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WO2024132901A1 - Dérivés microbiocides de pyridazine dihydrooxadiazine - Google Patents

Dérivés microbiocides de pyridazine dihydrooxadiazine Download PDF

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WO2024132901A1
WO2024132901A1 PCT/EP2023/086003 EP2023086003W WO2024132901A1 WO 2024132901 A1 WO2024132901 A1 WO 2024132901A1 EP 2023086003 W EP2023086003 W EP 2023086003W WO 2024132901 A1 WO2024132901 A1 WO 2024132901A1
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methyl
formula
compounds
phenyl
halogen
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Nicolas Germain
Atul Mahajan
Jagadeesh Prathap KILARU
Thomas James Hoffman
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Priority to CN202380086903.3A priority Critical patent/CN120379969A/zh
Publication of WO2024132901A1 publication Critical patent/WO2024132901A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C07D237/16—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • the present invention relates to pyridazine dihydrooxadiazines, as active ingredients, which have microbiocidal activity, and in particular, fungicidal activity.
  • the invention also relates to agrochemical compositions which comprise at least one of the pyridazine 5,6-dihydro-4H-1,2,4-oxadiazine derivatives, to processes of preparation of these compounds and to uses of the pyridazine 5,6-dihydro-4H-1,2,4- oxadiazine derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
  • Many plant protection compounds have been developed to prevent or reduce plant disease caused by micro-organisms, for instance, by fungi.
  • WO 2020/109391 discloses pyridazine (thio)amide derivatives.
  • WO 2020/127780 discloses pyridazine oxadiazine derivatives.
  • the present invention therefore provides, in a first aspect, compounds of formula (I) (I) or an agrochemically acceptable salt, stereoisomer, enantiomer, or N-oxide thereof, wherein: R 1 is phenyl unsubstituted or substituted with: - a single substituent selected from hydroxyl, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C2fluoroalkyl, C1-C4alkoxy, C1-C2fluoroalkoxy, C3-C4alkenyloxy, C3-C4alkenyloxy, C3-C4alkenyloxy, C3-C6cycloalkyl, C3-C6cycloalkyloxy,
  • the present invention also provides a method of preparation of compounds of formula (I) as well as intermediate compounds useful in the preparation of compounds of formula (I). Surprisingly, it has been found that the novel compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
  • a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a compound of formula (I) as a fungicide.
  • the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • the present invention makes available a plant propagation material, such as a seed, comprising, or treated with, or adhered thereto, a compound of formula (I) or a composition comprising such a compound.
  • hydroxyl or “hydroxy” means an -OH group.
  • mercapto means an -SH group.
  • cyano means a -CN group. 82761 – FF 4
  • amino means an -NH2 group.
  • nitro means an -NO2 group.
  • 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.
  • C1-C6alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. C1-C4alkyl should be construed accordingly.
  • C1-C6alkyl examples include, but are not limited to, methyl, ethyl, iso-propyl.
  • C 2 -C 4 alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that may be of either the (E) or (Z) configuration, having two or four carbon atoms, which is attached to the rest of the molecule by a single bond.
  • Examples of C2-C4alkenyl include, but are not limited to, vinyl (ethenyl), prop-1-enyl, allyl (prop-2-enyl).
  • C2-C4alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two or four carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of C2-C4alkynyl include, but are not limited to, prop-1-ynyl and propargyl (prop-2-ynyl).
  • C1-C2fluoroalkyl refers to a C1-C2alkyl radical as generally defined above substituted by one or more fluorine atoms.
  • C1-C2fluoroalkyl examples include, but are not limited to difluoromethyl and trifluoromethyl.
  • C1-C4alkoxy refers to a radical of the formula RaO- where Ra is a C1-C4alkyl radical as generally defined above.
  • Examples of C1-C4alkoxy include, but are not limited to, methoxy, ethoxy, iso-propoxy.
  • C1-C2fluoroalkoxy refers to a C1-C2alkoxy radical as generally defined above substituted by one or more fluorine atoms.
  • C1-C2fluoroalkoxy examples include, but are not limited to difluoromethoxy or trifluoromethoxy.
  • C3-C6cycloalkyl refers to a stable, monocyclic ring radical which is saturated and contains 3 to 6 carbon atoms.
  • C3-C4alkenyloxy refers to a radical of the formula RaO- where Ra is a C4-C4alkenyl radical as generally defined above. Examples of C3-C4alkenyloxy include, but are not limited to allyloxy.
  • C3-C4alkynyloxy refers to a radical of the formula RaO- where Ra is a C3-C4alkynyl radical as generally defined above.
  • Examples of C3-C4alkynyloxy include, but are not limited to propargyloxy
  • C3-C6cycloalkoxy refers to a radical of the formula RaO- where Ra is a C3-C6cycloalkyl radical as generally defined above.
  • Examples of C3-C6cycloalkoxy include, but are not limited to cyclopropoxy.
