially available as REGALIA®) + AX,
  • TAEGRO® i.e, Bacillus amyloliquefacien
  • 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), (l-A), or compounds selected from (X.01 ), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)) + AX, Reynoutria sachalinensis extract (commercially available as REGALIA®) + AX,
  • TAEGRO® i.e, Bacillus amyloliquefacien
  • 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), (l-A), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11 ), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)) + AX, Reynoutria sachalinensis extract (commercially available as REGALIA®) + 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), (l-A), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11 ), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)) + AX, Reynoutria sachalinensis extract (commercially available as REGALIA®) + A
  • 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), (l-A), or compounds selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11 ), listed in table X according to the present invention): TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24) + AX, melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)) + AX, Reynoutria sachalinensis extract (commercially available as REGALIA®) +
  • TAEGRO® i.e, Bacillus amyloliquefaciens strain F
  • component (A) is compound no. X.01 : [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereoftautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as
  • component (A) is compound no. X.02: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereoftautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALI)
  • component (A) is compound no. X.03: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4l-l-thieno[2,3- c]pyridin-6-yl]methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereoftautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REG
  • TAEGRO®
  • component (A) is compound no. X.04: [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract
  • TAEGRO®
  • component (A) is compound no. X.05: [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja sapon
  • TAEGRO®
  • component (A) is compound no. X.06: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja saponaria Molina (
  • component (A) is compound no. X.07: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazol-4-yl)-4,6-dihydrothieno[3,2-c]pyridin-5- yl]methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja saponaria Molina (commercial
  • TAEGRO®
  • component (A) is compound no. X.08: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6- yl]methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja saponaria
  • component (A) is compound no. X.09: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5- yl]methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja sap
  • TAEGRO®
  • component (A) is compound no. X.10: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl]methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the extract of Quillaja saponaria
  • component (A) is compound no. X.11 : [5-(2,4- difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H-thieno[3,2- c]pyridin-5-yl]methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO® (i.e, Bacillus amyloliquefaciens strain FZB24), melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broadspectrum botanical biofungicide)), Reynoutria sachalinensis extract (commercially available as REGALIA®), a plant extract based on the
  • component (A) is compound no. X.01 : [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.01 ), 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, pyra
  • component (A) is compound no. X.02: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02), 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.03: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3- c]pyridin-6-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, trif
  • component (A) is compound no. X.04: [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.04), 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, pyraclostro
  • component (A) is compound no. X.05: [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.05), 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, az
  • component (A) is compound no. X.06: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.06), 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.07: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazol-4-yl)-4,6-dihydrothieno[3,2-c]pyridin-5- yl]methanone (X.07), 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, met
  • component (A) is compound no. X.08: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6- yl]methanone (X.08), 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.09: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5- yl]methanone (X.09), 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, a
  • component (A) is compound no. X.10: [5-(2,4- difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl]methanone (X.10), 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.1 1 : [5-(2,4- difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H-thieno[3,2- c]pyridin-5-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,
  • component (A) is compound no. X.01 : [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.01 ), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-but
  • component (A) is compound no. X.02: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8
  • component (A) is compound no. X.03: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1- benzyl-1 ,3-dimethyl-butyl]
  • component (A) is compound no. X.04: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1- benzyl-1 ,3-dimethyl-
  • component (A) is compound no. X.05: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-
  • component (A) is compound no. X.06: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,
  • component (A) is compound no. X.07: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazol-4-yl)-4,6-dihydrothieno[3,2-c]pyridin-5- yl]methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N
  • component (A) is compound no. X.08: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6- yl]methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-car
  • component (A) is compound no. X.09: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5- yl]methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3
  • component (A) is compound no. X.10: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5- yl]methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-
  • component (A) is compound no. X.11 : [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H- thieno[3,2-c]pyridin-5-yl]methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8
  • component (A) is compound no. X.01 : [5-(2,4- difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.01 ), 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,
  • component (A) is compound no. X.02: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02), 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, pyraclostro
  • component (A) is compound no. X.03: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-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
  • component (A) is compound no. X.04: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.04), 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, pyr
  • component (A) is compound no. X.05: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.05), 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.06: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.06), 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.07: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazol-4-yl)-4,6-dihydrothieno[3,2-c]pyridin-5- yl]methanone (X.07), 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, azoxystro
