WO2020025807A1 - Dérivés de 1,2,5-oxadiazol-3(2h)-one microbiocides - Google Patents

Dérivés de 1,2,5-oxadiazol-3(2h)-one microbiocides Download PDF

Info

Publication number
WO2020025807A1
WO2020025807A1 PCT/EP2019/070924 EP2019070924W WO2020025807A1 WO 2020025807 A1 WO2020025807 A1 WO 2020025807A1 EP 2019070924 W EP2019070924 W EP 2019070924W WO 2020025807 A1 WO2020025807 A1 WO 2020025807A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
phenyl
formula
compound
c6alkyl
Prior art date
Application number
PCT/EP2019/070924
Other languages
English (en)
Inventor
Sebastian Volker Wendeborn
Stefano RENDINE
Christopher Charles SCARBOROUGH
Clemens Lamberth
Original Assignee
Syngenta Crop Protection Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection Ag filed Critical Syngenta Crop Protection Ag
Publication of WO2020025807A1 publication Critical patent/WO2020025807A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms

Definitions

  • the present invention relates to microbiocidal furazanone derivatives, 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 furazanone derivatives, to processes of preparation of these compounds and to uses of the furazanone derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or nonliving materials by phytopathogenic microorganisms, preferably fungi.
  • R 1 is Ci-C6alkyl or C3-C6cycloalkyl
  • R 2 is selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6haloalkyl and C3-C6cycloalkyl;
  • R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6haloalkyl and C3-C6cycloalkyl;
  • R 5 is selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6haloalkyl and C3-C6cycloalkyl;
  • W is O or S
  • A is a direct bond or CR 6 R 7 ;
  • E is CR 6 R 7 , O, S or S0 2 ;
  • X is CR 6 R 7 ;
  • n is 0, 1 or 2;
  • G is carbocyclyl, wherein the carbocyclyl is a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur, and wherein said carbocyclyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 8 substituents, which may be the same or different;
  • Z is hydrogen, carbocyclyl, carbocyclyloxy, wherein the carbocyclyl is a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, heterocyclyl or heterocyclyloxy, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur,
  • R 6 and R 7 are each independently selected from the group consisting of hydrogen, halogen and Ci-C6alkyl; each R 8 is independently selected from the group consisting of hydroxy, halogen, cyano, Ci- Cealkyl, C2-C6alkenyl, C2-C6alkynyl, Ci-C6alkoxy, C3-C6cycloalkyl, C3-C6cycloalkoxy, Ci-
  • each R 9 is independently selected from the group consisting of hydroxy, halogen, cyano, Ci- Cealkyl, C2-C6alkenyl, C2-C6alkynyl, Ci-C6alkoxy, C3-C6cycloalkyl, C3-C6cycloalkoxy, Ci-
  • Cealkylsulfonyl Ci-C6haloalkyl, Ci-C6haloalkoxy, C3-C6halocycloalkyl, Ci-C6alkoxyCi-C6alkyl, Ci-C6haloalkoxyCi-C6alkyl, Ci-C6haloalkylsulfonyl and Ci-C6alkylcarbonyl; or an agronomically acceptable salt; or N-oxide thereof.
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) and an agrochemically- acceptable diluent or carrier.
  • Such an agricultural composition may further comprise at least one additional active ingredient.
  • 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.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • hydroxy means a -OH group.
  • Ci-C4alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Ci-C4alkyl and Ci- C 2 alkyl are to be construed accordingly.
  • Examples of Ci-C6alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, and 1-dimethylethyl (f-butyl).
  • Ci-C6alkoxy refers to a radical of the formula -OR a where R a is a Ci Cealkyl radical as generally defined above.
  • Examples of Ci-4alkoxy include, but are not limited to, m ethoxy, ethoxy, propoxy, iso-propoxy and f-butoxy.
  • Ci-Cehaloalkyl refers to a Ci-Cealkyl radical, as generally defined above, substituted by one or more of the same or different halogen atoms. Ci-C4haloalkyl is to be construed accordingly. Examples of Ci-C6haloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.
  • Ci-C6haloalkoxy refers to a Ci-C6alkoxy group, as defined above, substituted by one or more of the same or different halogen atoms. Ci-C4haloalkoxy is to be construed accordingly. Examples of Ci-C6haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.
  • Ci-C6haloalkoxyCi-C6alkyl- refers to a Ci-C6haloalkoxy group, as defined above attached to the rest of the molecule by a Ci-C6alkylene radical as defined above.
  • C 2 -C6alkenyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • C2-C4alkenyl is to be construed accordingly.
  • Examples of C 2 -C6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) and but-1-enyl.
  • C2-C6alkynyl 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 to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C 2 -C 4 alkynyl is to be construed accordingly.
  • Examples of C2-C6alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl) and but-1-ynyl.
  • Ci-C6alkoxyCi-C6alkyl- refers to radical of the formula R a -0-Rb- where R a is a Ci-C6alkyl radical as generally defined above, and Rb is a Ci-C6alkylene radical as generally defined above. Ci-C2alkoxyCi-C2alkyl is to be construed accordingly.
  • C3-C6cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms.
  • C3-C 4 cycloalkyl is to be construed accordingly.
  • Examples of C3-C6cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C3-C6halocycloalkyl refers to a C3-C6cycloalkyl radical, as generally defined above, substituted by one or more of the same or different halogen atoms.
  • C3-C 4 halocycloalkyl is to be construed accordingly.
  • C3-C6cycloalkoxy refers to a radical of the formula -OR a where R a is a C3-C6cycloalkyl radical as generally defined above.
  • C3-C6cycloalkylCi-C3alkyl- refers to a C3-C6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-C3alkylene radical as defined above.
  • C3- C 4 cycloalkylCi-C 2 alkyl- is to be construed accordingly.
  • Examples of C3-C6cycloalkylCi-C3alkyl- include, but are not limited to cyclopropylmethyl- and cyclobutylethyk
  • Ci Cealkylsulfonyl refers to a radical of the formula -S(0) 2 R a where R a is a Ci-C6alkyl radical as generally defined above.
  • Ci-C6haloalkylsulfonyl refers to a Ci-C6alkylsulfonyl radical, as generally defined above, substituted by one or more of the same or different halogen atoms.
  • Ci Cealkylcarbonyl refers to a radical of the formula -C(0)R a where R a is a Ci-C6alkyl radical as generally defined above.
  • carbocyclyl refers to a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, which contains 6 to 10 carbon atoms.
  • Examples of carbocyclyl include, but are not limited to phenyl, naphthyl and indanyl.
  • carbocyclyloxy refers to a carbocyclyl ring as defined above attached to the rest of the molecule via an oxygen atom.
  • phenoxy refers to a phenyl ring attached to the rest of the molecule via an oxygen atom.
  • heterocyclyl or “heterocyclic” refers to a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur.
  • heterocyclyl includes, but is not limited to stable 4- to 6-membered saturated monocyclic radicals such as pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or d-lactamyl.
