WO2019011926A1 - Microbiocidal oxadiazole derivatives - Google Patents

Microbiocidal oxadiazole derivatives Download PDF

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Publication number
WO2019011926A1
WO2019011926A1 PCT/EP2018/068688 EP2018068688W WO2019011926A1 WO 2019011926 A1 WO2019011926 A1 WO 2019011926A1 EP 2018068688 W EP2018068688 W EP 2018068688W WO 2019011926 A1 WO2019011926 A1 WO 2019011926A1
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Prior art keywords
4alkyl
methyl
2alkyl
hydrogen
phenyl
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PCT/EP2018/068688
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French (fr)
Inventor
Thomas James HOFFMAN
Daniel Stierli
Thomas Pitterna
Ramya Rajan
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Syngenta Participations Ag
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Priority to BR112020000457-0A priority Critical patent/BR112020000457A2/en
Publication of WO2019011926A1 publication Critical patent/WO2019011926A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—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 carbon chain containing aromatic rings
    • 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

Definitions

  • the present invention relates to microbiocidal oxadiazole 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 oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
  • R , R 2 , R 3 , R 4 are independently selected from hydrogen or fluoro and wherein 0, 1 or 2 of R ⁇ R 2 , R 3 and R 4 are fluoro;
  • R 5 and R 6 are independently selected from hydrogen or methyl
  • Z represents Z 1 , Z , or Z 3 , wherein
  • R 7 represents -C(0)N(R 7a )(R 7b ), wherein R 7a is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, C2-
  • R 7b is Ci-4alkyl, Ci-4haloalkyl or cyclopropyl, or R 7a and R 7b together with the nitrogen atom to which they are bonded , form a cycle selected from azetidinyl, pyrrolidinyl, isoxazolidinyl or oxazolidinyl, or R 7a and R 7b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR 8 , wherein R 8 is hydrogen, methyl, methoxy, formyl or acyl; or
  • R 7 represents -C(0)N(R 7c )(R 7d ), wherein: R 7c is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC3-4alkyl, C2-
  • R 7c is C4-6cycloalkyl, C3-6cycloalkylC2alkyl, phenyl, phenylCi-2alkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, heterocyclyl, phenyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoro
  • R 7d is hydrogen
  • R 7 represents -C(0)OR 7e , wherein: R 7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-4haloalkenyl, or C3- 5alkynyl, or R 7e is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)
  • R 9 is hydroxyl, cyano, methyl, difluoromethyl, ⁇ , ⁇ -dimethylamino, methoxy, ethoxy, or difluoromethoxy, or
  • R 9 represents -C(0)N(R 9a )(R 9b ), wherein:
  • R 9a is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, aminoCi-4alkyl, amino, N,N-diCi-2alkylamino, N-C1- 2alkylaminoCi-4alkyl, N,N-diCi-2alkylaminoCi-4alkyl, hydroxyl, Ci-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy; or
  • R 9a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl,
  • R 9b is hydrogen, Ci-4alkyl, Ci-4haloalkyl, cyclopropyl, or
  • R 9a and R 9b together with the nitrogen atom to which they are bonded, form a 4- to 6-membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR 8 , or
  • R 9a and R 9b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR 8 , wherein R 8 is hydrogen, methyl, methoxy, formyl or acyl; or (ii) R 9 represents -C(0)OR 9c , wherein:
  • R 9c is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, Ci-2alkoxyCi-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, C3-4haloalkenyl, N-Ci- 3alkylaminoCi-4alkyl, N,N-di-Ci-3alkylaminoCi-4alkyl; or
  • R 9c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the groups consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano
  • R 0a is d ecycloalkyl, d-6cycloalkyld-2alkyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy
  • R 0a and R 0b together with the nitrogen atom to which they are bonded, form a 4- to 6- membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0) 2 , C(O) and NR 8 , or
  • R 0a and R 0b together with the nitrogen atom to which they are bonded, form a 5- to 8- membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR 8 , wherein R 8 is hydrogen, methyl, methoxy, formyl or acyl; or
  • R 0 represents -C(O)C(O)-OR 0c , wherein:
  • R 0c is hydrogen, d-salkyl, d-4haloalkyl, d-salkenyl, d-salkynyl, or
  • R 0c is d ecycloalkyl, d-6cycloalkyld-2alkyl, phenyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, or
  • R 0 represents -C(O)C(O)-R 0d , wherein R 0d is hydrogen, d-salkyl, or cyclopropyl; or a salt or an N-oxide thereof.
  • novel compounds of Formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • an agrochemical composition comprising a fungicidally effective amount of a compound of Formula (I).
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically- acceptable diluent or carrier.
  • a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms wherein a fungicidally effective amount of a compound of Formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a compound of Formula (I) as a fungicide.
  • the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • halogen or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine
  • bromine iodine
  • iodo iodine
  • cyano means a -CN group.
  • hydroxyl or "hydroxy” means an -OH group.
  • amino means an -NH2 group.
  • acyl means a -C(0)CH3 group.
  • formyl means a -C(0)H group.
  • Ci-6alkyl 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-4alkyl, d salkyl and Ci-2alkyl are to be construed accordingly.
  • Examples of Ci-ealkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (i-butyl).
  • Ci- C2alkylene refers to the corresponding definition of Ci-2alkyl, except that such radical is attached to the rest of the molecule by two single bonds.
  • Ci-4alkoxy refers to a radical of the formula -OR a where R a is a Ci- 4alkyl radical as generally defined above.
  • the terms d salkoxy and Ci-2alkoxy are to be construed accordingly.
  • Examples of Ci-4alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and i-butoxy.
  • Ci-4haloalkyl refers to a d salkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of Ci-4haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl.
  • C2-6alkenyl refers to a straight or branched hydrocarbon chain radical group 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.
  • Cs ealkenyl, C3-salkenyl, C2-4alkenyl and C2-3alkenyl are to be construed accordingly.
  • Examples of C2-6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop- 2-enyl), and but-1-enyl.
  • C2-6haloalkenyl refers to a C2-6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C3-4haloalkenyl is to be construed accordingly.
  • C3-4alkenoxy refers to a radical of the formula -OR a where R a is a C3- 4alkenyl radical as generally defined above.
  • C2-6alkynyl 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.
  • C3-salkynyl and C2-4alkynyl are to be construed accordingly.
  • Examples of C2-6alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl).
  • C3-4alkynoxy refers to a radical of the formula -OR a where R a is a C3- 4alkynyl radical as generally defined above.
  • C3-4alkynyloxyCi-4alkyl refers to a Ci-4alkyl radical as generally defined above substituted by a C3-4alkynyloxy group as defined above.
  • Ci-4alkoxyCi-4alkyl refers to radical of the formula Rb-0-R a - where Rb is a Ci-4alkyl radical as generally defined above, and R a is a Ci-4alkylene radical as generally defined above.
  • hydroxyCi-4alkyl refers to a Ci-4alkyl radical as generally defined above substituted by one or more hydroxy groups.
  • hydroxyCi-2alkyl should be construed accordingly.
  • cyanoCi-4alkyl refers to refers to a Ci-4alkyl radical as generally defined above substituted by one or more cyano groups.
  • Ci-4alkylcarbonyl refers to a radical of the formula -C(0)R a where R a is a Ci-4alkyl radical as generally defined above.
  • Ci-4alkylcarbonyloxyCi-4alkyl refers to a radical of the formula RbC(0)OR a - where Rb is a Ci-4alkyl radical as generally defined above, and R a is a Ci-4alkylene radical as generally defined above.
  • Ci-2alkoxyCi-2alkoxyCi-4alkyl refers to a radical of the formula RaORbORc-, where Rb and R c are Ci-2alkylene radicals as generally defined above, and R a is a Ci-4alkyl radical as generally defined above.
  • Ci-4alkoxycarbonyl refers to a radical of the formula R a OC(0)-, where R a is a Ci-4alkyl radical as generally defined above.
  • Ci-4alkoxycarbonylCi-4alkyl refers to a radical of the formula RaOC(0)Rb-, where R a is a Ci-4alkyl radical as generally defined above, and Rb is a Ci-4alkylene radical as generally defined above.
  • N-Ci-4alkylamino refers to a radical of the formula R a NH- where R a is a Ci-4alkyl radical as generally defined above.
  • N,N-diCi-4alkylamino refers to a radical of the formula R a (R a )N- where R a is a Ci-4alkyl radical as generally defined above.
  • Ci-4haloalkoxy refers to a Ci-4alkoxy group as defined above substituted by one or more of the same or different halogen atoms.
  • Examples of Ci-4haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, 2-fluoroethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy.
  • Ci-4alkylcarbonyl refers to a radical of the formula -C(0)R a where R a is a Ci-4alkyl radical as generally defined above.
  • Ci-4alkylcarbonylCi-4alkyl refers to a Ci-4alkyl radical as generally defined above substituted by a Ci-4alkylcarbonyl group as defined above.
  • C3-6cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-scycloalkyl and Cscycloalkyl are to be construed accordingly. Examples of C3-6cycloalkyl include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.
  • C3-6cycloalkylCi-2alkyl refers to a C3-6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-2alkylene radical as defined above.
  • Examples of C3- 6cycloalkylCi-3alkyl include, but are not limited to cyclopropyl-methyl and cyclobutyl-ethyl.
  • phenylCi-2alkyl refers to a phenyl ring attached to the rest of the molecule by a Ci-2alkylene radical as defined above.
  • phenylCi-2alkyl include, but are not limited to, benzyl.
  • heteroaryl generally refers to a 5- or 6-membered monocyclic aromatic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heteroaryl include but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl, and indolyl.
  • heterocyclyl or “heterocyclic” generally refers to a stable, saturated or partially saturated , 4- to 6-membered, non-aromatic monocyclic ring, which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heterocyclyl examples include, but are not limited to, azetidinyl, oxetanyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, and morpholinyl.
  • azetidinyl oxetanyl
  • pyrrolidyl tetrahydrofuryl
  • tetrahydrothienyl tetrahydrothiopyranyl
  • piperidinyl piperazinyl
  • tetrahydropyranyl dioxolanyl
  • morpholinyl morpholinyl
  • 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 oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g. , an agronomically usable or agrochemically acceptable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991 .
  • R , R 2 , R 3 , R 4 are independently selected from hydrogen or fluoro, wherein 0, 1 or 2 of R , R 2 , R 3 and R 4 are fluoro.
  • R , R 2 , R 3 and R 4 are hydrogen; R 2 , R 3 and R 4 are hydrogen and R is fluoro; R , R 2 and R 4 are hydrogen and R 3 is fluoro; R and R 2 are fluoro and R 3 and R 4 are hydrogen; R and R 3 are fluoro and R 2 and R 4 are hydrogen, or R and R 2 are hydrogen and R 3 and R 4 are fluoro.
  • R to R 4 are hydrogen, or R is fluoro and R 2 to R 4 are hydrogen.
  • R 5 and R 6 independently represent hydrogen or methyl.
  • R 5 and R 6 are both hydrogen, or R 5 is hydrogen and R 6 is methyl. More preferably, R 5 and R 6 are both hydrogen.
  • Z represents Z 1 , Z 2 , or Z 3 , wherein:
  • Z is Z .
  • Z is Z 2 . In some embodiments of the invention Z is Z 3 . Preferably, Z is Z .
  • R z may be R 7 , wherein
  • R 7 represents -C(0)N(R 7a )(R 7b ), wherein
  • R 7b is Ci-4alkyl, Ci-4haloalkyl or cyclopropyl, or
  • R 7a and R 7b together with the nitrogen atom to which they are bonded , form a cycle selected from azetidinyl, pyrrolidinyl, isoxazolidinyl or oxazolidinyl, or
  • R 7a and R 7b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR 8 ,
  • R 8 is hydrogen, methyl, methoxy, formyl or acyl
  • R 7 represents -C(0)N(R 7c )(R 7d ), wherein:
  • R 7c is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC3-4alkyl, C2- 3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C4-salkynyl, hydroxyl, aminoCi-4alkyl, N,N-diCi- 2alkylamino, N-formyl-N-Ci-2alkyl-amino, N-Ci-2alkylcarbonyl-N-Ci-2alkylamino, pyrroldin-1 -amino, piperdin-1-amino, morpholin-4-amino, N-Ci-4alkylaminoCi-4alkyl, formyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cycloprop
  • R 7d is hydrogen
  • R 7 represents -C(0)OR 7e , wherein: R 7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-4haloalkenyl, or C3- 5alkynyl, or
  • R 7e is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S,
  • R 7a is C3-salkyl, C3-4alkenyl or C3-4alkynyl. Even more preferably, R 7a is C3-salkyl (eg, methyl, ethyl or iso-propyl).
  • R 7b is methyl, ethyl, or cyclopropyl. More preferably, R 7b is methyl or cyclopropyl.
  • R 7c is C3-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC3-4alkyl, C2-3alkoxyethyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C4-salkynyl, hydroxyl, aminoCi-2alkyl, N,N-diCi- 2alkylamino, N-formyl-N-Ci-2alkyl-amino, N-Ci-2alkylcarbonyl-N-Ci-2alkylamino, pyrroldin-1 -amino, piperdin-1-amino, morpholin-4-amino, N-Ci-4alkylaminoCi-2alkyl, formyl, C2-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy,
  • R 7c is C3-5alkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, C3-4alkenyl, C4-salkynyl, aminoCi-2alkyl, formyl, C2-4alkoxy, hydroxyl, C3-4alkenyloxy, C3-4haloalkyloxy, C3-4alkynyloxy or cyclopropylCi-2alkoxy. Even more preferably, R 7c is C3-salkyl, Ci-2fluoroalkyl, C3-4alkenyl, C4-salkynyl or C2-4alkoxy.
  • R 7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C3- 4haloalkenyl or C3-4alkynyl.
  • R 7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2- dimethylpropyl, Ci-2fluoroalkyl, C3-4alkenyl or C3-4alkynyl.
  • R z may be R 9 , wherein:
  • R 9 is hydroxyl, cyano, methyl, difluoromethyl, ⁇ , ⁇ -dimethylamino, methoxy, ethoxy, or difluoromethoxy, or
  • R 9 represents -C(0)N(R 9a )(R 9b ), wherein:
  • R 9a is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, aminoCi-4alkyl, amino, N,N-diCi-2alkylamino, N-C1- 2alkylaminoCi-4alkyl, N,N-diCi-2alkylaminoCi-4alkyl, hydroxyl, Ci-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy; or
  • R 9a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S,
  • R 9b is hydrogen, Ci-4alkyl, Ci-4haloalkyl, cyclopropyl, or
  • R 9a and R 9b together with the nitrogen atom to which they are bonded, form a 4- to 6-membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR 8 ; or
  • R 9a and R 9b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR 8 ;
  • R 8 is hydrogen, methyl, methoxy, formyl or acyl
  • R 9 represents -C(0)OR 9c , wherein: R 9c is hydrogen, Ci-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, Ci-2alkoxyCi-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, C3-4haloalkenyl, N-Ci- 3alkylaminoCi-4alkyl, N,N-di-Ci-3alkylaminoCi-4alkyl; or
  • R 9c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the groups consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S,
  • R 9a is d-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl,
  • R 9a is Ci-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl, Ci-2fluoroalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, hydroxyl or Ci-2alkoxy.
  • R 9b is hydrogen, methyl, ethyl or cyclopropyl.
  • R 9c is Ci-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC2alkyl, Ci-2alkoxyCi-2alkoxyCi-2alkyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, C3-4haloalkenyl, N-C1- 3alkylaminoCi-2alkyl or N,N-di-Ci-2alkylaminoCi-2alkyl.
  • R 9c is Ci-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC2alkyl, C3-4alkenyl or C3-4alkynyl.
