WO2023166067A1 - Microbiocidal pyridazinone amide derivatives - Google Patents

Microbiocidal pyridazinone amide derivatives Download PDF

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WO2023166067A1
WO2023166067A1 PCT/EP2023/055202 EP2023055202W WO2023166067A1 WO 2023166067 A1 WO2023166067 A1 WO 2023166067A1 EP 2023055202 W EP2023055202 W EP 2023055202W WO 2023166067 A1 WO2023166067 A1 WO 2023166067A1
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methyl
phenyl
independently selected
compounds
ethyl
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PCT/EP2023/055202
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French (fr)
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Nicolas Germain
Andrew Edmunds
Thomas James Hoffman
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Syngenta Crop Protection Ag
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Publication of WO2023166067A1 publication Critical patent/WO2023166067A1/en

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    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to pyridazinone amide compounds, e.g., as active ingredients, which have microbiocidal activity, in particular, fungicidal activity.
  • the invention also relates to agrochemical compositions which comprise at least one of the pyridazinone amide compounds, to processes of preparation of these compounds and to uses of the pyridazinone amide compounds 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.
  • Fungicidal compounds are disclosed in WO 2020/109391 (pyridazine (thio)amide derivatives, WO 2020/127780 (heterocyclyl pyridazine), WO 2021/224220 (pyridine (thio)amides), WO 2021/228734 (triazine and pyrimidine (thio)amides), WO 2021/233861 (azabicyclic(thio)amides), WO 2021/245083 (heterocyclyl pyridines), WO 2021/245087 (heterocyclyl pyrimidines and triazines), WO 2021/249995 (azabicyclyl-substituted heterocycles), and WO 2021/245087 (heterocyclyl pyrimidines and triazines).
  • the present invention therefore provides, in a first aspect, a compound of formula (I): wherein:
  • R 1 is phenyl, wherein said phenyl is unsubstituted or substituted with 1 , 2 or 3 independently selected substituents R 11 ; or
  • R 1 is a 5- or 6-membered monocyclic heteroaryl ring, wherein any of said heteroaryl comprises 1 , 2 or 3 heteroatoms which may be the same or different, independently selected from N, O and S, wherein said heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R 11 ;
  • R 11 is hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci- C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl;
  • L 1 is a direct bond, -O- or -O-C(R L1A )(R L1B )-; wherein R L1A and R L1B are independently selected from hydrogen or methyl; or R L1A and R L1B together with the carbon atom to which they are attached, form a cyclopropyl; or wherein # marks the bond to the nitrogen atom and the staggered line marks the bond to the group G;
  • R 2 and R 3 are independently selected from hydrogen or methyl;
  • R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, hydroxy, or methoxy; or
  • R 4 and R 5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl, or cyclobutyl group;
  • G is selected from G-1 , G-2, G-3, and G-4, wherein:
  • G-1 is phenyl or phenoxy, wherein any of said phenyl or phenoxy are unsubstituted or substituted with 1 , 2 or 3 independently selected substituents R G1 ;
  • G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy; wherein any of said heteroaryl comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; and wherein said heteroaryl is unsubstituted or substituted with 1 or 2 independently selected substituents R G2 ;
  • G-3 is a 9- or 10-membered heterobicyclic ring system, wherein said - or 10-membered heterobicyclic ring system comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; wherein said heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said heterobicyclic ring system is unsubstitued or substituted with 1 or 2 independently selected substituents R G3 ;
  • G-4 is a 9- or 10-membered carbobicyclic ring system; wherein said carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents R G4 ;
  • Y is O or S
  • R 7 is selected from Ci-Csalkyl, C2-C3alkenyl, C2-C3alkynyl, Cs-Cecycloalkyl, Cs-Cecycloalkylmethyl, methylformyl, f-butylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo-ethyl; or
  • R 7 is selected from phenyl, thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, pyridazinyl or triazinyl, wherein any of said phenyl, thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, thiadiazolyl , pyridinyl, pyrimidinyl, pyridazinyl and triazinyl are unsubstituted or substituted with 1 or 2 independently selected substituents R 8 selected from halogen, mercapto, cyano, Ci-Csalkyl, O-Csalkoxy, O-Cshaloalky
  • R 7 is CR 12 R 13 R 14 wherein R 12 and R 13 are independently selected from hydrogen, or methyl; or
  • R 12 and R 13 form a cyclopropyl together with the carbon they are attached to;
  • R 14 is selected from cyano, methylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo- ethyl; or
  • R 14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, furanyl, isoxazolyl, oxadiazolyl, and thiadiazolyl, or a heterocyclyl selected from oxiranyl, azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetra hydro pyranyl, morpholinyl and dioxanyl, wherein any of said phenyl, heteroaryl and heterocyclyl are unsubstituted or substituted with 1 or 2 independently selected substituents R 9 selected from halogen, mercapto, cyano, Ci-Csalky
  • 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).
  • 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.
  • 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 haloalky I.
  • Ci-4alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Ci-salkyl should be construed accordingly. Examples of Ci-4alkyl include, but are not limited to, methyl, ethyl, /so-propyl.
  • C2-3alkenyl 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 three carbon atoms, which is attached to the rest of the molecule by a single bond.
  • Examples of C2-3alkenyl include, but are not limited to, vinyl (ethenyl), prop- 1-enyl, allyl (prop-2-enyl).
  • C2-3alkynyl 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 three carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of C2- salkynyl include, but are not limited to, prop-1 -ynyl and propargyl (prop-2-ynyl).
  • Ci-4haloalkyl refers respectively to a Ci-4alkyl, C2-3alkenyl, and C2-3alkynyl radical as defined above, substituted by one or more of the same or different halogen atoms.
  • Ci-4haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethy I.
  • Ci-3fluoroalkyl refers to a Ci-salkyl radical as generally defined above substituted by one or more fluorine atoms.
  • Examples of Ci-3fluoroalkyl include, but are not limited to difluoromethyl and trifluoromethyl.
  • Ci-3alkoxy refers to a radical of the formula R a O- where R a is a Ci-salkyl radical as generally defined above.
  • Examples of Ci-salkoxy include, but are not limited to, methoxy, ethoxy, /so-propoxy.
  • Ci-3fluoroalkoxy refers to a O-salkoxy radical as generally defined above substituted by one or more fluorine atoms.
  • Examples of Ci-3fluoroalkoxy include, but are not limited to trifluoromethoxy.
  • C3-4cycloalkyl refers to a stable, monocyclic ring radical which is saturated and contains 3 or 4 carbon atoms.
  • Ci-salkylsulfanyl refers to a radical of the formula -SR a wherein R a is a Ci- salkyl radical as generally defined above.
  • Ci-3alkylsulfonyl refers to a radical of the formula -S(O)2R a wherein R a is a Ci-salky I 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. Examples of heteroaryls include J-1 to J— 41 shown in Table J below. The staggered line in heteroaryls J-1 to J-43 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.
  • heterocyclyls include K-1 to K-26 shown in Table K below.
  • the staggered line in heterocyclyls K-1 to K-26 represents 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.
  • optionally substituted means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, “C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms” means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3- C4cycloalkyl substituted with 2 halo atoms.
  • staggered line as used herein for example in heteroaryls shown in Table J and heterocyclyls shown in Table K, represent the point of connection / attachment to the rest of the compound.
  • 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 Ci-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die
  • the compounds of formula (I) according to the invention 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.
  • R 1 is: A. phenyl optionally substituted with a one, two or three independently selected substituents R 11 ; for instance, one or two independently selected substituents R 11 ; preferably one substituent R 11 ; wherein R 11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
  • R 11 is selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
  • phenyl substituted with one or two substituents for instance one substituent, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
  • phenyl optionally substituted with a one or two substituents, for instance one substituent, independently selected from chloro, fluoro, cyano, methyl, methoxy, and cyclopropyl; or
  • R 1 is :
  • R 1 is:
  • R 11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
  • R 11 is selected hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
  • R 11 is selected hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
  • phenyl, or pyridyl each optionally substituted with a one or two independently selected substituents R 11 ; wherein R 11 is selected chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or
  • phenyl, or pyridyl each optionally substituted with a one or two independently selected substituents R 11 ; wherein R 11 is selected chloro, cyano, methyl, and cyclopropyl; or
  • phenyl, or pyridyl each optionally substituted with a one or two independently selected substituents R 11 ; wherein R 11 is selected chloro, cyano and cyclopropyl.
  • R 11 is:
  • L 1 is a direct bond, -O- or -O-C(R L1A )(R L1B )-; wherein R L1A and R L1B are independently selected from hydrogen and methyl; or R L1A and R L1B together with the carbon atom to which they are attached, form a cyclopropyl; or wherein # marks the bond to the nitrogen atom and the staggered line marks the bond to the group G; wherein
  • R 2 and R 3 are independently selected from hydrogen and methyl
  • R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, hydroxy, and methoxy; or
  • R 4 and R 5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl or cyclobutyl group.
  • R 2 and R 3 are hydrogen; R 4 and R 5 are independently selected from hydrogen and fluoro; or
  • R 2 and R 3 are hydrogen; R 4 and R 5 , together with the carbon atom to which they are attached, form a cyclopropyl; or
  • R 2 , R 3 , R 4 , and R 5 are hydrogen; or
  • R 2 , R 3 , and R 4 are hydrogen, and R 5 is fluoro.
  • G is selected from G-1 , G-2, G-3, and G-4, wherein: G-1 is phenyl or phenoxy, wherein said phenyl or phenoxy is optionally substituted with 1 , 2 or 3 independently selected substituents R G1 ;
  • G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy; wherein said heteroaryl comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; and wherein said heteroaryl is optionally substituted with 1 or 2 independently selected substituents R G2 ;
  • G-3 is a 9- or 10-membered heterobicyclic ring system comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S; wherein said heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said heterobicyclic ring system is optionally substituted with 1 or 2 independently selected substituents R G3 ;
  • G-4 is a 9- or 10-membered carbobicyclic ring system; wherein said carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic ring system is optionally substituted with 1 or 2 independently selected substituents R G4 ; wherein R G1 , R G2 , R G3 , and R G4 are independently hydroxyl, halogen, mercapto, amino, cyano, Ci- C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, C2-C4alkynyloxy, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl.
  • G-1 is: A. phenyl or phenoxy, optionally substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
  • phenyl optionally substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
  • phenyl optionally substituted with one or two substituents, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
  • phenyl optionally substituted with 1 , 2 or 3 substituents, for instance 2 or 3 substituents, each independently selected from chloro, fluoro, methyl, and methoxy; or
  • G-2 is:
  • B pyridine, pyrimidine, or pyridazine, substituted with one or two substituents, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
  • G-3 is:
  • 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, benzothiophen-6-yl optionally substituted with 1 , 2 or 3 substituents, for instance one or two substituents, each independently selected from chloro, fluoro, cyano
  • 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, or benzothiophen-2-yl, benzothiophen-3-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or
  • chroman-4-yl isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, or 2,3- dihydrobenzofuran-3-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or
  • G-4 is:
  • B tetralin-1 -yl, tetralin-2-yl, indan-1-yl, or indan-2-yl, or optionally substituted with one or two substituents, for instance one substituent, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or
  • R G1 , R G2 , R G3 , and R G4 are independently:
  • Group A represents wherein # marks the bond to -O-R 1 ; and % marks the bond to -
  • Y is oxygen or sulfur, preferably oxygen.
  • R 7 is
  • Ci-Csalkyl selected from Ci-Csalkyl, C2-C3alkenyl, C2-C3alkynyl, Cs-Cecycloalkyl, Cs-Cecycloalkylmethyl, methylformyl, f-butylformyl, 2-(dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo-ethyl; or
  • Ci-C2alkyl selected from Ci-C2alkyl, allyl, propargyl, C4-C6cycloalkyl, methylformyl, f-butylformyl, 2- (dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo-ethyl; or
  • A4 selected from methyl, ethyl, allyl, propargyl, cyclopentyl, cyclohexyl, methylformyl, 2- (dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo-ethyl; or
  • A5. selected from methyl, ethyl, allyl, propargyl, methylformyl, and 2-(methylamino)-2-oxo-ethyl.
  • R 7 may also be:
  • phenyl or heteroaryl selected from thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, and thiadiazolyl; said phenyl or heteroaryl being optionally substituted with 1 or 2 independently selected substituents R 8 selected from halogen, mercapto, cyano, Ci-Csalkyl, Ci- Csalkoxy, Ci-Cshaloalkyl, Ci-Cshaloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C3alkenyl, C2- Csalkynyl, and Ci-Csalkylsulfonyl; or
  • phenyl or heteroaryl selected from thiazolyl, imidazolyl, and thienyl, said phenyl or heteroaryl being optionally substituted with 1 or 2 independently selected substituents R 8 selected from halogen, mercapto, cyano, methyl, ethyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or
  • phenyl or heteroaryl selected from pyrazolyl, and thiazolyl, said phenyl or heteroaryl being optionally substituted with 1 or 2 independently selected substituents R 8 selected from halogen, cyano, methyl, ethyl, ethynyl, methoxy, methylsulfonyl, cyclopropyl, and cyclopropyloxy; or
  • phenyl and pyrazolyl selected from phenyl and pyrazolyl, said phenyl and pyrazolyl being optionally substituted with 1 or 2 independently selected substituents R 8 selected from fluoro, chloro, cyano, methyl, ethyl, and methoxy; or B5. phenyl optionally substituted with 1 or 2 independently selected R 8 selected from fluoro, chloro, cyano, methyl, ethyl, and methoxy.
  • R 7 is CR 12 R 13 R 14 , where
  • R 12 and R 13 are independently selected from hydrogen, and methyl; or R 12 and R 13 form a cyclopropyl together with the carbon they are attached to; and R 14 is cyano, methylformyl, 2- (dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo-ethyl; or R 14 is phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, furanyl, isoxazolyl, oxadiazolyl, and thiadiazolyl (e.g.
  • a heterocyclyl selected from oxiranyl, azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetrahydropyranyl, morpholinyl and dioxanyl (e.g.
  • phenyl, heteroaryl and heterocyclyl is optionally substituted with 1 or 2 independently selected substituents R 9 selected from halogen, mercapto, cyano, Ci-Csalkyl, O-Csalkoxy, Ci-Cshaloalkyl, O-Cshaloalkoxy, Cs-Cecycloalkyl, C3- Cecycloalkoxy, C2-C3alkynyl, and Ci-Csalkylsulfonyl; or
  • R 12 and R 13 are independently selected from hydrogen, and methyl; and R 14 is cyano, methylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo-ethyl, or R 14 is phenyl, heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, imidazolyl, and thienyl (e.g.
  • J-1 to J-9, J-21 to J-23, J-27 to J-29, J-36 to J-38, J-40 and J-41 or a heterocyclyl selected from azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl (e.g.