  • heterocyclyl further includes, but is not limited to“heteroaryl” radicals that are a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, such as furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl, indolyl, indazolyl, benzimidazolyl, pyrrolopyridinyl, triazolopyridinyl or tetrahydroindazolyl.
  • the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heterocyclyloxy refers to a heterocyclyl ring as defined above attached to the rest of the molecule via an oxygen atom.
  • 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).
  • the compounds of formula (I) according to the invention are in free form, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
  • R 1 is Ci-C6alkyl or C3-C6cycloalkyl.
  • R 1 is selected from the group consisting of methyl, ethyl and cyclopropyl. More preferably, R 1 is methyl or ethyl, most preferably R 1 is methyl.
  • R 2 is selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6haloalkyl and C3-C6cycloalkyl.
  • R 2 is selected from the group consisting of hydrogen, halogen and Ci- Cealkyl. More preferably, R 2 is selected from the group consisting of hydrogen, chloro, methyl and ethyl. Even more preferably, R 2 is hydrogen or methyl. Most preferably, R 2 is hydrogen.
  • R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6haloalkyl and C3-C6cycloalkyl.
  • R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen and Ci-C6alkyl. More preferably, R 3 and R 4 are each independently selected from the group consisting of hydrogen, chloro, methyl and ethyl. Even more preferably, R 3 and R 4 are each independently hydrogen or methyl. Most preferably, R 3 and R 4 are hydrogen.
  • R 5 is selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6haloalkyl and C3-C6cycloalkyl.
  • R 5 is selected from the group consisting of hydrogen, halogen and Ci- Cealkyl. More preferably, R 5 is halogen or Ci-C6alkyl. Even more preferably, R 5 is selected from the group consisting of chloro, methyl and ethyl. Most preferably R 5 is methyl.
  • W is O or S. Preferably W is O.
  • A is a direct bond or CR 6 R 7 .
  • A is a direct bond or CH2. More preferably, A is CH2.
  • E is CR 6 R 7 , O, S or SO2.
  • E is CR 6 R 7 or O. More preferably, E is CH2 or O. Most preferably E is O.
  • X is CR 6 R 7 , preferably X is CH2.
  • n is 0, 1 or 2.
  • n is 0 or 1 . More preferably, n is 0.
  • G is carbocyclyl, wherein the carbocyclyl is a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur, and wherein said carbocyclyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 8 substituents, which may be the same or different.
  • G is carbocyclyl, wherein the carbocyclyl is a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur, and wherein said carbocyclyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 8 substituents, which may be the same or different.
  • G is phenyl or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur, and wherein said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 8 substituents, which may be the same or different.
  • the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur, and wherein said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 8 substituents, which may be the same or different.
  • G is phenyl or heteroaryl, wherein the heteroaryl is a 5- or 6-membered aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulphur, wherein said phenyl or heteroaryl are optionally substituted by 1 or 2 R 8 substituents, which may be the same or different.
  • G is phenyl, pyridyl or pyrazolyl, wherein said phenyl, pyridyl or pyrazolyl are optionally substituted by 1 or 2 R 8 substituents, which may be the same or different.
  • G is phenyl or pyrazolyl, wherein said phenyl or pyrazolyl are optionally substituted by 1 R 8 substituent.
  • Z is hydrogen, carbocyclyl, carbocyclyloxy, wherein the carbocyclyl is a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, heterocyclyl or heterocyclyloxy, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated or saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur,
  • any of said carbocyclyl, carbocyclyloxy, heterocyclyl or heterocyclyloxy are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • Z is hydrogen, carbocyclyl, carbocyclyloxy, wherein the carbocyclyl is a 6- to 10-membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, heterocyclyl or heterocyclyloxy, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur,
  • any of said carbocyclyl, carbocyclyloxy, heterocyclyl or heterocyclyloxy are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • Z is hydrogen, phenyl, phenoxy, heterocyclyl or heterocyclyloxy, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur,
  • Z is phenyl or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulphur,
  • any of said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • Z is phenyl or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2 or 3 heteroatoms individually selected from nitrogen and oxygen,
  • any of said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • Z is phenyl or heteroaryl, wherein the heteroaryl is a 5- or 6-membered aromatic ring which comprises 1 , 2 or 3 nitrogen atoms,
  • any of said phenyl or heteroaryl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • Z is phenyl or pyrazolyl, wherein said phenyl or pyrazolyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 6 and R 7 are each independently selected from the group consisting of hydrogen, halogen and Ci- Cealkyl.
  • R 6 and R 7 are each independently selected from the group consisting of hydrogen, halogen, methyl and ethyl. More preferably, R 6 and R 7 are each independently hydrogen or halogen. Most preferably, R 6 and R 7 are each hydrogen.
  • each R 8 is independently selected from the group consisting of hydroxy, halogen, cyano, Ci-C6alkyl, C2- Cealkenyl, C2-C6alkynyl, Ci-C6alkoxy, C3-C6cycloalkyl, C3-C6cycloalkoxy, Ci-C6alkylsulfonyl, C1- Cehaloalkyl, Ci-C6haloalkoxy, C3-C6halocycloalkyl, Ci-C6alkoxyCi-C6alkyl, Ci-C6haloalkoxyCi-C6alkyl, Ci-C6haloalkylsulfonyl and Ci-C6alkylcarbonyl.
  • each R 8 is independently selected from the group consisting of halogen, cyano, Ci-C6alkyl, C2-C6alkenyl, Ci-C6alkoxy, C3-C6cycloalkyl, C3- Cecycloalkoxy, Ci-C6alkylsulfonyl, Ci-C6haloalkyl, Ci-C6haloalkoxy and Ci-C6haloalkylsulfonyl. More preferably, each R 8 is independently selected from the group consisting of halogen, cyano, Ci-C6alkyl, Ci-C6alkoxy, C3-C6cycloalkyl, Ci-C6haloalkyl and Ci-C6haloalkoxy.
  • each R 8 is independently selected from the group consisting of halogen, Ci-C6alkyl, Ci-C6alkoxy, C3-C6cycloalkyl and Ci-C6haloalkyl. Even more preferably still, each R 8 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl. Yet even more preferably still, each R 8 is independently selected from the group consisting of chloro, fluoro, bromo, methyl and trifluoromethyl. Most preferably, each R 8 is independently chloro or methyl.
  • each R 9 is independently selected from the group consisting of hydroxy, halogen, cyano, Ci-C6alkyl, C2- Cealkenyl, C2-C6alkynyl, Ci-C6alkoxy, C3-C6cycloalkyl, C3-C6cycloalkoxy, Ci-C6alkylsulfonyl, C1- Cehaloalkyl, Ci-C6haloalkoxy, C3-C6halocycloalkyl, Ci-C6alkoxyCi-C6alkyl, Ci-C6haloalkoxyCi-C6alkyl, Ci-C6haloalkylsulfonyl and Ci-C6alkylcarbonyl.