  • R z may be R 0 , wherein
  • R 0 represents -C(O)C(O)-N(R 0a )(R 0b ), wherein
  • R 0b is hydrogen, Ci-4alkyl, Ci-4fluoroalkyl, cyclopropyl, cyclopropylmethyl, or
  • R 0a and R 0b together with the nitrogen atom to which they are bonded , form a 4- to 6- membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0) 2 , C(O) and NR 8 ; or
  • R 0a and R 0b together with the nitrogen atom to which they are bonded , form a 5- to 8- membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR 8 ,
  • R 8 is hydrogen, methyl, methoxy, formyl or acyl
  • R 0 represents -C(O)C(O)-OR 0c , wherein:
  • R 0c is hydrogen, d-salkyl, Ci-4haloalkyl, C3-salkenyl, C3-salkynyl, or
  • R 0c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, or
  • R 0 represents -C(O)C(O)-R 0d , wherein R 0d is hydrogen, d-salkyl, or cyclopropyl.
  • the compound according to Formula (I) is selected from a compound 1.1 to 1.28 described in Table T1 (below), compound 2.1 to 2.107 described in Table T2 (below), compound 3.1 to 3.81 described in Table T3 (below), compound 4.1 to 4.9 described in Table T4 (below), and compound 5.1 to 5.26 described in Table T5 (below).
  • the compounds of the present invention may be enantiomers of the compound of Formula (I) as represented b a Formula (la) or a Formula (lb), wherein R 5 and R 6 are different substituents.
  • Compounds of formula (I) can be prepared from compounds of formula (II), wherein X is a halogen, preferably CI, Br or I, via treatment with compounds of formula (III), in the presence of a base (e.g. K2CO3, CS2CO3, or NaH) in a suitable solvent (e.g. dimethylformamide or tetrahydrofuran) at a temperature between 25°C and 1 10°C.
  • a catalyst eg, Nal or 4-dimethylaminopyridine
  • This reaction is shown in Scheme 1.
  • compounds of formula (I) can be prepared from compounds of formula (IV) by treatment with trifluoroacetic fluoride, trifluoroacetic chloride, trifluoroacetic anhydride, optionally in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C.
  • a base eg, pyridine or 4-dimethylaminopyridine
  • suitable solvent such as tetrahydrofuran or ethanol
  • Compounds of formula (IV) can be prepared from compounds of formula (V) by treatment with a hydroxylamine hydrochloride salt in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature between 0°C and 100°C.
  • a base such as triethylamine
  • a suitable solvent such as methanol
  • Compounds of formula (II), wherein X is CI or Br can be prepared from compounds of formula (VIII) by treatment with a halogen source (eg, /V-bromosuccinimide (NBS) or A/-chlorosuccinimide (NCS)) and a radical initiator (eg, (PhC(0)0)2 or azobisisobutyronitrile (AIBN)) in a suitable solvent, such as tetrachloromethane, at temperatures between 55°C and 100°C in the presence of ultraviolet light.
  • a halogen source eg, /V-bromosuccinimide (NBS) or A/-chlorosuccinimide (NCS)
  • a radical initiator eg, (PhC(0)0)2 or azobisisobutyronitrile (AIBN)
  • suitable solvent such as tetrachloromethane
  • compounds of formula (II) can be prepared from compounds of formula (IX) by treatment with trifluoroacetic chloride, trifluoroacetic fluoride, or trifluoroacetic anhydride in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C.
  • a base eg, pyridine or 4-dimethylaminopyridine
  • suitable solvent such as tetrahydrofuran or ethanol
  • Compounds of formula (IX) can be prepared from compounds of formula (X) by treatment with a hydroxylamine hydrochloride salt in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature between 0°C and 100°C.
  • a base such as triethylamine
  • a suitable solvent such as methanol
  • compounds of formula (VII), wherein X is CI, Br, I or OSCteMe and Y is Br, I or CN are either commercially available or can be prepared from compounds of formula (XII), by treatment with a halogen source (eg, CC Br, CCU or ) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CISC Me), in a suitable solvent, (eg, dichloromethane) at a temperature between 0°C and 100°C.
  • a halogen source eg, CC Br, CCU or
  • CISC Me methanesulfonyl chloride
  • suitable solvent eg, dichloromethane
  • the compounds of Formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • the compounds of Formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants.
  • the compounds of Formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of Formula (I) is applied to the plants, to parts thereof or the locus thereof. It is also possible to use compounds of Formula (I) as a fungicide.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all dew ' ation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • compositions of Formula (I) can be used as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the propagation material can be treated with a composition comprising a compound of Formula (I) before planting: seed, for example, can be dressed before being sown.
  • the active compounds of Formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds of Formula (I) can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • the compounds of Formula (I) are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:
  • Absidia corymbifera Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terms, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
  • 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 CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl 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 ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdy
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cryl 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.
  • 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 Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab 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
  • Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • 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 * 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.
  • the compounds of Formula (I) may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants.
  • transgenic soybean plants expressing toxins for example insecticidal proteins such as delta-endotoxins, e.g. Cry1 Ac (Cry1 Ac Bt protein).
  • toxins for example insecticidal proteins such as delta-endotoxins, e.g. Cry1 Ac (Cry1 Ac Bt protein).
  • this may include transgenic soybean plants comprising event MON87701 (see U.S. Patent No. 8,049,071 and related applications and patents, as well as WO 2014/170327 A1 (eg, see paragraph [008] reference to Intacta RR2 PROTM soybean)), event MON87751 (US. Patent Application Publication No. 2014/0373191 ) or event DAS- 81419 (U.S. Patent No. 8632978 and related applications and patents).
  • event MON87701 see U.S. Patent No. 8,049,071 and related applications and patents, as well as WO 2014/170327 A1 (eg, see paragraph [008] reference to In
  • transgenic soybean plants may comprise event SYHT0H2 - HPPD tolerance (U.S. Patent Application Publication No. 2014/0201860 and related applications and patents), event MON89788 - glyphosate tolerance (U.S. Pat. No. 7,632,985 and related applications and patents), event MON87708 - dicamba tolerance (U.S. Patent Application Publication No. US 201 1/0067134 and related applications and patents), event DP-356043-5 - glyphosate and ALS tolerance (U.S. Patent Application Publication No. US 2010/0184079 and related applications and patents), event A2704-12 - glufosinate tolerance (U.S. Patent Application Publication No.
  • event DAS-40278-9 - tolerance to 2,4- dichlorophenoxyacetic acid and aryloxyphenoxypropionate see WO 201 1/022469, WO 201 1/022470, WO 201 1/022471 , and related applications and patents
  • event 127 - ALS tolerance WO 2010/080829 and related applications and patents
  • event GTS 40-3-2 - glyphosate tolerance event DAS-68416-4- 2,4-dichlorophenoxyacetic acid and glufosinate tolerance
  • event FG72 - glyphosate and isoxaflutole tolerance event BPS-CV127-9 - ALS tolerance and GU262 - glufosinate tolerance or event SYHT04R - HPPD tolerance.
  • compounds of Formula (I) according to the present invention when used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants (in particular any of the transgenic soybean plants as described above), may display a synergistic interaction between the active ingredients.
  • phytopathogenic diseases especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants (in particular any of the transgenic soybean plants as described above
  • fungicidal-resistant strains of Phakopsora pachyrhizi have been reported in the scientific literature, with strains resistant to one or more fungicides from at least each of the following fungicidal mode of action classes being observed: sterol demethylation-inhibitors (DMI), quinone-outside- inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI).
  • DMI sterol demethylation-inhibitors
  • Qol quinone-outside- inhibitors
  • SDHI succinate dehydrogenase inhibitors
  • fungicidal compositions according to the present invention comprising a compound of Formula (I), are used to control Phakopsora pachyrhizi which are resistant to one or more fungicides from any of the following fungicidal MoA classes: sterol demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI).
  • DMI sterol demethylation-inhibitors
  • Qol quinone-outside-inhibitors
  • SDHI succinate dehydrogenase inhibitors
  • the compounds of Formula (I) (including any one of compounds 1.1 to 1 .28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below)) or fungicidal compositions according to the present invention comprising a compound of Formula (I) may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants.
  • phytopathogenic diseases especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants.
  • An elite plant is any plant from an elite line, such that an elite plant is a representative plant from an elite variety.
  • elite soybean varieties that are commercially available to farmers or soybean breeders include: AG00802, A0868, AG0902, A1923, AG2403, A2824, A3704, A4324, A5404, AG5903, AG6202 AG0934; AG1435; AG2031 ; AG2035; AG2433; AG2733; AG2933; AG3334; AG3832; AG4135; AG4632; AG4934; AG5831 ; AG6534; and AG7231 (Asgrow Seeds, Des Moines, Iowa, USA); BPR0144RR, BPR 4077NRR and BPR 4390NRR (Bio Plant Research, Camp Point, III., USA); DKB17-51 and DKB37-51 (DeKalb Genetics, DeKalb, III., USA); DP 4546 RR, and DP 7870 RR (Delta & Pine Land Company, Lubbock,
  • the compounds of Formula (I) (including any one of compounds 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below)), or fungicidal compositions according to the present invention comprising a compound of Formula (I), are used to control Phakopsora pachyrhizi, (including fungicidally-resistant strains thereof, as outlined above) on Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome.
  • 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 nonvolatile 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, ⁇ , ⁇ -dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glyco
  • 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
  • dialkyi 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 dialkyi phosphate esters such as mono and dialkyi phosphate esters.
  • compositions of the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention.
  • these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank.
  • These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • Pesticidal agents are referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • 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 nonselective 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.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fung
  • Suitable additional active ingredients also include the following: 3-difluoromethyl-
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP- 444964 and EP-594291.
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO- 9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2- dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate,
  • 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 as represented in Tables 1A.1 to 1A.8, Tables 1 B.1 to 1 B.8, Tables 2.1 to 2.8, Tables 3.1 to 3.4, Tables 4.1 to 4.4, and Tables 5A.1 to 5A.4, Tables 5B.1 to 5B.4, or a compound 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below).
  • an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
  • an acaricide selected from the group of substances consisting of 1 , 1-bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1-naphthylacetamide (lUPAC name) (1295) + TX,
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1 /- -pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) +
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name)
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethylamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1-dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1-bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (lUPAC
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2- dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3- dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1 , 1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4- chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3- ylacetic acid (lUPAC name) (1286)
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, co
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
  • an animal repellent selected from the group of substances consisting of anthraquinone (32) +
  • TX chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (lUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
  • a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
  • 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.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • Another aspect of the invention is related to the use of a compound of Formula (I) or of a preferred individual compound as defined herein, of a composition comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • a further aspect of the invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of Formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
  • a compound of Formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts
  • Controlling or preventing means reducing infestation 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.
  • a composition comprising a compound of Formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • 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 1A.1 This table discloses 9 specific compounds of the formula (T-1 A):
  • R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, and R 7a -N-R 7b is as defined below in Table 1A.
  • Tables 1 A.2 to 1 A.8 make available 9 individual compounds of the formula (T-1 A) in which R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 1A.2 to 1A.8, which refer to Table 1 A wherein R 7a -N-R 7b is specifically defined.
  • Table 1A
  • Table 1A.2 This table discloses 9 specific compounds of formula (T-1 A) wherein R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, R is fluorine, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1A.3 This table discloses 9 specific compounds of formula (T-1A) wherein, R , R 2 , R 4 , R 5 , and R 6 are hydrogen, R 3 is fluorine, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1A.4 This table discloses 9 specific compounds of formula (T-1 A) wherein R 2 , R 4 , R 5 , and R 6 are hydrogen, R and R 3 are fluorine, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1A.5 This table discloses 9 specific compounds of formula (T-1 A) wherein R 3 , R 4 , R 5 , and R 6 are hydrogen, R and R 2 are fluorine, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1A.6 This table discloses 9 specific compounds of formula (T-1 A) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1A.7 This table discloses 9 specific compounds of formula (T-1 A) wherein R , R 2 , R 5 and R 6 are hydrogen, R 3 and R 4 are fluorine, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1A.8 This table discloses 9 specific compounds of formula (T-1 A) wherein R 2 , R 3 , R 5 and R 6 are hydrogen, R and R 4 are fluorine, and R 7a -N-R 7b is as defined above in Table 1A.
  • Table 1 B.1 This table discloses 29 specific compounds of the formula (T-1 B):
  • Tables 1 B.2 to 1 B.8 make available 29 individual compounds of the formula (T-1 B) in which R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 1 B.2 to 1 B.8, which refer to Table 1 B wherein R 7c -N-R 7d is specifically defined.
  • R 7c -N-R 7d R 7c -N-R 7d no. no.
  • Table 1B.2 This table discloses 29 specific compounds of formula (T-1B) wherein R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, R is fluorine, and R 7c -N-R 7d is as defined above in Table 1B.
  • Table 1B.3 This table discloses 29 specific compounds of formula (T-1B) wherein R , R 2 , R 4 , R 5 , and R 6 are hydrogen, R 3 is fluorine, and R 7c -N-R 7d is as defined above in Table 1B.
  • Table 1B.4 This table discloses 29 specific compounds of formula (T-1B) wherein R 2 , R 4 , R 5 , and R 6 are hydrogen, R and R 3 are fluorine, and R 7c -N-R 7d is as defined above in Table 1B.
  • Table 1B.5 This table discloses 29 specific compounds of formula (T-1B) wherein R 3 , R 4 , R 5 , and R 6 are hydrogen, R and R 2 are fluorine, and R 7c -N-R 7d is as defined above in Table 1B.
  • Table 1B.6 This table discloses 29 specific compounds of formula (T-1B) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and R 7c -N-R 7d is as defined above in Table 1B.
  • Table 1B.7 This table discloses 29 specific compounds of formula (T-1B) wherein R , R 2 , R 5 and R 6 are hydrogen, R 3 and R 4 are fluorine, and R 7c -N-R 7d is as defined above in Table 1B.
  • Table 1B.8 This table discloses 29 specific compounds of formula (T-1B) wherein R 2 , R 3 , R 5 and R 6 are hydrogen, R and R 4 are fluorine, and R 7c -N-R 7d is as defined above in Table 1B.
  • R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, and R 7e is as defined below in Table 2.
  • Tables 2.2 to 2.8 make available 22 individual compounds of the formula (T-2) in which R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 2.2 to 2.8, which refer to Table 2 wherein R 7e is specifically defined.
  • Table 2.2 This table discloses 22 specific compounds of formula (T-2) wherein R 2 , R 3 , R 4 , R 5 , and R' are hydrogen, R is fluorine, and R 7e is as defined above in Table 2.
  • Table 2.3 This table discloses 22 specific compounds of formula (T-2) wherein R , R 2 , R 4 , R 5 , and R' are hydrogen, R 3 is fluorine, and R 7e is as defined above in Table 2.
  • Table 2.4 This table discloses 22 specific compounds of formula (T-2) wherein R 2 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R and R 3 are fluorine, and R 7e is as defined above in Table 2.
  • Table 2.5 This table discloses 22 specific compounds of formula (T-2) wherein R 3 , R 4 , R 5 , and R 6 are hydrogen, R and R 2 are fluorine, and R 7e is as defined above in Table 2.
  • Table 2.6 This table discloses 22 specific compounds of formula (T-2) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and R 7e is as defined above in Table 2.
  • Table 2.7 This table discloses 22 specific compounds of formula (T-2) wherein R , R 2 , R 5 and R 6 are hydrogen, R 3 and R 4 are fluorine, and R 7e is as defined above in Table 2.
  • Table 2.8 This table discloses 22 specific compounds of formula (T-2) wherein R 2 , R 3 , R 5 and R 6 are hydrogen, R and R 4 are fluorine, and R 7e is as defined above in Table 2.
  • Table 3.1 This table discloses 78 specific compounds of the formula (T-3):
  • R , R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, and R 0 -Nu is as defined below in Table 3.
  • Tables 3.2 to 3.4 make available 78 individual compounds of the formula (T-3) in which R , R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 3.2 to 3.4, which refer to Table 3 wherein R 0 -Nu is specifically defined.