  • X.08 [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6- yl]methanone (X.08), 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, fenpic
  • component (A) is compound no. X.09: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5- yl]methanone (X.09), 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.10: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5- yl]methanone (X.10), 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.11 : [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H- thieno[3,2-c]pyridin-5-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, pyraclostro
  • component (A) is compound no. X.01 : [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7- dihydrothieno[2,3-c]pyridin-6-yl]methanone (X.01 ), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1 - benzyl-1 , 3-dimethyl
  • component (A) is compound no. X.02: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7- dihydrothieno[2,3-c]pyridin-6-yl]methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1- benzyl-1 ,3-dimethyl-butyl]
  • component (A) is compound no. X.03: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1- benzyl-1 ,3-dimethyl-butyl
  • component (A) is compound no. X.04: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro- 4H-thieno[2,3-c]pyridin-6-yl]methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1- benzyl-1 ,3-dimethyl
  • component (A) is compound no. X.05: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3
  • component (A) is compound no. X.06: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin- 6-yl]methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,
  • component (A) is compound no. X.07: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazol-4-yl)-4,6-dihydrothieno[3,2-c]pyridin-
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-
  • component (A) is compound no. X.08: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-
  • component (A) is compound no. X.09: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5- c]pyridin-5-yl]methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline
  • component (A) is compound no. X.10: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5- yl]methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]-8-fluoro-quinoline-3
  • component (A) is compound no. X.11 : [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H- thieno[3,2-c]pyridin-5-yl]methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, acibenzolar-S-methyl, N-[(1 R)-1-benzyl-1 ,3- dimethyl-butyl]
  • component (A) is compound no. X.01 : [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7- dihydrothieno[2,3-c]pyridin-6-yl]methanone (X.01 ), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1
  • component (A) is compound no. X.02: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1
  • component (A) is compound no. X.03: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1
  • component (A) is compound no. X.04: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H- thieno[2,3-c]pyridin-6-yl]methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:
  • component (A) is compound no. X.05: [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3- c]pyridin-6-yl]methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1 :10 (or even more preferably
  • component (A) is compound no. X.06: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6- yl]methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1 :10 (or even more preferably, 5:1
  • component (A) is compound no. X.07: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazol-4-yl)-4,6-dihydrothieno[3,2-c]pyridin-5- yl]methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1 :10 (or even more preferably, 5:1 to
  • component (A) is compound no. X.08: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6- yl]methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof
  • component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1 :10 (or even more preferably,
  • component (A) is compound no. X.09: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5- yl]methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1 :10 (or even more
  • component (A) is compound no. X.10: [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5- yl]methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1 :10 (or even more preferably
  • component (A) is compound no. X.11 : [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H- thieno[3,2-c]pyridin-5-yl]methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from pydiflumetofen, benzovindiflupyr, azoxystrobin, florylpicoxamid, difenoconazole, prothioconazole, mefentrifluconazole, cyprodinil, fludioxonil, or acibenzolar-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1
  • 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)-l ,2,4-oxadiazol-3-yl]phen
  • 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)-l ,2,4-oxadiazol-3-yl]
  • 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), or (X.11), 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, sedaxane, boscalid, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, isofetamid, fluind
  • 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), or (X.11 ), 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, fluopyram, thifluzamide, pyraziflumid, isoflucypram, inpyrfluxam, fluindapyr, cyclobutrifluram, pyra
  • 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), or (X.11), 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, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, me
  • 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), or (X.11 ), 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, florylpicoxamid, metarylpicoxamid, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazo
  • the component (C) compounds are referred to herein and above by a so-called "ISO common name” or another "common name” being used in individual cases or a trademark name.
  • the component (C) compounds are known and are commercially available and/or can be prepared using procedures known in the art and/or procedures reported in the literature such as indicated above.
  • Components (B) and (C) in combination with component (A) may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the fungicidal compositions may be effective against a wider spectrum of fungal pathogens that can be combated with the individual active ingredients when used solely.
  • 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, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750.
  • Those mixing ratios are understood to include, on the one hand, ratios by weight and also,
  • 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 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. More specifically, compounds of formula (I) may be prepared from compounds of formula (III) or a salt thereof, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I) by reaction with a compound of formula (V), wherein A 1 , A 2 , A 3 and Z 1 are as defined above for the compound of formula (I). This reaction is shown in Scheme 1 .
  • compounds of formula (Va), where X° is halogen are formed by treatment of compounds of formula (V) 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 from 20°C to 100°C, preferably 25°C.
  • DMF N,N-dimethylformamide
  • DCM dichloromethane
  • THF tetrahydrofuran
  • compounds of formula (I) may be prepared by treatment of compounds of formula (V) with dicyclohexyl carbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl)carbodiimide (EDC) or 1 -[bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5- b]pyridinium 3-oxide hexafluorophosphate (HATU) to give the activated compound of formula (Va), wherein X° is X 01 , X 02 orX 03 as set forth below, in an inert solvent, e.g.