  • each R 9 is independently selected from the group consisting of halogen, cyano, Ci-C6alkyl, C2-C6alkenyl, Ci-C6alkoxy, C3-C6cycloalkyl, C3- Cecycloalkoxy, Ci-C6alkylsulfonyl, Ci-C6haloalkyl, Ci-C6haloalkoxy and Ci-C6haloalkylsulfonyl. More preferably, each R 9 is independently selected from the group consisting of halogen, cyano, Ci-C6alkyl, Ci-C6alkoxy, C3-C6cycloalkyl, Ci-C6haloalkyl and Ci-C6haloalkoxy.
  • each R 9 is independently selected from the group consisting of halogen, Ci-C6alkyl, Ci-C6alkoxy, C3-C6cycloalkyl and Ci-C6haloalkyl. Even more preferably still, each R 9 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl. Yet even more preferably still, each R 9 is independently selected from the group consisting of chloro, fluoro, bromo, methyl and trifluoromethyl. Most preferably, each R 9 is independently chloro or methyl.
  • R 1 is methyl
  • R 2 is hydrogen
  • R 3 and R 4 are hydrogen
  • R 5 is selected from the group consisting of chloro, methyl and ethyl
  • W is O
  • A is CH 2 ;
  • n 0;
  • G is phenyl or heteroaryl, wherein the heteroaryl is a 5- or 6-nnennbered aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulphur, wherein said phenyl or heteroaryl are optionally substituted by 1 or 2 R 8 substituents, which may be the same or different;
  • Z is phenyl or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2 or 3 heteroatoms individually selected from nitrogen and oxygen,
  • any of said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • each R 8 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl;
  • each R 9 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl.
  • R 1 is methyl
  • R 2 is hydrogen
  • R 3 and R 4 are hydrogen
  • R 5 is methyl
  • W is O
  • A is CH 2 ;
  • n 0;
  • G is phenyl or pyrazolyl, wherein said phenyl or pyrazolyl are optionally substituted by 1 R 8 substituent;
  • Z is phenyl or pyrazolyl, wherein said phenyl or pyrazolyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • each R 8 is independently selected from the group consisting of chloro, fluoro, bromo, methyl and trifluoromethyl;
  • each R 9 is independently selected from the group consisting of chloro, fluoro, bromo, methyl and trifluoromethyl.
  • R 1 is methyl
  • R 2 is hydrogen
  • R 3 and R 4 are hydrogen
  • R 5 is methyl
  • W is O
  • A is CH 2 ;
  • n 0;
  • G is phenyl or pyrazolyl, wherein said phenyl or pyrazolyl are optionally substituted by 1 R 8 substituent;
  • Z is phenyl or pyrazolyl, wherein said phenyl or pyrazolyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different; each R 8 is independently chloro or methyl; and
  • each R 9 is independently chloro or methyl.
  • R 1 is methyl
  • R 2 is hydrogen
  • R 3 and R 4 are hydrogen
  • R 5 is selected from the group consisting of chloro, methyl and ethyl
  • W is O
  • A is CH 2 ;
  • E is CH 2 ;
  • n 0;
  • G is phenyl or heteroaryl, wherein the heteroaryl is a 5- or 6-membered aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulphur, wherein said phenyl or heteroaryl are optionally substituted by 1 or 2 R 8 substituents, which may be the same or different;
  • Z is phenyl or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2 or 3 heteroatoms individually selected from nitrogen and oxygen,
  • any of said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • each R 8 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl;
  • each R 9 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl.
  • R 1 is methyl
  • R 2 is hydrogen
  • R 3 and R 4 are hydrogen
  • R 5 is selected from the group consisting of chloro, methyl and ethyl
  • W is O
  • A is a direct bond
  • X is CH 2 ;
  • n 1 ;
  • G is phenyl or heteroaryl, wherein the heteroaryl is a 5- or 6-membered aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulphur, wherein said phenyl or heteroaryl are optionally substituted by 1 or 2 R 8 substituents, which may be the same or different;
  • Z is phenyl or heterocyclyl, wherein the heterocyclyl is a 5- to 10- membered mono- or fused bicyclic ring system, which may be aromatic and/or partially saturated, comprising 1 , 2 or 3 heteroatoms individually selected from nitrogen and oxygen, and wherein any of said phenyl or heterocyclyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • each R 8 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci-C6haloalkyl;
  • each R 9 is independently selected from the group consisting of halogen, Ci-C6alkyl and Ci- Cehaloalkyl.
  • the compounds of formula (I) according to the invention may be useful for combating phytopathogenic fungi (e.g Alternaria alternata, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola) containing a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or fenamidone or famoxadon e).
  • phytopathogenic fungi e.g Alternaria alternata, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola
  • Qo inhibitors e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or f
  • the compounds of formula (I) according to the invention may be useful for combating phytopathogenic fungi (e.g Alternaria alternata, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola) containing a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or fenamidone or famoxadone), wherein the mutation is G143A.
  • phytopathogenic fungi e.g Alternaria alternata, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola
  • Qo inhibitors e.g strobilurins such as azoxystrobin, pyraclostrobin and tri
  • the compounds of formula (I) according to the invention may be useful for combating phytopathogenic fungi (e.g Phakopsora pachyrhizi) containing a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin, picoxystrobin and trifloxystrobin or fenamidone or famoxadone), wherein the mutation is F129L.
  • phytopathogenic fungi e.g Phakopsora pachyrhizi
  • Qo inhibitors e.g strobilurins such as azoxystrobin, pyraclostrobin, picoxystrobin and trifloxystrobin or fenamidone or famoxadone
  • the invention also relates to a method of controlling or preventing infestation by phytopathogenic fungi in a plant (e.g Alternaria alternate, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola), wherein said phytopathogenic fungi contains a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or fenamidone or famoxadone), said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a compound of formula (I).
  • a plant e.g Alternaria alternate, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola
  • the level of resistance and therefore the impact on the performance of the fungicide can be measured by the use of a 'Resistance Factor' (RF).
  • RF EC50 value of the resistant strain/EC50 value of the sensitive strain.