  • Table 3.2 This table discloses 78 specific compounds of formula (T-3) wherein R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, R is fluorine, and R 0 -Nu is as defined above in Table 3.
  • Table 3.3 This table discloses 78 specific compounds of formula (T-3) wherein R , R 2 , R 4 , R 5 , and R 6 are hydrogen, R 3 is fluorine, and R 0 -Nu is as defined above in Table 3.
  • Table 3.4 This table discloses 78 specific compounds of formula (T-3) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and R 0 -Nu is as defined above in Table 3.
  • R , R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, and Z is as defined below in Table 4.
  • Tables 4.2 to 4.4 make available 34 individual compounds of the formula (T-4) in which R , R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 4.2 to 4.4, which refer to Table 4 wherein Z is specifically defined.
  • Table 4
  • Table 4.2 This table discloses 34 specific compounds of formula (T-4) wherein R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, R is fluorine, and Z is as defined above in Table 4.
  • Table 4.3 This table discloses 34 specific compounds of formula (T-4) wherein R , R 2 , R 4 , R 5 , and R 6 are hydrogen, R 3 is fluorine, and Z is as defined above in Table 4.
  • Table 4.4 This table discloses 34 specific compounds of formula (T-4) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and Z is as defined above in Table 4.
  • Table 5A.1 This table discloses 78 specific compounds of the formula (T-5A):
  • R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, and R 0 -Nu is as defined below in Table 5A.
  • Tables 5A.2 to 5A.4 make available 78 individual compounds of the formula (T-5A) in which R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 5A.2 to 5A.4, which refer to Table 5A wherein R 0 -Nu is specifically defined.
  • Table 5A.2 This table discloses 78 specific compounds of formula (T-5A) wherein R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, R is fluorine, and R 0 -Nu is as defined above in Table 5A.
  • Table 5A.3 This table discloses 78 specific compounds of formula (T-5A) wherein R , R 2 , R 4 , R 5 , and R 6 are hydrogen, R 3 is fluorine, and R 0 -Nu is as defined above in Table 5A.
  • Table 5A.4 This table discloses 78 specific compounds of formula (T-5A) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and R 0 -Nu is as defined above in Table 5A.
  • Table 5B.1 This table discloses 78 s ecific compounds of the formula (T-5B):
  • R , R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, and R 0 -Nu is as defined below in Table 5B.
  • Tables 5B.2 to 5B.4 make available 78 individual compounds of the formula (T-5B) in which R ⁇ R 2 , R 3 , R 4 , R 5 , and R 6 are as specifically defined in Tables 5B.2 to 5B.4, which refer to Table 5B wherein R 0 -Nu is specifically defined.
  • Table 5B.2 This table discloses 78 specific compounds of formula (T-5B) wherein R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen, R is fluorine, and R 0 -Nu is as defined above in Table 5B.
  • Table 5B.3 This table discloses 78 specific compounds of formula (T-5B) wherein R , R 2 , R 4 , R 5 , and R 6 are hydrogen, R 3 is fluorine, and R 0 -Nu is as defined above in Table 5B.
  • Table 5B.4 This table discloses 78 specific compounds of formula (T-5B) wherein R , R 2 , R 3 R 4 , and R 5 are hydrogen, R 6 is methyl, and R 0 -Nu is as defined above in Table 5B.
  • 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 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
  • Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.
  • Type of column Waters ACQUITY UPLC BEH C18; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .7 micron; Temperature: 35°C.
  • 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.
  • Active ingredient [compound of Formula (I)] 25 % 50 % 75 %
  • Kaolin 62 % 27 % 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.
  • Active ingredient [compound of Formula (I)] 25 % 50 % 75 %
  • 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.
  • 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.
  • Kaolin 82 % 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.
  • Active ingredient [compound of Formula (I)] 40 %
  • 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.
  • Active ingredient [compound of Formula (I)] 40 %
  • 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.
  • To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension Formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • AIBN azobisisobutyronitrile
  • DIBAL-H diisobutyl aluminum hydride
  • DIPEA N,N-di-isopropylethylamine
  • NBS N-bromosuccinimide
  • Example 1 This example illustrates the preparation of building block 1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid
  • Step 1 ethyl 1-[(4-cyanophenyl)methvnpyrazole-4-carboxylate
  • Step 3 ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpyrazole-4-carboxylate
  • Step 4 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpyrazole-4-carboxylic acid
  • ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4- carboxylate 5.0 g, 13.7 mmol
  • 37% hydrochloric acid 130 mL
  • trifluoroacetic acid 52 mL
  • the reaction was heated at 55°C for 50 hours, cooled to room temperature and poured into ice water (400 mL), and basified by slow addition of aqueous saturated NaHCCh solution.
  • reaction mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99:1 to 9: 1 ) to afford 4.62 g of the title compound as an off-white solid, mp: 182-192°C.
  • Example 2 This example illustrates the preparation building block 1-[1-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]eth l]pyrazole-4-carboxylic acid
  • Step 1 Preparation of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzoyl chloride
  • Step 2 Preparation of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzamide
  • DIBAL-H 1.0M in toluene (16 mL, 16.0 mmol) was added drop-wise a solution of A/-methoxy-A/-methyl- 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (4.10 g, 13.3 mmol) in 2-methyltetrahydrofuran (90 mL).
  • the mixture was stirred for two hours at -78°C and for one hour temperature was increase to 0°C via ice bath.
  • the mixture was quenched by drop-wise addition of a saturated ammonium chloride solution. Precipitation of a white solid resulted and 4M HCI was added until full solubilisation occurred.
  • Step 4 Preparation of 1-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethanol
  • Step 5 Preparation of 1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllethanone
  • Step 6 Preparation of 3-[4-(1-bromoethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
  • Step 7 Preparation of ethyl 1-[1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllethyllpyrazole-4- carboxylate
  • Ethyl 1 H-pyrazole-4-carboxylate (0.061 g, 0.46 mmol), potassium carbonate (0.13 g, 0.93 mmol), 3-[4-(1-bromoethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.15 g, 0.47 mmol), and acetonitrile (1.5 mL) were reacted at room temperature overnight then concentrated under reduced pressure. Water was added and the organics were extracted twice with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, and filtered.
  • Step 8 Preparation of 1-[1-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethyllpyrazole-4- carboxylic acid
  • Example 3 This example illustrates the preparation building block 1-[[3-fluoro-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phen l]methyl]pyrazole-4-carboxylic acid
  • Step 2 Preparation of 3-(2-fluoro-4-methyl-phenvn-5-(trifluoromethvn-1 ,2,4-oxadiazole
  • Step 3a Preparation of 3-[4-(bromomethyl)-2-fluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3b Preparation of 3-[4-(bromomethvn-2-fluoro-phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole from 3-[4-(dibromomethvn-2-fluoro-phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
  • Step 4 Preparation of2-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-4,4- dimethyl-isoxazolidin-3-one
  • Ethyl 1 H-pyrazole-4-carboxylate (0.066 g, 0.46 mmol), potassium carbonate (0.086 g, 0.62 mmol), 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.10 g, 0.31 mmol), and acetonitrile (1.5 mL) were sealed in a vial.
  • the reaction contents were irradiated with microwaves and heated at 130°C for 0.5 hour. After cooling to 25°C, all solids were filtered off, rinsed with ethyl acetate, and the volatiles were removed under reduced pressure.
  • Step 5 Preparation of 1-[[3-fluoro-4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllmethyllpyrazole-4- carboxylic acid solution of 2-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-4,4- dimethyl-isoxazolidin-3-one (2.5 g, 6.5 mmol) dissolved in 37% hydrochloric acid (65 mL) was added trifluoroacetic acid (26 mL).
  • the reaction was heated at 55°C for 50 hours, cooled to room temperature and poured into ice water (200 mL), and basified by slow addition of aqueous saturated NaHCCh solution.
  • the reaction mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc 3:1 to EtOAc:EtOH 9: 1 eluent gradient) to afford 2.3 g of the title compound as an off-white solid, mp: 185-186°C.
  • Example 4 This example illustrates the preparation of building block ethyl 2-oxo-2-[1-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetate (Compound 4.1 of Table T4)
  • Example 5 This example illustrates the preparation of building block 2-oxo-2-[1-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetic acid
  • Example 6 This example illustrates the preparation of 2-oxo-2-[1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phen l]methyl]pyrazol-4-yl]acetyl chloride (Compound 4.5 of Table T4)
  • Example 7 This example illustrates the preparation of N-methyl-2-oxo-2-[1-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetamide (Compound 4.3 of Table T4)
  • methanamine hydrochloride (0.014 g, 0.205 mmol) was added followed by [dimethylamino(triazolo[4,5-b]pyridin-3- yloxy)methylene]-dimethyl-ammonium hexafluorophosphate (0.078 g, 0.205 mmol) and the reaction was stirred 2 hours at room temperture.
  • EtOAc (10 mL) and H2O (5 mL) were added, the layers were separated, and the aqueous layer was extractedwith EtOAc. The combined organic layers were washed with water, dried with Na2S04, filtered, and evaporated, to get a beige solid of crude.
  • Example 8 This example illustrates the preparation of methyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]pyrazole-3-carboxylate (Compound 5.1 of Table T5)
  • Example 9 This example illustrates the preparation of N,N-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l]pyrazole-3-carboxamide (Compound 5.19 of Table T5)
  • Protocol A A stock solution of the 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- azole-carboxylic acid derivative of formula (IB) (600 mg) wherein Z is Z ⁇ Z 2 , or Z was prepared in N,N- dimethylacetamide (9.6 mL).
  • Protocol B A stock solution of the 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- azole-carboxylic acid derivative of formula (IB) (24 times 0.04 mmol) wherein Z is Z , Z 2 , or Z was prepared in 24 portions of DMF (each 0.3 mL) in a deep well plate.
  • Table T1 Melting point (mp) data and/or retention times (T.R) for compounds 1.1 to 1.28 according to
  • Table T2 Melting point (mp) data and/or retention times HR) for compounds 2.1 to 2.107 according to Formula (I):
  • Table T3 Melting point (mp) data and/or retention times HR) for compounds 3.1 to 3.81 according to
  • Table T4 Melting point (mp) data and/or retention times HR) for compounds 4.1 to 4.9 according to
  • Table T5 Melting point (mp) data and/or retention times HR) for compounds 5.1 to 5.26 according to Formula (I):
  • Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse.
  • the cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar.
  • the leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation.
  • Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying.
  • the inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system.
  • a single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.
  • General examples of liquid culture tests in well plates :
  • Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth.
  • DMSO solutions of the test compound (max. 10 mg/ml) are diluted with 0.025% Tween20 by a factor of 50 and 10 ⁇ of this solution is pipetted into a microtiter plate (96-well format).
  • the nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound.
  • the test plates are incubated in the dark at 24°C and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check is calculated.
  • Example 1 Fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)
  • Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks were inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf segments were incubated at 19 C and 75% relative humidity (rh) under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 to 9 days after application).
  • Example 2 Fungicidal activity against Puccinia recondita f. sp. triticil wheat / leaf disc curative (Brown rust)
  • Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 to 8 days after application).
  • the following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
  • Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • leaf discs are inoculated by spraying a spore suspension on the lower leaf surface.
  • the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 to 14 days after application).
  • Example 4 Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liguid culture / cucumber / preventative (Anthracnose)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB - potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96- well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is measured photometrically 3 to 4 days after application.
  • nutrient broth PDB - potato dextrose broth
  • the following compounds at 20 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

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Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as pesticides, especially as fungicides.

Description

Microbiocidal Oxadiazole Derivatives
The present invention relates to microbiocidal oxadiazole 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 oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
According to the present invention, there is rovided a compound of formula (I):
Figure imgf000002_0001
wherein R , R2, R3, R4 are independently selected from hydrogen or fluoro and wherein 0, 1 or 2 of R\ R2, R3 and R4 are fluoro;
R5 and R6 are independently selected from hydrogen or methyl;
Z represents Z1, Z , or Z3, wherein
Figure imgf000002_0002
(Z1) (Z2) wherein, when Z is Z1, Rz is R7, wherein
(i) R7 represents -C(0)N(R7a)(R7b), wherein R7a is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, C2-
3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, hydroxyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl-, C3-scycloalkyl, or C3-5cycloalkylCi-2alkyl, and
R7b is Ci-4alkyl, Ci-4haloalkyl or cyclopropyl, or R7a and R7b together with the nitrogen atom to which they are bonded , form a cycle selected from azetidinyl, pyrrolidinyl, isoxazolidinyl or oxazolidinyl, or R7a and R7b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8, wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or
(ii) R7 represents -C(0)N(R7c)(R7d), wherein: R7c is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC3-4alkyl, C2-
3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C4-salkynyl, hydroxyl, aminoCi-4alkyl, N,N-diCi- 2alkylamino, N-formyl-N-Ci-2alkyl-amino, N-Ci-2alkylcarbonyl-N-Ci-2alkylamino, pyrroldin-1 -amino, piperdin-1-amino, morpholin-4-amino, N-Ci-4alkylaminoCi-4alkyl, formyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl-; or
R7c is C4-6cycloalkyl, C3-6cycloalkylC2alkyl, phenyl, phenylCi-2alkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, heterocyclyl, phenyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 oxo (=0) group, and
R7d is hydrogen; or
(iii) R7 represents -C(0)OR7e, wherein: R7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-4haloalkenyl, or C3- 5alkynyl, or R7e is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0); or wherein, when Z is Z2 or Z3, Rz is R9, wherein
R9 is hydroxyl, cyano, methyl, difluoromethyl, Ν,Ν-dimethylamino, methoxy, ethoxy, or difluoromethoxy, or
(i) R9 represents -C(0)N(R9a)(R9b), wherein:
R9a is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, aminoCi-4alkyl, amino, N,N-diCi-2alkylamino, N-C1- 2alkylaminoCi-4alkyl, N,N-diCi-2alkylaminoCi-4alkyl, hydroxyl, Ci-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy; or
R9a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0);
R9b is hydrogen, Ci-4alkyl, Ci-4haloalkyl, cyclopropyl, or
R9a and R9b together with the nitrogen atom to which they are bonded, form a 4- to 6-membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR8, or
R9a and R9b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8, wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or (ii) R9 represents -C(0)OR9c, wherein:
R9c is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, Ci-2alkoxyCi-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, C3-4haloalkenyl, N-Ci- 3alkylaminoCi-4alkyl, N,N-di-Ci-3alkylaminoCi-4alkyl; or
R9c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the groups consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0); or wherein, when Z is Z1, Z2, or Z3, Rz is R 0, wherein (i) R 0 represents -C(O)C(O)-N(R 0a)(R 0b), wherein
R 0a is hydrogen, d-salkyl, d-4haloalkyl, cyanod-4alkyl, hydroxyd-4alkyl, d-3alkoxyd-4alkyl, Ci-2haloalkoxyCi-4alkyl, d-salkenyl, d-salkynyl, hydroxyl, aminod-4alkyl, N-d-4alkylaminod-4alkyl, N,N-diCi-2alkylamino, pyrroldin-1-amino, piperdin-1 -amino, morpholin-4-amino, d-salkoxy, d- 4haloalkyloxy, d-4alkenyloxy, d-4alkynyloxy, cyclopropyld-2alkoxy, (d-4alkyl)-0-N=C(H)d-4alkyl-, or
R 0a is d ecycloalkyl, d-6cycloalkyld-2alkyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0); R 0b is hydrogen, d-4alkyl, d-4fluoroalkyl, cyclopropyl, cyclopropylmethyl, or
R 0a and R 0b together with the nitrogen atom to which they are bonded, form a 4- to 6- membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR8, or
R 0a and R 0b together with the nitrogen atom to which they are bonded, form a 5- to 8- membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8, wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or
(ii) R 0 represents -C(O)C(O)-OR 0c, wherein:
R 0c is hydrogen, d-salkyl, d-4haloalkyl, d-salkenyl, d-salkynyl, or
R 0c is d ecycloalkyl, d-6cycloalkyld-2alkyl, phenyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, or
(iii) R 0 represents -C(O)C(O)-R 0d, wherein R 0d is hydrogen, d-salkyl, or cyclopropyl; or a salt or an N-oxide thereof.