  • a compound of formula (V) can also be activated by reaction with a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (Va), wherein X° is X 04 as set forth below, as described for example in Synthesis 2013, 45, 1569. Further reaction with the compound of formula (III) or a salt thereof leads to compounds of formula (I).
  • a coupling reagent such as propanephosphonic acid anhydride (T3P) to provide compounds of formula (Va), wherein X° is X 04 as set forth below, as described for example in Synthesis 2013, 45, 1569.
  • compounds of formula (Illa), wherein R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), may be prepared from compounds of formula (IVa), wherein R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), by treatment with a reducing agent such as NaBHsCN and an acid, for example hydrochloric acid, or acetic acid in a protic solvent such as methanol or ethanol and the like.
  • a reducing agent such as NaBHsCN
  • an acid for example hydrochloric acid, or acetic acid in a protic solvent such as methanol or ethanol and the like.
  • compounds of formula (Illa) may be prepared from compounds of formula (IV) by reduction with hydrogen in the presence of a suitable metal catalyst, such as Rd, Ir, Rh with a suitable ligand, e.g. diphosphine [1 ,2-bis(diphenylphosphino)ethane (dppe), 1 ,3-bis(diphenylphosphino)propane (dppp) or 1 ,4-bis(diphenylphosphino)butane (dppb)].
  • a suitable metal catalyst such as Rd, Ir, Rh
  • a suitable ligand e.g. diphosphine [1 ,2-bis(diphenylphosphino)ethane (dppe), 1 ,3-bis(diphenylphosphino)propane (dppp) or 1 ,4-bis(diphenylphosphino)butane (dppb)].
  • compounds of formula (VII) may be prepared by treatment with an anhydride of formula (R°C0)20, wherein R° is Ci-C4-alkyl, in an inert solvent such as DCM, THF or 2-methyl-THF, optionally in the presence of a base, such as triethylamine or dimethylaminopyridine at temperatures between 0°Cand 60°C.
  • R° is Ci-C4-alkyl
  • a base for example an alkyl metal base, such as tert-butyl lithium, and an additive such as N,N,N',N'- tetramethylethylendiamine (TMEDA) at low temperature, for example -78°C to room temperature, in an inert polar solvent such as THF or 2-methyl-THF.
  • a base for example an alkyl metal base, such as tert-butyl lithium
  • an additive such as N,N,N',N'- tetramethylethylendiamine (TMEDA)
  • THF N,N,N',N'- tetramethylethylendiamine
  • Compounds of formula (Vila) may be converted to compounds of formula (Illa), wherein R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), by methods known to a person skilled in the art.
  • compounds of formula (Vila), wherein R° is tert-butyl may be treated with an organic or inorganic acid such as trifluoroacetic acid or HCI to give compounds of formula (Illa). This reaction is shown in Scheme 4.
  • Compounds of formula (IVa), wherein R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), may be prepared by reacting compounds of formula (IX), wherein R 1 , R 2 and R 3 are as defined above for the compound of formula (I) and X° is halogen, preferably chlorine, bromine or iodine, with compounds of formula (VIII), wherein R 5 is hydrogen or methyl and R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), by means of a C-C bond formation reaction typically under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions (Scheme 5).
  • Suzuki-Miyaura cross-coupling reactions between compounds of formula (VIII) and compound of formula (IX) are well known to a person skilled in the art and are usually carried out in the presence of a palladium catalyst, such as tetrakls(triphenylphosphine)-palladium(0) or [1 ,1'-bis(diphenylphosphino)ferrocene]palladium(ll) dichloride dichloromethane complex, and a base, such as sodium or potassium carbonate, in a solvent, such as N,N-dimethylformamide, dioxane or dioxane-water mixtures, at temperatures between room temperature and 160°C, optionally under microwave heating conditions, and preferably under inert atmosphere.
  • a palladium catalyst such as tetrakls(triphenylphosphine)-palladium(0) or [1 ,1'-bis(diphenylphosphino)ferrocene]palladium(ll) dich
  • a further cross-coupling chemistry namely C-H activation, can also be used to prepare compounds of formula (IVa), wherein R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I). This reaction is shown in Scheme 7.
  • compounds of formula (III) may be prepared from compounds of formula (XIII) (Scheme 8).