  • phenyl, heteroaryl or heterocyclyl is optionally substituted with 1 or 2 independently selected substituents R 9 selected from halogen, mercapto, cyano, methyl, ethyl, ethynyl, difluoromethyl, methoxy, ethoxy, methylsulfonyl, cyclopropyl, and cyclopropyloxy; or
  • R 12 and R 13 form a cyclopropyl together with the carbon they are attached to; and R 14 is cyano, methylformyl, or 2-(methylamino)-2-oxo-ethyl; or R 14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, and imidazolyl (e.g.
  • R 12 is hydrogen and R 13 is methyl;
  • R 14 is cyano, methylformyl, or 2-(methylamino)-2-oxo-ethyl; and
  • R 14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, and imidazolyl (e.g. J-1 to J-9, J-21 to J-23, J-27 to J-29 and J-36 to J-38), or a heterocyclyl selected from pyrrolidinyl, piperidinyl, piperazinyl, and tetra hydro pyranyl (e.g.
  • R 12 and R 13 are hydrogen; and R 14 is cyano, methylformyl, or 2-(methylamino)-2-oxo-ethyl; or
  • R 14 is a phenyl, pyridinyl, thiazolyl, pyrrolidinyl, piperazinyl or tetra hydro pyranyl (e.g. J-1 to J-3, J-36 to J-38, K-11 , K-18 and K-22), the latter being optionally substituted with 1 or 2 independently selected substituents R 9 selected from fluoro, chloro, cyano, methyl and methoxy.
  • R 7 is A1 or B1 or C1 ; or R 7 is A1 or B1 or C2; or R 7 is A1 or B1 or C3; or R 7 is A1 or B1 or C4; or R 7 is A1 or B1 or C5; or R 7 is A1 or B2 or C1 ; or R 7 is A1 or B2 or C2; or R 7 is A1 or B2 or C3; or R 7 is A1 or B2 or C4; or R 7 is A1 or B2 or C5; or R 7 is A1 or B3 or C1 ; or R 7 is A1 or B3 or C2; or R 7 is A1 or B3 or C3; or R 7 is A1 or B3 or C4; or R 7 is A1 or B3 or C5; or R 7 is A1 or B4 or C1 ; or R 7 is A1 or B4 or C1 ; or R 7 is A1 or B4 or C2; or R 7 is A1 or B4 or C3; or R 7
  • the compounds of formula (I) can be prepared by those skilled in the art as shown in the following schemes 1 to 14, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 11 , R 12 , R 13 , R 14 , Y, L, G-1 , G-2, G-3, G-4, R L1A , R L1B , R G1 , R G2 , R G3 , R G4 are as defined for a compound of formula (I), unless otherwise stated. Certain stereogenic centers have been left unspecified for the clarity and are not intended to limit the teaching of the schemes in any way.
  • the compounds of formula (I) are obtained by an amide-coupling transformation with compounds of formula (II), wherein X 1 is OH, and amine compounds of formula (III) by activating the carboxylic acid function of the compounds of formula (II), 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 (COCI)2 or SOCh, prior to treatment with the compounds of formula (III), preferably in a suitable solvent (e.g., N- methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at temperatures between 25°C and 60°C, and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or alternatively under conditions described in the literature for an amide coupling such as 1 -propanephosphonic acid cyclic anhydride (T3
  • Compounds of formula (I) are prepared from reacting nucleophilic compounds of formula (IV) with electrophilic compounds of formula (V), wherein X 2 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.
  • a metal catalyst complex e.g. Cu or Pd.
  • a metal catalyst complex e.g. Cu or Pd.
  • the compounds of formula (V), wherein X 3 is halogen or OH can be obtained by an amide coupling transformation with compounds of formula (VI), wherein X 1 is OH and X 3 is halogen or OH, and amine compounds of formula (III) by activating the carboxylic acid function of the compounds of formula (VI), 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 (COCI)2 or SOCh, prior to treatment with the compounds of formula (III), preferably in a suitable solvent (e.g., N-methylpyrrolidone dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at temperatures between 25°C and 60°C, and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or alternatively under conditions described in the literature for an amide coupling such as 1 -propane
  • dichloromethane 1 ,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, N-methylpyrrolidone, dimethylacetamide
  • a metal source e.g. Cu(OAc)2
  • an oxidant such as O2 or a suitable palladium pre-catalyst, such as RockPhos Pd G3
  • a base e.g. K3PO4
  • suitable solvent e.g. dimethyl ether or toluene
  • compounds of formula (XII) are prepared from reacting nucleophilic compounds of formula (IV) with electrophilic compounds of formula (VIII), wherein X 5 is a suitable leaving group such as halogen, in the presence of base (e.g. KO-f-Bu, K3PO4, K2CO3, triethylamine, or CS2CO3, in a suitable solvent (e.g. N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyl tetra hydrofuran, sulfolane, dimethylsulfoxide) at temperatures between 25°C and reflux and optionally using a metal catalyst and ligand complex (e.g.
  • a base eg. sodium hydride, potassium carbonate, sodium carbonate, cesium carbonate
  • solvent or solvent mixtures eg.
  • dimethylformamide, tetra hydrofuran, dioxane at temperatures between 25 °C and 120 °C, preferably between 90 °C and 110 °C.
  • temperatures between 25 °C and 120 °C, preferably between 90 °C and 110 °C.
  • 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.
  • Salts of compounds of formula (I) may be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I), which have saltforming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, or diastereomer mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule, the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomeric mixtures or racemic mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomeric mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns.
  • SFC supercritical fluid chromatography
  • Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention.
  • the compounds of formula (I) 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) 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 protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of Formula (I) is applied to the plants, to parts thereof or the locus thereof.
  • 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 dev/ation 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.
  • compositions of formula (I) can be used as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown.
  • the active compounds of Formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds of Formula (I) 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. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C.
  • Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp.
  • P. infestans Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P.
  • the compounds of Formula (I) may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.
  • target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), millet, oats
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • useful plants is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl- shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • 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 CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cry 111 B(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as 8- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins
  • 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
  • ribosomeinactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdy
  • 8-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see 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.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the 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 CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab 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 phytopathogenic fungi, such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae, and Fabaceae; Glomerella lagenarium on Cucurbitaceae; Sclerotinia sclerotiorum on Fabaceae, Brassicaceae, and Asteraceae, such as soybean, rapeseed, and sunflower respectively; or Alternaria solani on Solanaceae, such as tomato and potato.
  • phytopathogenic fungi such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae, and Fabaceae
  • Glomerella lagenarium on Cucurbitaceae such as Sclerotinia sclerotiorum on Fabaceae, Brassicaceae, and Asteraceae, such as soybean, rapeseed, and sunflower respectively
  • locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.
  • the compounds of Formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation.
  • compositions may be conveniently Formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • Such carriers are for example described in 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. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular Formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium 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.
  • 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.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • 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.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, divinyl glycol, divinyl glycol abietate, divinyl glycol butyl ether, divinyl glycol ethyl ether, divinyl glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, di
  • Water is generally the carrier of choice for the dilution of concentrates.
  • suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
  • These agents when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
  • alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyvinyl glycol esters of fatty acids such as polyvinyl glycol stearate
  • block copolymers of vinyl oxide and propylene oxide such as salts of mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming 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. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further 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.
  • compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the compounds of Formula (I) 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).
  • TX means “one compound selected from the compounds defined in the Tables A-1 to A- 21 , Tables B-1 to B-21 , or compounds P-1 to P-19 as listed in Table T 1 (below)”: 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, aramit
  • 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); 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 active ingredient mixture of the compounds of formula (I) is selected from one compound as represented in Tables A-1 to A-21 , Tables B-1 to B-21 , or a compound selected from P-1 to P-19 as 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,
  • 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-21 or B-1 to B-21 (below), or a compound P-1 to P-19 as 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 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.
  • 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 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
  • 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.
  • the compounds of the invention may be used in combination with 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, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • 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, fenval
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • antiparasitics acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fen pyroxi mate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox,
  • 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 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
  • a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts
  • 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. a composition 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 I kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • rates of 0.001 to 50 g of a compound of Formula (I) per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • composition comprising a compound of Formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a 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
  • 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. as slow release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of Formula (I) 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.
  • Table A Compounds of the formula (la) wherein G and R 7 are defined in Tables A-1 to A-21 , and R 1 is as defined in Table Z below
  • Table A-1 This table provides 48 compounds A-1 .01 and A-1 .48 of formula (la) wherein G is O-[(2,4- difluorophenyl)methyl]oxyimino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-2 This table provides 48 compounds A-2.01 and A-2.48 of formula (la) wherein G is O-[(2- chloro-4-methylphenyl)methyl]oxyamino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-3 This table provides 48 compounds A-3.01 and A-3.48 of formula (la) wherein G is O-[(2,4- dichlorophenyl)methyl]oxyamino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-4 This table provides 48 compounds A-4.01 and A-4.48 of formula (la) G is O-[(2- methoxy)methyl]oxyamino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-5 This table provides 48 compounds A-5.01 and A-5.48 of formula (la) G is O-[(4- methoxy)methyl]oxyamino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-6 This table provides 48 compounds A-6.01 and A-6.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-7 This table provides 48 compounds A-7.01 and A-7.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-8 This table provides 48 compounds A-8.01 and A-8.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-9 This table provides 48 compounds A-9.01 and A-9.48 of formula (la) wherein G is [(2S)-2- (2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-10 This table provides 48 compounds A-10.01 and A-10.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-11 This table provides 48 compounds A-11 .01 and A-11 .48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)-2-fluoro-ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-12 This table provides 48 compounds A-12.01 and A-12.48 of formula (la) wherein G is [(2S)-
  • R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-13 This table provides 48 compounds A-13.01 and A-13.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)-2-fluoro-ethyll]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-14 This table provides 48 compounds A-14.01 and A-14.48 of formula (la) wherein G is [(2S)- (6-chloro-3-pyridyl)-2-fluoro-ethyll]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-15 This table provides 48 compounds A-15.01 and A-15.48 of formula (la) wherein G is (6- methoxyindan-1-yl)amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-16 This table provides 48 compounds A-16.01 and A-16.48 of formula (la) wherein G is (6- chloroindan-1-yl)amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-17 This table provides 48 compounds A-17.01 and A-17.48 of formula (la) wherein G is (5- methoxyindan-1-yl)amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-18 This table provides 48 compounds A-18.01 and A-18.48 of formula (la) wherein G is (5- chloroindan-1-yl)amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-19 This table provides 48 compounds A-19.01 and A-19.48 of formula (la) wherein G is [(2R)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table A-21 This table provides 48 compounds A-21 .01 and A-21 .48 of formula (la) wherein G is [(2R)- (6-chloro-3-pyridyl)-2-fluoro-ethyll]amino, R 7 is methyl and R 1 substituents are as defined in Table Z above.
  • Table B Compounds of the formula (la), wherein G and R 7 are defined in Tables B-1 to B-21 , and R 1 is as defined in Table Z above:
  • Table B-1 This table provides 48 compounds B-1.01 and B-1.48 of formula (la) wherein G is O-[(2,4- difluorophenyl)methyl]oxyamino, R 7 is propargyl and R 1 substituents are as defined in Table Z above.
  • Table B-2 This table provides 48 compounds B-2.01 and B-2.48 of formula (la) wherein G is O-[(2- chloro-4-methylphenyl)methyl]oxyamino, R 7 is propargyl and R 1 substituents are as defined in Table Z above.
  • Table B-3 This table provides 48 compounds B-3.01 and B-3.48 of formula (la) wherein G is O-[(2,4- dichlorophenyl)methyl]oxyamino, R 7 is benzyl and R 1 substituents are as defined in Table Z above.
  • Table B-4 This table provides 48 compounds B-4.01 and B-4.48 of formula (la) wherein G is O-[(2- methoxy)methyl]oxyamino, R 7 is benzyl and R 1 substituents are as defined in Table Z above.
  • Table B-5 This table provides 48 compounds B-5.01 and B-5.48 of formula (la) wherein G is O-[(4- methoxy)methyl]oxyamino, R 7 is 1-tetrahydropyran-4-ylmethyl and R 1 substituents are as defined in Table Z above.
  • Table B-6 This table provides 48 compounds B-6.01 and B-6.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)ethyl]amino, R 7 is 1-tetrahydropyran-4-ylmethyl and R 1 substituents are as defined in Table Z above.
  • Table B-7 This table provides 48 compounds B-7.01 and B-7.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)ethyl]amino, R 7 is 1-thiazol-4-ylmethyl and R 1 substituents are as defined in Table Z above.
  • Table B-8 This table provides 48 compounds B-8.01 and B-8.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is 1-thiazol-4-ylmethyl and R 1 substituents are as defined in Table Z above.
  • Table B-9 This table provides 48 compounds B-9.01 and B-9.48 of formula (la) wherein G is [(2S)-2- (2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is A/-methyl-acetamide and R 1 substituents are as defined in Table Z above.
  • Table B-10 This table provides 48 compounds B-10.01 and B-10.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)ethyl]amino, R 7 is A/-methyl-acetamide and R 1 substituents are as defined in Table Z above.
  • Table B-11 This table provides 48 compounds B-11 .01 and B-11 .48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)-2-fluoro-ethyl]amino, R 7 is 1 H-pyrazol-3-yl and R 1 substituents are as defined in Table Z above.
  • Table B-12 This table provides 48 compounds B-12.01 and B-12.48 of formula (la) wherein G is [(2S)- 2-(2,4-dichlorophenyl)-2-fluoro-ethyl]amino, R 7 is 1 H-pyrazol-3-yl and R 1 substituents are as defined in Table Z above.
  • Table B-13 This table provides 48 compounds B-13.01 and B-13.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)ethyl]amino, R 7 is 1-tetrahydropyran-4-ylmethyl and R 1 substituents are as defined in Table Z above.
  • Table B-14 This table provides 48 compounds B-14.01 and B-14.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)ethyl]amino, R 7 is 1-thiazol-4-ylmethyl and R 1 substituents are as defined in Table Z above.
  • Table B-15 This table provides 48 compounds B-15.01 and B-15.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is ethyl and R 1 substituents are as defined in Table Z above.
  • Table B-16 This table provides 48 compounds B-16.01 and B-16.48 of formula (la) wherein G is [(2S)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is ethyl and R 1 substituents are as defined in Table Z above.
  • Table B-17 This table provides 48 compounds B-17.01 and B-17.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)ethyl]amino, R 7 is allyl and R 1 substituents are as defined in Table Z above.
  • Table B-18 This table provides 48 compounds B-18.01 and B-18.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)-2-fluoro-ethyl]amino, R 7 is allyl and R 1 substituents are as defined in Table Z above.
  • Table B-19 This table provides 48 compounds B-19.01 and B-19.48 of formula (la) wherein G is [(2R)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is A/-methyl-acetamide and R 1 substituents are as defined in Table Z above.