Surprisingly, it has been found that the novel compounds of Formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of Formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically- acceptable diluent or carrier.
According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of Formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
According to a fourth aspect of the invention, there is provided the use of a compound of Formula (I) as a fungicide. According to this particular aspect of the invention, the use may exclude methods for the treatment of the human or animal body by surgery or therapy. As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine
(bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
As used herein, cyano means a -CN group.
As used herein, the term "hydroxyl" or "hydroxy" means an -OH group.
As used herein, amino means an -NH2 group.
As used herein, acyl means a -C(0)CH3 group.
As used herein, formyl means a -C(0)H group.
As used herein, the term "Ci-6alkyl" 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-4alkyl, d salkyl and Ci-2alkyl are to be construed accordingly. Examples of Ci-ealkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (i-butyl). A "Ci- C2alkylene" group refers to the corresponding definition of Ci-2alkyl, except that such radical is attached to the rest of the molecule by two single bonds. Examples of Ci-2alkylene, are -CH2- and -CH2CH2-.
As used herein, the term "Ci-4alkoxy" refers to a radical of the formula -ORa where Ra is a Ci- 4alkyl radical as generally defined above. The terms d salkoxy and Ci-2alkoxy are to be construed accordingly. Examples of Ci-4alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and i-butoxy.
As used herein, the term "Ci-4haloalkyl" refers to a d salkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Examples of Ci-4haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl.
As used herein, the term "C2-6alkenyl" refers to a straight or branched hydrocarbon chain radical group 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. Cs ealkenyl, C3-salkenyl, C2-4alkenyl and C2-3alkenyl are to be construed accordingly. Examples of C2-6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop- 2-enyl), and but-1-enyl.
As used herein, the term "C2-6haloalkenyl" refers to a C2-6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms. C3-4haloalkenyl is to be construed accordingly.
As used herein, the term "C3-4alkenoxy" refers to a radical of the formula -ORa where Ra is a C3- 4alkenyl radical as generally defined above.
As used herein, the term "C2-6alkynyl" 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. C3-salkynyl and C2-4alkynyl are to be construed accordingly. Examples of C2-6alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl).
As used herein, the term "C3-4alkynoxy" refers to a radical of the formula -ORa where Ra is a C3- 4alkynyl radical as generally defined above.
As used herein, the term "C3-4alkynyloxyCi-4alkyl" refers to a Ci-4alkyl radical as generally defined above substituted by a C3-4alkynyloxy group as defined above.
As used herein, the term "Ci-4alkoxyCi-4alkyl" refers to radical of the formula Rb-0-Ra- where Rb is a Ci-4alkyl radical as generally defined above, and Ra is a Ci-4alkylene radical as generally defined above.
As used herein, the term "hydroxyCi-4alkyl" refers to a Ci-4alkyl radical as generally defined above substituted by one or more hydroxy groups. The term "hydroxyCi-2alkyl" should be construed accordingly.
As used herein, the term "cyanoCi-4alkyl" refers to refers to a Ci-4alkyl radical as generally defined above substituted by one or more cyano groups. As used herein, the term "Ci-4alkylcarbonyl" refers to a radical of the formula -C(0)Ra where Ra is a Ci-4alkyl radical as generally defined above.
As used herein, the term "Ci-4alkylcarbonyloxyCi-4alkyl" refers to a radical of the formula RbC(0)ORa- where Rb is a Ci-4alkyl radical as generally defined above, and Ra is a Ci-4alkylene radical as generally defined above.
As used herein, the term "Ci-2alkoxyCi-2alkoxyCi-4alkyl" refers to a radical of the formula RaORbORc-, where Rb and Rc are Ci-2alkylene radicals as generally defined above, and Ra is a Ci-4alkyl radical as generally defined above.
As used herein, the term "Ci-4alkoxycarbonyl" refers to a radical of the formula RaOC(0)-, where Ra is a Ci-4alkyl radical as generally defined above.
As used herein, the term "Ci-4alkoxycarbonylCi-4alkyl" refers to a radical of the formula RaOC(0)Rb-, where Ra is a Ci-4alkyl radical as generally defined above, and Rb is a Ci-4alkylene radical as generally defined above.
As used herein, the term "N-Ci-4alkylamino" refers to a radical of the formula RaNH- where Ra is a Ci-4alkyl radical as generally defined above.
As used herein, the term "N,N-diCi-4alkylamino" refers to a radical of the formula Ra(Ra)N- where Ra is a Ci-4alkyl radical as generally defined above.
As used herein, the term "Ci-4haloalkoxy" refers to a Ci-4alkoxy group as defined above substituted by one or more of the same or different halogen atoms. Examples of Ci-4haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, 2-fluoroethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy.
As used herein, the term "Ci-4alkylcarbonyl" refers to a radical of the formula -C(0)Ra where Ra is a Ci-4alkyl radical as generally defined above.
As used herein, the term "Ci-4alkylcarbonylCi-4alkyl" refers to a Ci-4alkyl radical as generally defined above substituted by a Ci-4alkylcarbonyl group as defined above.
As used herein, the term "C3-6cycloalkyl" refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-scycloalkyl and Cscycloalkyl are to be construed accordingly. Examples of C3-6cycloalkyl include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.
As used herein, the term "C3-6cycloalkylCi-2alkyl" refers to a C3-6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-2alkylene radical as defined above. Examples of C3- 6cycloalkylCi-3alkyl include, but are not limited to cyclopropyl-methyl and cyclobutyl-ethyl.
As used herein, the term "phenylCi-2alkyl" refers to a phenyl ring attached to the rest of the molecule by a Ci-2alkylene radical as defined above. Examples of phenylCi-2alkyl include, but are not limited to, benzyl.
As used herein, the term "heteroaryl" generally refers to a 5- or 6-membered monocyclic aromatic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heteroaryl include but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl, and indolyl.
As used herein, the term "heterocyclyl" or "heterocyclic" generally refers to a stable, saturated or partially saturated , 4- to 6-membered, non-aromatic monocyclic ring, which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, azetidinyl, oxetanyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, and morpholinyl. The presence of one or more possible asymmetric carbon atoms in a compound of Formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond . Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of Formula (I). Likewise, Formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto- enol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of Formula (I).
In each case, the compounds of Formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g. , an agronomically usable or agrochemically acceptable salt form.
N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991 . The following list provides definitions, including preferred definitions, for substituents Z (Z Z2, Z3), R , R2, R3, R4, R5, R6 and Rz (R7 (R7a, R7b, R7c, R7d, R7e), R8, R9 (R9a, R9b, R9c) and R 0 (R 0a, R 0b, R 0c, R 0d)) with reference to the compounds of Formula (I) according to the invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.
R , R2, R3, R4 are independently selected from hydrogen or fluoro, wherein 0, 1 or 2 of R , R2, R3 and R4 are fluoro.
In certain embodiments of the invention, R , R2, R3 and R4 are hydrogen; R2, R3 and R4 are hydrogen and R is fluoro; R , R2 and R4 are hydrogen and R3 is fluoro; R and R2 are fluoro and R3 and R4 are hydrogen; R and R3 are fluoro and R2 and R4 are hydrogen, or R and R2 are hydrogen and R3 and R4 are fluoro. Preferably, R to R4 are hydrogen, or R is fluoro and R2 to R4 are hydrogen.
R5 and R6 independently represent hydrogen or methyl. Preferably, R5 and R6 are both hydrogen, or R5 is hydrogen and R6 is methyl. More preferably, R5 and R6 are both hydrogen. Z represents Z1, Z2, or Z3, wherein:
Figure imgf000011_0001
(Z1 ) (Z2) (Z3)
In some embodiments of the invention Z is Z .
In some embodiments of the invention Z is Z2. In some embodiments of the invention Z is Z3. Preferably, Z is Z .
When Z is Z1, Rz may be R7, wherein
(i) R7 represents -C(0)N(R7a)(R7b), wherein
R7a is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, C2- 3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, hydroxyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl-, C3-scycloalkyl, or C3-5cycloalkylCi-2alkyl, and
R7b is Ci-4alkyl, Ci-4haloalkyl or cyclopropyl, or
R7a and R7b together with the nitrogen atom to which they are bonded , form a cycle selected from azetidinyl, pyrrolidinyl, isoxazolidinyl or oxazolidinyl, or
R7a and R7b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8,
wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or
(ii) R7 represents -C(0)N(R7c)(R7d), wherein:
R7c is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC3-4alkyl, C2- 3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C4-salkynyl, hydroxyl, aminoCi-4alkyl, N,N-diCi- 2alkylamino, N-formyl-N-Ci-2alkyl-amino, N-Ci-2alkylcarbonyl-N-Ci-2alkylamino, pyrroldin-1 -amino, piperdin-1-amino, morpholin-4-amino, N-Ci-4alkylaminoCi-4alkyl, formyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl, or R7c is C4-6cycloalkyl, C3-6cycloalkylC2alkyl, phenyl, phenylCi-2alkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S,
and wherein the cycloalkyi, heterocyclyl, phenyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyi or heterocyclyl moiety is optionally substituted by 1 oxo (=0) group, and
R7d is hydrogen; or
(iii) R7 represents -C(0)OR7e, wherein: R7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-4haloalkenyl, or C3- 5alkynyl, or
R7e is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S,
and wherein the cycloalkyi, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyi or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0).
Preferably, R7a is C3-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC2alkyl, C2-3alkoxyethyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, hydroxyl, C2-4alkoxy, C3-4alkenyloxy, C3-4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-2alkyl)-0-N=C(H)Ci-2alkyl-, C3-scycloalkyl, or C3-5cycloalkylCi-2alkyl. More preferably, R7a is C3-salkyl, C3-4alkenyl or C3-4alkynyl. Even more preferably, R7a is C3-salkyl (eg, methyl, ethyl or iso-propyl). Preferably, R7b is methyl, ethyl, or cyclopropyl. More preferably, R7b is methyl or cyclopropyl.
Preferably, R7c is C3-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC3-4alkyl, C2-3alkoxyethyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C4-salkynyl, hydroxyl, aminoCi-2alkyl, N,N-diCi- 2alkylamino, N-formyl-N-Ci-2alkyl-amino, N-Ci-2alkylcarbonyl-N-Ci-2alkylamino, pyrroldin-1 -amino, piperdin-1-amino, morpholin-4-amino, N-Ci-4alkylaminoCi-2alkyl, formyl, C2-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-2alkyl)-0-N=C(H)Ci-2alkyl. More preferably, R7c is C3-5alkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, C3-4alkenyl, C4-salkynyl, aminoCi-2alkyl, formyl, C2-4alkoxy, hydroxyl, C3-4alkenyloxy, C3-4haloalkyloxy, C3-4alkynyloxy or cyclopropylCi-2alkoxy. Even more preferably, R7c is C3-salkyl, Ci-2fluoroalkyl, C3-4alkenyl, C4-salkynyl or C2-4alkoxy.
Preferably, R7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C3- 4haloalkenyl or C3-4alkynyl. More preferably, R7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2- dimethylpropyl, Ci-2fluoroalkyl, C3-4alkenyl or C3-4alkynyl.
When Z is Z2 or Z3, Rz may be R9, wherein:
R9 is hydroxyl, cyano, methyl, difluoromethyl, Ν,Ν-dimethylamino, methoxy, ethoxy, or difluoromethoxy, or
(i) R9 represents -C(0)N(R9a)(R9b), wherein:
R9a is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, aminoCi-4alkyl, amino, N,N-diCi-2alkylamino, N-C1- 2alkylaminoCi-4alkyl, N,N-diCi-2alkylaminoCi-4alkyl, hydroxyl, Ci-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy; or
R9a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S,
and wherein the cycloalkyl, phenyl, heterocyclyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0);
R9b is hydrogen, Ci-4alkyl, Ci-4haloalkyl, cyclopropyl, or
R9a and R9b together with the nitrogen atom to which they are bonded, form a 4- to 6-membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR8; or
R9a and R9b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8;
wherein R8 is hydrogen, methyl, methoxy, formyl or acyl;
or
(ii) R9 represents -C(0)OR9c, wherein: R9c is hydrogen, Ci-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, Ci-2alkoxyCi-2alkoxyCi-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, C3-4haloalkenyl, N-Ci- 3alkylaminoCi-4alkyl, N,N-di-Ci-3alkylaminoCi-4alkyl; or
R9c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the groups consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S,
and wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0); Preferably, R9a is d-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl,
Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, aminoCi-2alkyl, amino, N,N-diCi-2alkylamino, N-Ci- 2alkylaminoCi-2alkyl, N,N-diCi-2alkylaminoCi-2alkyl, hydroxyl, Ci-2alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy. More preferably, R9a is Ci-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl, Ci-2fluoroalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, hydroxyl or Ci-2alkoxy.
Preferably, R9b is hydrogen, methyl, ethyl or cyclopropyl.
Preferably, R9c is Ci-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC2alkyl, Ci-2alkoxyCi-2alkoxyCi-2alkyl, Ci-2haloalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, C3-4haloalkenyl, N-C1- 3alkylaminoCi-2alkyl or N,N-di-Ci-2alkylaminoCi-2alkyl. More preferably, R9c is Ci-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC2alkyl, C3-4alkenyl or C3-4alkynyl.
When Z is Z1, Z2, or Z3, Rz may be R 0, wherein
(i) R 0 represents -C(O)C(O)-N(R 0a)(R 0b), wherein
R 0a is hydrogen, Ci-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, hydroxyl, aminoCi-4alkyl, N-Ci-4alkylaminoCi-4alkyl, N,N-diCi-2alkylamino, pyrroldin-1-amino, piperdin-1-amino, morpholin-4-amino, Ci-salkoxy, C3- 4haloalkyloxy, C3-4alkenyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl-, or R 0a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0);
R 0b is hydrogen, Ci-4alkyl, Ci-4fluoroalkyl, cyclopropyl, cyclopropylmethyl, or
R 0a and R 0b together with the nitrogen atom to which they are bonded , form a 4- to 6- membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR8; or
R 0a and R 0b together with the nitrogen atom to which they are bonded , form a 5- to 8- membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8,
wherein R8 is hydrogen, methyl, methoxy, formyl or acyl;
or
(ii) R 0 represents -C(O)C(O)-OR 0c, wherein:
R 0c is hydrogen, d-salkyl, Ci-4haloalkyl, C3-salkenyl, C3-salkynyl, or
R 0c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, or
(iii) R 0 represents -C(O)C(O)-R 0d, wherein R 0d is hydrogen, d-salkyl, or cyclopropyl. Preferably, the compound according to Formula (I) is selected from a compound 1.1 to 1.28 described in Table T1 (below), compound 2.1 to 2.107 described in Table T2 (below), compound 3.1 to 3.81 described in Table T3 (below), compound 4.1 to 4.9 described in Table T4 (below), and compound 5.1 to 5.26 described in Table T5 (below). The compounds of the present invention may be enantiomers of the compound of Formula (I) as represented b a Formula (la) or a Formula (lb), wherein R5 and R6 are different substituents.