  • compounds of formula (III) may be prepared by a person skilled in the art by a carbamate deprotection reaction of compounds of formula (XIII), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I) and R 01 may be a member of a common carbamate protecting group substituent, for example methyl, terf-butyl, allyl, 2,2,2-trichloroethyl or benzyl.
  • R 01 is methyl
  • a suitable solvent such as dichloromethane and a suitable reagent such as iodotrimethylsilane may be employed to afford the product upon heating at temperatures between rt and 200°C, preferably between 20°C and the boiling point of the reaction mixture as described, for example, in J. Am. Chem. Soc. 1992, 114, 5959.
  • the compounds of formula (III) thus obtained are converted to compounds of formula (I) as shown in Scheme 1 .
  • Grignard reagents R 5 MgBr or R 6 MgBr, wherein R 5 and R 6 are as defined above for the compound of formula (I) may be added as nucleophiles to compounds of formula (XVII), sequentially or simultaneously, to allow more highly substituted amines of formula (XVI) to be prepared.
  • Such Grignard additions to nitriles are carried out in an inert solvent such as diethyl ether, tert-butylmethyl ether, and cyclopentyl methyl ether in the presence of a Lewis acid such as Ti(O-'Pr)4 (see Synlett 2007, (4), 652-654). This reaction is shown in Scheme 11.
  • compounds of formula (XVII), wherein R 1 , R 2 , R 3 , R 4 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I) and R 4 is different from hydrogen may be prepared by a person skilled in the art by deprotonation of compound of formula (XVIIa), wherein R 4 is hydrogen and R 1 , R 2 , R 3 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), using a strong base such as n-butyl lithium or sodium hydride at cryogenic temperatures in an inert solvent such as THF, followed by addition of a suitable alkylating agent R 4 -X, wherein X is halogen, for example iodomethane.
  • Compounds of formula (XVIIa), wherein R 4 is hydrogen and R 1 , R 2 , R 3 , X 1 , X 2 and X 3 are as defined above for the compound of formula (I), may be prepared from alcohols of formula (XVIII) by treatment with cyanotri methylsilane (TMSCN) in the presence of a base such as lithium carbonate in a nonpolar solvent such as dichloromethane at temperatures between 0°C and the boiling point of the reaction mixture.
  • TMSCN cyanotri methylsilane
  • a compound of formula (I) as defined in any of the embodiments of the present invention can be converted in a manner known per se into another compound as defined in any of the embodiments of the present invention by replacing one or more substituents of the starting compound in the customary manner by (an)other substituent(s) according to the invention.
  • compounds of formula (I) can be further transformed to further derivatives of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C-C-bond forming reactions in the presence of metal catalysts, heteroatom-carbon bond formation in the presence of metal catalysts, oxidation, and reduction.
  • Salts of compounds of formula (I) may be prepared in a manner known perse.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I), which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, or diastereomer mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule, the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomeric mixtures or racemic mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomeric mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns.
  • SFC supercritical fluid chromatography
  • Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention.
  • the compounds of formula (I) (also shown for compounds of formula (l-A)) of the present invention exhibit two asymmetric carbon atoms, wherein the star (*) indicates the asymmetric carbon atom, such there are four stereoisomers available. These four stereoisomers consist of two sets of enantiomers.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • composition according to the invention is effective against harmful microorganisms, such as microorganisms, that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.
  • composition of the invention may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blastocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.
  • the composition is effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
  • pathogens may include: Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimurrr, diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmo
  • Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bi
  • Gerlachia nivale Gibberella fujikuroi
  • Gibberella zeae Gibberella zeae
  • Gliocladium spp. Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae;
  • Basidiomycetes including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.
  • Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae
  • rusts for example those caused by Pucciniales such as Cerotelium fici, Chr
  • Puccinia striiformis f.sp. Secalis Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-virginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani,
  • Blastocladiomycetes such as Physoderma maydis
  • Mucoromycetes such as Choanephora cucurbitarum; Mucor spp.; Rhizopus arrhizus; as well as diseases caused by other species and genera closely related to those listed above.
  • 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 particularly 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 imperfect!
  • Ascomycetes e.g., Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula
  • Basidiomycetes e.g., the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia
  • Deuteromycetes 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, Pseudosclerospora, Plasmopara).
  • 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).
  • 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.
  • 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 toxinproducing bacteria. Examples of toxins which can be expressed include S-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
  • Vip vegetative insecticidal proteins
  • insecticidal proteins of bacteria colonising nematodes and toxins produced by scorpions, arachnids, wasps and fungi.
  • An example of a crop that has been modified to express 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).