  • Table B-20 This table provides 48 compounds B-20.01 and B-20.48 of formula (la) wherein G is [(2R)- 2-(2,4-dichlorophenyl)-2-fluoro-ethyl]amino, R 7 is 1 H-pyrazol-3-yl and R 1 substituents are as defined in Table Z above.
  • Table B-21 This table provides 48 compounds B-21 .01 and B-21 .48 of formula (la) wherein G is [(2R)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R 7 is ethyl and R 1 substituents are as defined in Table Z above.
  • Table P Table of intermediates in reaction schemes 1 , 2, 3, 7, 8, 9, 10
  • 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 physicochemical properties, or increased biodegradability).
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows.
  • Solvent A Water with 0.1 % formic acid : Acetonitrile : 95 : 5 v/v
  • Solvent B Acetonitrile with 0.1 % formic acid
  • enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector.
  • 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 ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % Kaolin 65 % 40 % - Talcum 20 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % 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.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo- emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • LC/MS Liquid Chromatography Mass Spectrometry. LC/MS apparatus and methods are:
  • Example P1 Preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2- methyl-3-oxo-pyridazine-4-carboxamide (Compound 1.1 of Table T1). a) Preparation of 4-bromo-5-(3-cyclopropylphenoxy)-2-methyl-pyridazin-3-one
  • lithium 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylate (1 equiv., 70 mg, 0.204 mmol), 2-(2,4-Dichlorophenyl)-2-fluoro-ethanamine (1.3 equiv., 58 mg, 0.265 mmol) and A/,A/-diisopropylethylamine (5 equiv., 133 mg, 1.02 mmol, 0.179 mL) were stirred in EtOAc (2.1 mL).
  • Example P2 Preparation of 5-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2- methyl-3-oxo-pyridazine-4-carboxamide (Compound P-3 , Table T)
  • reaction mixture was diluted with water and extracted with EtOAc
  • organic layers were washed using sat. NaHCO3 solution and brine, dried over Na2SO4, filtered and concentrated under reduced pressure to get crude.
  • the crude material was purified by Combi-flash using EtOAc and cyclohexane, followed by a reverse phase purification using water and acetonitrile as eluent to get 5-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4- dichlorophenyl)-2-fluoro-ethyl]-2-methyl-3-oxo-pyridazine-4-carboxamide.
  • Example B1 Alternaria solani / tomato / leaf disc (early blight)
  • Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf disks are incubated at 23 °C / 21 °C (day /night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).
  • Example B2 Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
  • DMSO fetal sulfate
  • Example B3 Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (Anthracnose) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is measured photometrically 3-4 days after application.
  • DMSO DMSO
  • Example B4 Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch)
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated test leaf disks are incubated at 20 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • the following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
  • Example B5 Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
  • DMSO DMSO
  • Example B6 Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
  • DMSO DMSO
  • Example B7 Puccinia recondita f. sp. tritici / wheat / leaf disc curative (Brown rust)
  • Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. Plates are stored in darkness at 19 °C and 75% rh. The formulated test compound diluted in water is applied 1 day after inoculation. The leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 - 8 days after application).
  • Mycelia fragments and oospores of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 2-3 days after application.
  • DMSO DMSO
  • Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • Example B10 Sclerotinia sclerotiorum / liquid culture (cottony rot)
  • Mycelia fragments of a newly grown liquid culture of the fungus 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 material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
  • DMSO fetal sulfate
  • Example B11 Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
  • DMSO DMSO

Abstract

A compound of Formula (I) wherein the substituents are as defined in claim 1, useful as pesticides, especially as fungicides.

Description

82588_FF_FINAL PCT
1
MICROBIOCIDAL PYRIDAZINONE AMIDE DERIVATIVES
The present invention relates to pyridazinone amide compounds, e.g., as active ingredients, which have microbiocidal activity, in particular, fungicidal activity. The invention also relates to agrochemical compositions which comprise at least one of the pyridazinone amide compounds, to processes of preparation of these compounds and to uses of the pyridazinone amide compounds 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.
Fungicidal compounds are disclosed in WO 2020/109391 (pyridazine (thio)amide derivatives, WO 2020/127780 (heterocyclyl pyridazine), WO 2021/224220 (pyridine (thio)amides), WO 2021/228734 (triazine and pyrimidine (thio)amides), WO 2021/233861 (azabicyclic(thio)amides), WO 2021/245083 (heterocyclyl pyridines), WO 2021/245087 (heterocyclyl pyrimidines and triazines), WO 2021/249995 (azabicyclyl-substituted heterocycles), and WO 2021/245087 (heterocyclyl pyrimidines and triazines).
The present invention therefore provides, in a first aspect, a compound of formula (I):
Figure imgf000002_0001
wherein:
R1 is phenyl, wherein said phenyl is unsubstituted or substituted with 1 , 2 or 3 independently selected substituents R11; or
R1 is a 5- or 6-membered monocyclic heteroaryl ring, wherein any of said heteroaryl comprises 1 , 2 or 3 heteroatoms which may be the same or different, independently selected from N, O and S, wherein said heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R11;
R11 is hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci- C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl;
L1 is a direct bond, -O- or -O-C(RL1A)(RL1B)-; wherein RL1A and RL1B are independently selected from hydrogen or methyl; or RL1A and RL1B together with the carbon atom to which they are attached, form a cyclopropyl; or
Figure imgf000002_0002
wherein # marks the bond to the nitrogen atom and the staggered line marks the bond to the group G;
R2 and R3 are independently selected from hydrogen or methyl; R4 and R5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, hydroxy, or methoxy; or
R4 and R5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl, or cyclobutyl group;
G is selected from G-1 , G-2, G-3, and G-4, wherein:
G-1 is phenyl or phenoxy, wherein any of said phenyl or phenoxy are unsubstituted or substituted with 1 , 2 or 3 independently selected substituents RG1;
G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy; wherein any of said heteroaryl comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; and wherein said heteroaryl is unsubstituted or substituted with 1 or 2 independently selected substituents RG2;
G-3 is a 9- or 10-membered heterobicyclic ring system, wherein said - or 10-membered heterobicyclic ring system comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; wherein said heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said heterobicyclic ring system is unsubstitued or substituted with 1 or 2 independently selected substituents RG3;
G-4 is a 9- or 10-membered carbobicyclic ring system; wherein said carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents RG4;
RG1, RG2, RG3, and RG4 are independently hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci- C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2- C4alkynyl, C2-C4alkynyloxy, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl;
Figure imgf000003_0001
wherein # marks the bond to -O-R1; and % marks the bond to -C(=O)-N(H)-L1-G;
Y is O or S;
R7 is selected from Ci-Csalkyl, C2-C3alkenyl, C2-C3alkynyl, Cs-Cecycloalkyl, Cs-Cecycloalkylmethyl, methylformyl, f-butylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo-ethyl; or
R7 is selected from phenyl, thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, pyridazinyl or triazinyl, wherein any of said phenyl, thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, thiadiazolyl , pyridinyl, pyrimidinyl, pyridazinyl and triazinyl are unsubstituted or substituted with 1 or 2 independently selected substituents R8 selected from halogen, mercapto, cyano, Ci-Csalkyl, O-Csalkoxy, O-Cshaloalkyl, Ci- Cshaloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C3alkenyl, C2-C3alkynyl, or Ci-Csalkylsulfonyl; or
R7 is CR12R13R14 wherein R12 and R13 are independently selected from hydrogen, or methyl; or
R12 and R13 form a cyclopropyl together with the carbon they are attached to; and
R14 is selected from cyano, methylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo- ethyl; or
R14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, furanyl, isoxazolyl, oxadiazolyl, and thiadiazolyl, or a heterocyclyl selected from oxiranyl, azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetra hydro pyranyl, morpholinyl and dioxanyl, wherein any of said phenyl, heteroaryl and heterocyclyl are unsubstituted or substituted with 1 or 2 independently selected substituents R9 selected from halogen, mercapto, cyano, Ci-Csalkyl, Ci-Csalkoxy, Ci-Cshaloalkyl, Ci-Cshaloalkoxy, Cs-Cecycloalkyl, C3- Cecycloalkoxy, C2-C3alkynyl, or Ci-Csalkylsulfonyl; or an agrochemically acceptable salt, N-oxide, stereoisomer, or enantiomer of the compound of Formula (I).
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.
According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of Formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically- acceptable diluent or carrier.
According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of Formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
According to a fourth aspect of the invention, there is provided the use of a compound of Formula (I) as a fungicide. According to this particular aspect of the invention, the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
According to a fifth aspect, 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.
As used herein, the term “hydroxyl” or “hydroxy” means an -OH group.
As used herein, the term “mercapto” means an -SH group.
As used herein, the term “cyano” means a -CN group.
As used herein, amino means an -NH2 group. As used herein, nitro means an -NO2 group.
As used herein, oxo means an =0 group (eg, as in a carbonyl (C=O) group).
As used herein, the term "halogen" or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalky I.
As used herein, the term "Ci-4alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Ci-salkyl should be construed accordingly. Examples of Ci-4alkyl include, but are not limited to, methyl, ethyl, /so-propyl.
As used herein, the term "C2-3alkenyl" 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 three carbon atoms, which is attached to the rest of the molecule by a single bond. Examples of C2-3alkenyl include, but are not limited to, vinyl (ethenyl), prop- 1-enyl, allyl (prop-2-enyl).
As used herein, the term "C2-3alkynyl" 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 three carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C2- salkynyl include, but are not limited to, prop-1 -ynyl and propargyl (prop-2-ynyl).
As used herein, the terms "Ci-4haloalkyl", "C2-3haloalkenyl", and "C2-3haloalkynyl" refer respectively to a Ci-4alkyl, C2-3alkenyl, and C2-3alkynyl radical as defined above, substituted by one or more of the same or different halogen atoms. Examples of Ci-4haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethy I.
As used herein, the term "Ci-3fluoroalkyl" refers to a Ci-salkyl radical as generally defined above substituted by one or more fluorine atoms. Examples of Ci-3fluoroalkyl include, but are not limited to difluoromethyl and trifluoromethyl.
As used herein, the term "Ci-3alkoxy" refers to a radical of the formula RaO- where Ra is a Ci-salkyl radical as generally defined above. Examples of Ci-salkoxy include, but are not limited to, methoxy, ethoxy, /so-propoxy.
As used herein, the term "Ci-3fluoroalkoxy" refers to a O-salkoxy radical as generally defined above substituted by one or more fluorine atoms. Examples of Ci-3fluoroalkoxy include, but are not limited to trifluoromethoxy.
As used herein, the term "C3-4cycloalkyl" refers to a stable, monocyclic ring radical which is saturated and contains 3 or 4 carbon atoms.
As used herein, the term “Ci-salkylsulfanyl” refers to a radical of the formula -SRa wherein Ra is a Ci- salkyl radical as generally defined above.
As used herein, the term “Ci-3alkylsulfonyl” refers to a radical of the formula -S(O)2Ra wherein Ra is a Ci-salky I radical as generally defined above. The term “heteroaryl” as used herein refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O and S. Examples of heteroaryls include J-1 to J— 41 shown in Table J below. The staggered line in heteroaryls J-1 to J-43 represents the point of attachment to the rest of the compound. Preferred heteroaryls include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and thiazolyl; preferably pyridinyl, and thiazolyl.
Table J: Heteroaryl J-1 to J-43:
Figure imgf000006_0001
The term “heterocyclyl” as used herein 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. The staggered line in heterocyclyls K-1 to K-26 represents 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.
Figure imgf000007_0001
Figure imgf000007_0002
The term “optionally substituted” as used herein means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example, “C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms” means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3- C4cycloalkyl substituted with 2 halo atoms. The term “optionally substituted” can be used interchangeably with “unsubstituted or substituted” The staggered line as used herein, for example in heteroaryls shown in Table J and heterocyclyls shown in Table K, represent the point of connection / attachment to the rest of the compound.
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). Likewise, 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 Ci-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable 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 A, G, L1, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and Y with reference to the compounds of formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.
In an embodiment of each aspect of the invention, R1 is: A. phenyl optionally substituted with a one, two or three independently selected substituents R11; for instance, one or two independently selected substituents R11; preferably one substituent R11; wherein R11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
B. phenyl substituted with one or two substituents R11, for instance one substituent R11; wherein R11 is selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
C. phenyl substituted with one or two substituents, for instance one substituent, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
D. phenyl optionally substituted with a one or two substituents, for instance one substituent, independently selected from chloro, fluoro, cyano, methyl, methoxy, and cyclopropyl; or
E. phenyl substituted with a single substituent selected from methyl and cyclopropyl; or
F. cyclopropylphenyl.
In an embodiment of each aspect of the invention, R1 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, wherein said heteroaryl ring is optionally substituted with 1 or 2 independently selected substituents R11; or
B. a 6-membered monocyclic heteroaryl ring comprising 1 , 2 or 3 nitrogen atoms, wherein said heteroaryl ring is optionally substituted with 1 or 2 independently selected substituents R11; or
C. pyridine, pyrimidine, pyridazine, or 1 ,2,4-triazine wherein said pyridine, pyrimidine, pyridazine, 1 ,2,4-triazine is optionally substituted with one or two substituents, independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
D. pyridine substituted with a one or two substituents, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
E. pyridine substituted with a single substituent selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or
F. pyridine substituted with a single substituent selected from chloro, cyano, and methyl.
In an embodiment of each aspect of the invention, R1 is:
A. phenyl, pyridyl, pyrimidyl, or pyridazinyl, each optionally substituted with a one or two independently selected substituents R11 ; wherein R11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
B. phenyl, pyridyl, or pyrimidyl, each optionally substituted with a one or two independently selected substituents R11; wherein R11 is selected hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
C. phenyl, or pyridyl, each optionally substituted with a one or two independently selected substituents R11; wherein R11 is selected hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
D. phenyl, or pyridyl, each optionally substituted with a one or two independently selected substituents R11; wherein R11 is selected chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or
E. phenyl, or pyridyl, each optionally substituted with a one or two independently selected substituents R11; wherein R11 is selected chloro, cyano, methyl, and cyclopropyl; or
F. phenyl, or pyridyl, each optionally substituted with a one or two independently selected substituents R11; wherein R11 is selected chloro, cyano and cyclopropyl.