  • resistant fungal strains In order to obtain resistant fungal strains, a researcher is to locate a host crop and geographical region where the relevant resistance had been reported in literature. Leaf samples infected by the target disease are then collected from the locations/host crops and sent to a laboratory, where pure cultures would be isolated. The resistant phenotype of the fungal cultures is determined either by conducting a full dose response bioassay and comparing the bioassay results to similar bioassay results for a known susceptible strain of the same species. Alternatively the resistance genotype of the fungal strain can be determined by molecular techniques (e.g. qPCR) if the resistance mechanism for the relevant species is known.
  • molecular techniques e.g. qPCR
  • the compounds of formula (I) according to the invention wherein A, E, G, W, X, Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (II), wherein A, E, G, W, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), with an alkylation reagent, such as diazomethane or iodomethane. This is shown in Scheme 1 below.
  • the compounds of formula (II), wherein A, E, G, W, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (III), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I) and R 10 is optionally substituted phenyl, and a base, such as sodium hydroxide or potassium hydroxide. This is shown in Scheme 2 below.
  • the compounds of formula (I), A, E, G, W, X, Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and n are as defined for formula (I)
  • the compounds of formula (I), A, E, G, W, X, Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (VIII), wherein A, E, W, R 1 , R 2 , R 3 , R 4 and R 5 are as defined for formula (I with a compound of formula (IX), wherein G, X, Z and n are as defined for formula (I) and R 13 is a leaving group, such as a halogen. This is shown in Scheme 5 below. Scheme 5
  • the compounds of formula (VI), wherein A, W, R 1 , R 2 , R 3 , R 4 and R 5 are as defined for formula (I) and R 12 is a protecting group, such as an ether or a ketal, can be obtained by transformation of a compound of formula (X), wherein A, W, R 2 , R 3 , R 4 and R 5 are as defined for formula (I) and R 12 is a protecting group, such as an ether or a ketal, with an alkylation reagent, such as diazomethane or iodomethane. This is shown in Scheme 6 below.
  • the compounds of formula (XI), wherein A, R 2 , R 3 , R 4 and R 5 are as defined for formula (I), R 10 is optionally substituted phenyl and R 12 is a protecting group, such as an ether or a ketal, can be obtained by transformation of a compound of formula (XII), wherein A, R 2 , R 3 , R 4 and R 5 are as defined for formula (I), R 11 is halogen and R 12 is a protecting group, such as an ether or a ketal, with a compound of formula (V), wherein R 10 is optionally substituted phenyl, and with a reagent suitable for halogen-metal exchange, such as n-butyl lithium, tert-butyl lithium, isopropylmagnesium chloride or magnesium turnings and a suitable activator.
  • a reagent suitable for halogen-metal exchange such as n-butyl lithium, tert-butyl lithium, isopropylmag
  • the compounds of formula (II), wherein A, E, G, W, X, Z, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (XIII), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), and with a base, such as sodium hydroxide or potassium hydroxide. This is shown in Scheme 9 below.
  • the compounds of formula (XIII), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (XIV), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), and with an oxidation reagent, such as hydrogen peroxide and sulfuric acid or sodium nitrite. This is shown in Scheme 10 below.
  • the compounds of formula (XIV), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (XV), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are is as defined for formula (I) and R 14 is Ci-C6alkyl, and base, such as sodium acetate. This is shown in Scheme 11 below.
  • the compounds of formula (XV), wherein wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are is as defined for formula (I) and R 14 is Ci-C6alkyl, can be obtained by transformation of a compound of formula (XVI), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), and with an alkanoic acid halide or alkanoic acid anhydride. This is shown in Scheme 12 below.
  • the compounds of formula (XVI), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (XVII), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), and with hydroxylamine hydrochloride and a base, such as sodium hydroxide or potassium hydroxide. This is shown in Scheme 13 below.
  • the compounds of formula (XIV), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are as defined for formula (I), can be obtained by transformation of a compound of formula (XVI), wherein A, E, G, X, Z, R 2 , R 3 , R 4 , R 5 and n are is as defined for formula (I), and with carbonyldiimidazole. This is shown in Scheme 14 below.
  • novel compounds of Formula (I) of the present invention have a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • the compounds of formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants.
  • the compounds of formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time 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 means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • compounds of formula (I) 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. terms, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B.
  • B. obtusa Botrytis spp. comprising B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.
  • 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 Cryll IB(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton 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 d-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 d-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticid
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • d-endotoxins for example 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, W095/34656, 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:
  • 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 Cry1 Ab toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 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-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes.
  • vegetative material such as cuttings or tubers, for example potatoes.
  • seeds in the strict sense
  • roots in the strict sense
  • fruits in the tubers
  • bulbs rhizomes
  • parts of plants 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.
  • 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 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
  • 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, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol
  • 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
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • salts of mono and dialkyl phosphate esters such as mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • 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 (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in 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).
  • the compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fung
  • 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 96/1 1945, 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, f
  • 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-1 18, 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, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydra
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • TX means one compound selected from the group consisting of the compounds described in Table 1 (below) or Table 2 (compound l.aa.005 or l.c.005) (below).
  • 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 active ingredient mixture of the compounds of formula (I) selected from a compound described in Table 1 (below) or Table 2 (compound l.aa.005 or l.c.005) (below) and an active ingredient as described above are 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
  • 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 of formula (I) selected from a compound described in Table 1 (below) or Table 2 (compound l.aa.005 or l.c.005) (below), and one or more active ingredients as described above can be applied, for example, in a single“ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, 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 (l) 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 by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I), 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 1 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 (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
  • 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 1 below illustrates examples of individual compounds of formula (I) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 and W are as defined in Table 1.
  • Especially preferred compounds are:
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 60 ppm, 20 ppm or 2 ppm.
  • Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • Method A ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 pm particle size, 30 x 2.1 mm column, 0.85 mL/min., 60 °C, H 2 0/MeOH 95:5 + 0.05% HCOOH (90%) / CHsCN + 0.05% HCOOH (10%) - 1.2 min.
  • Method B ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 pm particle size, 30 x 2.1 mm column, 0.85 mL/min., 60 °C, H 2 0/MeOH 95:5 + 0.05% HCOOH (90%) / CF CN + 0.05% HCOOH (10%) - 2.7 min.
  • 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.
  • the active ingredient 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.
  • the active ingredient 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 ingredient [compound of formula (I)] 10 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 %
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the active ingredient 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.
  • polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground active ingredient 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.
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient 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 a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • DIAD diisopropyl azodicarboxylate
  • HATU 1-[Bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium-3-oxide
  • TPP triphenylphosphine
  • LC/MS Liquid Chromatography Mass Spectrometry (description of the apparatus and the methods used for LC/MS analysis are given above)
  • Example 1 This example illustrates the preparation of
  • the reaction mixture was diluted with ethyl acetate (100 ml_) and water (50 ml_). The organic layer was separated, aqueous layer was extracted with ethyl acetate (2 * 50 ml_). The combined organic layer was dried over anhydrous Na 2 SC> 4 and concentrated under reduced pressure to afford crude reaction mixture.
  • the crude compound was purified by combi-flash (10 to 15% EtOAc/hexanes) to obtain an impure material which was again purified by reverse phase chromatography (combi-flash, C18 column) (80 to 100% ACN/water).
  • reaction mixture After stirring at 0 °C for 10 min, resulting reaction mixture was warmed to at room temperature continued stirring for 1 h. Then reaction mixture was again cooled to -10 °C and a solution of 3,4-bis(benzenesulfonyl)isoxazole (437 mg, 1 .25 mmol) in THF was added drop wise for 10 min. The resulting reaction mixture was slowly warmed to room temperature and stirred for 1 h. Reaction mixture was analyzed by TLC (30% EtOAc /hexanes), and it showed no starting material. The reaction mixture was quenched with aq.NH 4 CI (6.0 ml_), diluted with ethyl acetate (50 ml_) and water (20 ml_).
  • the reaction mixture was slowly neutralized with 2N HCI (0.3 mL), diluted with ethyl acetate (50 mL) and water (20 mL). Organic layer was separated and aqueous layer was extracted with ethyl acetate (2 c 50 mL). The combined organic layer was dried over anhydrous Na 2 S0 4 and concentrated under reduced pressure to obtain 4-(3-methyl-2-((2-methyl-4- (3,4,5-trimethyl-1 H-pyrazol-1-yl)phenoxy)methyl)phenyl)-1 ,2,5-oxadiazol-3-ol (80 mg, crude) as green color liquid. The obtained crude compound was used in next step without further purification.
  • reaction mixture was diluted with CH2CI2 (50 mL) and water (20 mL). Organic layer was separated and aqueous layer was extracted with CH2CI2 ( 2 c 50 mL). The combined organic layer was dried over anhydrous Na2S0 4 and concentrated under reduced pressure to afford crude reaction mixture which was purified by combi-flash (10 to 50% EtOAc/hexanes). Pure fractions were combined and evaporated under reduced pressure to obtain 2-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5- trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]-1 ,2,5-oxadiazol-3-one (Compound l.aa.005, 8.0 mg, 0.0172 mmol, 8.7%) as an off white solid.
  • Table 2 provides selected compounds of the present invention.
  • the compound according to formula (I) is compound l.aa.005 or l.c.005 listed in Table 2 (below).
  • 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
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the test compound formulated with DMSO and Tween20 and diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).
  • Botrvotinia fuckeliana Botrvtis cinerea
  • Botrvtis cinerea I liguid 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
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3 to 4 days after application.
  • nutrient broth PDB potato dextrose broth
  • 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.
  • nutrient broth PDB potato dextrose broth
  • Mvcosphaerella 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.
  • nutrient broth PDB potato dextrose broth
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Wheat leaf segments cv. Kanzler 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 1 day after application.
  • the inoculated 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 (7 - 9 days after application).
  • Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segmens are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des composés de formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1, utiles en tant que pesticides, en particulier en tant que fongicides.
PCT/EP2019/070924 2018-08-03 2019-08-02 Dérivés de 1,2,5-oxadiazol-3(2h)-one microbiocides WO2020025807A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1812692.0 2018-08-03
GBGB1812692.0A GB201812692D0 (en) 2018-08-03 2018-08-03 Microbiocidal compounds