  • C3-C6cycloalkylC1-C2alkyl refers to a radical of the formula RaO- where Ra is a C3-C6cycloalkylC1-C2alkyl radical as generally defined above.
  • Examples of C3-C6cycloalkyl C1-C2alkyloxy include, but are not limited to cyclopropylmethyl.
  • C3-C6cycloalkylC1-C2alkyloxy refers to a radical of the formula RaO- where Ra is a C3-C6cycloalkylC1-C2alkyl radical as generally defined above.
  • C3-C6cycloalkyl C1-C2alkyloxy examples include, but are not limited to cyclohexylmethoxy.
  • C1-C3alkylsulfanyl refers to a radical of the formula -SRa wherein Ra is a C1- C3alkyl radical as generally defined above.
  • C1-C3alkylsulfonyl refers to a radical of the formula -S(O)2Ra wherein Ra is a C1- C3alkyl radical as generally defined above.
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O and S.
  • heteroaryls include J-1 to J--43 shown in Table J below. The staggered line in heteroaryls J-1 to J-39 represents the point of attachment to the rest of the compound.
  • Preferred heteroaryls include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and thiazolyl; preferably pyridinyl, and thiazolyl.
  • heterocyclyl refers to a 3-, 4-, 5-, and 6-membered saturated monocyclic rings having 1 or 2 heteroatoms independently selected from nitrogen and oxygen. Examples of heterocyclyls include K-1 to K-26 shown in Table K below.
  • heterocyclyls K-1 to K-26 represent the point of attachment to the rest of the compound.
  • Some of the heterocyclyls shown below contain an asymmetric carbon, which means that compounds containing them may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.
  • Preferred heterocyclyls include pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl; preferably pyrrolidinyl, piperazinyl, and tetrahydropyranyl.
  • K K-1 K- K-1 K-2 K-3 K-4 K-5 K-6 K-7 K-8 K-9 K-10 K-11 K-12 K-13 K-14 K-15 K-16 K-17 K-18 K-19 K-20 K-21 K-22 K-23 K-24 82761 – FF 7 K-25 K-26
  • phenyl is optionally substituted with 1 or 2 halo atoms” means phenyl substituted with 1 halo atom and phenyl substituted with 2 halo atoms.
  • the term “optionally substituted” can be used interchangeably with “unsubstituted or substituted”.
  • 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.
  • 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.
  • the presence of one or more possible asymmetric carbon atoms in a compound of Formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of Formula (I).
  • Formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of Formula (I).
  • Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example 82761 – FF 8 acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are un
  • Compounds of Formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower- alkylamine, for example mono-, di- or triethanolamine.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the following lists provide definitions, including preferred definitions, for substituents R 1 , R 2 , and G with reference to the compounds of Formula (I) of the present invention.
  • R 1 is: A. phenyl, pyridine, pyrazine, pyrimidine, or pyridazine, wherein said phenyl, pyridine, pyrazine, pyrimidine, or pyridazine is unsubstituted or substituted with a one or two substituents, for instance a single substituent, independently selected hydroxyl, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1- ynoxy, iso-propoxy, tert-butoxy, propynoxy, NHMe
  • phenyl, pyridine, pyrazine, pyrimidine, or pyridazine wherein said phenyl, pyridine, pyrazine, pyrimidine, or pyridazine is unsubstituted or substituted with a one or two substituents, for instance a single substituent, independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, tert- butoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or C.
  • phenyl, pyridine, pyrazine, pyrimidine or pyridazine wherein said phenyl, pyridine, pyrazine, pyrimidine or pyridazine is unsubstituted or substituted with a one or two substituents, for instance one substituent, independently selected from hydroxyl, chloro, fluoro, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or 82761 – FF 9 D.
  • pyridine, pyrazine, pyrimidine or pyridazine wherein said pyridine, pyrazine, pyrimidine or pyridazine is unsubstituted or substituted with a one or two substituents, for instance one substituent, independently selected from hydroxyl, chloro, fluoro, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or E.
  • phenyl substituted with a one or two substituents for instance one substituent, independently selected from hydroxyl, chloro, fluoro, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or F.
  • R 1 is: A.
  • phenyl unsubstituted or substituted with a 1 or 2 substituents each independently selected from hydroxyl, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, iso-propoxy, tert- butoxy, propynoxy, NHMe, N(Me)2, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or B.
  • substituents each independently selected from hydroxyl, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, iso-propyl,
  • phenyl unsubstituted or substituted with 1 or 2 substituents each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or C.
  • phenyl unsubstituted or substituted with 1 or 2 substituents each independently selected selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or 82761 – FF 10 D.
  • R 1 is: A.
  • a 5- or 6-membered monocyclic heteroaryl ring comprising 1, 2 or 3 heteroatoms which may be the same or different, independently selected from N, O and S, with the proviso that no more than one is O or S; wherein said heteroaryl ring is unsubstituted or substituted with 1 or 2 substituents, each independently selected from hydroxyl, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, iso-propoxy, tert-butoxy, propynoxy, NHMe, N(Me)2, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or B.