In an embodiment of each aspect of the invention, R11 is:
A. Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl; or
B. hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
C. hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
D. hydroxyl, cyano, methyl, vinyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
E. halogen, cyano, methyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or
F. cyano, methyl, methoxy, allyloxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
G. chloro, fluoro, cyano, methoxy, allyloxy, tri fluoro meth oxy, cyclopropyl, and cyclobutyl; or
H. halogen, cyano, methoxy, allyloxy, trifluoromethoxy, and cyclopropyl; or
I. chloro, fluoro, cyano, cyclopropyl and cyclobutyl; or
J. chloro, cyano, cyclopropyl and methyl. In an embodiment of each aspect of the invention, L1 is a direct bond, -O- or -O-C(RL1A)(RL1B)-; wherein RL1A and RL1B are independently selected from hydrogen and methyl; or RL1A and RL1B together with the carbon atom to which they are attached, form a cyclopropyl; or
Figure imgf000011_0001
wherein # marks the bond to the nitrogen atom and the staggered line marks the bond to the group G; wherein
R2 and R3 are independently selected from hydrogen and methyl;
R4 and R5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, hydroxy, and methoxy; or
R4 and R5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl or cyclobutyl group.
In an embodiment of each aspect of the invention:
A. R2 and R3 are hydrogen; R4 and R5 are independently selected from hydrogen and fluoro; or
B. R2 and R3 are hydrogen; R4 and R5, together with the carbon atom to which they are attached, form a cyclopropyl; or
C. R2, R3, R4, and R5 are hydrogen; or
D. R2, R3, and R4 are hydrogen, and R5 is fluoro.
In an embodiment of each aspect of the invention, G is selected from G-1 , G-2, G-3, and G-4, wherein: G-1 is phenyl or phenoxy, wherein said phenyl or phenoxy is optionally substituted with 1 , 2 or 3 independently selected substituents RG1;
G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy; wherein said heteroaryl comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; and wherein said heteroaryl is optionally substituted with 1 or 2 independently selected substituents RG2;
G-3 is a 9- or 10-membered heterobicyclic ring system comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S; wherein said heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said heterobicyclic ring system is optionally substituted with 1 or 2 independently selected substituents RG3;
G-4 is a 9- or 10-membered carbobicyclic ring system; wherein said carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic ring system is optionally substituted with 1 or 2 independently selected substituents RG4; wherein RG1, RG2, RG3, and RG4 are independently hydroxyl, halogen, mercapto, amino, cyano, Ci- C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, C2-C4alkynyloxy, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl.
In an embodiment of each aspect of the invention, G-1 is: A. phenyl or phenoxy, optionally substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
B. phenyl, optionally substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
C. phenyl optionally substituted with one or two substituents, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
D. phenyl optionally substituted with 1 , 2 or 3 substituents, for instance 2 or 3 substituents, each independently selected from chloro, fluoro, methyl, and methoxy; or
E. phenyl substituted with one or two substituents, for instance one substituent, selected from chloro and methyl; or
F. phenoxy substituted with one substituent selected from chloro and methyl.
In an embodiment of each aspect of the invention, G-2 is:
A. pyridine, pyrimidine, pyridazine, or 1 ,2,4-triazine wherein said pyridine, pyrimidine, pyridazine, 1 ,2,4-triazine is optionally substituted with one or two substituents, independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or
B. pyridine, pyrimidine, or pyridazine, substituted with one or two substituents, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
C. pyrimidine, or pyridazine, substituted with one or two substituents, independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
D. pyridine substituted with 1 , 2 or 3 substituents, for instance 2 or 3 substituents, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or
E. pyridine substituted with one or two substituents, for instance one substituent, selected from chloro and methyl.
In an embodiment of each aspect of the invention, G-3 is:
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, benzothiophen-6-yl optionally substituted with 1 , 2 or 3 substituents, for instance one or two substituents, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or
B. 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, or benzothiophen-2-yl, benzothiophen-3-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or
C. chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, or 2,3- dihydrobenzofuran-3-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or
D. 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; or
In an embodiment of each aspect of the invention, G-4 is:
A. naphthalen-2-yl, tetralin-1 -yl, tetralin-2-yl, tetralin-6-yl, indan-1-yl, indan-2-yl, or indan-5-yl optionally substituted with 1 , 2 or 3 substituents, for instance one or two substituents, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or
B. tetralin-1 -yl, tetralin-2-yl, indan-1-yl, or indan-2-yl, or optionally substituted with one or two substituents, for instance one substituent, each independently selected from chloro, fluoro, cyano, methyl, and methoxy; or
C. tetralin-1 -yl or indan-1-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy.
In an embodiment of each aspect of the invention, RG1 , RG2, RG3, and RG4 are independently:
A. hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci- C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, C2-C4alkynyloxy, Ci- Csalkylsulfanyl, or Ci-Csalkylsulfonyl; or
B. hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci- C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, or C2-C4alkynyl; or
C. chloro, fluoro, cyano, Ci-Csalkyl, Ci-Csalkoxy, Ci-C2haloalkyl, Ci-C2haloalkoxy, C3-C4cycloalkyl, C2-C3alkenyl, or C2-C3alkynyl; or
D. chloro, fluoro, cyano, Ci-C2alkyl, O-Csalkoxy, or Ci-C2haloalkyl; or
E. hydroxyl, halogen, such as chloro or fluoro, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tertbutoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; or
F. hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, or cyclobutyl; or
G. hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or
H. chloro, fluoro, cyano, methyl, or methoxy; or I. chloro or methyl.
Group A represents
Figure imgf000014_0001
wherein # marks the bond to -O-R1; and % marks the bond to -
C(=O)-N(H)-L1-G.
In an embodiment of each aspect of the invention, Y is oxygen or sulfur, preferably oxygen.
In an embodiment of each aspect of the invention, R7 is
A1. selected from Ci-Csalkyl, C2-C3alkenyl, C2-C3alkynyl, Cs-Cecycloalkyl, Cs-Cecycloalkylmethyl, methylformyl, f-butylformyl, 2-(dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo-ethyl; or
A2. selected from Ci-C2alkyl, allyl, propargyl, C4-C6cycloalkyl, methylformyl, f-butylformyl, 2- (dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo-ethyl; or
A3. selected from methyl, ethyl, propyl, /-propyl, allyl, propargyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, methylformyl, Abutylformyl, 2-(dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo- ethyl; or
A4. selected from methyl, ethyl, allyl, propargyl, cyclopentyl, cyclohexyl, methylformyl, 2- (dimethylamino)-2-oxo-ethyl, and 2-(methylamino)-2-oxo-ethyl; or
A5. selected from methyl, ethyl, allyl, propargyl, methylformyl, and 2-(methylamino)-2-oxo-ethyl.
In an embodiment of each aspect of the invention, R7 may also be:
B1. phenyl or heteroaryl selected from thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, and thiadiazolyl; said phenyl or heteroaryl being optionally substituted with 1 or 2 independently selected substituents R8 selected from halogen, mercapto, cyano, Ci-Csalkyl, Ci- Csalkoxy, Ci-Cshaloalkyl, Ci-Cshaloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C3alkenyl, C2- Csalkynyl, and Ci-Csalkylsulfonyl; or
B2. phenyl or heteroaryl selected from thiazolyl, imidazolyl, and thienyl, said phenyl or heteroaryl being optionally substituted with 1 or 2 independently selected substituents R8 selected from halogen, mercapto, cyano, methyl, ethyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or
B3. phenyl or heteroaryl selected from pyrazolyl, and thiazolyl, said phenyl or heteroaryl being optionally substituted with 1 or 2 independently selected substituents R8 selected from halogen, cyano, methyl, ethyl, ethynyl, methoxy, methylsulfonyl, cyclopropyl, and cyclopropyloxy; or
B4. selected from phenyl and pyrazolyl, said phenyl and pyrazolyl being optionally substituted with 1 or 2 independently selected substituents R8 selected from fluoro, chloro, cyano, methyl, ethyl, and methoxy; or B5. phenyl optionally substituted with 1 or 2 independently selected R8 selected from fluoro, chloro, cyano, methyl, ethyl, and methoxy.
In an embodiment of each aspect of the invention, R7 is CR12R13R14, where
C1. R12 and R13 are independently selected from hydrogen, and methyl; or R12 and R13 form a cyclopropyl together with the carbon they are attached to; and R14 is cyano, methylformyl, 2- (dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo-ethyl; or R14 is phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, furanyl, isoxazolyl, oxadiazolyl, and thiadiazolyl (e.g. J-1 to J-43), or a heterocyclyl selected from oxiranyl, azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetrahydropyranyl, morpholinyl and dioxanyl (e.g. K-1 to K-26), wherein said phenyl, heteroaryl and heterocyclyl is optionally substituted with 1 or 2 independently selected substituents R9 selected from halogen, mercapto, cyano, Ci-Csalkyl, O-Csalkoxy, Ci-Cshaloalkyl, O-Cshaloalkoxy, Cs-Cecycloalkyl, C3- Cecycloalkoxy, C2-C3alkynyl, and Ci-Csalkylsulfonyl; or
C2. R12 and R13 are independently selected from hydrogen, and methyl; and R14 is cyano, methylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2-oxo-ethyl, or R14 is phenyl, heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, imidazolyl, and thienyl (e.g. J-1 to J-9, J-21 to J-23, J-27 to J-29, J-36 to J-38, J-40 and J-41 ), or a heterocyclyl selected from azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl (e.g. K-1 , K-2, K-4, K-6, K-7, K-11 , K-14, K-18 and K-22); wherein said phenyl, heteroaryl or heterocyclyl is optionally substituted with 1 or 2 independently selected substituents R9 selected from halogen, mercapto, cyano, methyl, ethyl, ethynyl, difluoromethyl, methoxy, ethoxy, methylsulfonyl, cyclopropyl, and cyclopropyloxy; or
C3. R12 and R13 form a cyclopropyl together with the carbon they are attached to; and R14 is cyano, methylformyl, or 2-(methylamino)-2-oxo-ethyl; or R14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, and imidazolyl (e.g. J-1 to J-9, J-21 to J-23, J-27 to J-29 and J-36 to J-38), or a heterocyclyl selected from pyrrolidinyl, piperidinyl, piperazinyl, and tetra hydro pyranyl (e.g. K-11 , K-14, K-18 and K-22); wherein said phenyl, heteroaryl or heterocyclyl is optionally substituted with 1 or 2 independently selected substituents R9 selected from fluoro, chloro, cyano, methyl, ethyl, methoxy, and cyclopropyl; or
C4. R12 is hydrogen and R13 is methyl; R14 is cyano, methylformyl, or 2-(methylamino)-2-oxo-ethyl; and R14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, and imidazolyl (e.g. J-1 to J-9, J-21 to J-23, J-27 to J-29 and J-36 to J-38), or a heterocyclyl selected from pyrrolidinyl, piperidinyl, piperazinyl, and tetra hydro pyranyl (e.g. K-11 , K-14, K-18 and K- 22); wherein said phenyl, heteroaryl or heterocyclyl is optionally substituted with 1 or 2 independently selected substituents R9 selected from fluoro, chloro, cyano, methyl, ethyl, methoxy, and cyclopropyl; or
C5. R12 and R13 are hydrogen; and R14 is cyano, methylformyl, or 2-(methylamino)-2-oxo-ethyl; or
R14 is a phenyl, pyridinyl, thiazolyl, pyrrolidinyl, piperazinyl or tetra hydro pyranyl (e.g. J-1 to J-3, J-36 to J-38, K-11 , K-18 and K-22), the latter being optionally substituted with 1 or 2 independently selected substituents R9 selected from fluoro, chloro, cyano, methyl and methoxy.
In an embodiment of each aspect of the invention: R7 is A1 or B1 or C1 ; or R7 is A1 or B1 or C2; or R7 is A1 or B1 or C3; or R7 is A1 or B1 or C4; or R7 is A1 or B1 or C5; or R7 is A1 or B2 or C1 ; or R7 is A1 or B2 or C2; or R7 is A1 or B2 or C3; or R7 is A1 or B2 or C4; or R7 is A1 or B2 or C5; or R7 is A1 or B3 or C1 ; or R7 is A1 or B3 or C2; or R7 is A1 or B3 or C3; or R7 is A1 or B3 or C4; or R7 is A1 or B3 or C5; or R7 is A1 or B4 or C1 ; or R7 is A1 or B4 or C2; or R7 is A1 or B4 or C3; or R7 is A1 or B4 or C4; or R7 is A1 or B4 or C5; or R7 is A1 or B5 or C1 ; or R7 is A1 or B5 or C2; or R7 is A1 or B5 or C3; or R7 is A1 or B5 or C4; or R7 is A1 or B5 or C5; or R7 is A2 or B1 or C1 ; or R7 is A2 or B1 or C2; or R7 is A2 or B1 or C3; or R7 is A2 or B1 or C4; or R7 is A2 or B1 or C5; or R7 is A2 or B2 or C1 ; or R7 is A2 or B2 or C2; or R7 is A2 or B2 or C3; or R7 is A2 or B2 or C4; or R7 is A2 or B2 or C5; or R7 is A2 or B3 or C1 ; or R7 is A2 or B3 or C2; or R7 is A2 or B3 or C3; or R7 is A2 or B3 or C4; or R7 is A2 or B3 or C5; or R7 is A2 or B4 or C1 ; or R7 is A2 or B4 or C2; or R7 is A2 or B4 or C3; or R7 is A2 or B4 or C4; or R7 is A2 or B4 or C5; or R7 is A2 or B5 or C1 ; or R7 is A2 or B5 or C2; or R7 is A2 or B5 or C3; or R7 is A2 or B5 or C4; or R7 is A2 or B5 or C5; or R7 is A3 or B1 or C1 ; or R7 is A3 or B1 or C2; or R7 is A3 or B1 or C3; or R7 is A3 or B1 or C4; or R7 is A3 or B1 or C5; or R7 is A3 or B2 or C1 ; or R7 is A3 or B2 or C2; or R7 is A3 or B2 or C3; or R7 is A3 or B2 or C4; or R7 is A3 or B2 or C5; or R7 is A3 or B3 or C1 ; or R7 is A3 or B3 or C2; or R7 is A3 or B3 or C3; or R7 is A3 or B3 or C4; or R7 is A3 or B3 or C5; or R7 is A3 or B4 or C1 ; or R7 is A3 or B4 or C2; or R7 is A3 or B4 or C3; or R7 is A3 or B4 or C4; or R7 is A3 or B4 or C5; or R7 is A3 or B5 or C1 ; or R7 is A3 or B5 or C2; or R7 is A3 or B5 or C3; or R7 is A3 or B5 or C4; or R7 is A3 or B5 or C5; or R7 is A4 or B1 or C1 ; or R7 is A4 or B1 or C2; or R7 is A4 or B1 or C3; or R7 is A4 or B1 or C4; or R7 is A4 or B1 or C5; or R7 is A4 or B2 or C1 ; or R7 is A4 or B2 or C2; or R7 is A4 or B2 or C3; or R7 is A4 or B2 or C4; or R7 is A4 or B2 or C5; or R7 is A4 or B3 or C1 ; or R7 is A4 or B3 or C2; or R7 is A4 or B3 or C3; or R7 is A4 or B3 or C4; or R7 is A4 or B3 or C5; or R7 is A4 or B4 or C1 ; or R7 is A4 or B4 or C2; or R7 is A4 or B4 or C3; or R7 is A4 or B4 or C4; or R7 is A4 or B4 or C5; or R7 is A4 or B5 or C1 ; or R7 is A4 or B5 or C2; or R7 is A4 or B5 or C3; or R7 is A4 or B5 or C4; or R7 is A4 or B5 or C5; or R7 is A5 or B1 or C1 ; or R7 is A5 or B1 or C2; or R7 is A5 or B1 or C3; or R7 is A5 or B1 or C4; or R7 is A5 or B1 or C5; or R7 is A5 or B2 or C1 ; or R7 is A5 or B2 or C2; or R7 is A5 or B2 or C3; or R7 is A5 or B2 or C4; or R7 is A5 or B2 or C5; or R7 is A5 or B3 or C1 ; or R7 is A5 or B3 or C2; or R7 is A5 or B3 or C3; or R7 is A5 or B3 or C4; or R7 is A5 or B3 or C5; or R7 is A5 or B4 or C1 ; or R7 is A5 or B4 or C2; or R7 is A5 or B4 or C3; or R7 is A5 or B4 or C4; or R7 is A5 or B4 or C5; or R7 is A5 or B5 or C1 ; or R7 is A5 or B5 or C2; or R7 is A5 or B5 or C3; or R7 is A5 or B5 or C4; or R7 is A5 or B5 or C5.