Publications (1)

Publication Number Publication Date
WO2020025807A1 true WO2020025807A1 (fr) 2020-02-06

Family

ID=63518489

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/070924 WO2020025807A1 (fr) 2018-08-03 2019-08-02 Dérivés de 1,2,5-oxadiazol-3(2h)-one microbiocides

Country Status (2)

Country Link
GB (1) GB201812692D0 (fr)
WO (1) WO2020025807A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022117653A1 (fr) * 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Compositions fongicides

Citations (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4639771A (en) 1984-10-31 1987-01-27 Kabushiki Kaisha Toshiba Image processing system
EP0357460A2 (fr) 1988-09-02 1990-03-07 Sankyo Company Limited Dérivés de la milbémycine, leur préparation et leur utilisation
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0382173A2 (fr) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. Substance PF 1022, procédé pour sa préparation et composition anthelmintique contenant cette substance
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
EP0444964A1 (fr) 1990-03-01 1991-09-04 Sankyo Company Limited Dérivés d'éthers milbémycine, leur préparation et leur utilisation comme anthelmintiques
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
EP0503538A1 (fr) 1991-03-08 1992-09-16 Meiji Seika Kaisha Ltd. Composition médicale contenant un dépepsipeptide cyclique ayant une activité anthelminthique
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1993019053A1 (fr) 1992-03-17 1993-09-30 Fujisawa Pharmaceutical Co., Ltd. Derive de depsipeptide, production et utilisation
WO1993025543A2 (fr) 1992-06-11 1993-12-23 Bayer Aktiengesellschaft Enniatines et derives d'enniatines utilises dans la lutte contre les endoparasites
EP0594291A1 (fr) 1992-09-01 1994-04-27 Sankyo Company Limited Procédés pour la préparation de dérivés des milbémycines ayant un groupe d'éther sur la position 13
WO1994015944A1 (fr) 1993-01-18 1994-07-21 Pfizer Limited Nouveaux agents antiparasitaires apparentes aux milbemycines et aux avermectines
WO1994019334A1 (fr) 1993-02-19 1994-09-01 Meiji Seika Kaisha, Ltd. Derive du pf 1022 utilise comme depsipeptide cyclqiue
JPH06306064A (ja) * 1993-04-21 1994-11-01 Tosoh Corp アリールチアジアゾロン誘導体及びそれを有効成分とする殺菌剤
EP0626375A1 (fr) 1993-05-26 1994-11-30 Bayer Ag Octacyclodepsipeptides ayant une activité endoparasiticide
WO1995019363A1 (fr) 1994-01-14 1995-07-20 Pfizer Inc. COMPOSéS ANTIPARASITAIRES A BASE DE PYRROLOBENZOXAZINE
WO1995022552A1 (fr) 1994-02-16 1995-08-24 Pfizer Limited Agents antiparasitaires
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
US5478855A (en) 1992-04-28 1995-12-26 Yashima Chemical Industry Co., Ltd. 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butylphenyl)-2-oxazoline
WO1996011945A2 (fr) 1994-10-18 1996-04-25 Bayer Aktiengesellschaft Procede de sulfonylation, de sulfenylation et de phosphorylation de depsipeptides cycliques
WO1996015121A1 (fr) 1994-11-10 1996-05-23 Bayer Aktiengesellschaft Utilisation de dioxomorpholines pour lutter contre les endoparasites, nouvelles dioxomorpholines et leur procede de production
DE19520936A1 (de) 1995-06-08 1996-12-12 Bayer Ag Ektoparasitizide Mittel
WO1997005120A1 (fr) * 1995-07-26 1997-02-13 Sumitomo Chemical Company, Limited Derives de triazolone, utilisation de ces derives et d'intermediaires dans leur production
WO1997033890A1 (fr) 1996-03-11 1997-09-18 Novartis Ag Derives de pyrimidine-4-one utilises comme pesticide
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2004072086A2 (fr) 2003-02-14 2004-08-26 Pfizer Limited Terpene alcaloides antiparasitiques
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2011138281A2 (fr) 2010-05-06 2011-11-10 Bayer Cropscience Ag Procédé de production de dithiine-tétracarboxy-diimides
WO2013162072A1 (fr) * 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Composés de tétrazolinone et leur utilisation en tant que pesticides
WO2014006945A1 (fr) 2012-07-04 2014-01-09 アグロカネショウ株式会社 Dérivé d'ester d'acide 2-aminonicotinique et bactéricide le contenant comme principe actif
WO2014095675A1 (fr) 2012-12-19 2014-06-26 Bayer Cropscience Ag Utilisation de carboxamides difluorométhyl-nicotinique-indanyle comme fongicides
WO2016156290A1 (fr) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Nouveaux dérivés d'imidazole à substitution en position 5
WO2016202742A1 (fr) 2015-06-15 2016-12-22 Bayer Cropscience Aktiengesellschaft Phénoxyphénylamidines à substitution halogène et utilisation de celles-ci en tant que fongicides
WO2017029179A1 (fr) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Dérivés de triazole, leurs intermédiaires et leur utilisation comme fongicides
WO2017055473A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017055469A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017093348A1 (fr) 2015-12-02 2017-06-08 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017118689A1 (fr) 2016-01-08 2017-07-13 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