Figure imgf000015_0001
(la) (lb) It is understood that when in aqueous media, the compounds of formula (I) according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms (ie, the compounds of formula (l-la) and formula (l-l la) as shown below, which may exist in tautomeric form as the compounds of formula (l-lb) and formula (l-l lb)) at the CF3-oxadiazole motif). This dynamic equilibrium may be important for the biological activity of the compounds of Formula (I). The designations Z (Z\ Z2, Z3), R\ R2, R3, R4, R5, R6 and Rz (R7 (R7a, R7b, R7c, R7d, R7e), R8, R9 (R9a, R9b, R9c) and R 0 (R 0a, R 0b, R 0c, R 0d)) with reference to the compounds of formula (I) of the present invention, apply generally to the compounds of Formula (l-la), Formula (l-l la), Formula (l-lb), and Formula (l-l lb), as well as to the specific disclosures of combinations Z (Z Z2, Z3), R , R2, R3, R4, R5, R6 and Rz (R7 (R7a, R7b, R7c, R7d, R7e), R8, R9 (R9a, R9b, R9c) and R 0 (R 0a, R 0b, R 0c, R 0d)) as represented in Tables 1 A.1 to 1A.8, Tables 1 B.1 to 1 B.8, Tables 2.1 to 2.8, Tables 3.1 to 3.4, Tables 4.1 to 4.4, and Tables 5A.1 to 5A.4, Tables 5B.1 to 5B.4, or in the compounds 1 .1 to 1 .28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below).
Figure imgf000017_0001
Figure imgf000017_0002
Figure imgf000017_0003
(l-lb) (l-llb)
Compounds of the present invention can be made as shown in the following schemes 1 to 1 1 , in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
Compounds of formula (I) can be prepared from compounds of formula (II), wherein X is a halogen, preferably CI, Br or I, via treatment with compounds of formula (III), in the presence of a base (e.g. K2CO3, CS2CO3, or NaH) in a suitable solvent (e.g. dimethylformamide or tetrahydrofuran) at a temperature between 25°C and 1 10°C. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, Nal or 4-dimethylaminopyridine) and with microwave irradiation. For _ related examples, see: WO 2013/132253 and Garcia, M. ef al Org. Biomol. Chem. (2004), 11, 1633. This reaction is shown in Scheme 1.
Figure imgf000018_0001
Additionally, compounds of formula (I) can be prepared from compounds of formula (IV) by treatment with trifluoroacetic fluoride, trifluoroacetic chloride, trifluoroacetic anhydride, optionally in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C. For related examples, see WO 2003/028729 and WO 2010/045251. This reaction is shown in Scheme 2.
Figure imgf000018_0002
Scheme
Compounds of formula (IV) can be prepared from compounds of formula (V) by treatment with a hydroxylamine hydrochloride salt in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature between 0°C and 100°C. For related examples, see Kitamura, S. ef al Chem. Pharm. Bull. (2001 ), 49, 268 and WO 2013/066838. This reaction is shown in Scheme 3.
Figure imgf000018_0003
(V) (IV)
Scheme 3 Compounds of formula (V) can be prepared from compounds of formula (VI), wherein Y is Br or I, via metal-promoted reaction with a suitable cyanide reagent, such as Pd(0)/Zn(CN)2 or CuCN, in a suitable solvent (eg, dimethylformamide or N-methylpyrrolidone) at elevated temperature between 100°C and 120°C. For related examples, see US 2007/0155739 and WO 2009/022746. This reaction is shown in Scheme 4.
Figure imgf000019_0001
Scheme
Compounds of formula (VI) wherein Y is Br, I or CN, can be prepared from compounds of formula (VII), wherein X is a halogen, preferably CI, Br or I, via treatment with compounds of formula (III), in the presence of a base (e.g. K2CO3, CS2CO3, or NaH) in a suitable solvent (e.g. dimethylformamide or tetrahydrofuran) at a temperature between 25°C and 1 10°C. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, Nal or 4-dimethylaminopyridine) and with microwave irradiation. For related examples, see: WO 2013/132253 and Garcia, M. ef al Org. Biomol. Chem. (2004), 11, 1633. This reaction is shown in Scheme 5.
Figure imgf000019_0002
(VII) (VI)
Scheme 5
Compounds of formula (II), wherein X is CI or Br, can be prepared from compounds of formula (VIII) by treatment with a halogen source (eg, /V-bromosuccinimide (NBS) or A/-chlorosuccinimide (NCS)) and a radical initiator (eg, (PhC(0)0)2 or azobisisobutyronitrile (AIBN)) in a suitable solvent, such as tetrachloromethane, at temperatures between 55°C and 100°C in the presence of ultraviolet light. For related examples, see Liu, S. ef al Synthesis (2001 ), 14, 2078 and Kompella, A. ef al Org. Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 6.
Figure imgf000020_0001
(VIII) (II)
Scheme 6
Alternatively, compounds of formula (II) can be prepared from compounds of formula (IX) by treatment with trifluoroacetic chloride, trifluoroacetic fluoride, or trifluoroacetic anhydride in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C. For related examples, see WO 2003/028729 and WO 2010/045251. This reaction is shown in Scheme 7.
Figure imgf000020_0002
Scheme 7
Compounds of formula (IX) can be prepared from compounds of formula (X) by treatment with a hydroxylamine hydrochloride salt in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature between 0°C and 100°C. For related examples, see Kitamura, S. et al Chem. Pharm. Bull. (2001 ), 49, 268 and WO 2013/066838. This reaction is shown in Scheme 8.
Figure imgf000020_0003
(X) (IX)
Scheme 8
Compounds of formula (VII), wherein Y is Br, I or CN and X is CI, Br or I, are either commercially available or can be prepared from compounds of formula (XI), by treatment with a halogen source, (eg, /V-bromosuccinimide (NBS) or A/-chlorosuccinimide (NCS)) and a radical initiator, such as (PhC02)2 or azobisisobutyronitrile (AIBN), in the presence of ultraviolet light, in a suitable solvent, such as tetrachloromethane, at temperatures between 55°C and 100°C. For related examples, see Liu, S. ei al Syntheis (2001 ), 14, 2078 and Kompella, A. ei al Org. Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 9.
Figure imgf000021_0001
(XI) (VII)
Scheme 9
Alternatively, compounds of formula (VII), wherein X is CI, Br, I or OSCteMe and Y is Br, I or CN, are either commercially available or can be prepared from compounds of formula (XII), by treatment with a halogen source (eg, CC Br, CCU or ) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CISC Me), in a suitable solvent, (eg, dichloromethane) at a temperature between 0°C and 100°C. For related examples, see Liu, H. et al Bioorg. Med. Chem. (2008), 16, 10013, WO 2014/020350 and Kompella, A. et al Bioorg. Med. Chem. Lett. (2001 ), 1, 3161. Compounds of formula (XII) are commercially available. This reaction is shown in Scheme 10.
Figure imgf000021_0002
The compounds of formula (IA), wherein Z represents Z Z2, or Z3; and R -Nu-H represents HN(R7a)R7b, HN(R7c)R7d, HN(R9a)R9b, HN(R 0a)R 0b, HOR7c, HOR9c, or HOR 0c or can be obtained by an amide coupling transformation with compounds of formula (IB) and nucleophiles of formula (XIII), by activating the carboxylic acid function of the compounds of formula (IB), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI)2 or SOCI2, prior to treatment with the nucleophiles of formula (XIII), preferably in a suitable solvent (eg, dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base such as triethylamine or A/,A/-diisopropylethylamine, or under conditions described in the literature for an ester or amide coupling. For examples, see WO 2003/028729. Compounds of formula (XIII) are commercially available or prepared using known methods. For related examples, see: Nelson, T. D et al Tetrahedron Lett. (2004), 45, 8917; Senthil, K. et al Pest. Res. Journal (2009), 21 , 133; and Crich, D., Zou, Y. J. Org. Chem. 2005), 70, 3309. This reaction is shown in Scheme 1 1.
Figure imgf000022_0001
(IB) (IA)
Scheme 1 1
As already indicated, surprisingly, it has now been found that the compounds of Formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
The compounds of Formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants. The compounds of Formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms. The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of Formula (I) is applied to the plants, to parts thereof or the locus thereof. It is also possible to use compounds of Formula (I) as a fungicide. The term "fungicide" as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount" where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all dew'ation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
It may also be possible to use compounds of Formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of Formula (I) before planting: seed, for example, can be dressed before being sown. The active compounds of Formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
Furthermore, the compounds of Formula (I) can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
The compounds of Formula (I) are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:
Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terms, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp,Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.
The compounds of Formula (I) may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.
Within the scope of present invention, target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
The term "useful plants" is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol- pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
The term "useful plants" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
Further, in the context of the present invention there are to be understood by δ-endotoxins, for example CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®. Further examples of such transgenic crops are:
1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cryl F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 * 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.
The compounds of Formula (I) (including any one of compounds 1.1 to 1 .28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below), and 5.1 to 5.26) according to the present invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants.
In particular, transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g. Cry1 Ac (Cry1 Ac Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (see U.S. Patent No. 8,049,071 and related applications and patents, as well as WO 2014/170327 A1 (eg, see paragraph [008] reference to Intacta RR2 PRO™ soybean)), event MON87751 (US. Patent Application Publication No. 2014/0373191 ) or event DAS- 81419 (U.S. Patent No. 8632978 and related applications and patents).
Other transgenic soybean plants may comprise event SYHT0H2 - HPPD tolerance (U.S. Patent Application Publication No. 2014/0201860 and related applications and patents), event MON89788 - glyphosate tolerance (U.S. Pat. No. 7,632,985 and related applications and patents), event MON87708 - dicamba tolerance (U.S. Patent Application Publication No. US 201 1/0067134 and related applications and patents), event DP-356043-5 - glyphosate and ALS tolerance (U.S. Patent Application Publication No. US 2010/0184079 and related applications and patents), event A2704-12 - glufosinate tolerance (U.S. Patent Application Publication No. US 2008/0320616 and related applications and patents), event DP-305423-1 - ALS tolerance (U.S. Patent Application Publication No. US 2008/0312082 and related applications and patents), event A5547-127 - glufosinate tolerance (U.S. Patent Application Publication No. US 2008/0196127 and related applications and patents), event DAS-40278-9 - tolerance to 2,4- dichlorophenoxyacetic acid and aryloxyphenoxypropionate (see WO 201 1/022469, WO 201 1/022470, WO 201 1/022471 , and related applications and patents), event 127 - ALS tolerance (WO 2010/080829 and related applications and patents), event GTS 40-3-2 - glyphosate tolerance, event DAS-68416-4- 2,4-dichlorophenoxyacetic acid and glufosinate tolerance, event FG72 - glyphosate and isoxaflutole tolerance, event BPS-CV127-9 - ALS tolerance and GU262 - glufosinate tolerance or event SYHT04R - HPPD tolerance.
Under certain circumstances, compounds of Formula (I) according to the present invention when used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants (in particular any of the transgenic soybean plants as described above), may display a synergistic interaction between the active ingredients.
Additionally, to date, no cross-resistance has been observed between the compounds of Formula (I) (including any one of compounds 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below)) and the current fungicidal solutions used to control Phakopsora pachyrhizi.
Indeed, fungicidal-resistant strains of Phakopsora pachyrhizi have been reported in the scientific literature, with strains resistant to one or more fungicides from at least each of the following fungicidal mode of action classes being observed: sterol demethylation-inhibitors (DMI), quinone-outside- inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI). See for example: "Sensitivity of Phakopsora pachyrhizi towards quinone-outside-inhibitors and demethylation-inhibitors, and corresponding resistance mechanisms. " Schmitz HK ef al, Pest Manag Sci (2014) 70: 378-388; "First detection of a SDH variant with reduced SDHI sensitivity in Phakopsora pachyrhizi' Simoes K et al, J Plant Dis Prot (2018) 125: 21-2; "Compef/f/Ve fitness of Phakopsora pachyrhizi isolates with mutations in the CYP51 and CYTB genes." Klosowski AC et al, Phytopathology (2016) 106: 1278-1284; "Detection of the F129L mutation in the cytochrome b gene in Phakopsora pachyrhizi." Klosowski AC ef al, Pest Manag Sci (2016) 72: 121 1-1215.
Thus, in a preferred embodiment, the compounds of Formula (I) (including any one of compounds
1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below)), or fungicidal compositions according to the present invention comprising a compound of Formula (I), are used to control Phakopsora pachyrhizi which are resistant to one or more fungicides from any of the following fungicidal MoA classes: sterol demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI).
The compounds of Formula (I) (including any one of compounds 1.1 to 1 .28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below)) or fungicidal compositions according to the present invention comprising a compound of Formula (I) may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants. In particular, there are known in the scientific literature certain Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome, see for example: "Fighting Asian Soybean Rust", Langenbach C, ef al, Front Plant Science 7(797) 2016).
An elite plant is any plant from an elite line, such that an elite plant is a representative plant from an elite variety. Non-limiting examples of elite soybean varieties that are commercially available to farmers or soybean breeders include: AG00802, A0868, AG0902, A1923, AG2403, A2824, A3704, A4324, A5404, AG5903, AG6202 AG0934; AG1435; AG2031 ; AG2035; AG2433; AG2733; AG2933; AG3334; AG3832; AG4135; AG4632; AG4934; AG5831 ; AG6534; and AG7231 (Asgrow Seeds, Des Moines, Iowa, USA); BPR0144RR, BPR 4077NRR and BPR 4390NRR (Bio Plant Research, Camp Point, III., USA); DKB17-51 and DKB37-51 (DeKalb Genetics, DeKalb, III., USA); DP 4546 RR, and DP 7870 RR (Delta & Pine Land Company, Lubbock, Tex., USA); JG 03R501 , JG 32R606C ADD and JG 55R503C (JGL Inc., Greencastle, Ind., USA); NKS 13-K2 (NK Division of Syngenta Seeds, Golden Valley, Minnesota, USA); 90M01 , 91 M30, 92M33, 93M1 1 , 94M30, 95M30, 97B52, P008T22R2; P16T17R2; P22T69R; P25T51 R; P34T07R2; P35T58R; P39T67R; P47T36R; P46T21 R; and P56T03R2 (Pioneer Hi-Bred International, Johnston, Iowa, USA); SG4771 NRR and SG5161 NRR/STS (Soygenetics, LLC, Lafayette, Ind., USA); S00-K5, S1 1-L2, S28-Y2, S43-B1 , S53-A1 , S76-L9, S78-G6, S0009-M2; S007-Y4; S04-D3; S14-A6; S20-T6; S21-M7; S26-P3; S28-N6; S30-V6; S35-C3; S36-Y6; S39-C4; S47-K5; S48-D9; S52-Y2; S58-Z4; S67-R6; S73-S8; and S78-G6 (Syngenta Seeds, Henderson, Ky., USA); Richer (Northstar Seed Ltd. Alberta, CA); 14RD62 (Stine Seed Co. la., USA); or Armor 4744 (Armor Seed, LLC, Ar., USA).
Thus, in a further preferred embodiment, the compounds of Formula (I) (including any one of compounds 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below)), or fungicidal compositions according to the present invention comprising a compound of Formula (I), are used to control Phakopsora pachyrhizi, (including fungicidally-resistant strains thereof, as outlined above) on Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome. Numerous benefits may be expected to ensue from said use, e.g. improved biological activity, an advantageous or broader spectrum of activity (inc. sensitive and resistant strains of Phakopsora pachyrhizi), an increased safety profile, improved crop tolerance, synergistic interactions or potentiating properties, improved onset of action or a longer lasting residual activity, a reduction in the number of applications and/or a reduction in the application rate of the compounds and compositions required for effective control of the phytopathogen (Phakopsora pachyrhizi), thereby enabling beneficial resistance-management practices, reduced environmental impact and reduced operator exposure. The term "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.
The compounds of Formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently Formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
Suitable carriers and adjuvants, e.g. for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent. Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other nonvolatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular Formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular Formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.
Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyi esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyi phosphate esters.
Other 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. In addition, further, other biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The compounds of Formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or nonselective 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. Preferably said composition may comprise at least one or more pesticidally-active compounds, for example an additional fungicidal active ingredient in addition to the compound of Formula (I).
The compound of Formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.
Examples of 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 fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonamide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.