The compounds of formula (I) can be prepared by those skilled in the art as shown in the following schemes 1 to 14, wherein R1, R2, R3, R4, R5, R7, R8, R9, R11, R12, R13, R14, Y, L, G-1 , G-2, G-3, G-4, RL1A, RL1B, RG1, RG2, RG3, RG4 are as defined for a compound of formula (I), unless otherwise stated. Certain stereogenic centers have been left unspecified for the clarity and are not intended to limit the teaching of the schemes in any way. The compounds of formula (I) are obtained by an amide-coupling transformation with compounds of formula (II), wherein X1 is OH, and amine compounds of formula (III) by activating the carboxylic acid function of the compounds of formula (II), 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 (COCI)2 or SOCh, prior to treatment with the compounds of formula (III), preferably in a suitable solvent (e.g., N- methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at temperatures between 25°C and 60°C, and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or alternatively under conditions described in the literature for an amide coupling 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). For examples, see Chem. Soc. Rev. (2009), 38, 606 and Chem. Soc. Rev. (2011), 40, 5084. Compounds of formula (II) and compounds of formula (III) are either known or commercially available. This is shown in Scheme 1 .
Figure imgf000017_0001
Scheme 1
Compounds of formula (I) are prepared from reacting nucleophilic compounds of formula (IV) with electrophilic compounds of formula (V), wherein X2 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, tetra hydrofuran, 2-methyl tetrahydrofuran, sulfolane, or dimethylsulfoxide) at temperatures between 60°C and 110°C and preferably using a metal catalyst complex (e.g. Cu or Pd). For related examples, see Eur. J. Org. Chem., (2011), 18, 3353; J. Org. Chem., (2009), 74, 7951 ; Tetrahedron Lett., (2012), 53, 5318. Compounds of formula (IV) are either known or commercially available. This is shown in Scheme 2.
Figure imgf000017_0002
(IV) (V)
Scheme 2
Compounds of formula (II), wherein X is Ci-C4-alkoxy, are prepared from reacting nucleophilic compounds of formula (IV) with electrophilic compounds of formula (VI), wherein X is OH or C1-C4- alkoxy and X3 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-f-Bu, K3PO4, K2CO3, triethylamine, or CS2CO3, in a suitable solvent (e.g. N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyl tetra hydrofuran, sulfolane, dimethylsulfoxide) at temperatures between 60°C and 110°C and preferably using a metal catalyst complex (e.g. Cu or Pd). For related examples, see Eur. J. Org. Chem., (2011), 18, 3353; J. Org. Chem., (2009), 74, 7951 ; Tetrahedron Lett., (2012), 53, 5318; WO 2008/110313 and WO 2012/136604. Additionally, compounds of formula (II), wherein X is Ci-C4-alkoxy, are readily hydrolyzed under conditions described in the literature to afford compounds of formula (II), wherein X is OH. Compounds of formula (VI) are either known or commercially available. This is shown in Scheme 3.
Figure imgf000018_0001
(IV) (VI) (II)
Scheme 3
The compounds of formula (V), wherein X3 is halogen or OH, can be obtained by an amide coupling transformation with compounds of formula (VI), wherein X1 is OH and X3 is halogen or OH, and amine compounds of formula (III) by activating the carboxylic acid function of the compounds of formula (VI), 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 (COCI)2 or SOCh, prior to treatment with the compounds of formula (III), preferably in a suitable solvent (e.g., N-methylpyrrolidone dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at temperatures between 25°C and 60°C, and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or alternatively under conditions described in the literature for an amide coupling 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). For examples, see Chem. Soc. Rev. (2009), 38, 606 and. Chem. Soc. Rev. (2011), 40, 5084. This is shown in Scheme 4.
Figure imgf000018_0002
(VI) (V)
Scheme 4
Compounds of formula (II), wherein X1 is OH or Ci-C4-alkoxy, are prepared from reacting nucleophilic compounds of formula (VI), wherein X3 is OH and X1 is OH or Ci-C4-alkoxy, with electrophilic compounds of formula (VII), wherein and X4 is fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol), in a suitable solvent (e.g. dichloromethane, 1 ,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, N-methylpyrrolidone, dimethylacetamide) at temperatures between 40°C and 80°C and using a metal source (e.g. Cu(OAc)2), and preferably in the presence of an oxidant such as O2 or a suitable palladium pre-catalyst, such as RockPhos Pd G3, in the presence of a base (e.g. K3PO4) and suitable solvent (e.g. dimethyl ether or toluene) at temperatures between 20°C and 80°C. For related examples, see Org. Lett., (2003), 5, 1381 ; Tetrahedron Lett. (1998), 39, 2933; Tetrahedron Lett., (2003), 44, 3863; and Org. Lett., (2013), 15, 2876. Compounds of formula (VII) and compounds of formula (VI) are either known or commercially available. This is shown in Scheme 5.
Figure imgf000019_0001
Scheme 5
Compounds of formula (I), wherein are prepared from reacting nucleophilic compounds of formula (V), wherein X2 is OH, with electrophilic compounds of formula (VII), wherein and X4 is chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol), in a suitable solvent (e.g. dichloromethane, 1 ,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyl tetra hydrofuran) at temperatures between 40°C and 80°C and using a metal source (e.g. Cu(OAc)2), optionally in the presence of an oxidant such as O2 or a suitable palladium pre-catalyst, such as RockPhos Pd G3, in the presence of a base (e.g. K3PO4) and suitable solvent (e.g. dimethyl ether or toluene) at temperatures between 20°C and 80°C. For related examples, see Org. Lett., (2003), 5, 1381 ; tetrahedron Lett. (1998), 39, 2933; Tetrahedron Lett., (2003), 44, 3863; and Org. Lett., (2013), 15, 2876. Compounds of formula (VI I) are either known or commercially available. This is shown in Scheme 6.
Figure imgf000019_0002
Scheme 6
Compounds of Formula (VI), wherein X1 is OH or Ci-C4-alkoxy, and X3 is OH or halogen can be obtained from compounds of formula (VIII), wherein X5 is OH or halogen, via an oxidation method using a suitable oxidant, suchs 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. For related examples, see: Can. J. Chem. (1978), 56, 1273; WO2021160470. Compounds of formula (VIII) are known or can be prepared as described in Bulletin de la Societe Chimique de France (1972), 8, 3198-202. This reaction is shown in Scheme 7.
Figure imgf000019_0003
Scheme 7 Compounds of Formula (II), wherein X1 is OH, alkoxy, or halogen, can be obtained from compounds of formula (XI) via an oxidation method using a suitable oxidant, suchs as KMnO4 or a suitable cobalt(ll) salt and trihydroxyisocyanuric acid (THICA) in a suitable solvent (e.g., acetic acid) at temperatures between 25°C and 200°C. For related examples, see: Can. J. Chem. (1978), 56, 1273; WO2021160470. Compounds of formula (XI) can be prepared as described in Bulletin de la Societe Chimique de France (1972), 8, 3198-3202.
Furthermore, compounds of formula (XII), are prepared from reacting nucleophilic compounds of formula (IV) with electrophilic compounds of formula (VIII), wherein X5 is a suitable leaving group such as halogen, in the presence of base (e.g. KO-f-Bu, K3PO4, K2CO3, triethylamine, or CS2CO3, in a suitable solvent (e.g. N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyl tetra hydrofuran, sulfolane, dimethylsulfoxide) at temperatures between 25°C and reflux and optionally using a metal catalyst and ligand complex (e.g. Cui, N,N-dimethylglycine). For related examples, see Eur. J. Org. Chem., (2011), 18, 3353; J. Org. Chem., (2009), 74, 7951 ; Tetrahedron Lett., (2012), 53, 5318; WO 2008/110313 and WO 2012/136604. Compounds of formula (VIII) are either known or commercially available. This is shown in Scheme 8.
Figure imgf000020_0001
Scheme 8
Compounds of formula (II), wherein X1 is OH or Ci-C4-alkoxy can be prepared by reaction of compounds of formula (X) in aqueous solvent mixture such as /so-propanol or ethanol, optionally in an alkaline media at temperature between 90°C and 11 °C. For related examples, see: J. Med. Chem. (2012), 55, 10118- 10129. This is shown in Scheme 9.
Figure imgf000020_0002
Scheme 9
Compounds of formula (X), are known or can be obtained from compounds of formula (XIX) wherein X6 is chloro, bromo, iodo, trifluoromethanesulfonyl-O- at temperature between 50°C and 120°C, preferably between 80°C and 110 °C using a metal source, such as XPhos Pd G1 , in the presence of a cyanide source selected from potassium ferrocyanide, cooper cyanide, zinc cyanide or potassium cyanide and a base (e.g. KOAc) in a suitable solvent or a mixture of two solvents (e.g. dioxane, water, toluene, tetra hydrofuran, 2-methyl-tetrahydrofuran, xylene). For related examples, see: J. Org. Chem. (2018), 83, 4922-4931 or Org. Lett. (2006), 8, 1189-1191. This is shown in Scheme 10.
Figure imgf000021_0001
Scheme 10
Related compounds of formula (XIII), wherein X7 is chloro, bromo or iodo can be obtained from compounds of formula (XII) wherein X7 is chloro, bromo or iodo by reacting them with hydrazines in a suitable solvent or a mixture of solvent such as methanol, ethanol or water at a temperature between room temperature and 100 °C, preferably between 50 °C and 80 °C. Compounds of formula (XII) are either known or commercially available. For related examples, see: J. Med. Chem. (2017), 60, 695-709 or J. Het. Chem. (1996), 33, 1579-1582. Compounds of formula (XVII) or related examples are known, for instance in WO 2015/071206; Tetrahedron Lett. (2006), 47, 8733-8735; Synth. Comm. (2006), 36, 2719-2726 or Tetrahedron Lett. (2006), 47, 8733-8735. This is shown in Scheme 11.
Figure imgf000021_0002
(XII) (XIII)
Scheme 11
Related compounds of formula (XIV), wherein X7 is halogen, are prepared by reaction of compounds of formula (XIII) with cyanide salt such as sodium or potassium cyanide in the presence or not of a copper salt (eg. copper cyanide) in a suitable solvent or solvent mixtures (eg. dimethylformamide, tetra hydrofuran, 2-methyl-tetrahydrofuran) at temperature between 50 and 120 °C, preferably between 80 °C and 100 °C. Compounds of formula (XIII) are either known or prepared according to Scheme 11. For related examples, see: WO 1995/07264. This is shown in Scheme 12.
Figure imgf000021_0003
Scheme 12
Related compounds of formula (XV), wherein X7 is halogen, are prepared by reaction of compounds of formula (XIII) with methyl magnesium halide wherein halide is bromide or chloride in the optional presence of a copper salt (eg. copper iodide, copper cyanide, copper chloride, copper acetate) in a suitable solvent or solvent mixtures (eg. diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2- methyl-tetrahydrofuran, tert-butyl methyl ether) at temperature ranging from -20 °C to 10°C. Compounds of formula (XIII) are either known or prepared according to Scheme 11 . For related examples, see: WO 1995/07264. This is shown in Scheme 13.
Figure imgf000022_0001
(XIII) (XV)
Scheme 13
Related compounds of formula (XVII) are obtained by reacting compounds of formula (XVII) with compounds of formula (XVI), wherein X8 is OH, halogen, alkoxy, aryloxy, hetereoaryloxy or any other suitable leaving group and X9 is halogen, methyl, trifluoromethanesulfonyl-O-, cyano, ester or carboxamide and The reaction of compounds of formula (XVI) with compounds of formula (XVII) can either be:
A) a nucleophilic displacement compounds of formula (XVII) by compounds of formula (XVI), wherein X10 is alkyl, cycloalkyl, akenyl, alkynyl, propargyl, allyl, -CQ1Q2Q3 wherein Q1 and Q2 are independently hydrogen, alkyl or they form a cycloalkyl with the carbon they are attached to and Q3 is aryl or an heterocycle saturated or partially saturated and X11 is a halogen or any suitable leaving group, in the presence of a base (eg. sodium hydride, potassium carbonate, sodium carbonate, cesium carbonate) in a suitable solvent or solvent mixtures (eg. dimethylformamide, dimethylsulfoxide, ethyl acetate, 2-methyl-tetrahydrofuran, tetrahydrofuran) at temperature between 25 °C and 120 °C. For related example, see: Synth. Comm. (2002), 32, 1675; WO 2018/201167; WO 2009/142732; WO 2017/190669 or WO 2011/025690; or
B) a coupling between compounds of formula (XVII) with compounds of formula (XVI) wherein X10 is an aryl or heteroaryl and X11 is halogen, trifluoromethanesulfonyl-O-, a boronic acid or ester, a hypervalent iodine connected to two aryles, in presence of catalyst, for intance a copper salt (eg. copper oxyide, copper iodide, copper chloride, copper bromide) or a palladium salt (eg. palladium acetate, bis(dibenzylideneacetone)palladium) in a suitable solvent or solvent mixtures (eg. dimethylformamide, tetra hydrofuran, dioxane) at temperatures between 25 °C and 120 °C, preferably between 90 °C and 110 °C. For related examples, see: Chem. Eur. J. (2004) 10, 5607; Tetrahedron Lett. (2006) 1, 149 or WO 2004/094420; or
C) a carbonylation between compounds of formula (XVII) by compounds of formula (XVI), wherein X10 is alkoxycarbonly, aryloxycarbonyl, alkylcarbomoyl or arylcarbamoyl and X11 is halogen, preferably chloride, in the presence of an organic base, for instance triethylamine, 4-dimethylamino-pyridine or pyridine in a suitable solvent or solvent mixtures (eg. ethylacetate, dimethylformamide, tetrahydrofuran, dimethylsulfoxide) at temperature between 0 °C and 80 °c preferably between 25 °C and 40 °C. For related examples, see: WO 2008/023357 or J. Het. Chem. (2021) 58, 2163;
This is shown in Scheme 14.