EP3246316A1 (fr) * 2015-01-13 2017-11-22 Sumitomo Chemical Company, Limited Composé carbamate et utilisation associée
WO2018153707A1 (fr) 2017-02-22 2018-08-30 Basf Se Formes cristallines d'un composé de type strobilurine pour lutter contre des champignons phytopathogènes

Patent Citations (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4639771A (en) 1984-10-31 1987-01-27 Kabushiki Kaisha Toshiba Image processing system
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
EP0357460A2 (fr) 1988-09-02 1990-03-07 Sankyo Company Limited Dérivés de la milbémycine, leur préparation et leur utilisation
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
EP0382173A2 (fr) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. Substance PF 1022, procédé pour sa préparation et composition anthelmintique contenant cette substance
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
EP0444964A1 (fr) 1990-03-01 1991-09-04 Sankyo Company Limited Dérivés d'éthers milbémycine, leur préparation et leur utilisation comme anthelmintiques
EP0503538A1 (fr) 1991-03-08 1992-09-16 Meiji Seika Kaisha Ltd. Composition médicale contenant un dépepsipeptide cyclique ayant une activité anthelminthique
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1993019053A1 (fr) 1992-03-17 1993-09-30 Fujisawa Pharmaceutical Co., Ltd. Derive de depsipeptide, production et utilisation
US5478855A (en) 1992-04-28 1995-12-26 Yashima Chemical Industry Co., Ltd. 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butylphenyl)-2-oxazoline
WO1993025543A2 (fr) 1992-06-11 1993-12-23 Bayer Aktiengesellschaft Enniatines et derives d'enniatines utilises dans la lutte contre les endoparasites
EP0594291A1 (fr) 1992-09-01 1994-04-27 Sankyo Company Limited Procédés pour la préparation de dérivés des milbémycines ayant un groupe d'éther sur la position 13
WO1994015944A1 (fr) 1993-01-18 1994-07-21 Pfizer Limited Nouveaux agents antiparasitaires apparentes aux milbemycines et aux avermectines
WO1994019334A1 (fr) 1993-02-19 1994-09-01 Meiji Seika Kaisha, Ltd. Derive du pf 1022 utilise comme depsipeptide cyclqiue
JPH06306064A (ja) * 1993-04-21 1994-11-01 Tosoh Corp アリールチアジアゾロン誘導体及びそれを有効成分とする殺菌剤
EP0626375A1 (fr) 1993-05-26 1994-11-30 Bayer Ag Octacyclodepsipeptides ayant une activité endoparasiticide
WO1995019363A1 (fr) 1994-01-14 1995-07-20 Pfizer Inc. COMPOSéS ANTIPARASITAIRES A BASE DE PYRROLOBENZOXAZINE
WO1995022552A1 (fr) 1994-02-16 1995-08-24 Pfizer Limited Agents antiparasitaires
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO1996011945A2 (fr) 1994-10-18 1996-04-25 Bayer Aktiengesellschaft Procede de sulfonylation, de sulfenylation et de phosphorylation de depsipeptides cycliques
WO1996015121A1 (fr) 1994-11-10 1996-05-23 Bayer Aktiengesellschaft Utilisation de dioxomorpholines pour lutter contre les endoparasites, nouvelles dioxomorpholines et leur procede de production
DE19520936A1 (de) 1995-06-08 1996-12-12 Bayer Ag Ektoparasitizide Mittel
WO1997005120A1 (fr) * 1995-07-26 1997-02-13 Sumitomo Chemical Company, Limited Derives de triazolone, utilisation de ces derives et d'intermediaires dans leur production
WO1997033890A1 (fr) 1996-03-11 1997-09-18 Novartis Ag Derives de pyrimidine-4-one utilises comme pesticide
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2004072086A2 (fr) 2003-02-14 2004-08-26 Pfizer Limited Terpene alcaloides antiparasitiques
WO2011138281A2 (fr) 2010-05-06 2011-11-10 Bayer Cropscience Ag Procédé de production de dithiine-tétracarboxy-diimides
WO2013162072A1 (fr) * 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Composés de tétrazolinone et leur utilisation en tant que pesticides
WO2014006945A1 (fr) 2012-07-04 2014-01-09 アグロカネショウ株式会社 Dérivé d'ester d'acide 2-aminonicotinique et bactéricide le contenant comme principe actif
WO2014095675A1 (fr) 2012-12-19 2014-06-26 Bayer Cropscience Ag Utilisation de carboxamides difluorométhyl-nicotinique-indanyle comme fongicides
EP3246316A1 (fr) * 2015-01-13 2017-11-22 Sumitomo Chemical Company, Limited Composé carbamate et utilisation associée
WO2016156290A1 (fr) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Nouveaux dérivés d'imidazole à substitution en position 5
WO2016202742A1 (fr) 2015-06-15 2016-12-22 Bayer Cropscience Aktiengesellschaft Phénoxyphénylamidines à substitution halogène et utilisation de celles-ci en tant que fongicides
WO2017029179A1 (fr) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Dérivés de triazole, leurs intermédiaires et leur utilisation comme fongicides
WO2017055473A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017055469A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017093348A1 (fr) 2015-12-02 2017-06-08 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017118689A1 (fr) 2016-01-08 2017-07-13 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2018153707A1 (fr) 2017-02-22 2018-08-30 Basf Se Formes cristallines d'un composé de type strobilurine pour lutter contre des champignons phytopathogènes