Examples of suitable additional active ingredients also include the following: 3-difluoromethyl-
1- methyl-1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano- naphthalen-5-yl)-amide , 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid methoxy-[1-methyl-
2- (2,4,6-trichlorophenyl)-ethyl]-amide , 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1 ), 1-methyl-3-difluoromethyl-1 H- pyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H- pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide, (5-Chloro-2,4- dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, (5-Bromo-4-chloro-2-methoxy- pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1- methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methyl-acetamide, 3- [5-(4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, (E)-N-methyl-2- [2- (2, 5- dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N, N-dimethyl-6- trifluoromethylbenzimidazole-1-sulphonamide, D-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-y- butyrolactone, 4-chloro-2-cyano-N,N - dimethyl-5-p-tolylimidazole-1-sulfonamide, N-allyl-4, 5,-dimethyl- 2-trimethylsilylthiophene-3-carboxamide, N- (l-cyano-1 , 2-d i m ethyl p ropy I )-2- (2, 4-dichlorophenoxy) propionamide, N- (2-methoxy-5-pyridyl)-cyclopropane carboxamide, (.+-.)-cis-1-(4-chlorophenyl)-2- (1 H-1 ,2,4-triazol-1-yl)-cycloheptanol, 2-(1-iert-butyl)-1-(2-chlorophenyl)-3-(1 ,2,4-triazol-1-yl)-propan-2- ol, 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1 ,3-thiazole- 5-carboxanilide, 1- imidazolyl-1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl (E)-2-[2-[6-(2- cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl (E)-2-[2-[6-(2- thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2- fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2,6- difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(pyrimidin-2- yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)- phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(phenyl-sulphonyloxy)phenoxy]phenyl-3- methoxyacrylate, methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2-phenoxyphenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1-yl]-3- methoxyacrylate, methyl (E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2[2-(2- phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3- methoxyacrylate, methyl (E)-2-(2-(3-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl (E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, methyl (E)-2-(2-(4- phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3- methoxyacrylate, methyl (E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2- [3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-ethoxyphenoxy)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(4-ieri-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl (E)-2- [2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[(3-methyl-pyridin-2- yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4- yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(5-bromo-pyridin-2-yloxymethyl)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyac rylate, methyl (E),(E)-2-[2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-{2-[6-(6- methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-acrylate, methyl (E),(E)-2-{ 2-(3- methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxyacrylate, methyl (E)-2-{2-(6-(2- azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl (E),(E)-2-{2-[6-phenylpyrimidin-4- yl)-methyloximinomethyl]phenyl}-3-methox yacrylate, methyl (E),(E)-2-{2-[(4-chlorophenyl)- methyloximinomethyl]-phenyl}-3-methoxyacrylate, methyl (E)-2-{2-[6-(2-n-propylphenoxy)-1 ,3,5- triazin-4-yloxy]phenyl}-3-methoxyacrylate, methyl (E),(E)-2-{2-[(3- nitrophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate, 3-chloro-7-(2-aza-2,7J-trimethyl-oct-3- en-5-ine), 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodo-2-propinyl alcohol, 4- chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexyl-carbamate, 3-iodo-2-propinyl phenylcarbamate; phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl- 4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2- benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1 ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1 ,3,5- thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs, alanycarb, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin, amisulbrom, amobam, ampropylfos, anilazine, asomate, aureofungin, azaconazole, azafendin, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril, benzamorf, benzohydroxamic acid, benzovindiflupyr, berberine, bethoxazin, biloxazol, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chitosan, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, chlozolinate, climbazole, clotrimazole, clozylacon, copper containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid, di-2- pyridyl disulphide 1 ,1 '-dioxide, dichlofluanid, diclomezine, dichlone, dicloran, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-iso-propyl- S-benzyl thiophosphate, dimefluazole, dimetachlone, dimetconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin, dodine, doguadine, drazoxolon, edifenphos, enestroburin, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin, ethyl (Z)-N-benzyl-N ([methyl (methyl-thioethylideneamino- oxycarbonyl) amino] thio)^-alaninate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexa chlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam, mefentrifluconazole, mepanipyrim, mepronil, mercuric chloride, mercurous chloride, meptyldinocap, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate, metiram, metiram-zinc, metominostrobin, metrafenone, metsulfovax, milneb, moroxydine, myclobutanil, myclozolin, nabam, natamycin, neoasozin, nickel dimethyldithiocarbamate, nitrostyrene, nitrothal-iso- propyl, nuarimol, octhilinone, ofurace, organomercury compounds, orysastrobin, osthol, oxadixyl, oxasulfuron, oxathiapiprolin, oxine-copper, oxolinic acid, oxpoconazole, oxycarboxin, parinol, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenamacril, phenazin oxide, phosdiphen, phosetyl-AI, phosphorus acids, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin D, polyoxrim, polyram, probenazole, prochloraz, procymidone, propamidine, propamocarb, propiconazole, propineb, propionic acid, proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametrostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinacetol, quinazamid, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenzazole, santonin, sedaxane, silthiofam, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, sultropen, tebuconazole, tebfloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiophanate-methyl, thioquinox, thiram, tiadinil, timibenconazole, tioxymid, tolclofos-m ethyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole, uniconazole, urbacide, validamycin, valifenalate, vapam, vinclozolin, zarilamid, zineb, ziram, and zoxamide.
The compounds of the invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP- 444964 and EP-594291. Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO- 9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
The compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
The compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
The compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:
Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.
Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2- dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t- fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.
Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-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, hydramethylnon, IKI- 220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651 , WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1 1 1 1 , R-195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301.
Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
Bactericides: chlortetracycline, oxytetracycline, streptomycin.
Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, thiabendazole.
The following mixtures of the compounds of formula (I) with active ingredients are preferred. The abbreviation "TX" means one compound selected from the group consisting of the compounds as represented in Tables 1A.1 to 1A.8, Tables 1 B.1 to 1 B.8, Tables 2.1 to 2.8, Tables 3.1 to 3.4, Tables 4.1 to 4.4, and Tables 5A.1 to 5A.4, Tables 5B.1 to 5B.4, or a compound 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below).
an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
an acaricide selected from the group of substances consisting of 1 , 1-bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1-naphthylacetamide (lUPAC name) (1295) + TX,
4- chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha- cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881 ) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (lUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71 ) + TX, benzyl benzoate (lUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (lUPAC name) (1 11 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971 ) + TX, chlorfenvinphos (131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201 ) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-
5- methyl (224) + TX, demeton-S-methylsulfon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071 ) + TX, dimefox (1081 ) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1 102) + TX, diphenyl sulfone (lUPAC name) (1 103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1 1 13) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1 134) + TX, etoxazole (320) + TX, etrimfos (1 142) + TX, fenazaflor (1 147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1 157) + TX, fentrifanil (1 161 ) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1 166) + TX, flubenzimine (1 167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1 174) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441 ) + TX, iodomethane (lUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261 ) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531 ) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 : 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, Sl- 0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1 /- -pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (lUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (61 1 ) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX, a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51 ) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151 ) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191 ) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431 ) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491 ) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Onus spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741 ) + TX, Steinemema bibionis (alternative name) (742) + TX, Steinemema carpocapsae (alternative name) (742) + TX, Steinemema feltiae (alternative name) (742) + TX, Steinemema glaseri (alternative name) (742) + TX, Steinemema riobrave (alternative name) (742) + TX, Steinemema riobravis (alternative name) (742) + TX, Steinemema scapterisci (alternative name) (742) + TX, Steinemema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX, bacillus subtilis var. amyloliquefaciens Strain FZB24 (available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A. and known under the trade name Taegro®) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name)
(542) and methyl bromide (537) + TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX, an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (lUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (lUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (E,Z)-tetradeca-4, 10-dien-1-yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (lUPAC name) (285) + TX, (Z)-hexadec- 1 1-enal (lUPAC name) (436) + TX, (Z)-hexadec-l 1-en-1-yl acetate (lUPAC name) (437) + TX, (Z)- hexadec-13-en-1 1-yn-1-yl acetate (lUPAC name) (438) + TX, (Z)-icos-13-en-10-one (lUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (lUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (lUPAC name) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (lUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (lUPAC name) (283) + TX, (9Z, 1 1 E)-tetradeca-9, 1 1-dien-1-yl acetate (lUPAC name) (780) + TX, (9Z, 12E)-tetradeca-9, 12-dien-1-yl acetate (lUPAC name) (781 ) + TX, 14-methyloctadec-1-ene (lUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (lUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (lUPAC name) (286) + TX, dodec-9-en-1-yl acetate (lUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (lUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (lUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421 ) + TX, grandlure I (alternative name) (421 ) + TX, grandlure II (alternative name) (421 ) + TX, grandlure III (alternative name) (421 ) + TX, grandlure IV (alternative name) (421 ) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481 ) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1-yl acetate (lUPAC name) (588) + TX, octadeca-3,13-dien-
1- yl acetate (lUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-11-en-1-yl acetate (lUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,
an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethylamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1-dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1-bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (lUPAC name) (1066) + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate (lUPAC/ Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate (lUPAC/ Chemical Abstracts name) (1084) + TX,
2- (4-chloro-3,5-xylyloxy)ethanol (lUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (lUPAC name) (984) + TX, 2-imidazolidone (lUPAC name) (1225) + TX, 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (lUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (lUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (lUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (lUPAC name) (1283) + TX, 4- methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (lUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate (lUPAC name) (1085) + TX, abamectin (1 ) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (lUPAC name) (861 ) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41 ) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (lUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (lUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbon disulfide (lUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (lUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (1 19) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131 ) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141 ) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (101 1 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201 ) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, cf-limonene (alternative name) [CCN] + TX, cf-tetramethrin (alternative name) (788) + TX, DAEP (1031 ) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton- S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051 ) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (lUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081 ) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271 ) + TX, diofenolan (1099) + TX, dioxabenzofos (1 100) + TX, dioxacarb (1 101 ) + TX, dioxathion (1 102) + TX, disulfoton (278) + TX, dithicrofos (1 108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1 1 15) + TX, ecdysterone (alternative name) [CCN] + TX, El 1642 (development code) (1 1 18) + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, EMPC (1 120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, endrin (1 122) + TX, EPBP (1 123) + TX, EPN (297) + TX, epofenonane (1 124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1 134) + TX, ethoprophos (312) + TX, ethyl formate (lUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1 136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1 142) + TX, EXD (1 143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1 147) + TX, fenchlorphos (1 148) + TX, fenethacarb (1 149) + TX, fenfluthrin (1 150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1 153) + TX, fenoxycarb (340) + TX, fenpirithrin (1 155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451-65-7) + TX, flucofuron (1 168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1 171 ) + TX, flumethrin (372) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, fonofos (1 191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, fosmethilan (1 194) + TX, fospirate (1 195) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (121 1 ) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (lUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231 ) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251 ) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (lUPAC name) (1014) + TX, magnesium phosphide (lUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261 ) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (lUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531 ) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (lUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (131 1 ) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 : 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (lUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo-2A -chromen-7-yl phosphorothioate (lUPAC name) (1074) + TX, Ο,Ο-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (lUPAC name) (1075) + TX, 0,0, 0',Ο'-tetrapropyl dithiopyrophosphate (lUPAC name) (1424) + TX, oleic acid (lUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (lUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (lUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651 ) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (lUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (71 1 ) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (lUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (lUPAC name) (1401 ) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791 ) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431 ) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441 ) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, Yl- 5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19 + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012/0921 15) + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,
a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2- dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3- dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1 , 1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4- chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3- ylacetic acid (lUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1 ) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (1 18) + TX, carbon disulfide (945) + TX, carbosulfan (1 19) + TX, chloropicrin (141 ) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051 ) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (lUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231 ) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (lUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301 ) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1 183) + TX, flupropadine hydrochloride (1 183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (lUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (lUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (lUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341 ) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371 ) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851 ) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
an animal repellent selected from the group of substances consisting of anthraquinone (32) +
TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (lUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
and biologically active compounds selected from the group consisting of ametoctradin [865318- 97-4] + TX, amisulbrom [348635-87-0] + TX, azaconazole [60207-31-0] + TX, benzovindiflupyr [1072957-71-1] + TX, bitertanol [70585-36-3] + TX, bixafen [581809-46-3] + TX, bromuconazole [1 16255-48-2] + TX, coumoxystrobin [850881-70-8] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657-24-3] + TX, enoxastrobin [238410-1 1-2] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fenpyrazamine [473798-59-3] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, fluxapyroxad [907204-31-3] + TX, fluopyram [658066-35-4] + TX, fenaminstrobin [366815-39-6] + TX, isofetamid [875915-78-9] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imiben- conazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, ipfentrifluconazole [1417782-08-1] + TX, isotianil [224049-04-1] + TX, mandestrobin [173662-97-0] (can be prepared according to the procedures described in WO 2010/093059) + TX, mefentrifluconazole [1417782-03-6] + TX, metconazole [1251 16- 23-6] + TX, myclobutanil [88671-89-0] + TX, paclobutrazol [76738-62-0] + TX, pefurazoate [101903-30- 4] + TX, penflufen [494793-67-8] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70- 6] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [1 12281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60- 6] + TX, dodemorph [1593-77-7] + TX, fenpropidin [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [1 18134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [1 10235-47-7] + TX, pyrimethanil [531 12-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, fluindapyr [1383809-87-7] + TX, benalaxyl [71626-1 1-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332- 96-5] + TX, flutianil [958647-10-4] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [1 12-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860- 33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1 , 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [1 17428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, pyraoxystrobin [862588-1 1-2] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205- 21-4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731-27-1] + TX, bordeaux mixture [801 1-63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20- 9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347- 22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917- 52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004- 44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, picarbutrazox [500207-04-5] + TX, polyoxins [1 11 13- 80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12- 4] + TX, pydiflumetofen [1228284-64-7] + TX, pyrametostrobin [915410-70-7] + TX, pyroquilon [57369- 32-1] + TX, pyriofenone [688046-61-9] + TX, pyribencarb [799247-52-2] + TX, pyrisoxazole [847749- 37-5] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulfur [7704-34-9] + TX, Timorex Gold™ (plant extract containing tea tree oil from the Stockton Group) + TX, tebufloquin [376645-78-2] + TX, tiadinil [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tolprocarb [911499-62-2] + TX, triclopyricarb [902760-40-1] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, valifenalate [283159-90-0] + TX, zoxamide (RH7281 ) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, phenamacril + TX, sedaxane [874967-67-6] + TX, trinexapac-ethyl [95266-40-3] + TX, 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro- biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3- [(cyclopropylcarbonyl)oxy]- 1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl- 11-oxo-9-(3-pyridinyl)-2/-/,11/-/naphtho[2,1-ib]pyrano[3,4-e]pyran-4-yl]nriethyl-cyclopropanecarboxylate [915972-17-7] + TX and 1 ,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2- trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1 H-pyrazole-4-carboxamide [926914-55-8] + TX, or a biologically active compound selected from the group consisting of N-[(5-chloro-2- isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2010/130767) + TX, 2,6-Dimethyl- 1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetrone (can be prepared according to the procedures described in WO 2011/138281 ) + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1 ,4]dithiino[1 ,2- c]isothiazole-3-carbonitrile + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5- dimethyl-pyrazol-3-amine (can be prepared according to the procedures described in WO 2012/031061 ) + TX, 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4- carboxamide (can be prepared according to the procedures described in WO 2012/084812) + TX, CAS 850881-30-0 + TX, 3-(3,4-dichloro-1 ,2-thiazol-5-ylmethoxy)-1 ,2-benzothiazole 1 ,1-dioxide (can be prepared according to the procedures described in WO 2007/129454) + TX, 2-[2-[(2,5- dimethylphenoxy)methyl]phenyl]-2-methoxy-N-methyl-acetamide + TX, 3-(4,4-difluoro-3,4-dihydro-3,3- dimethylisoquinolin-1-yl)quinolone (can be prepared according to the procedures described in WO 2005/070917) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol (can be prepared according to the procedures described in WO 201 1/081 174) + TX, 2-[2-[(7,8-difluoro-2- methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (can be prepared according to the procedures described in WO 201 1/081 174) + TX, oxathiapiprolin + TX [1003318-67-9], tert-butyl N-[6-[[[(1- methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, N-[2-(3,4- difluorophenyl)phenyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (can be prepared according to the procedures described in WO 2007/ 072999) + TX, 3-(difluoromethyl)-1-methyl-N-[(3R)-1 , 1 ,3- trimethylindan-4-yl]pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2014/013842) + TX, 2,2,2-trifluoroethyl N-[2-methyl-1-[[(4- methylbenzoyl)amino]methyl]propyl]carbamate + TX, (2RS)-2-[4-(4-chlorophenoxy)-a,a,a-trifluoro-o- tolyl]-1-(1 H-1 ,2,4-triazol-1-yl)propan-2-ol + TX, (2RS)-2-[4-(4-chlorophenoxy)-a,a,a-trifluoro-o-tolyl]-3- methyl-1-(1 H-1 ,2,4-triazol-1-yl)butan-2-ol + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 , 1-dimethyl-indan- 4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[3-ethyl-1 , 1-dimethyl-indan-4-yl]pyridine-3- carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formanriidine + TX, N'-[4-(4,5- dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (can be prepared according to the procedures described in WO 2007/031513) + TX, [2-[3-[2-[1-[2-[3,5- bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro- phenyl] methanesulfonate (can be prepared according to the procedures described in WO 2012/025557) + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]- 2-pyridyl]carbamate (can be prepared according to the procedures described in WO 2010/000841 ) + TX, 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1 ,2,4-triazole-3-thione (can be prepared according to the procedures described in WO 2010/146031 ) + TX, methyl N-[[5-[4-(2,4- dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4- (2,4,6-trifluorophenyl)pyridazine (can be prepared according to the procedures described in WO 2005/121 104) + TX, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (can be prepared according to the procedures described in WO 2013/024082) + TX, 3-chloro-4-(2,6- difluorophenyl)-6-methyl-5-phenyl-pyridazine (can be prepared according to the procedures described in WO 2012/020774) + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile (can be prepared according to the procedures described in WO 2012/020774) + TX, (R)-3-(difluoromethyl)-1- methyl-N-[1 , 1 ,3-trimethylindan-4-yl]pyrazole-4-carboxanriide (can be prepared according to the procedures described in WO 201 1/162397 ) + TX, 3-(difluoromethyl)-N-(7-fluoro-1 , 1 ,3-trimethyl-indan- 4-yl)-1-methyl-pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2012/084812) + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl- tetrazol-5-one (can be prepared according to the procedures described in WO 2013/162072) + TX, 1 - methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one
(can be prepared according to the procedures described in WO 2014/051 165) + TX, (Z,2E)-5-[1-(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX, N-(5-chloro-2-isopropylbenzyl)- N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methylpyrazole-4-carboxanriide [1255734-28-1] (can be prepared according to the procedures described in WO 2010/130767) + TX, 3-(difluoromethyl)-N-[(R)- 2,3-dihydro-1 , 1 ,3-trimethyl-1 H-inden-4-yl]-1-methylpyrazole-4-carboxami [1352994-67-2] + TX, N'- (2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichloro-thiazol-2- yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)- N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl- N-meth l-formamidine + TX,
Figure imgf000053_0001
u (fenpicoxamid [517875-34-2]) + TX (as described in WO
2003/035617), 2-(difluoromethyl)-N-(1 , 1 ,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2- (difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N- (1 , 1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-(3-isobutyl-1 , 1- dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3R)-1 , 1 ,3-trimethylindan-4- yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 , 1-dimethyl-indan-4-yl]pyridine-3- carboxamide + TX, and 2-(difluoromethyl)-N-[(3R)-1 , 1-dimethyl-3-propyl-indan-4-yl]pyridine-3- carboxamide + TX, wherein each of these carboxamide compounds can be prepared according to the procedures described in WO 2014/095675 and/or WO 2016/139189.