Figure imgf000023_0001
(XVI) (XVII) (XVIII)
Scheme 14
As already indicated, surprisingly, it has now been found that the compounds of Formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
Salts of compounds of formula (I) may be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
Depending on the procedure or the reaction conditions, the compounds of formula (I), which have saltforming properties, can be obtained in free form or in the form of salts.
The compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, or diastereomer mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule, the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.
Diastereomeric mixtures or racemic mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
Enantiomeric mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.
Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
As an example, compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns. Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention.
The compounds of formula (I) 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) 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 protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of Formula (I) 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. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all dev/ation 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. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown. The active compounds of Formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
Furthermore, the compounds of Formula (I) can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
The compounds of Formula (I) are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:
Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp,Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi- virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.
The compounds of Formula (I) may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.
Within the scope of present invention, target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
The term "useful plants" is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl- shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
The term "useful plants" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cry 111 B(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "crops" is to be understood as including also crop plants which have been so transformed 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 8- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosomeinactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bi benzyl synthase, chitinases and glucanases.
Further, in the context of the present invention there are to be understood by 8-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see 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.
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. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in 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.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab 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 phytopathogenic fungi, such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae, and Fabaceae; Glomerella lagenarium on Cucurbitaceae; Sclerotinia sclerotiorum on Fabaceae, Brassicaceae, and Asteraceae, such as soybean, rapeseed, and sunflower respectively; or Alternaria solani on Solanaceae, such as tomato and potato.
The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
The term “plant propagation material” is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds. The compounds of Formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently Formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
Suitable carriers and adjuvants, e.g. for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in 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. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular Formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins. Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein 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.
Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, divinyl glycol, divinyl glycol abietate, divinyl glycol butyl ether, divinyl glycol ethyl ether, divinyl glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, vinyl carbonate, 1 ,1 ,1- trichloroethane, 2-heptanone, alpha pinene, d-limonene, vinyl glycol, vinyl glycol butyl ether, vinyl glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, mvinyl chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o- xylene, phenol, polyvinyl glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, trivinyl glycol, xylene sulfonic acid, paraffin, mineral oil, trichlorovinyl, perchlorovinyl, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., vinyl glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates. Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyvinyl glycol esters of fatty acids, such as polyvinyl glycol stearate; block copolymers of vinyl oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
In addition, further, other 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. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further 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.
In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The compounds of Formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula (I) 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. Preferably 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).
The following mixtures of the compounds of formula (I) with active ingredients are preferred (where the abbreviation “TX” means “one compound selected from the compounds defined in the Tables A-1 to A- 21 , Tables B-1 to B-21 , or compounds P-1 to P-19 as listed in Table T 1 (below)”): 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 oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, carbophenothion + TX, cymiazole + TX, chino- methionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, cufraneb + TX, cyanthoate + TX, DCPM + TX, DDT + TX, demephion + TX, demephion-0 + TX, demephion-S + TX, demeton- methyl + TX, demeton-0 + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dienochlor + TX, dimefox + TX, dinex + TX, dinex-diclexine + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinosulfon + TX, dinoterbon + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate -methyl + TX, etrimfos + TX, fenazaflor + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpyrad + TX, fen- pyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, flubenzimine + TX, flucycloxuron + TX, fluenetil + TX, fluorbenside + TX, FMC 1137 + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, gamma-HCH + TX, glyodin + TX, halfenprox + TX, hexadecyl cyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, lindane + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, mesulfen + TX, methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl- propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifluridide + TX, nikkomycins + TX, nitrilacarb + TX, nitrilacarb 1 :1 zinc chloride complex + TX, omethoate + TX, oxydeprofos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phenkapton + TX, phosalone + TX, phosfolan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, proclonol + TX, promacyl + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pyrimitate + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, phosglycin + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, sophamide + TX, SSI- 121 + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, diflovidazin + TX, tau-fluvalinate + TX, TEPP + TX, terbam + TX, tetradifon + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trifenofos + TX, trinactin + TX, vamidothion + TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichlone + TX, dichlorophen + TX, endothal + TX, fentin + TX, hydrated lime + TX, nabam + TX, quinoclamine + TX, quinonamid + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, crufomate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1 -hydroxy-1 H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8- hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodicin + TX, fenaminosulf + TX, formaldehyde + TX, hydrargaphen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, apholate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6- methylhept-2-en-4-ol + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-l l-enal + TX, (Z)-hexadec-l 1-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)- tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11 E)-tetradeca-9,11- dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1 -yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, alpha-multistriatin + TX, brevicomin + TX, codlelure + TX, codlemone + TX, cuelure + TX, disparlure + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, 10-dien-1 -yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, frontalin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineati n + TX, litlure + TX, looplure + TX, medlure + TX, megatomoic acid + TX, methyl eugenol + TX, muscalure + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate + TX, trimedlure + TX, trimedlure A + TX, trimedlure B, + TX, trimedlure B2 + TX, trimedlure C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methylneodecanamide + TX, oxamate + TX, picaridin + TX, 1 -dichloro-1 -nitroethane + TX, 1 , 1 -dichloro- 2,2-bis(4-ethylphenyl)ethane + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene + TX, 1 -bromo-2- chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2- ethylsulfinylethyl methyl phosphate + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2- butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2- isovalerylindan-1 ,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2- thiocyanatoethyl laurate + TX, 3-bromo-1 -chloroprop-1 -ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate + TX, acethion + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, anabasine + TX, athidathion + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2- chloroethyl) ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiofos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidafos + TX, dicapthon + TX, dichlofenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dilor + TX, dimefluthrin + TX, dimetan + TX, dimethrin + TX, dimethylvinphos + TX, dimetilan + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, diofenolan + TX, dioxabenzofos + TX, dithicrofos + TX, DSP + TX, ecdysterone + TX, El 1642 + TX, EMPC + TX, EPBP + TX, etaphos + TX, ethiofencarb + TX, ethyl formate + TX, vinyl dibromide + TX, vinyl dichloride + TX, vinyl oxide + TX, EXD + TX, fenchlorphos + TX, fenethacarb + TX, fenitrothion + TX, fenoxacrim + TX, fenpirithrin + TX, fensulfothion + TX, fenthion-ethyl + TX, flucofuron + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, furathiocarb + TX, furethrin + TX, guazatine + TX, guazatine acetates + TX, sodium tetrathiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hyquincarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprothiolane + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kelevan + TX, kinoprene + TX, lead arsenate + TX, leptophos + TX, lirimfos + TX, lythidathion + TX, m-cumenyl methylcarbamate + TX, magnesium phosphide + TX, mazidox + TX, mecarphon + TX, menazon + TX, mercurous chloride + TX, mesulfenfos + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methocrotophos + TX, methoprene + TX, methothrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methylchloroform + TX, mvinyl chloride + TX, metoxadiazone + TX, mirex + TX, naftalofos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, 0,0-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, 0,0-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, phenkapton + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + TX, quassia + TX, quinalphos-methyl + TX, quinothion + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, kadethrin + TX, ryania + TX, ryanodine + TX, sabadilla + TX, schradan + TX, sebufos + TX, SI-0009 + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tazimcarb + TX, TDE + TX, tebupirimfos + TX, temephos + TX, terallethrin + TX, tetrachloroethane + TX, thicrofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thionazin + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronat + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triprene + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, trifenmorph + TX, 1 ,2-dibromo-3-chloropropane + TX, 1 ,3-dichloropropene + TX, 3,4- dichlorotetrahydrothiophene 1 ,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6- thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, anisiflupurin + TX, benclothiaz + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + TX, potassium ethylxanthate + TX,acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, alpha-chlorohydrin + TX, antu + TX, barium carbonate + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbormide + TX, phosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, scilliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2- butoxyethoxy)ethyl piperonylate + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, verbutin + TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, chloroinconazide + TX, mercuric oxide + TX, thiophanate- methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazole + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropidin + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl -+ TX, Rmetalaxyl + TX, ofurace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestroburin + TX, fenaminstrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim- methyl + TX, metominostrobin + TX, trifloxystrobin + TX, orysastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid + TX, bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothal-isopropyl + TX, edifenphos + TX, iprobenphos + TX, phosdiphen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, cyclobutrifluram + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, flumetylsulforim + TX, fluopicolide + TX, fluoxytioconazole + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminium + TX, hymexazol + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamid + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucypram + TX, isotianil + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1 ,4]dithiino[1 ,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3- ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl- pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4- carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3- amine + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1 , 3- dimethyl- 1 H- pyrazol- 5- amine + TX, fluindapyr + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, Ivbenmixianan + TX, dichlobentiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1- yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiprolin + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-mvinyl]amino]oxymethyl]-2- pyridyl]carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole+ TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3- carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5- dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5- bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro- phenyl] methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- mvinyl]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2- methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4- carboxamide + TX, 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol- 5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1- yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctradin + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3- enamide + TX, florylpicoxamid + TX, fenpicoxamid + TX, meta ry I pi cox a mid + TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin + TX, isofetamid + TX, ethyl 1 -[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (may be prepared from the methods described in WO 2020/056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3- carboxylate + TX (may be prepared from the methods described in WO 2020/056090), methyl N-[[4-[1- (4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (may be prepared from the methods described in WO 2020/097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl- phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (may be prepared from the methods described in WO 2020/097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)- 2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (may be prepared from the methods described in WO 2020/109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3- cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (may be prepared from the methods described in WO 2020/109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4- dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (may be prepared from the methods described in WO 2020/109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1- methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3- (difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, phenamacril + TX, 5- amino-1 ,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flufenoxadiazam + TX, flutianil + TX, fluopimomide + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1 ,1- dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol- 1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1 ,1 ,3- trimethylindan-4-yl)pyridine-3-carboxamide + TX, a-(1 ,1-dimethylethyl)-a-[4'-(trifluoromethoxy)[1 , 1 '- biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, 4-[[6-[2-(2,4- difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1 -yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6- [2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1 ,2,4-triazol-1 - yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, coumoxystrobin + TX, zhongshengmycin + TX, thiodiazole copper + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1 S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl- formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N- methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2015/155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine + TX (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-4-(2, 2, 2-trifluoro-1 -hydroxy-1 -phenyl- ethyl)phenyl]-N-methyl-formamidine+ TX, N’-[4-(1 -cyclopropyl-2,2,2-trifluoro-1 -hydroxy-ethyl)-5- methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2019/1 10427); N-[(1 R)-1-benzyl-3-chloro-1-methyl-but-3- enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro- quinoline-3-carboxamide + TX, N-[(1 R)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3- carboxamide + TX, N-[(1 S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1-benzyl-
1 .3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1 R)-1-[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1 S)-1-[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1 R)-1 -benzyl-1 ,3-dimethyl- butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1 -benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide + TX, N-((1 R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds may be prepared from the methods described in WO2017/153380); 1 -(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1 -(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3- dimethyl-1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7- methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + TX, 1 -(6-chloro-7-methyl-pyrazolo[1 ,5-a]pyridin-3-yl)-
4.4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds may be prepared from the methods described in WO2017/025510); 1 -(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl- isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6- chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5- fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1- isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1 -methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]urea + TX, 1 ,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl- 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-1 ,2,4-triazol-3-amine + TX. The compounds in this paragraph may be prepared from the methods described in 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); 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 in WO 2016/156290); 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290); (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound may be prepared from the methods described in WO 2014/006945); 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6- c']dipyrrole-1 ,3,5,7(2H,6H)-tetrone + TX (this compound may be prepared from the methods described in WO 2011/138281); N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4- dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound may be prepared from the methods described in WO 2018/153707); N'-(2-chloro-5-methyl-4-phenoxy- phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N- ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound may be prepared from the methods described in WO 2014/095675); (5-methyl-2- pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds may be prepared from the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]acetamide + TX (this compound may be prepared from the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4- carboxylate + TX (this compound may be prepared from the methods described in WO 2018/158365); 2,2-difluoro-N-methy l-2-[4-[5-(trifluoromethy l)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)- methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)- methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C- methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX (these compounds may be prepared from the methods described in WO 2018/202428).
The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment 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) is selected from one compound as represented in Tables A-1 to A-21 , Tables B-1 to B-21 , or a compound selected from P-1 to P-19 as 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, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight.
The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
The mixtures comprising a compound as represented in Tables A-1 to A-21 or B-1 to B-21 (below), or a compound P-1 to P-19 as 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 Tables A-1 to A-21 or B-1 to B-21 (below), or a compound P-1 to P-19 as 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. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in 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.
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 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
The compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
The compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:
Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.
Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(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, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.
Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fen pyroxi mate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, I KI-220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651 , WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1111 , R-195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301 .
Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
Bactericides: chlortetracycline, oxytetracycline, streptomycin.
Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole.
The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds (I) for the preparation of these compositions are also a subject of the invention.
Another aspect of the invention is related to the use of a compound of formula (I) 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.
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 ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
Controlling or preventing means reducing infestation 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. However, 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. a composition 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).
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to I kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.
When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of Formula (I) per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient.
Suitably, a composition comprising a compound of Formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a 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) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly Formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of Formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The compounds according to the following Tables A-1 to A-21 and Tables B-1 to B-21 below can be prepared following the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (la).
Figure imgf000046_0001
Table A: Compounds of the formula (la) wherein G and R7 are defined in Tables A-1 to A-21 , and R1 is as defined in Table Z below
Table Z
Figure imgf000046_0002
Figure imgf000047_0001
Table A-1 : This table provides 48 compounds A-1 .01 and A-1 .48 of formula (la) wherein G is O-[(2,4- difluorophenyl)methyl]oxyimino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-2: This table provides 48 compounds A-2.01 and A-2.48 of formula (la) wherein G is O-[(2- chloro-4-methylphenyl)methyl]oxyamino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-3: This table provides 48 compounds A-3.01 and A-3.48 of formula (la) wherein G is O-[(2,4- dichlorophenyl)methyl]oxyamino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-4: This table provides 48 compounds A-4.01 and A-4.48 of formula (la) G is O-[(2- methoxy)methyl]oxyamino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-5: This table provides 48 compounds A-5.01 and A-5.48 of formula (la) G is O-[(4- methoxy)methyl]oxyamino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-6: This table provides 48 compounds A-6.01 and A-6.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)ethyl]amino, R7 is methyl and R1substituents are as defined in Table Z above.