  • pyridine, pyrimidine, or pyridazine wherein said pyridine, pyrimidine, or pyridazine, is unsubstituted or substituted with 1 or 2 substituents, independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, tert-butoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or C.
  • substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl
  • pyridine substituted with 1 or 2 substituents each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop- 1-ynoxy, difluoromethoxy, and cyclopropyl; or D. pyridine substituted with a single substituent selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or E. pyridine substituted with a single substituent selected from chloro, cyano, methyl, and cyclopropyl.
  • R 2 is: A. hydrogen, hydroxyl, halogen, mercapto, amino, cyano, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 - C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-fluoroalkoxy, or C3-C4-cycloalkyl; or B.
  • G is G-1: A.
  • phenyl or phenoxy unsubstituted or substituted with 1 or 2 substituents each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or C.
  • phenyl unsubstituted or substituted with 1, 2 or 3 substituents for instance 2 or 3 substituents, each independently selected from chloro, fluoro, bromo, methyl, methoxy, and cyclopropyl; or D.
  • G is G-2: A. pyridine, pyrimidine, pyridazine, pyridine-oxy, pyrimidine-oxy, pyridazine-oxy, wherein said pyridine, pyrimidine, or pyridazine ring is unsubstituted or substituted with 1 or 2 substituents, each independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, tert-butoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, methylsulf
  • pyridine unsubstituted or substituted with 1 or 2 substituents, each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, difluoromethoxy, and cyclopropyl; or C.
  • pyrimidine or pyridazine, wherein said pyrimidine or pyridazine is unsubstituted or substituted with 1 or 2 substituents, each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, prop-2-ynoxy, prop-1-ynoxy, difluoromethoxy, and cyclopropyl; or D. pyridine unsubstituted or substituted with 1 or 2 substituents, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or E.
  • G is G-3: A. chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3- dihydrobenzofuran-3-yl, 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzooxazol-2-yl, benzooxazol-5-yl, benzooxazol-6-yl, benzofuran-2-yl, benzofuran-3-yl, benzofuran-5-yl, benzofuran-6-yl, benzothiophen-2-yl, benzothiophen-3-yl, benzothiophen-5-yl, or be
  • chroman-4-yl isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3- dihydrobenzofuran-3-yl, 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzooxazol-2-yl, benzofuran-2-yl, benzofuran-3-yl, benzothiophen-2-yl, or benzothiophen-3-yl, unsubstituted or substituted with a single substituent selected from chloro, fluoro, cyano, methyl, and methoxy C.
  • chroman-4-yl isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, or 2,3- dihydrobenzofuran-3-yl unsubstituted or substituted with a single substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or D.
  • G is G-4: A.
  • naphthalen-2-yl tetralin-1-yl, tetralin-2-yl, tetralin-6-yl, indan-1-yl, indan-2-yl, or indan-5-yl unsubstituted or substituted with 1 or 2 substituents, for instance a single substituent, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or B.
  • G is A.
  • the compound of the formula (I) may comprise a stereogenic centrre, shown with an asterisk in formula (I*), wherein R 1 , R 2 and G are as defined in the first aspect, each with the corresponding embodiments as described above. 82761 – FF 13
  • the compounds of the present invention may be enantiomers of the compound of Formula (I) as represented by formula (I-1) or formula (I-2): can be prepared by those skilled in the art as shown in the following schemes 1 to 32, wherein G, R 1 and R 2 are as defined above.
  • compounds of formula (I), wherein G and R 1 are as defined for compounds of formula (I) can be obtained by intramolecular cyclization of compounds of formula (II), wherein G and R 1 are as defined for compounds of formula (I), using a chlorinating agent, for example by using POCl3, PCl5, (COCl)2 or SOCl2 in the optional presence of dimethylformamide, preferably at temperatures between 0°C and 80°C, more preferable between 25°C and 60°C, in an appropriate solvent or mixture of solvent (e.g.
  • protective groups include, for instance, tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, p-toluenesulfonyl, phthalimide, or succinimide.
  • Protective groups can be removed using standard techniques; see Greene’s Protective Groups in Organic Synthesis, 4th Ed., Wiley-Interscience.
  • compounds of formula (III) may be obtained under conditions described in the literature for an amide coupling, using an amidation coupling reagent, such as 1-propanephosphonic acid cyclic anhydride (T3P), in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine).
  • an amidation coupling reagent such as 1-propanephosphonic acid cyclic anhydride (T3P)
  • T3P 1-propanephosphonic acid cyclic anhydride
  • a suitable solvent e.g., acetonitrile
  • a base e.g., triethylamine or N,N-diisopropylethylamine
  • compounds of formula (II) may be obtained under conditions described in the literature for an amide coupling, using an amidation coupling reagent, such as 1-propanephosphonic acid cyclic anhydride (T3P), in suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N- diisopropylethylamine).