  • 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 CrylA(b) toxin); YieldGard Rootworm ® (maize variety that expresses a Cryl IIB(b1 ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryll IB(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton
  • 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 5-endotoxins, e.g., CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae or insecticidal proteins from Bacillus thuringiensis, such as 5-endotoxins, e.g., CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid- UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • 5-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, W002/15701 ).
  • Truncated toxins for example a truncated Cry1 Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see W003/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plant tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects but are especially commonly found in the beetles (Coleoptera), twowinged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard ® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • composition comprising a mixture of components (A) and (B) and any fungicidal solutions used to control phytopathogenic fungi such as Absidia corymblfera, 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.
  • any fungicidal solutions used to control phytopathogenic fungi such as Absidia corymblfera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidul
  • B. obtusa Botrytis spp. comprising B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa gram inis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
  • fungicidal-resistant strains in any of the species as outlined above have been reported in the scientific literature, with strains resistant to one or more fungicides from at least one of the following fungicidal modes of action classes: quinone-outside-inhibitors (Qol), quinone-inside-inhibitors (Qil), succinate dehydrogenase inhibitors (SDHI) and sterol demethylation-inhibitors (DMI).
  • quinone-outside-inhibitors Qol
  • quinone-inside-inhibitors Qil
  • SDHI succinate dehydrogenase inhibitors
  • DMI sterol demethylation-inhibitors
  • Such fungicidal-resistant strains may contain:
  • Gisi et al. Pest Manag Sei. 2000, 56, 833-841 , Lucas, Pestic Outlook 2003, 14(6), 268-70, Fraaije et al., Phytopathol 2005, 95(8), 933-41 , Sierotzki et al., Pest Manag. Sci. 2007, 63(3), 225-233 (2007), Semar et al., J. Plant Dis. Prot. 2007, (3), 117-119; and Pasche et al., J. Crop Prot. 2008, 27(3-5), 427-435 (2008).
  • sdhB N225T, N225I, R265P, T268I, T268A.
  • sdhC T79N, T79I, W80S, W80A, A84F, N86S, N86A, P127A, R151 M/S/T/G, R151 S, R151T, H152R/Y, V166M, T168R.
  • sdhD I50F, M114V, D129G, T20P+K186R;
  • sdhB S66P, N235I, H277Y.
  • sdhC K49E, R64K, N75S, G79R, H134R, S135R.
  • sdhD D124E, H134R, G138V, D145G;
  • Ramularia collo-cypni In sdhB: N224T, T267I. In sdhC: N87S, G91 R, H146R/L, G171 D, H153R;
  • Phakopsera pachyrhizi C-I86F
  • Sclerotinia sclerotiorum In sdhB: H273Y. In sdhC: G91 R, H146R. In sdhD: T108K, H132R, G150R.
  • Major source of information is www.frac.info, Cools et al., Plant Pathol. 2013, 62: 36-42 and Schmitz HK et al., Pest Manag. Sci. 2014, 70: 378-388.
  • 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 (Qol), quinone-inside-inhibitors (Qil), succinate dehydrogenase inhibitors (SDHI) and sterol demethylation-inhibitors (DMI).
  • quinone-outside-inhibitors Qol
  • quinone-inside-inhibitors Qil
  • SDHI succinate dehydrogenase inhibitors
  • DMI 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- chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, ethirimol, 3'-chloro-2-methoxy-N-[(3RS)-t
  • Insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinote
  • Bactericides such as streptomycin
  • Acaricides such as amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
  • 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 of formula (l-A), or compounds selected from (X.01 ), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.9), (X.10), or (X.11) 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-ol + TX; (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX; (E)
  • the mixtures of compounds of formula (I) (selected from compounds of formula (I), (l-A) or compounds selected from (X.01 ), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.9), (X.10), or (X.11), 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, above all in a ratio of 1 :1, or 5:1 , or 5:2, or 5:
  • 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.
  • the order of applying the compounds of formula (I) selected from Table X (above) and the active ingredients as described above is not essential for working the present invention.
  • 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
  • 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
  • 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 not limited to, an increased tolerance and/or resistance 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).
  • 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 e.g., in
  • 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.
  • such improved tolerances may be due to, for example, more efficient uptake, use or retention of water and nutrients.
  • 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.
  • 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 (iii) an
  • 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.
  • land i.e. land which was previously unavailable or sub-optimal for cultivation
  • 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 and/or diseases.
  • pests and/or diseases may be controlled by a pesticidal treatment that is applied prior to, or at the same time as, the method of the present invention.
  • improvements in plant vigour, stress tolerance, quality and/or yield are made in the absence of pest and/or disease pressure.