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Comprehensive Organic Functional Group Transformations", 1995, PERGAMON PRESS (ELSEVIER SCIENCE LTD.
"Comprehensive Organic Transformations: A Guide to Functional Group Preparations", 1999, WILEY-VCH
"The Pesticide Manual", 2009, BRITISH CROP PROTECTION COUNCIL
A. WOOD, COMPENDIUM OF PESTICIDE COMMON NAMES, pages 1995
LEONID L. FERSHTAT ET AL: "Side-chain prototropic tautomerism of 4-hydroxyfuroxans in methylation reactions", TETRAHEDRON LETTERS, vol. 57, no. 50, 7 November 2016 (2016-11-07), AMSTERDAM, NL, pages 5685 - 5689, XP055620884, ISSN: 0040-4039, DOI: 10.1016/j.tetlet.2016.11.023 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022117653A1 (fr) * 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Compositions fongicides

Also Published As

Publication number Publication date
GB201812692D0 (en) 2018-09-19

Similar Documents

Publication Publication Date Title
EP3941898B1 (fr) Composés fongicides
WO2020079111A1 (fr) Composés microbiocides
AU2019386994B2 (en) Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
AU2019389778B2 (en) Microbiocidal thiazole derivatives
WO2020208095A1 (fr) Dérivés de picolinamide microbiocides
WO2021224102A1 (fr) Composés microbiocides
US11629129B2 (en) Microbiocidal picolinamide derivatives
WO2020165403A1 (fr) Dérivés de thiazole substitués par phényle en tant que composés microbiocides
WO2020193618A1 (fr) Dérivés de thiazole microbiocides
WO2021219780A1 (fr) Composés microbiocides
WO2021219778A1 (fr) Composés microbiocides
WO2021219775A1 (fr) Composés microbiocides
WO2020025807A1 (fr) Dérivés de 1,2,5-oxadiazol-3(2h)-one microbiocides
WO2020078732A1 (fr) Dérivés d'oxadiazole microbiocides
RU2817796C2 (ru) Фунгицидные соединения
WO2022058580A1 (fr) Composés microbiocides
WO2021009026A1 (fr) Dérivés de méthyl 2-[(4-méthoxyimino-tétraline-6-yl]prop-2-énoate, chromane, isochromane,6,7,8,9-tétrahydrobenzo[7]annulène, 1h-isobenzofurane et analogues d'indane correspondants, et composés similaires servant de fongicides agrochimiques
OA21382A (en) Fungicidal compounds.
WO2023118011A1 (fr) Dérivés d'aza-hétérobiaryle microbiocides
WO2023148206A1 (fr) Dérivés de n-amide microbiocides
WO2023094303A1 (fr) Dérivés d'amide d'hétérobiaryle microbiocides
WO2022207479A1 (fr) Dérivés d'amide isonicotinique microbiocides
WO2023166067A1 (fr) Dérivés microbiocides de pyridazinone amide
WO2021204855A1 (fr) Dérivés de quinoléine dihydropyrrolopyrazine microbiocides
WO2024132895A1 (fr) Composés microbiocides de dihydrooxadiazinyl pyridazinone

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19755299

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19755299

Country of ref document: EP

Kind code of ref document: A1