  • an amidation coupling reagent such as 1-propanephosphonic acid cyclic anhydride (T3P)
  • suitable solvent e.g., acetonitrile
  • a base e.g., triethylamine or N,N- diisopropylethylamine
  • compounds of formula (IX) may be obtained under conditions described in the literature for an amide coupling, using an amidation coupling reagent such as 1-propanephosphonic acid cyclic anhydride (T3P) in suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine).
  • T3P 1-propanephosphonic acid cyclic anhydride
  • suitable solvent e.g., acetonitrile
  • a base e.g., triethylamine or N,N-diisopropylethylamine
  • compounds of formula (X), wherein G is as defined for compounds of formula (I), and X 3 is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol), may also be obtained by an amide coupling transformation with compounds of formula (XI), wherein X 3 is as defined for compounds of formula (X), and amine compounds of formula (VI), wherein G is as defined for compounds of formula (I), by activating the carboxylic acid function of the compounds of formula (XI), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCl)2 or SOCl2, prior to treatment with the compounds of formula (VI), preferably in a suitable solvent (e.g., N-methylpyrrolidone dimethylacetamide, dichloromethane or tetrahydrofuran
  • a suitable solvent e.g., N
  • compounds of formula (X) may be obtained under conditions described in the literature for an amide coupling, using an amidation coupling reagent, such as 1-propanephosphonic acid cyclic anhydride (T3P), in suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N- diisopropylethylamine).
  • an amidation coupling reagent such as 1-propanephosphonic acid cyclic anhydride (T3P)
  • suitable solvent e.g., acetonitrile
  • a base e.g., triethylamine or N,N- diisopropylethylamine
  • the subsequent cyclization may be achieved using an acid, typically acetic acid at temperatures between 20°C and 120°C, preferably between 80°C and 120°C.
  • an acid typically acetic acid at temperatures between 20°C and 120°C, preferably between 80°C and 120°C.
  • Scheme 13 As shown below in Scheme 14, compounds of formula (XVI), wherein X 4 is OH or OR 1 , with R 1 as defined for compounds of formula (I), and X 5 is C1-C4-alkoxy, such as methoxy or ethoxy, may be obtained by reaction of a compound of formula (XVIII) using an alkoxide, typically in solution in the corresponding alcohol (e.g.
  • compounds of formula (XVI) may be obtained by hydrolysing compounds of formula (XVIII) in the presence of an acid, preferably but not limited to hydrochloric acid, in a suitable solvent or mixture of solvents, such as methanol, ethanol, dichloromethane, or 1,4-dioxane at temperatures between -30°C to 40°C.
  • an acid preferably but not limited to hydrochloric acid
  • a suitable solvent or mixture of solvents such as methanol, ethanol, dichloromethane, or 1,4-dioxane at temperatures between -30°C to 40°C.
  • compounds of formula (IV), wherein R 1 is as defined for compounds of formula (I) may be prepared by hydrolysis of compounds of formula (XIX), wherein R 1 is as defined for compounds of formula (I), in an aqueous solvent mixture of solvents, such as tetrahydrofuran, optionally in an alkaline media, at temperatures between 60°C and 110°C.
  • solvents such as tetrahydrofuran
  • acetic acid either neat or in an appropriate solvent, such as methanol or ethanol, at temperatures between 20°C to 75°C, followed by a reduction in the 82761 – FF 22 presence of a hydride (e.g. sodium cyanoborohydride, sodium borohyride, sodium triacetoxyborohydride or lithium borohydride) in a solvent or mixture of solvents, such as tetrahydrofuran, toluene, or methanol.
  • a hydride e.g. sodium cyanoborohydride, sodium borohyride, sodium triacetoxyborohydride or lithium borohydride
  • solvent or mixture of solvents such as tetrahydrofuran, toluene, or methanol.
  • ester can be cleaved in acidic conditions using, for instance, hydrochloric acid.
  • hydrochloric acid For related examples, see: WO2021086879 or Org. Biomol. Chem.2015, 13, 7928.
  • Compounds of formula (XXVIII), wherein X 5 is C1-C4-alkoxy, such as methoxy or ethoxy, and X 9 is OH or halogen, may be obtained from compounds of formula (XXVII), wherein X 9 is OH or halogen, via an oxidation method using a suitable oxidant, such as KMnO4 or a cobalt(ll) salt and trihydroxyisocyanuric acid (THICA) in a suitable solvent (e.g., acetic acid) at temperatures between 25°C and 200°C.
  • a suitable oxidant such as KMnO4 or a cobalt(ll) salt and trihydroxyisocyanuric acid (THICA)
  • a suitable solvent e.g., acetic acid
  • compounds of formula (XXV) may be prepared as described in Bulletin de la Societe Chimique de France 1972, 8, 3198.