  • improvements in plant vigour, quality and/or yield are made in the absence, or substantial absence, of abiotic stress.
  • compositions of the present invention may also be used in the field of protecting storage goods against attack of fungi.
  • the term “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, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted.
  • 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.
  • 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.
  • 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.
  • 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 ora water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e g., from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010).
  • Such formulations can either be used directly or
  • the formulations can be prepared e.g., by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances, or combinations thereof.
  • the active ingredients can also be contained in microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g., slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropy
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty
  • 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.
  • 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.
  • compositions comprising a compound of formula (I) described above may show a synergistic effect. This occurs whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.
  • Y % action by active ingredient B) using q ppm of active ingredient.
  • the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is:
  • synergism corresponds to a positive value for the difference of (O-E).
  • 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.
  • composition according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack.
  • composition according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms.
  • compositions according to the invention to be applied will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of fungi to be controlled or the application time.
  • 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 10g 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 10g per kg of seed, are generally sufficient.
  • 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).
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows.
  • LC-MS Method A Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, diode-array detector and ELSD detector.
  • LC-MS Method D Spectra were recorded on a mass spectrometer from Acquity QDA Mass Spectrometer from Waters (HPLC: UPLC 'H' class) equipped with an electrospray source (Polarity: positive and negative ions (Ionisation method: Electrospray (ESI), Polarity: Positive and Negative Polarity Switch); Scan Type: Full Scan; Capillary (kV): 0.8; Cone Voltage: 25.00 V; Source Temperature: 120°C; Desolvation Gas Flow: 1000 L/Hr; Desolvation Temperature: 600°C; Gas Flow @ Cone: 50 L/Hr; Mass range: 1 10 to 850 Da; PDA Wavelength range: 230 to 400 nm.
  • 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 to 8 of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % Kaolin 65 % 40 % -
  • 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 to 5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is 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.
  • 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 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo-emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • EG
  • T3P propanephosphonic acid anhydride also called 2,4,6-tripropyl-1 , 3, 5, 2,4,6- trioxatriphosphorinane-2,4,6-trioxide
  • the compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.
  • Mp means melting point in °C. Free radicals represent methyl groups.
  • 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400MHz spectrometer (or 600MHz as indicated), chemical shifts are given in ppm relevant to a TMS ( 1 H) and CFCI3 ( 19 F) standard. Spectra measured in deuterated solvents as indicated. Either one of the LC-MS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) + or (M-H)'.
  • Syn- and anti-isomers could be distinguished using high field NMR techniques such as ROESY 2D NMR.
  • high field NMR techniques such as ROESY 2D NMR.
  • Example P1 Preparation of f5-(2,4-difluorophenyl)isoxazol-3-yl1-frac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4- yl)-5,7-dihvdro-4H-thienof2,3-clpyridin-6-yl1methanone (compound X.03, Table P)
  • Step D Preparation of N-[2-(1-methyloyrazol-4-yl)-2-(3-thienyl)ethyl1acetamide
  • Step E Preparation of 7-methyl-4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahvdrothieno[2,3-c]pyridine and 4-methyl- 7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahvdrothienor3,4-clpyridine
  • Step F Preparation of r5-(2,4-difluorophenyl)isoxazol-3-yl1-rrac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)- 5,7-dihvdro-4H-thienor2,3-c]pyridin-6-yl1methanone (compound X.03, Table P).
  • Example P2 Preparation of r5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl1-[rac-(4R,7R)-7-methyl-4-(1- methylpyrazol-4-yl)-5,7-dihvdro-4H-thieno[2,3-c]pyridin-6-yl1methanone and (5-(2,4-difluorophenyl)-1 ,3,4- thiadiazol-2-yl1-rrac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihvdro-4H-thienor2,3-clpyridin-6- yllmethanone (compound X.04, Table P)
  • Example P3 Preparation of [5-(2,4-difluorophenyl)-1 ,3,4-thiadiazol-2-yl1-f(4S,7R)-7-methyl-4-(1- methylpyrazol-4-yl)-5,7-dihvdro-4H-thieno[2,3-c]pyridin-6-yllmethanone and 5-(2,4-difluorophenyl)-1 ,3,4- thiadiazol-2-yl1-r(4R.7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5.7-dihvdro-4H-thienor2.3-c]pyridin-6- yllmethanone (compound X.04, Table P)
  • Step B Preparation of 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propan-1-amine
  • reaction mixture was extracted with EtOAc (2X20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to get N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propyl]acetamide.