Table A-7: This table provides 48 compounds A-7.01 and A-7.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)ethyl]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-8: This table provides 48 compounds A-8.01 and A-8.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)-2-fluoro-ethyl]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-9: This table provides 48 compounds A-9.01 and A-9.48 of formula (la) wherein G is [(2S)-2- (2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R7 is methyl and R1substituents are as defined in Table Z above.
For the sake of clarity, compounds A-9.35 is:
Figure imgf000048_0001
Table A-10 This table provides 48 compounds A-10.01 and A-10.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)ethyl]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-11 This table provides 48 compounds A-11 .01 and A-11 .48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)-2-fluoro-ethyl]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-12 This table provides 48 compounds A-12.01 and A-12.48 of formula (la) wherein G is [(2S)-
2-(2,4-dichlorophenyl)-2-fluoro-ethyl]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-13: This table provides 48 compounds A-13.01 and A-13.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)-2-fluoro-ethyll]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-14: This table provides 48 compounds A-14.01 and A-14.48 of formula (la) wherein G is [(2S)- (6-chloro-3-pyridyl)-2-fluoro-ethyll]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-15: This table provides 48 compounds A-15.01 and A-15.48 of formula (la) wherein G is (6- methoxyindan-1-yl)amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-16: This table provides 48 compounds A-16.01 and A-16.48 of formula (la) wherein G is (6- chloroindan-1-yl)amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-17: This table provides 48 compounds A-17.01 and A-17.48 of formula (la) wherein G is (5- methoxyindan-1-yl)amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-18: This table provides 48 compounds A-18.01 and A-18.48 of formula (la) wherein G is (5- chloroindan-1-yl)amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-19: This table provides 48 compounds A-19.01 and A-19.48 of formula (la) wherein G is [(2R)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R7 is methyl and R1substituents are as defined in Table Z above.
For the sake of clarity, compounds A-19.35 is:
Figure imgf000048_0002
Table A-20: This table provides 48 compounds A-20.01 and A-20.48 of formula (la) wherein G is [(2S)- 2-(2,4-dichlorophenyl)-2-fluoro-ethyl]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table A-21 : This table provides 48 compounds A-21 .01 and A-21 .48 of formula (la) wherein G is [(2R)- (6-chloro-3-pyridyl)-2-fluoro-ethyll]amino, R7 is methyl and R1 substituents are as defined in Table Z above.
Table B: Compounds of the formula (la), wherein G and R7 are defined in Tables B-1 to B-21 , and R1 is as defined in Table Z above:
Table B-1 : This table provides 48 compounds B-1.01 and B-1.48 of formula (la) wherein G is O-[(2,4- difluorophenyl)methyl]oxyamino, R7 is propargyl and R1 substituents are as defined in Table Z above.
Table B-2: This table provides 48 compounds B-2.01 and B-2.48 of formula (la) wherein G is O-[(2- chloro-4-methylphenyl)methyl]oxyamino, R7 is propargyl and R1 substituents are as defined in Table Z above.
Table B-3: This table provides 48 compounds B-3.01 and B-3.48 of formula (la) wherein G is O-[(2,4- dichlorophenyl)methyl]oxyamino, R7 is benzyl and R1 substituents are as defined in Table Z above.
Table B-4: This table provides 48 compounds B-4.01 and B-4.48 of formula (la) wherein G is O-[(2- methoxy)methyl]oxyamino, R7 is benzyl and R1 substituents are as defined in Table Z above.
Table B-5: This table provides 48 compounds B-5.01 and B-5.48 of formula (la) wherein G is O-[(4- methoxy)methyl]oxyamino, R7 is 1-tetrahydropyran-4-ylmethyl and R1 substituents are as defined in Table Z above.
Table B-6: This table provides 48 compounds B-6.01 and B-6.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)ethyl]amino, R7 is 1-tetrahydropyran-4-ylmethyl and R1 substituents are as defined in Table Z above.
Table B-7: This table provides 48 compounds B-7.01 and B-7.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)ethyl]amino, R7 is 1-thiazol-4-ylmethyl and R1 substituents are as defined in Table Z above.
Table B-8: This table provides 48 compounds B-8.01 and B-8.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)-2-fluoro-ethyl]amino, R7 is 1-thiazol-4-ylmethyl and R1 substituents are as defined in Table Z above.
Table B-9: This table provides 48 compounds B-9.01 and B-9.48 of formula (la) wherein G is [(2S)-2- (2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R7 is A/-methyl-acetamide and R1substituents are as defined in Table Z above.
Table B-10: This table provides 48 compounds B-10.01 and B-10.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)ethyl]amino, R7 is A/-methyl-acetamide and R1 substituents are as defined in Table Z above.
For the sake of clarity, compounds B-10.05 is:
Figure imgf000050_0001
Table B-11 : This table provides 48 compounds B-11 .01 and B-11 .48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)-2-fluoro-ethyl]amino, R7 is 1 H-pyrazol-3-yl and R1 substituents are as defined in Table Z above.
Table B-12: This table provides 48 compounds B-12.01 and B-12.48 of formula (la) wherein G is [(2S)- 2-(2,4-dichlorophenyl)-2-fluoro-ethyl]amino, R7 is 1 H-pyrazol-3-yl and R1 substituents are as defined in Table Z above.
Table B-13: This table provides 48 compounds B-13.01 and B-13.48 of formula (la) wherein G is [2-(6- chloro-3-pyridyl)ethyl]amino, R7 is 1-tetrahydropyran-4-ylmethyl and R1 substituents are as defined in Table Z above.
Table B-14: This table provides 48 compounds B-14.01 and B-14.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)ethyl]amino, R7 is 1-thiazol-4-ylmethyl and R1 substituents are as defined in Table Z above.
Table B-15: This table provides 48 compounds B-15.01 and B-15.48 of formula (la) wherein G is [2-(2,4- dimethylphenyl)-2-fluoro-ethyl]amino, R7 is ethyl and R1 substituents are as defined in Table Z above.
Table B-16: This table provides 48 compounds B-16.01 and B-16.48 of formula (la) wherein G is [(2S)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R7 is ethyl and R1 substituents are as defined in Table Z above.
Table B-17: This table provides 48 compounds B-17.01 and B-17.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)ethyl]amino, R7 is allyl and R1 substituents are as defined in Table Z above.
Table B-18: This table provides 48 compounds B-18.01 and B-18.48 of formula (la) wherein G is [2-(2,4- dichlorophenyl)-2-fluoro-ethyl]amino, R7 is allyl and R1 substituents are as defined in Table Z above.
Table B-19: This table provides 48 compounds B-19.01 and B-19.48 of formula (la) wherein G is [(2R)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R7 is A/-methyl-acetamide and R1 substituents are as defined in Table Z above.
Table B-20: This table provides 48 compounds B-20.01 and B-20.48 of formula (la) wherein G is [(2R)- 2-(2,4-dichlorophenyl)-2-fluoro-ethyl]amino, R7 is 1 H-pyrazol-3-yl and R1 substituents are as defined in Table Z above. Table B-21 : This table provides 48 compounds B-21 .01 and B-21 .48 of formula (la) wherein G is [(2R)- 2-(2,4-dimethylphenyl)-2-fluoro-ethyl]amino, R7 is ethyl and R1 substituents are as defined in Table Z above.
Also made available are certain intermediate compounds of formulae (II), (V), (VI), (XI), (XII), (XIII), (XIV), as shown in reaction schemes 1 , 2, 3, 7, 8, 9, 10, some of which are novel. Developed formulae (ll)(i), (V)(i), (Vl)(i), (Vlll)(i), (XIX)(i), (X)(i), (Xl)(i), of the intermediates of formula (II), (V), (VI), (VIII), (XIX), (X), (XI), are given in Table P below, where R1, R2, R3, R4, R5, R7, R8, R9, R11, R12, R13, R14, Y, L, G-1 , G-2, G-3, G-4, RL1A, RL1B, RG1, RG2, RG3, RG4, A, have the same meaning as for compounds of Formula (I), such as defined in Tables A-1 to A-21 , Tables B-1 to B-21 and Table Z, and wherein X1, X2, X3, X4, X5, X6 and X7 have the same meaning as given in Schemes 1 , 2, 3, 7, 8, 9, 10 and in the table below.
Table P: Table of intermediates in reaction schemes 1 , 2, 3, 7, 8, 9, 10
Figure imgf000051_0001
Figure imgf000052_0001
EXAMPLES
The Examples which follow serve to illustrate the invention and are not meant in any way to limit the invention.
The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 60 ppm, 20 ppm or 2 ppm.
Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physicochemical properties, or increased biodegradability).
Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus, and the methods is as follows.
1H NMR and 19F NMR measurements were recorded on a Bruker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS (1H) and CFCI3 (19F) standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H)+ or (M-H)-.
Method A
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) 4.00, Scan Type MS2 Scan, Fragmentor (V) 100.00, Gas Temperature (°C) 350, Gas Flow (L/min) 11 , Nebulizer Gas (psi) 45, Mass range : 110 to 1000 Da) and an Agilent 1200 Series HPLC: DAD Wavelength range : 210 to 400 nm, Column : KINETEX EVO C18, Column length : 50 mm, Internal diameter of column : 4.6 mm, Particle Size : 2.6 pm, 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 (%) B (%) Flow rate (ml/min)
0 90 10 1.8
0.9 0 100 1.8
1.8 0 100 1.8
2.2 90 10 1.8
Where necessary, enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
Method B:
Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1 % formic acid, B= Acetonitrile + 0.1 % formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75.
Method C:
Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector. Column: Acquity UPLC HSS T3 C18, 1.8 pm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.0-0.5 min 10% B; 0.5-2 min 100% B; 2-3 min 100% B; 3- 3.5 min 10% B; 3.5-4 min 10% B; Flow (mL/min) 0.6.
Method D:
Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 40 °C, PDA Wavelength range (nm): 200 to 400, Solvent Gradient: A = Water with 0.1 % formic acid: Acetonitrile: 95: 5 v/v, B= Acetonitrile with 0.05% formic acid, : Gradient: 0 min-1 .0min,10% B- 90%A; 1 .0min-4.50min 10% -100% B; 4.51 min-5.30min,100% B, 0 %A; 5.31 min-5.50min 100% -10% B; 5.51 min-6.00 min, 10% B, 90%A; Flow (ml/min) 0.6.
Method E:
Spectra were recorded on a Mass Spectrometer from Waters (Acquity QDa Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8 kV, Cone range: 25 V, Extractor: V (No extractor voltage for QDa detector) Source Temperature: 120°C, Desolvation Temperature: 600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector. Column: Acquity UPLC HSS T3 C18, 1 .8 pm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-50% B; 0.2-0.6 min 50-100% B; 0.6-1 .3 min 100% B; 1.3-1 .4 min 100-10% B; 1.4-1 .6 min 10% B; Flow (mL/min) 0.6.
FORMULATION EXAMPLES
Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether (7-8 mol ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 % -
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % Kaolin 65 % 40 % - Talcum 20 %
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Dusts a) b) c)
Active ingredients 5 % 6 % 4 %
Talcum 95 % -
Kaolin 94 % - mineral filler 96 %
Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
Extruder granules
Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %
Kaolin 82 %
The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
Coated granules
Active ingredients 8% polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 %
The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrate active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %
Tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %
Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
Water 45.3 %
The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow Release Capsule Suspension
28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
LIST OF ABBREVIATIONS:
Abbreviations used in synthesis schemes and preparatory examples
DMSO dimethyl sulfoxide
DMSO-cP deuterated dimethylsulfoxide
EtaN triethylamine
EtOAc ethyl acetate
MeCN acetonitrile
MeOH ethanol n-Bu n-butyl
TBME tert-butyl methyl ether, or MTBE
TEA triethylamine THF tetra hydrofuran
Ts p-toluenesulfonyl (tosyl) aq. aqueous equiv. equivalent h hour(s)
LC/MS or LC-MS liquid chromatography mass spectrometry
M molar
MHz megahertz min minutes mp or MP melting point
NMR nuclear magnetic resonance ppm parts per million
RT or rt room temperature
Rt retention time
PREPARATION EXAMPLES
The following examples further illustrate, but do not limit, the invention. Those skilled in the art will promptly recognize appropriate variations from the procedures both as to reactants and as to reaction conditions and techniques.
Unless indicated otherwise, 1H NMR spectra are recorded at 400 MHz and 19F NMR spectra are recorded at 377 MHz, and chemical shifts are recorded in ppm. The following abbreviations are used: s = singlet; br s = broad singlet; d = doublet; br d = broad doublet; dd = double doublet; dt = double triplet; t = triplet, ft = triple triplet, q = quartet, quin = quintuplet, sept = septet; m = multiplet.
Throughout this description, temperatures are given in degrees Celsius (°C). “MP” means melting point. “Rt” means retention time. LC/MS means Liquid Chromatography Mass Spectrometry. LC/MS apparatus and methods are:
Example P1 : Preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2- methyl-3-oxo-pyridazine-4-carboxamide (Compound 1.1 of Table T1). a) Preparation of 4-bromo-5-(3-cyclopropylphenoxy)-2-methyl-pyridazin-3-one
In a Schlenk flask, 4,5-dibromo-2-methyl-pyridazin-3-one (1 equiv., 1 g, 3.51 mmol), 3- cyclopropylphenol (1.05 equiv., 520 mg, 3.68 mmol) and cesium carbonate (2.5 equiv., 1.69 g, 8.77 mmol) were stirred in dry dimethylsulfoxide (10 mL) and purged with a stream of argon. Copper(l) iodide (5 mol%, 33.6 mg, 0.175 mmol) and A/,A/-dimethylglycine (15 mol%, 56 mg, 0.526 mmol) were added and the mixture was purged with argon. The vial was sealed and the reaction mixture was stirred at 110°C for 2 h. The reaction mixture was then diluted with EtOAc, quenched with water. The desired material was extracted EtOAc and the organic layer was washed with water, brine, dried over sodium sulfate and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (cyclohexane/EtOAc) to afford pure 4-bromo-5-(3-cyclopropylphenoxy)-2-methyl- pyridazin-3-one (902 mg, 2.81 mmol) as a white solid. 1H NMR (400 MHz, CDCb) 6 ppm 7.35 (s, 1 H), 7.30 (t, J = 7.8 Hz, 1 H), 6.99 (d, J = 7.6 Hz, 1 H), 6.88 - 6.83 (m, 1 H), 6.79 (t, J = 2.0 Hz, 1 H), 3.83 (s, 3H), 1 .92 (tt, J = 8.4, 5.0, Hz, 1 H), 1 .06 - 1 .00 (m, 2H), 0.75 - 0.69 (m, 2H). b) Preparation of methyl 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylate
In an autoclave, 4-bromo-5-(3-cyclopropylphenoxy)-2-methyl-pyridazin-3-one (1 equiv., 700 mg, 2.07 mmol) and triethylamine (1.5 equiv., 317 mg, 3.11 mmol, 0.437 mL) were dissolved in methanol (17.5 mL). Pd(BINAP)(allyl)CI (5 mol%, 83.4 mg, 0.104 mmol) was added and the mixture was purged with Argon. The autoclave was then loaded with carbon dioxide (5 bar). The autoclave was sealed and the reaction mixture was stirred 18 h at 80°C. The crude was concentrated under reduced pressure and directly purified by silica gel chromatography (cyclohexane/EtOAc) to afford pure methyl 5-(3- cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylate (103 mg, 0.343 mmol) as a red resin.