  • compounds of formula (XXXI) may be prepared by reacting nucleophilic compounds of formula (VII), wherein R 1 is as defined for compounds of formula (I), with electrophilic compounds of formula (XXX), wherein X 3 is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol), in the presence of base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3), in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, sulfolane,
  • base e.g., KO-t-Bu, K3PO4,
  • compounds of formula (IV), wherein R 1 is as defined for compounds of formula (I) may also be obtained by reacting a compound of formula (XXXII) wherein R 1 is as defined for compounds of formula (I), and X 10 is chloro, bromo or iodo, with a lithium reagent (e.g., n- butyl lithium, sec-butyl lithium, tert-butyl lithium or lithium diisopropylamine) at temperatures between -78°C and -30°C in an appropriate solvent, for instance hexane, diethyl ether or tetrahydrofuran, followed by the addition of carbon dioxide.
  • a lithium reagent e.g., n- butyl lithium, sec-butyl lithium, tert-butyl lithium or lithium diisopropylamine
  • compounds of formula (IV), wherein R 1 is as defined for compounds of formula (I) may also be prepared by reacting a compound of formula (XXXIV), wherein R 1 is as defined for compounds of formula (I), at temperatures between -78°C and 10°C with a base, typically lithium diisopropylamine or n-butyl lithium, in the presence or not of a catalyst (e.g., potassium tert-butoxide), in a suitable solvent (e.g., diethyl ether, cyclopentyl methyl ether, methyl tert-butyl ether or tetrahyrofuran) followed by the addition of carbon dioxide.
  • a catalyst e.g., potassium tert-butoxide
  • a suitable solvent e.g., diethyl ether, cyclopentyl methyl ether, methyl tert-butyl ether or tetrahyrofuran
  • Scheme 27 compounds of formula (V) may be obtained by treatment of compound of formula (XXXV), wherein X 1 is H and X 2 is a protective group, or X 1 and X 2 are identical or different protective groups, or X 1 and X 2 form a protective group together with the nitrogen they are attached to, and wherein X 1a is H and X 2a is a protective group, or X 1a and X 2a are identical or different protective groups, or X 1a and X 2a form a protective group together with the nitrogen they are attached to; and X 2 is different from X 2a .
  • X 1 and X 1a may both be hydrogen.
  • protective groups include, for instance, tert-butyloxycarbonyl, benzylcarbonyl, 9- fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, p-toluenesulfonyl, phthalimide, or succinimide.
  • Treatment of compound of formula (XXXV) is performed, with an acid (e.g., hydrochloric acid, trifluoroacetic acid), optionally in a suitable solvent or mixture of solvents, for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or diethyl ether at temperatures between 0°C and 50°C.
  • an acid e.g., hydrochloric acid, trifluoroacetic acid
  • a suitable solvent or mixture of solvents for instance dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or diethyl ether at temperatures between 0°C and 50°C.
  • organometalloid e.g. trimethylboroxine
  • a suitable metal e.g. CuBr
  • catalyst complex e.g., 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride
  • a base e.g. K2CO3
  • an inert solvent such as toluene or 2-methyl tetrahydrofuran
  • Compounds of formula (XXXVI), wherein R 2 is C 1 -C 4 alkoxy, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, phenoxy, heteroaryloxy, or C3-C6cycloalkyloxy can be prepared by treatment of compounds of formula (XXXVII), wherein Z is is suitable leaving group, such as halogen, with a suitable nucleophilic compound of formula (XXXVIII), wherein R 2 is C1-C6alkyl, C3-C4alkenyl, C3-C4alkynyl, C1-C3alkoxyC2-C3alkyl, C3-C6cycloalkyl, C3- C 6 cycloalkylC 1-2 alkyl, phenyl, heteroaryl, or C 3 -C 6 cycloalkyl, and X 11 is selected from
  • N-methylpyrrolidone dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, sulfolane, or dimethylsulfoxide
  • tetrahydrofuran 2-methyl tetrahydrofuran
  • sulfolane or dimethylsulfoxide
  • Scheme 30 As shown below in Scheme 31, related compounds of formula (XLI), wherein X 7 is chloro, bromo, or iodo, are prepared by reaction of a compound of formula (XLII), wherein X 7 are identically selected from chloro, bromo, and iodo, with a methyl magnesium halide, wherein halide is bromide or chloride, in the optional presence of a copper salt (e.g., copper iodide, copper cyanide, copper chloride, copper acetate), in a suitable solvent or solvent mixtures (eg.
  • a copper salt e.g., copper iodide, copper cyanide, copper chloride, copper acetate
  • suitable solvent or solvent mixtures eg.
  • organometalloid e.g. trimethylboroxine
  • a suitable metal e.g. CuBr
  • catalyst complex e.g., 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride
  • a base e.g. K2CO3
  • an inert solvent such as toluene or 2-methyl tetrahydrofuran
  • N-methylpyrrolidone dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, sulfolane, dimethylsulfoxide), at temperatures between 25°C and reflux temperature.
  • F. Terrier Modern Nucleophilic Aromatic Substitution, Wiley-VCH, Weinheim, 2013.