  • Step D Preparation of 4,7-dimethyl-4-(1-methylpyrazol-4-yl)-6,7-dihvdro-5H-thienor2,3-c]pyridine
  • Solvent A: water; Solvent: B: acetonitrile; modifier: formic acid. Gradient: 40% B - 50% B. Runtime: 10 min) to afford as first eluting product [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-
  • the second eluting product was [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1- methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (compound X.02, Table P).
  • Example P5 Preparation of r5-(2,4-difluorophenyl)isoxazol-3-yl1-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihvdro-4H- thieno(3.2-clpyridin-5-yl1methanone (compound X.10, Table P)
  • Step A Preparation of 7-(1 .5-dimethylpyrazol-4-yl)thieno(3.2-clpyridine
  • the resulting suspension was degassed with argon for several minutes, followed by the addition of terakis(triphenylphosphine) palladium(O) (0.86 g, 0.74 mmol).
  • the vial was sealed, and the reaction mixture was heated to 100°C and stirred for 1 hour under microwave irradiation. After cooling to rt, the reaction mixture was partitioned between a saturated solution of ammonium chloride and EtOAc. The aqueous layer was back extracted twice with EtOAc and the combined organic layers dried over sodium sulfate, filtered and concentrated in vacuo. Purification of the crude material by flash chromatography over silica gel (EtOAc ethanol 0 to 30 %) afforded the title compound as a brown solid.
  • Step B Preparation of 7-(1 ,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahvdrothieno[3,2-c]pyridine
  • Step C Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl1-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihvdro-4H- thienor3.2-clpyridin-5-yl]methanone (compound X.10, Table -T1 )
  • Example P6 This example illustrates the preparation of r5-(2,4-difluorophenyl)isoxazol-3-yl1-r7-(1 ,5- dimethylpyrazol-4-yl)-6,7-dihvdro-4H-thiadiazolo[4,5-clDyridin-5-yl1methanone (compound X.09, Table P)
  • Step E Preparation of 7-(1 ,5-dimethylpyrazol-4-yl)thiadiazolo[4,5-c]pyridine
  • reaction mass was then diluted with water and extracted twice with EtOAc. The combined organic layers were washed with water, brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was purified by trituration with pentane to afford 7-(1 ,5-dimethylpyrazol-4-yl)thiadiazolo[4,5- c]pyridine.
  • Step F Preparation of 7-(1 ,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahvdrothiadiazolo[4,5-clpyridine
  • Step G Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl1-[7-(1 ,5-dimethylpyrazol-4-yl)-6,7-dihvdro-4H- thiadiazolor4,5-clpyridin-5-yl1methanone (compound X.09, Table P)
  • Example P7 This example illustrates the preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1- methylpyrazol-4-yl)-5,7-dihvdro-4H-isothiazolof5,4-clpyridin-6-yllmethanone (compound X.08, Table P)
  • Step B Preparation of 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehvde
  • Step D Preparation of 4-(1-methylpyrazol-4-yl)isothiazolof5,4-clpyridine
  • a microwave vial was charged with 4-bromoisothiazolo[5,4-c]pyridine (0.17 g, 0.79 mmol), 1-methyl-1 H- pyrazole-4-boronic acid (0.15 g, 1.18 mmol), sodium carbonate (0.25 g, 2.37 mmol), 1 ,4-dioxane (1 .7 mL) and water (1.6 mL).
  • the reaction mixture was degassed with nitrogen for 5.0 minutes, then XPhos-Pd-G2 (0.031 g, 0.039 mmol) was added, and the mixture heated to 120°C for 2 hours under microwave irradiation.
  • Step E Preparation of 4-(1-methylpyrazol-4-yl)-4,5,6.7-tetrahvdroisothiazolof5,4-c]pyridine
  • 4-(1-methylpyrazol-4- yl)isothiazolo[5,4-c]pyridine (0.15 g, 0.69 mmol) and methanol (10.4 mL) to obtain a clear solution.