1H NMR (400 MHz, CDCb) 6 ppm 7.48 (s, 1 H), 7.32 - 7.26 (t, 1 H), 6.98 (d, J = 7.6 Hz, 1 H), 6.87 (ddd, J = 8.1 , 2.5, 1 .1 Hz, 1 H), 6.81 - 6.76 (m, 1 H), 3.86 (s, 3H), 3.77 (s, 3H), 1 .90 (tt, J = 8.4, 5.1 Hz, 1 H), 1 .07
- 0.96 (m, 2H), 0.75 - 0.66 (m, 2H) c) Preparation of lithium 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylate
In a round bottom flask, methyl 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylate (1 equiv., 103 mg, 0.326 mmol) was stirred in a 3:1 mixture tetra hydrofuran and water (3.1 mL). To this lithium hydroxide monohydrate (1 .2 equiv., 16.7 mg, 0.391 mmol) was added and the mixture was stirred at room temperature for 18 h. After total consumption of the starting material, the crude mixture was evaporated to dryness and crude lithium 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4- carboxylate directly used in the next step.
LCMS (Method A): retention time 0.82 min, 287 (carboxylate, M+H). d) Preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-3-oxo- pyridazine-4-carboxamide
In a round bottom flask, lithium 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylate (1 equiv., 70 mg, 0.204 mmol), 2-(2,4-Dichlorophenyl)-2-fluoro-ethanamine (1.3 equiv., 58 mg, 0.265 mmol) and A/,A/-diisopropylethylamine (5 equiv., 133 mg, 1.02 mmol, 0.179 mL) were stirred in EtOAc (2.1 mL). To this, propylphosphonic anhydride (50% in MeTHF, 2.5 equiv., 324 mg, 0.509 mmol, 0.3 mL) was added and the mixture was stirred at room temperature for 2 h. The mixture was diluted with EtOAc, quenched with a saturated solution of sodium bicarbonate, and extracted with EtOAc. The organic layer was washed with water, brine, dried over sodium sulfate, filtrated and concentrated under reduced pressure. The crude mixture was purified by silica gel chromatography (cyclohexane/EtOAc) to afford pure off-white crystals (47 mg, 0.0987 mmol).
1H NMR (400 MHz, CDCb) 6 ppm 9.46 (t, J = 5.6 Hz, 1 H), 7.55 - 7.53 (m, 1 H), 7.53 - 7.49 (m, 1 H), 7.42
- 7.39 (m, 1 H), 7.33 - 7.30 (m, 1 H), 7.30 - 7.27 (t, 1 H), 7.03 - 6.98 (m, 1 H), 6.91 - 6.86 (m, 1 H), 6.82 (t, J = 2.0 Hz, 1 H), 6.07 - 5.89 (m, 1 H), 4.18 - 4.01 (m, 1 H), 3.83 (s, 3H), 3.69 (dddd, J = 20.0, 14.6, 7.7, 5.3 Hz, 1 H), 1 .91 (tt, J = 8.4, 5.0 Hz, 1 H), 1 .06 - 0.98 (m, 2H), 0.74 - 0.68 (m, 2H)
Melting point: 130 °C LCMS (Method A): retention time 1.10 min, 476 (M+H).
Example P2: Preparation of 5-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2- methyl-3-oxo-pyridazine-4-carboxamide (Compound P-3 , Table T)
To a suspension of 5-(3-cyclopropylphenoxy)-2-methyl-3-oxo-pyridazine-4-carboxylic acid (200 mg, 0.698 mmol) in EtOAc (8 mL/mmol), was added (2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (0.838 mmol), and N-ethyl-N-isopropyl-propan-2-amine (2.096 mmol) followed by 1 -propanephosphonic anhydride (2.096 mmol, 50 mass%). The resulting light yellow solution was stirred at room temperature for 16 h. Progress of the reaction was confirmed by LCMS. The reaction mixture was diluted with water and extracted with EtOAc The combined organic layers were washed using sat. NaHCO3 solution and brine, dried over Na2SO4, filtered and concentrated under reduced pressure to get crude. The crude material was purified by Combi-flash using EtOAc and cyclohexane, followed by a reverse phase purification using water and acetonitrile as eluent to get 5-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4- dichlorophenyl)-2-fluoro-ethyl]-2-methyl-3-oxo-pyridazine-4-carboxamide.
1H NMR (400 MHz, CDCb) 6 ppm 9.46 (br t, 1 H) 7.52 (s, 1 H) 7.50 (d, 1 H) 7.37 - 7.41 (m, 1 H) 7.24 - 7.34 (m, 2 H) 6.99 (d, 1 H) 6.87 (ddd, 1 H) 6.80 (t, 1 H) 6.02-5.91 (m, 1 H) 4.07 -4.17 (m, 1 H) 3.81 (s, 3 H) 3.61 - 3.74 (m, 1 H) 1 .86 - 1 .93 (m, 1 H) 0.96 - 1 .05 (m, 2 H) 0.67 - 0.73 (m, 2H).
Analysis by analytical Chiral HPLC (Column CHIRALPAK® IC, 250 x 4,6 mm, 5 pm, eluting TBME/EtOH) showed the R-isomer to have a retention time of 7.95 min, while the S-isomer has a retention time of 9.61 min. The ratio of R:S was 98:2.
Table T1 : Physical data of compounds of formula (I)
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0002
Table Tl: Physical data of prepared intermediates compounds - * [M+H] measured; ** Method used
Figure imgf000063_0001
Biological examples
Example B1 : Alternaria solani / tomato / leaf disc (early blight)
Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23 °C / 21 °C (day /night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).
The following compounds gave at least 80% control of Alternaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-1 , P-3, P-15
Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-1 , P-2, P-3, P-5, P-8, P-10, P-14, P-15, P-17, P-18, P-19
Example B3: Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (Anthracnose) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is measured photometrically 3-4 days after application.
The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-1 , P-2, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-10, P-11 , P-12, P-13, P-14, P-15, P-16, P-17, P-18, P-19
Example B4: Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch)
Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-19
Example B5: Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-2, P-5, P-7, P-10, P-15, P-16
Example B6: Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-14, P-16
Example B7: Puccinia recondita f. sp. tritici / wheat / leaf disc curative (Brown rust)
Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. Plates are stored in darkness at 19 °C and 75% rh. The formulated test compound diluted in water is applied 1 day after inoculation. The leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 - 8 days after application).
The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: P-14
Figure imgf000065_0001
Mycelia fragments and oospores of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 2-3 days after application.
The following compounds gave at least 80% control of Pythium ultimum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-16
B9: Sclerotinia sclerotiorum I liquid culture
Figure imgf000066_0001
Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-1 , P-2, P-3, P-8, P-10, P-15, P-17
Example B10: Sclerotinia sclerotiorum / liquid culture (cottony rot)
Mycelia fragments of a newly grown liquid culture of the fungus 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 material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.
The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
Example B11 : Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.
The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
P-16

Claims

1. A compound of Formula (I)
Figure imgf000067_0001
wherein:
R1 is phenyl, wherein said phenyl is unsubstituted or substituted with 1 , 2 or 3 independently selected substituents R11; or
R1 is a 5- or 6-membered monocyclic heteroaryl ring, wherein any of said heteroaryl comprises 1 , 2 or 3 heteroatoms which may be the same or different, independently selected from N, O and S, wherein said heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R11;
R11 is hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci- C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl;
L1 is a direct bond, -O- or -O-C(RL1A)(RL1B)-; wherein RL1A and RL1B are independently selected from hydrogen or methyl; or RL1A and RL1B together with the carbon atom to which they are attached, form a cyclopropyl; or
Figure imgf000067_0002
wherein # marks the bond to the nitrogen atom and the staggered line marks the bond to the group G;
R2 and R3 are independently selected from hydrogen or methyl;
R4 and R5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, hydroxy, or methoxy; or
R4 and R5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl, or cyclobutyl group;
G is selected from G-1 , G-2, G-3, and G-4, wherein:
G-1 is phenyl or phenoxy, wherein any of said phenyl or phenoxy are unsubstituted or substituted with 1 , 2 or 3 independently selected substituents RG1;
G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy ; wherein any of said heteroaryl comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; and wherein said heteroaryl is unsubstituted or substituted with 1 or 2 independently selected substituents RG2; G-3 is a 9- or 10-membered heterobicyclic ring system, wherein said - or 10-membered heterobicyclic ring system comprises 1 , 2 or 3 heteroatoms each independently selected from N, O and S; wherein said heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said heterobicyclic ring system is unsubstitued or substituted with 1 or 2 independently selected substituents RG3;
G-4 is a 9- or 10-membered carbobicyclic ring system; wherein said carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents RG4;
RG1, RG2, RG3, and RG4 are independently hydroxyl, halogen, mercapto, amino, cyano, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C4alkenyl, C2-C4alkynyl, C2-C4alkynyloxy, Ci-Csalkylsulfanyl, or Ci-Csalkylsulfonyl;
A is
Figure imgf000068_0001
wherein # marks the bond to -O-R1; and % marks the bond to -C(=O)-N(H)-
L1-G;
Y is O or S;
R7 is selected from Ci-Csalkyl, C2-C3alkenyl, C2-C3alkynyl, Cs-Cecycloalkyl, C3- Cecycloalkylmethyl, methylformyl, f-butylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2- (methylamino)-2-oxo-ethyl; or
R7 is selected from phenyl, thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, pyridazinyl or triazinyl, wherein any of said phenyl, thiazolyl, oxazolyl, pyrazolyl, triazolyl, imidazolyl, thienyl, isoxazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, pyridazinyl and triazinyl are unsubstituted or substituted with 1 or 2 independently selected substituents R8 selected from halogen, mercapto, cyano, Ci-Csalkyl, C1- Csalkoxy, Ci-Cshaloalkyl, Ci-Cshaloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C3alkenyl, C2- Csalkynyl, or Ci-Csalkylsulfonyl; or
R7 is CR12R13R14 wherein
R12 and R13 are independently selected from hydrogen, or methyl; or
R12 and R13 form a cyclopropyl together with the carbon they are attached to; and
R14 is selected from cyano, methylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2-(methylamino)-2- oxo-ethyl; or
R14 is a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, furanyl, isoxazolyl, oxadiazolyl, and thiadiazolyl, or a heterocyclyl selected from oxiranyl, azetidinyl, oxetanyl, aziridinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetrahydropyranyl, morpholinyl and dioxanyl, wherein any of said phenyl, heteroaryl and heterocyclyl are unsubstituted or substituted with 1 or 2 independently selected substituents R9 selected from halogen, mercapto, cyano, Ci-Csalkyl, Ci-Csalkoxy, Ci- Cshaloalkyl, Ci-Cshaloalkoxy, Cs-Cecycloalkyl, Cs-Cecycloalkoxy, C2-C3alkynyl, or Ci- Csalkylsulfonyl; or an agrochemically acceptable salt, N-oxide, stereoisomer, or enantiomer of the compound of Formula (I). The compound according to claim 1 , wherein R1 is phenyl, wherein said phenyl is unsubstitted or substituted with a 1 , 2 or 3 independently selected substituents R11; or
R1 is pyridinyl, pyrimidinyl, pyridazinyl, or 1 ,2,4-triazinyl, wherein said pyridinyl, pyrimidinyl, pyridazinyl, 1 ,2,4-triazinyl are unsubstituted or substituted with 1 or 2 substituents R11; wherein R11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy. The compound according to claim 1 or claim 2, wherein L1 is a direct bond, -O-, -O-CH2-, or
Figure imgf000069_0001
wherein # marks the bond to the nitrogen atom and the staggered line marks the bond to the group G; and
R2 and R3 are independently selected from hydrogen or methyl; and R4 and R5 are independently selected from hydrogen or fluoro. The compound according to any one of claims 1 to 3, wherein G is selected from G-1 , G-2, G-3, and G-4, and
G-1 is phenyl or phenoxy, wherein said phenyl and phenoxy are unsubstituted or substituted with 1 or 2 substituents, for instance one substituent, selected from chloro or methyl;
G-2 is pyridine substituted with 1 , 2 or 3 substituents, for instance 2 or 3 substituents, each independently selected from chloro, fluoro, cyano, methyl, or methoxy;
G-3 is a 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; and
G-4 is a tetralin-1-yl or indan-1-yl, wherein said tetralin-1-yl and indan-1-yl are unsubstituted or substituted with one substituent selected from chloro, fluoro, cyano, methyl, or methoxy; The compound according to any one of claims 1 to 4, wherein RG1, RG2, RG3, and RG4 are independently chloro, fluoro, cyano, methyl, or methoxy. The compound according to any one of claims 1 to 5, wherein Y is oxygen. The compound according to any one of claims 1 to 6, wherein R7 is selected from methyl, ethyl, allyl, propargyl, cyclopentyl, cyclohexyl, methylformyl, 2-(dimethylamino)-2-oxo-ethyl, or 2- (methylamino)-2-oxo-ethyl; or
R7 is selected from phenyl or pyrazolyl, wherein said phenyl and pyrazolyl are unsubbstitted or substituted with 1 or 2 independently selected substituents R8 selected from fluoro, chloro, cyano, methyl, ethyl, or methoxy. The compound according to any one of claims 1 to 6, wherein R7 is CR12R13R14, wherein R12 and R13 are independently selected from hydrogen, or methyl; and R14 is cyano, methylformyl, or 2- (methylamino)-2-oxo-ethyl, a phenyl, a heteroaryl selected from pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, oxazolyl, and imidazolyl, or a heterocyclyl selected from pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl; wherein said phenyl, heteroaryl or heterocyclyl are unsubstituted or substituted with 1 or 2 independently selected substituents R9 selected from fluoro, chloro, cyano, methyl, ethyl, methoxy, or cyclopropyl. An agrochemical composition comprising a fungicidally effective amount of a compound according to any one of claims 1 to 8. The composition according to claim 9, further comprising 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 according to any of claims 1 to 8, or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof. Use of a compound according to any one of claims 1 to 8 as a fungicide. A plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound as defined in any one of claims 1 to 8, or a composition comprising this compound as active ingredient.
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