  • compounds of formula (XLIII), wherein R 2 is C1-C4-alkoxy, C3-C4alkenyloxy, C3-C4alkynyloxy, C1-C2fluoroalkoxy, or C3-C6cycloalkyloxy are readily accessed from compounds of formula (XLIV), wherein is Z is OH or SH, using a suitable alkylating reagent of formula (XLV), wherein R 2 is C1-C6alkyl, C3- C4alkenyl, C3-C4alkynyl, C1-C3alkoxyC2-C3alkyl, C3-C6cycloalkyl, C3-C6cycloalkylC1-2alkyl, phenyl, heteroaryl, or C3-C6cycloalkyl, and X 11 is a suitable leaving group, such as chloro, bromo, iodo, trifluoromethanesulfonyl-O-, and
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • an inorganic salt which forms, for example silver chloride is insoluble and thus precipitates from the reaction mixture.
  • the compounds of formula (I) which have salt- forming properties, can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, 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 82761 – FF 31 so
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry. It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
  • compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns.
  • SFC supercritical fluid chromatography
  • Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • the compounds of formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants.
  • the compounds of formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time also protecting those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) is applied to the plants, to parts thereof or the locus thereof. It is also possible to use compounds of formula (I) as a fungicide.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation 82761 – FF 32 from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection. It may also be possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • plant propagation material e.g., seed, such as fruits, tubers or grains, or plant cuttings
  • the propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown.
  • the active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds of formula (I) can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • the compounds of formula (I) are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A.
  • Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. contributing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, 82761 – FF 33 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.
  • target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass,
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • useful plants is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
  • Useful plants is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Bollgard I® (cotton variety that expresses a CryIA(c) toxin); Bol
  • 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 d- endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vip1, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • d-endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • transgenic plants The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that express
  • transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.
  • 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. 4.
  • MON 863 Maize from Monsanto Europe S.A.270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 82761 – FF 36 5.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • the compounds of formula (I) may be used in controlling or preventing phytopathogenic diseases, especially caused by phytopathogenic fungi, such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae, and Fabaceae; Glomerella lagenarium on Cucurbitaceae; Blumeria graminis on Poaceae, such as wheat.
  • phytopathogenic fungi such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae, and Fabaceae; Glomerella lagenarium on Cucurbitaceae; Blumeria graminis on Poaceae, such as wheat.
  • locus as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes.
  • seeds in the strict sense
  • Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion.
  • plant propagation material is understood to denote seeds.
  • the compounds of formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently Formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants e.g. for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended.
  • Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor.
  • these concentrates are diluted in water and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular Formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter.
  • Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, 82761 – FF 38 sawdust and granular carbon.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1,2- dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1,4-
  • Water is generally the carrier of choice for the dilution of concentrates.
  • suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation.
  • Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.
  • soaps such as sodium stearate; 82761 – FF 39 alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl)
  • compositions of the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti- foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention.
  • these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank.
  • These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
  • the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No.
  • the compounds of Formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the compounds of Formula (I) may be used in the form of compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of Formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound Formula (I) an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art.
  • said composition may comprise at least one or more pesticidally-active compounds, for example an additional fungicidal active ingredient in addition to the compound of Formula (I).
  • an additional fungicidal active ingredient in addition to the compound of Formula (I).
  • the compound of Formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fung
  • suitable additional active ingredients also include a compound selected from the group of substances consisting of petroleum oils, 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofenvalerate, bromo-cyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulful
  • lecontei NPV, Orius spp. Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en-1-yl acetate
  • TX means one compound selected from the group consisting of the compounds as represented in Tables A-1 to A-13, a compound 1.1 listed in Table T1 (below): 82761 – FF 47 a compound selected from the group of substances consisting of petroleum oils + TX, 1,1-bis(4- chloro-phenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1- naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • the compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol- 1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 82761 – FF 54 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2- fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described
  • the designation is not a "common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a 82761 – FF 55 "chemical name”, a “traditional name”, a “compound name” or a “development code” is used or, if neither one of those designations nor a "common name” is used, an "alternative name” is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.
  • the active ingredient mixture of the compounds of formula (I) selected from one compound as represented in Tables A-1 to A-13 (below), or compound 1.1 listed in Table T1 (below), is preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound as represented in Tables A-1 to A-13 (below), or compound 1.1 listed in Table T1 (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying a compound as represented in in Tables A-1 to A-13 (below), or compound 1.1 listed in Table T1 (below) and the active ingredient(s) as described above, is not essential for working the present invention.
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP-444964 and EP-594291.
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel.
  • Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • flukicides such as triclabendazole and clorsulon
  • cestocides such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626375, EP 0382173, WO 94/19334, EP 0382173, and EP 0503538.