The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number.
The active ingredient mixture of the compounds of formula (I) selected from one compound as represented in Tables 1A.1 to 1A.8, Tables 1 B.1 to 1 B.8, Tables 2.1 to 2.8, Tables 3.1 to 3.4, Tables 4.1 to 4.4, and Tables 5A.1 to 5A.4, Tables 5B.1 to 5B.4, or in a compound 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below), preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5: 1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 : 1 , or 5: 1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3: 1 , or 3:2, or 2: 1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight.
The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
The mixtures comprising a compound as represented in Tables 1A.1 to 1A.8, Tables 1 B.1 to
1 B.8, Tables 2.1 to 2.8, Tables 3.1 to 3.4, Tables 4.1 to 4.4, and Tables 5A.1 to 5A.4, Tables 5B.1 to 5B.4, or a compound 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below), and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds as represented in Tables 1A.1 to 1A.8, Tables 1 B.1 to 1 B.8, Tables 2.1 to 2.8, Tables 3.1 to 3.4, Tables 4.1 to 4.4, and Tables 5A.1 to 5A.4, Tables 5B.1 to 5B.4, or compounds 1.1 to 1.28 described in Table T1 (below), 2.1 to 2.107 described in Table T2 (below), 3.1 to 3.81 described in Table T3 (below), 4.1 to 4.9 described in Table T4 (below), and 5.1 to 5.26 described in Table T5 (below), and the active ingredient(s) as described above, is not essential for working the present invention.
The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds (I) for the preparation of these compositions are also a subject of the invention. Another aspect of the invention is related to the use of a compound of Formula (I) or of a preferred individual compound as defined herein, of a composition comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of Formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
A further aspect of the invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of Formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
Controlling or preventing means reducing infestation 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. However, the compounds of Formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid Formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of Formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A formulation, e.g. a composition containing the compound of Formula (I), and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of Formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.
When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of Formula (I) per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient. Suitably, a composition comprising a compound of Formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly Formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of Formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. Table 1A.1 : This table discloses 9 specific compounds of the formula (T-1 A):
Figure imgf000057_0001
wherein R\ R2, R3, R4, R5, and R6 are hydrogen, and R7a-N-R7b is as defined below in Table 1A.
Each of Tables 1 A.2 to 1 A.8 (which follow Table 1 A) make available 9 individual compounds of the formula (T-1 A) in which R\ R2, R3, R4, R5, and R6 are as specifically defined in Tables 1A.2 to 1A.8, which refer to Table 1 A wherein R7a-N-R7b is specifically defined. Table 1A
Figure imgf000057_0002
Table 1A.2: This table discloses 9 specific compounds of formula (T-1 A) wherein R2, R3, R4, R5, and R6 are hydrogen, R is fluorine, and R7a-N-R7b is as defined above in Table 1A. Table 1A.3: This table discloses 9 specific compounds of formula (T-1A) wherein, R , R2, R4, R5, and R6 are hydrogen, R3 is fluorine, and R7a-N-R7b is as defined above in Table 1A.
Table 1A.4: This table discloses 9 specific compounds of formula (T-1 A) wherein R2, R4, R5, and R6 are hydrogen, R and R3 are fluorine, and R7a-N-R7b is as defined above in Table 1A. Table 1A.5: This table discloses 9 specific compounds of formula (T-1 A) wherein R3, R4, R5, and R6 are hydrogen, R and R2 are fluorine, and R7a-N-R7b is as defined above in Table 1A.
Table 1A.6: This table discloses 9 specific compounds of formula (T-1 A) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and R7a-N-R7b is as defined above in Table 1A.
Table 1A.7: This table discloses 9 specific compounds of formula (T-1 A) wherein R , R2, R5 and R6 are hydrogen, R3 and R4 are fluorine, and R7a-N-R7b is as defined above in Table 1A. Table 1A.8: This table discloses 9 specific compounds of formula (T-1 A) wherein R2, R3, R5 and R6 are hydrogen, R and R4 are fluorine, and R7a-N-R7b is as defined above in Table 1A.
Table 1 B.1 : This table discloses 29 specific compounds of the formula (T-1 B):
Figure imgf000058_0001
Each of Tables 1 B.2 to 1 B.8 (which follow Table 1 B.1 ) make available 29 individual compounds of the formula (T-1 B) in which R\ R2, R3, R4, R5, and R6 are as specifically defined in Tables 1 B.2 to 1 B.8, which refer to Table 1 B wherein R7c-N-R7d is specifically defined.
Table 1 B
Compound Compound
R7c-N-R7d R7c-N-R7d no. no.
1 B.001 O-et hy I hyd roxy la m i no 1 B.016 propan-1 -amino
1 B.002 cyclohexanamino 1 B.017 propan-2-amino
1 B.003 /V-methylformylhydrazido 1 B.018 1 , 1-dimethylhydrazino
1 B.004 2,2-dimethylpropan-1-amino 1 B.019 butan-2-amino
1 B.005 0-(prop-2-enyl)hydroxylamino 1 B.020 2-methylpropan-1 -amino
1 B.006 piperidin-1-amino 1 B.021 2-methylpropan-2-amino 1B.007 2-furylmethanamino 1B.022 cyclopentanamino
1B.008 2,2,2-trifluoroethanamino 1B.023 1-cyclopropylethanamino
1B.009 cyclopropylmethanamino 1B.024 ethyl 2-[amino(methyl)amino]acetate
1B.010 morpholin-4-amino 1B.025 0-(prop-2-ynyl)hydroxylamino
1B.011 /V-methylacetohydrazido 1B.026 0-(2,2,2-trifluoroethyl)hydroxylamino
1B.012 cyclobutanamino 1B.027 0-(2,2-difluoroethyl)hydroxylamino
1B.013 2-am inoaceton itri le 1B.028 0-(cyclopropylmethyl)hydroxylamino
1B.014 prop-2-en-1 -amino 1B.029 phenylmethanamino
1B.015 aniline
Table 1B.2: This table discloses 29 specific compounds of formula (T-1B) wherein R2, R3, R4, R5, and R6 are hydrogen, R is fluorine, and R7c-N-R7d is as defined above in Table 1B. Table 1B.3: This table discloses 29 specific compounds of formula (T-1B) wherein R , R2, R4, R5, and R6 are hydrogen, R3 is fluorine, and R7c-N-R7d is as defined above in Table 1B.
Table 1B.4: This table discloses 29 specific compounds of formula (T-1B) wherein R2, R4, R5, and R6 are hydrogen, R and R3 are fluorine, and R7c-N-R7d is as defined above in Table 1B.
Table 1B.5: This table discloses 29 specific compounds of formula (T-1B) wherein R3, R4, R5, and R6 are hydrogen, R and R2 are fluorine, and R7c-N-R7d is as defined above in Table 1B.
Table 1B.6: This table discloses 29 specific compounds of formula (T-1B) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and R7c-N-R7d is as defined above in Table 1B.
Table 1B.7: This table discloses 29 specific compounds of formula (T-1B) wherein R , R2, R5 and R6 are hydrogen, R3 and R4 are fluorine, and R7c-N-R7d is as defined above in Table 1B. Table 1B.8: This table discloses 29 specific compounds of formula (T-1B) wherein R2, R3, R5 and R6 are hydrogen, R and R4 are fluorine, and R7c-N-R7d is as defined above in Table 1B.
Table 2.1: This table discloses 22 specific compounds of the formula (T-2):
Figure imgf000060_0001
wherein R\ R2, R3, R4, R5, and R6 are hydrogen, and R7e is as defined below in Table 2.
Each of Tables 2.2 to 2.8 (which follow Table 2) make available 22 individual compounds of the formula (T-2) in which R\ R2, R3, R4, R5, and R6 are as specifically defined in Tables 2.2 to 2.8, which refer to Table 2 wherein R7e is specifically defined.
Table 2
Figure imgf000060_0002
Table 2.2: This table discloses 22 specific compounds of formula (T-2) wherein R2, R3, R4, R5, and R' are hydrogen, R is fluorine, and R7e is as defined above in Table 2.
Table 2.3: This table discloses 22 specific compounds of formula (T-2) wherein R , R2, R4, R5, and R' are hydrogen, R3 is fluorine, and R7e is as defined above in Table 2. „„
60
Table 2.4: This table discloses 22 specific compounds of formula (T-2) wherein R2, R4, R5, R6, and R7 are hydrogen, R and R3 are fluorine, and R7e is as defined above in Table 2.
Table 2.5: This table discloses 22 specific compounds of formula (T-2) wherein R3, R4, R5, and R6 are hydrogen, R and R2 are fluorine, and R7e is as defined above in Table 2.
Table 2.6: This table discloses 22 specific compounds of formula (T-2) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and R7e is as defined above in Table 2. Table 2.7: This table discloses 22 specific compounds of formula (T-2) wherein R , R2, R5 and R6 are hydrogen, R3 and R4 are fluorine, and R7e is as defined above in Table 2.
Table 2.8: This table discloses 22 specific compounds of formula (T-2) wherein R2, R3, R5 and R6 are hydrogen, R and R4 are fluorine, and R7e is as defined above in Table 2.
Table 3.1 : This table discloses 78 specific compounds of the formula (T-3):
Figure imgf000061_0001
wherein R , R2, R3, R4, R5, and R6 are hydrogen, and R 0-Nu is as defined below in Table 3.
Each of Tables 3.2 to 3.4 (which follow Table 3) make available 78 individual compounds of the formula (T-3) in which R , R2, R3, R4, R5, and R6 are as specifically defined in Tables 3.2 to 3.4, which refer to Table 3 wherein R 0-Nu is specifically defined.
Table 3
Compound Compound
R10-Nu R10-Nu
no. no.
3.001 cyclopentoxy 3.040 2-furylmethanamino
3.002 prop-2-ynyloxy 3.041 /V-methoxymethanamino
3.003 cyclopropylmethoxy 3.042 O-m ethyl hyd roxy la m i no
3.004 3-fluoropropoxy 3.043 ethanamino 3.005 cyclobutoxy 3.044 /V-methylethanamino
3.006 pentoxy 3.045 2,2,2-trifluoroethanamino
3.007 2,2,2-trifluoroethoxy 3.046 cyclopropanamino
3.008 2-ethoxyethoxy 3.047 prop-2-yn-1 -amino
3.009 benzyloxy 3.048 cyclopropylmethanamino
3.010 phenoxy 3.049 morpholin-4-amino
3.01 1 butoxy 3.050 /V-methylacetohydrazido
(2,2-
3.012 prop-2-enyloxy 3.051
dichlorocyclopropyl)methanamino
3.013 2 , 2-d i m et hy I p ro poxy 3.052 A/-methylpropan-2-anriino
3.014 cyclohexoxy 3.053 cyclobutanamino
3.015 2-fluoroethoxy 3.054 methanamino
3.016 tetra hyd rof u ran-3-y loxy 3.055 /V-methylmethanamino
3.017 2,2-difluoroethoxy 3.056 2-am inoaceton itri le
3.018 2-ethoxy-1-ethoxy 3.057 prop-2-en-1 -amino
3.019 but-2-ynyloxy 3.058 propan-1 -amino
3.020 isobutoxy 3.059 propan-2-amino
3.021 oxetan-3-yloxy 3.060 1 , 1-dimethylhydrazino
3.022 2-methoxyethoxy 3.061 A/-ethylethanamino
3.023 methoxy 3.062 butan-2-amino
3.024 1-propoxy 3.063 2-methylpropan-1 -amino
3.025 2-propoxy 3.064 2-methylpropan-2-amino
3.026 ethoxy 3.065 2-methoxyethanamino
3.027 cyclopropoxy 3.066 A/-morpholino
3.028 cyclohexanamino 3.067 aniline
3.029 /V-methylformylhydrazido 3.068 phenylmethanamino
3.030 2,2-dimethylpropan-1-amino 3.069 cyclopentanamino
3.031 0-(prop-2-enyl)hydroxylamino 3.070 cyclopropyl-1-ethanamino A/-(cyclopropylmethyl)propan-1-
3.032 3.071 ethyl 2-[amino(methyl)amino]acetate amino
0-
3.033 (cyclopropyl methyl )hyd roxylam in 3.072 A/-isoxazolidino
o
3.034 A/-5-azoniaspiro[2.4]heptane 3.073 /V-ethylcyclopropanamino
A/-cyclopropyl-N-(2,2-
3.035 3.074 0-(prop-2-ynyl)hydroxylamino
difluoroethyl)amino
0-
3.036 (cyclopropyl methyl )hyd roxylam in 3.075 0-(2,2,2-trifluoroethyl)hydroxylamino o
3.037 /V-methylcyclopropanamino 3.076 O-et hy I hyd roxy la m i no
0-(2,2-
3.038 3.077 amino
difluoroethyl)hydroxylamino
3.039 piperidin-1-amino 3.078 hydroxy
Table 3.2: This table discloses 78 specific compounds of formula (T-3) wherein R2, R3, R4, R5, and R6 are hydrogen, R is fluorine, and R 0-Nu is as defined above in Table 3. Table 3.3: This table discloses 78 specific compounds of formula (T-3) wherein R , R2, R4, R5, and R6 are hydrogen, R3 is fluorine, and R 0-Nu is as defined above in Table 3.