  • sodium cyanoborohydride (0.45 g, 6.93 mmol
  • Step F Preparation of r5-(2,4-difluorophenyl)isoxazol-3-yll-r4-(1-methylpyrazol-4-yl)-5,7-dihvdro-4H- isothiazolor5,4-c1pyridin-6-yl1methanone (compound X.08, Table P)
  • Example P8 Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-frac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4- methyl-6,7-dihvdro-4H-thienor3,2-clpyridin-5-yl1methanone (Compound X.11 in Table P)
  • 2-bromothiophene 13.0 g, 80.6 mmol
  • THF 250 mL
  • isopropyl magnesium chloride lithium chloride complex (1 .3 mol/L in THF, 62 mL
  • Step B Preparation of 2-(1 ,5-dimethylpyrazol-4-yl)-2-(2-thienyl)acetonitrile
  • Step C Preparation of 2-(1 ,5-dimethylpyrazol-4-yl)-2-(2-thienyl)ethanamine
  • Step C Preparation of methyl N-(2-(1 .5-dimethylpyrazol-4-yl)-2-(2-thienyl)ethyl1carbamate
  • Step D Preparation of methyl rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-6.7-dihydro-4H-thieno[3,2- cloyridine-5-carboxylate
  • Step E Preparation of rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl-4,5,6,7-tetrahydrothieno[3,2- clpyridine lodotrimethylsilane (1.52 mL, 10.8 mmol) was added to a solution of methyl rac-(4S,7S)-7-(1 ,5- dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H-thieno[3,2-c]pyridine-5-carboxylate (1.10 g, 3.6 mmol) in 1 ,2- dichloroethane (18 mL) at 20°C.
  • the resulting solution was warmed to 60°C and stirred for 3h at this 131 temperature.
  • the reaction was then cooled to rt and slowly poured into aqueous sodium bicarbonate solution.
  • the resulting emulsion was extracted with EtOAc, the organic phase was washed with aqueous thiosulfate solution and brine, dried over sodium sulfate, filtrated, and concentrated in vacuo to afford the title compound.
  • Step F Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yll-[rac-(4S,7S)-7-(1 ,5-dimethylpyrazol-4-yl)-4-methyl- 6,7-dihvdro-4H-thieno[3,2-clpyridin-5-yl1methanone (Compound X.11 in Table P)
  • Example B1 Alternaria solani / tomato / leaf disc (early blight)
  • Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus
  • Example B2 Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application.
  • the following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.10, X.11
  • Example B3 Glomerella laqenarium (Colletotrichum laqenarium) / liquid culture (Anthracnose)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3 to 4 days after application.
  • nutrient broth PDB potato dextrose broth
  • the following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11
  • Example B4 Blumeria qraminis f. sp. tritici (Erysiphe qraminis f. sp. tritici) / wheat / leaf disc preventative (Powdery mildew on wheat)
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 to 8 days after application).
  • the following compounds gave at least 80% control of Blumeria graminis f. sp.
  • Example B5 Fusarium culmorum / liquid culture (Head blight)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.03, X.04, X.05, X.10
  • Example B6 Fusarium culmorum / wheat / spikelet preventative (Head blight)
  • Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the spikelets are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated spikelets are incubated at 20°C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 to 8 days after application).
  • the inoculated test leaf disks are incubated at 20°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 to 7 days after application).
  • the following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11
  • Example B8 Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.07, X.08, X.09, X.10, X.11
  • Example B9 Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.03, X.04, X.05, X.06, X.07, X.10, X.11
  • Example B10 Magnaporthe grisea (Pyricularia orvzae) / rice / leaf disc preventative (Rice Blast)
  • Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segments are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 22°C and 80% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 to 7 days after application).
  • the following compounds gave at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.06
  • Example B11 Pyrenophora teres I barley / leaf disc preventative (Net blotch)
  • Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segmens are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 to 7 days after application).
  • Example B12 Sclerotinia sclerotiorum I liquid culture (cottony rot)
  • Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application.
  • the following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.03, X.05, X.06, X.10, X.11
  • Example B13 Mycosphaerella ciraminicola (Septoria tritici) / liquid culture (Septoria blotch)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application.
  • nutrient broth PDB potato dextrose broth
  • the following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.01 , X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11
  • component A or “comp. A” refers to the compound of formula (I).
  • Example M-B2 Glomerella lagenarium svn.
  • Example M-B3 Septaria tritici (leaf blotch):
  • Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically and visually after 72 hrs. The following mixture compositions (A:B) at the reported concentration (in ppm) gave at least 70% disease control in the test system.

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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/EP2024/066165 2023-06-14 2024-06-12 Compositions fongicides Ceased WO2024256433A1 (fr)

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CN202480039774.7A CN121311114A (zh) 2023-06-14 2024-06-12 杀真菌组合物
AU2024302452A AU2024302452A1 (en) 2023-06-14 2024-06-12 Fungicidal compositions
KR1020267000542A KR20260023011A (ko) 2023-06-14 2024-06-12 살진균 조성물
EP24732900.6A EP4727359A1 (fr) 2023-06-14 2024-06-12 Compositions fongicides
CONC2026/0000206A CO2026000206A2 (es) 2023-06-14 2026-01-09 Composiciones fungicidas

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