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • terpene alkaloids for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos- ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S- methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate,
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2-dimethyl-3-(2- oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvaler
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • Another aspect of the invention is related to the use of a compound of Formula (I) or of a preferred individual compound as defined herein, of a composition comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • a further aspect of the invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of Formula (I) or of a preferred individual compound as above-defined as active 82761 – FF 58 ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
  • Controlling or preventing means reducing infestation or spoilage by phytopathogenic microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid Formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of Formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation e.g.
  • compositions containing the compound of formula (I), and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • g a.i./ha refers to the application rate given in gram [g] of active ingredient [a.i.] per unit of surface [ha].
  • the unit hectare is the metric unit of area that equals a square with 100 m side (1 hm 2 ) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.
  • rates of 0.001 to 50 g of a compound of Formula (I) per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • compositions comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • the compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly Formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • seed dressing formulations are known in the art.
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of Formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
  • compound A-1.02 is: (A-1.02)
  • Table A-2 This table provides 48 compounds A-2.01 and A-2.48 of formula (I) wherein R 1 is 3- (trifluoromethyl)phenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-3 This table provides 48 compounds A-3.01 and A-3.48 of formula (I) wherein R 1 is 3-chloro-2- fluorophenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-4 This table provides 48 compounds A-4.01 and A-4.48 of formula (I) wherein R 1 is 3-chlorophenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-5 This table provides 48 compounds A-5.01 and A-5.48 of formula (I) wherein R 1 is 5-cyanopyridin- 3-yl and substituents R 2 and G are as defined in Table G above. 82761 – FF 61
  • Table A-6 This table provides 48 compounds A-6.01 and A-6.48 of formula (I) wherein R 1 is 3-methylphenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-7 This table provides 48 compounds A-7.01 and A-7.48 of formula (I) wherein R 1 is phenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-8 This table provides 48 compounds A-8.01 and A-8.48 of formula (I) wherein R 1 is 3- cyclopropylphenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-9 This table provides 48 compounds A-9.01 and A-9.48 of formula (I) wherein R 1 is 3- (difluoromethyl)phenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-10 This table provides 48 compounds A-10.01 and A-10.48 of formula (I) wherein R 1 is 3- (difluoromethoxy)phenyl, R 2 is methyl and substituents R 2 and G are as defined in Table G above.
  • Table A-11 This table provides 48 compounds A-11k.01 and A-11.48 of formula (I) wherein R 1 is 3- (trifluoromethyl)-2-fluorophenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-12 This table provides 48 compounds A-12.01 and A-12.48 of formula (I) wherein R 1 is 3- methoxyphenyl and substituents R 2 and G are as defined in Table G above.
  • Table A-13 This table provides 48 compounds A-13.01 and A-13.48 of formula (I) wherein R 1 is 2,3- difluorophenyl and substituents R 2 and G are as defined in Table G above Also made available are certain intermediate compounds of formulae (II-i), (IV-i), (VIII-i), (X-i), (XIII-i), (XX- i), (XXI-i), (XXXVI-i), and (XLIV-i), some of which are novel.
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, if necessary, for example 60 ppm, 20 ppm or 2 ppm.
  • Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico- chemical properties, or increased biodegradability).
  • temperatures are given in degrees Celsius (°C) and “m.p.” means melting point.
  • LC/MS or LC-MS or LCMS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows. Unless indicated otherwise, 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS ( 1 H) and CFCl3 ( 19 F) standard. Spectra measured in deuterated solvents as indicated.
  • Method B Spectra were recorded on a Mass Spectrometer 6410 Triple Quadruple Mass Spectrometer from Agilent Technologies equipped with an electrospray source (Positive and Negative Polarity Switch, Capillary (kV) 7.00, Scan Type MS2 Scan, Fragmentor (V) 120.00, Gas Temperature (°C) 350, Gas Flow (L/min) 11, Nebulizer Gas (psi) 40, Mass range : 110 to 650 Da) and an Agilent 1200 Series HPLC: DAD Wavelength: 254 nm, Column : KINETEX EVO C18, Column length : 50 mm, Internal diameter of column : 4.6 mm, Particle Size : 2.6 ⁇ m, Column oven temperature : 40 °C Gradient conditions: Solvent A: Water with 0.1% formic acid : Acetonitrile : 95 : 5 v/v Solvent B: Acetonitrile with 0.1% formic acid Time (minutes) A (%)
  • Method D Spectra were recorded on a Mass Spectrometer Acquity SDQ Mass Spectrometer from Waters equipped with an electrospray source (Positive and Negative Polarity Switch, Capillary (kV) 3.0, Full Scan, Cone voltage (V) 41.0, Source Temperature (°C) 150, Desolvation Temperature (°C) 500, Gas Flow @ Cone (L/Hr) 50, Mass range : 110 to 800 Da) and HPLC ‘H’ class: DAD Wavelength range: 210 to 400 nm, a column Acquity UPLC HSS T3 C18 Column length : 30 mm, Internal diameter of column : 2.1 mm, Particle Size : 1.8 ⁇ m, Column oven temperature : 40 °C Gradient conditions: Solvent A: Water with 0.1% formic acid: Acetonitrile: 95: 5 v/v Solvent B: Acetonitrile with 0.05% formic acid Time (minutes) A (%) B (%)
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % - The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - 82761 – FF 66 Kaolin 65 % 40 % - Talcum - - 20 % The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders, that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Dusts a) b) c) Active ingredients 5 % 6 % 4 % Talcum 95 % - - Kaolin - 94 % - mineral filler - - 96 % Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressings for seed.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % 82761 – FF 67 carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % Tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment.
  • 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
  • temperatures are given in degrees Celsius (°C).
  • MP means melting point.
  • Rt means retention time.
  • LC/MS Liquid Chromatography Mass Spectrometry.
  • Example P1 3-[5-(3-cyclopropylphenoxy)-3-methyl-pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6- dihydro-4H-1,2,4-oxadiazine (Compound 1.1 of Table T1) 82761 – FF 69 (Compound 1.1 of Table T1) a) Preparation of 5-bromo-4-(3-cyclopropylphenoxy)-1H-pyridazin-6-one To a mixture of 4,5-dibromopyridazin-3-ol (10 g, 37.4 mmol), 3-cyclopropylphenol (41.16 mmol) were taken in DMSO (80 mL) in a round bottom flask, cesium carbonate (93.5 mmol) was added and purged with a stream of Nitrogen for 10 minutes.
  • reaction mass was cooled to 25 °C, the pressure was released and the reaction mixture was flushed with nitrogen.
  • the reaction mass was discharged to a clean conical flask.
  • the reaction mass was diluted with water, extracted twice with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude which was washed with pentane to get methyl 4-(3-cyclopropylphenoxy)-6-oxo-1H-pyridazine-5-carboxylate (1.4 g, 45% yield).
  • reaction mixture was then cooled down to room temperature and slowly quenched with a saturated solution of sodium bicarbonate sat.NaHCO3 solution, diluted with water and extracted with EtOAc twice. Combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude.
  • Table T1 Physical data of compounds of formula (I) - * [M+H] measured *e ) y i n g r d r t a Name Structu h o n re m ( c h t E t s e R sa M M 3-[6-(3- cyclopropylphenoxy)pyrazolo[1, 1.1 5-a]pyrimidin-7-yl]-5-[(2,4- 1.25 469 C dichlorophenyl)methyl]-5,6- dihydro-4H-1,2,4-oxadiazine 82761 – FF 72 *e ) y i n g r d r t a Name Str h o n ucture m ( h t E t c e R ssa M M 3-[5-(3-cyclopropyl-2-fluoro- phenoxy)-3-isopropoxy- 1.2 pyridazin-4
  • 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 the person skilled in the art using the experimental procedures outlined in the Examples, using 82761 – FF 73 lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 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).
  • Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse.
  • the cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar.
  • the leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation.
  • Compounds to be tested are prepared as DMSO solutions (max.10 mg/mL) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying.
  • the inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system.
  • a single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem.
  • Percent disease control relative to the untreated check leaf disks or segments is then calculated.
  • Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth.
  • DMSO solutions of the test compound (max.10 mg/mL) are diluted with 0.025% Tween20 by a factor of 50 and 10 ⁇ L of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound.
  • the test plates are incubated in the dark at 24 °C and 96% relative humidity.
  • Example B1 Botryotinia fuckeliana syn. Botrytis cinerea (Gray mould of grapevine) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.
  • DMSO DMSO
  • Example B2 Glomerella lagenarium syn Colletotrichum lagenarium (Anthracnose of cucurbits) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added.
  • DMSO DMSO
  • test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.
  • 82761 – FF 74 The following compounds from Table T1 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: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6
  • Example B3 Blumeria graminis f. sp. tritici (Powdery mildew on wheat) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 – 8 days after application).
  • the following compounds from Table T1 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: 1.1, 1.2

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Abstract

L'invention concerne un composé de formule (I) dans laquelle R1, R2 et G sont tels que définis dans la revendication 1, et sont utiles en tant que pesticides, en particulier en tant que fongicides.
PCT/EP2023/086003 2022-12-19 2023-12-15 Dérivés microbiocides de pyridazine dihydrooxadiazine Pending WO2024132901A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025032038A1 (fr) 2023-08-09 2025-02-13 Bayer Aktiengesellschaft Pyridazin-4-yloxadiazines utilisées comme nouveaux fongicides
WO2025078128A1 (fr) 2023-10-11 2025-04-17 Bayer Aktiengesellschaft Pyridazin-3-one-4-yloxadiazines comme nouveaux fongicides
WO2025168620A1 (fr) 2024-02-07 2025-08-14 Bayer Aktiengesellschaft 4,5-dihydro-1h-2,4,5-oxadiazines substituées par hétéroaryle utilisées en tant que nouveaux fongicides

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