Table 3.4: This table discloses 78 specific compounds of formula (T-3) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and R 0-Nu is as defined above in Table 3.
Table 4.1 : This table discloses 34 specific compounds of the formula T-4):
Figure imgf000063_0001
wherein R , R2, R3, R4, R5, and R6 are hydrogen, and Z is as defined below in Table 4.
Each of Tables 4.2 to 4.4 (which follow Table 4) make available 34 individual compounds of the formula (T-4) in which R , R2, R3, R4, R5, and R6 are as specifically defined in Tables 4.2 to 4.4, which refer to Table 4 wherein Z is specifically defined. Table 4
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Table 4.2: This table discloses 34 specific compounds of formula (T-4) wherein R2, R3, R4, R5, and R6 are hydrogen, R is fluorine, and Z is as defined above in Table 4. Table 4.3: This table discloses 34 specific compounds of formula (T-4) wherein R , R2, R4, R5, and R6 are hydrogen, R3 is fluorine, and Z is as defined above in Table 4.
Table 4.4: This table discloses 34 specific compounds of formula (T-4) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and Z is as defined above in Table 4.
Table 5A.1 : This table discloses 78 specific compounds of the formula (T-5A):
Figure imgf000067_0001
wherein R\ R2, R3, R4, R5, and R6 are hydrogen, and R 0-Nu is as defined below in Table 5A.
Each of Tables 5A.2 to 5A.4 (which follow Table 5A) make available 78 individual compounds of the formula (T-5A) in which R\ R2, R3, R4, R5, and R6 are as specifically defined in Tables 5A.2 to 5A.4, which refer to Table 5A wherein R 0-Nu is specifically defined.
Table 5A
Compound Compound
R10-Nu R10-Nu
no. no.
5A.001 cyclopentoxy 5A.040 2-furylmethanamino
5A.002 prop-2-ynyloxy 5A.041 /V-methoxymethanamino
5A.003 cyclopropylmethoxy 5A.042 O-m ethyl hyd roxy la m i no
5A.004 3-fluoropropoxy 5A.043 ethanamino
5A.005 cyclobutoxy 5A.044 /V-methylethanamino
5A.006 pentoxy 5A.045 2,2,2-trifluoroethanamino
5A.007 2,2,2-trifluoroethoxy 5A.046 cyclopropanamino
5A.008 2-ethoxyethoxy 5A.047 prop-2-yn-1 -amino
5A.009 benzyloxy 5A.048 cyclopropylmethanamino
5A.010 phenoxy 5A.049 morpholin-4-amino
5A.01 1 butoxy 5A.050 /V-methylacetohydrazido
(2,2-
5A.012 prop-2-enyloxy 5A.051
dichlorocyclopropyl)methanamino
5A.013 2 , 2-d i m et hy I p ro poxy 5A.052 A/-methylpropan-2-amino
5A.014 cyclohexoxy 5A.053 cyclobutanamino
5A.015 2-fluoroethoxy 5A.054 methanamino A.016 tetra hyd rof u ran-3-y loxy 5A.055 /V-methylmethanamino
A.017 2,2-difluoroethoxy 5A.056 2-am inoaceton itri le
A.018 2-ethoxy-1-ethoxy 5A.057 prop-2-en-1 -amino
A.019 but-2-ynyloxy 5A.058 propan-1 -amino
A.020 isobutoxy 5A.059 propan-2-amino
A.021 oxetan-3-yloxy 5A.060 1 , 1-dimethylhydrazino
A.022 2-methoxyethoxy 5A.061 /V-ethylethanamino A.023 methoxy 5A.062 butan-2-amino
A.024 1-propoxy 5A.063 2-methylpropan-1 -amino
A.025 2-propoxy 5A.064 2-methylpropan-2-amino
A.026 ethoxy 5A.065 2-methoxyethanamino
A.027 cyclopropoxy 5A.066 /V-morpholino A.028 cyclohexanamino 5A.067 aniline
A.029 /V-methylformylhydrazido 5A.068 phenylmethanamino
A.030 2,2-dimethylpropan-1-amino 5A.069 cyclopentanamino
A.031 0-(prop-2-enyl)hydroxylamino 5A.070 cyclopropyl-1-ethanamino
A/-(cyclopropylmethyl)propan-1-A.032 5A.071 ethyl 2-[amino(methyl)amino]acetate amino
0-A.033 5A.072 A/-isoxazolidinO
(cyclopropylmethyl)hydroxylamino
A.034 A/-5-azoniaspiro[2.4]heptane 5A.073 A/-ethylcyclopropanamino
A/-cyclopropyl-N-(2,2-A.035 5A.074 0-(prop-2-ynyl)hydroxylamino
difluoroethyl)amino
0-A.036 5A.075 0-(2,2,2-trifluoroethyl)hydroxylamino
(cyclopropylmethyl)hydroxylamino
A.037 /V-methylcyclopropanamino 5A.076 O-et hy I hyd roxy la m i no
0-(2,2-A.038 5A.077 hydroxy
difluoroethyl)hydroxylamino
A.039 piperidin-1-amino 5A.078 amino „„
68
Table 5A.2: This table discloses 78 specific compounds of formula (T-5A) wherein R2, R3, R4, R5, and R6 are hydrogen, R is fluorine, and R 0-Nu is as defined above in Table 5A.
Table 5A.3: This table discloses 78 specific compounds of formula (T-5A) wherein R , R2, R4, R5, and R6 are hydrogen, R3 is fluorine, and R 0-Nu is as defined above in Table 5A.
Table 5A.4: This table discloses 78 specific compounds of formula (T-5A) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and R 0-Nu is as defined above in Table 5A.
Table 5B.1 : This table discloses 78 s ecific compounds of the formula (T-5B):
Figure imgf000069_0001
wherein R , R2, R3, R4, R5, and R6 are hydrogen, and R 0-Nu is as defined below in Table 5B.
Each of Tables 5B.2 to 5B.4 (which follow Table 5B) make available 78 individual compounds of the formula (T-5B) in which R\ R2, R3, R4, R5, and R6 are as specifically defined in Tables 5B.2 to 5B.4, which refer to Table 5B wherein R 0-Nu is specifically defined.
Table 5B
Compound Compound
R10-Nu R10-Nu
no. no.
5B.001 cyclopentoxy 5B.040 2-furylmethanamino
5B.002 prop-2-ynoxy 5B.041 /V-methoxymethanamino
5B.003 cyclopropylmethoxy 5B.042 O-m ethyl hyd roxy la m i no
5B.004 3-fluoropropoxy 5B.043 ethanamino
5B.005 cyclobutoxy 5B.044 /V-methylethanamino
5B.006 pentoxy 5B.045 2,2,2-trifluoroethanamino
5B.007 2,2,2-trifluoroethoxy 5B.046 cyclopropanamino
5B.008 2-ethoxyethoxy 5B.047 prop-2-yn-1 -amino
5B.009 benzyloxy 5B.048 cyclopropylmethanamino B.010 phenoxy 5B.049 morpholin-4-aminoB.01 1 butoxy 5B.050 /V-methylacetohydrazide
(2,2-B.012 allyloxy 5B.051
dichlorocyclopropyl)methanaminoB.013 2 , 2-d i m et hy I p ro poxy 5B.052 A/-methylpropan-2-anriino
B.014 cyclohexoxy 5B.053 cyclobutanamino
B.015 2-fluoroethoxy 5B.054 methanamino
B.016 3-tetrahyd rofu ranoxy 5B.055 /V-methylmethanamino
B.017 2,2-difluoroethoxy 5B.056 2-am inoaceton itri le
B.018 2-ethoxy-1-ethoxy 5B.057 prop-2-en-1 -amino
B.019 but-2-ynoxy 5B.058 propan-1 -amino
B.020 isobutoxy 5B.059 propan-2-amino
B.021 3-oxetanoxy 5B.060 1 , 1-dimethylhydrazine
B.022 2-methoxyethoxy 5B.061 /V-ethylethanamino B.023 methoxy 5B.062 butan-2-amino
B.024 1-propoxy 5B.063 2-methylpropan-1 -amino
B.025 2-propoxy 5B.064 2-methylpropan-2-amino
B.026 ethoxy 5B.065 2-methoxyethanamino
B.027 cyclopropoxy 5B.066 morpholino
B.028 cyclohexanamino 5B.067 aniline
B.029 /V-methylformylhydrazide 5B.068 phenylmethanamino
B.030 2,2-dimethylpropan-1-amino 5B.069 cyclopentanamino
B.031 O-allylhydroxylamino 5B.070 1-cyclopropylethanamino
A/-(cyclopropylmethyl)propan-1-B.032 5B.071 ethyl 2-[amino(methyl)amino]acetate amino
0-B.033 5B.072 isoxazolidine
(cyclopropylmethyl)hydroxylamino
B.034 5-azoniaspiro[2.4]heptane 5B.073 A/-ethylcyclopropanamino A/-cyclopropyl-N-(2,2-
5B.035 5B.074 0-prop-2-ynylhydroxylamino
difluoroethyl)amino
0-
5B.036 5B.075 0-(2,2,2-trifluoroethyl)hydroxylamino
(cyclopropylmethyl)hydroxylamino
5B.037 /V-methylcyclopropanamino 5B.076 0-et hy I hyd roxy la m i no
0-(2,2-
5B.038 5B.077 hydroxy
difluoroethyl)hydroxylamino
5B.039 piperidin-1-amino 5B.078 amino
Table 5B.2: This table discloses 78 specific compounds of formula (T-5B) wherein R2, R3, R4, R5, and R6 are hydrogen, R is fluorine, and R 0-Nu is as defined above in Table 5B. Table 5B.3: This table discloses 78 specific compounds of formula (T-5B) wherein R , R2, R4, R5, and R6 are hydrogen, R3 is fluorine, and R 0-Nu is as defined above in Table 5B.
Table 5B.4: This table discloses 78 specific compounds of formula (T-5B) wherein R , R2, R3 R4, and R5 are hydrogen, R6 is methyl, and R 0-Nu is as defined above in Table 5B.
EXAMPLES
The Examples which follow serve to illustrate the invention. The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
Throughout this description, temperatures are given in degrees Celsius (°C) and "mp." means melting point. LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method (Methods A, B and C) is as follows:
The description of the LC/MS apparatus and the method A is:
SQ Detector 2 from Waters lonisation method: Electrospray
Polarity: positive and negative ions
Capillary (kV) 3.0, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650
Mass range: 100 to 900 Da
DAD Wavelength range (nm): 210 to 500
Method Waters ACQUITY UPLC with the following HPLC gradient conditions:
(Solvent A: Water/Methanol 20:1 + 0.05% formic acid and Solvent B: Acetonitrile+ 0.05% formic acid)
Time (minutes) A (%) B (%) Flow rate (ml/min)
0 100 0 0.85
1.2 0 100 0.85
1.5 0 100 0.85
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C. The description of the LC/MS apparatus and the method B is:
SQ Detector 2 from Waters
lonisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.5, Cone (V) 30.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 140 to 800 Da
DAD Wavelength range (nm): 210 to 400 Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water/Methanol 9: 1 + 0.1 % formic acid and Solvent B: Acetonitrile + 0.1 % formic acid) Time (minutes) A (%) B (%) Flow rate (ml/min)
0 100 0 0.75
2.5 0 100 0.75
2.8 0 100 0.75
3.0 100 0 0.75
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.
The description of the LC/MS apparatus and the method C is: SQ Detector 2 from Waters
lonisation method: Electrospray
ACQUITY H Class UPLC, Mass Spectrometer from Waters
Polarity: positive and Negative Polarity Switch
Scan Type MS1 Scan
Capillary (kV) 3.00, Cone (V) 40.00, Desolvation Temperature (°C) 500, Cone Gas Flow (L/Hr) 50,
Desolvation Gas Flow (L/Hr) 1000
Mass range: 0 to 2000 Da
DAD Wavelength range (nm): 200 to 350
Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water +,0.1 % formic acid and Solvent B: Acetonitrile)
Time (minutes) A (%) B (%) Flow rate (ml/min)
0 70 30 0.5
0.05 70 30 0.5
0.8 5 95 0.5
1.8 5 95 0.5
2.45 70 30 0.5
2.50 70 30 0.5
Type of column: Waters ACQUITY UPLC BEH C18; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .7 micron; Temperature: 35°C.
Where necessary, enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
Formulation Examples
Wettable powders a) b) c)
Active ingredient [compound of Formula (I)] 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate 6 % 10 %
phenol polyethylene glycol ether 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 % 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.
Powders for dry seed treatment a) b) c)
Active ingredient [compound of Formula (I)] 25 % 50 % 75 %
light mineral oil 5 % 5 % 5 %
highly dispersed silicic acid 5 % 5 %
Kaolin 65 % 40 %
Talcum 20 %
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 %
octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
Cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Dusts a) b) c)
Active ingredient [compound of Formula (I)] 5 % 6 % 4 %
Talcum 95 %
Kaolin 94 %
mineral filler 96 %
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.
Extruder granules
Active ingredient [compound of Formula (I)] 15 %
sodium lignosulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 82 % 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.
Coated granules
Active ingredient [compound of Formula (I)] 8 %
polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 %
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.
Suspension concentrate
Active ingredient [compound of Formula (I)] 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 %
Carboxymethylcellulose 1 %
Silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
The finely ground 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. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Flowable concentrate for seed treatment
Active ingredient [compound of Formula (I)] 40 %
propylene glycol 5 %
copolymer butanol PO/EO 2 %
tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 %
monoazo-pigment calcium salt 5 %
Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
Water 45.3 %
The finely ground 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. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Slow-Release Capsule Suspension
28 parts of 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. To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension Formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
List of Abbreviations:
AIBN = azobisisobutyronitrile
DMF = dimethylformamide
DIBAL-H = diisobutyl aluminum hydride
DIPEA = N,N-di-isopropylethylamine
EtOAc = ethyl acetate
HCI = hydrochloric acid
mp = melting point
°C = degrees Celsius
MeOH = methyl alcohol
NaOH = sodium hydroxide
NBS = N-bromosuccinimide
min = minutes
RT = room temperature
h = hour(s)
TFAA = trifluoroacetic acid anhydride Preparation Examples
Example 1 : This example illustrates the preparation of building block 1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid
Figure imgf000077_0001
Step 1 : ethyl 1-[(4-cyanophenyl)methvnpyrazole-4-carboxylate
Figure imgf000077_0002
A solution of 4-(chloromethyl)benzonitrile (10.0 g, 64.65 mmol), ethyl 1 H-pyrazole-4- carboxylate (9.24 g, 64.65 mmol), and potassium carbonate (10.03 g, 71.1 mmol) in acetonitrile (100.0 mL) was heated for 4 hours at 80°C. The contents cooled to room temperature and the volatiles were removed under reduced pressure. To the resultant white solid mass was added 150 mL of water and stirred for 15 minutes. Solids were collected by filtration and dried under high vacuum to afford 16.8 g of the title compound as a white solid. LC/MS (Method A) retention time = 0.69 minutes, 295 (M+H). mp: 45-55°C.
Ή NMR (400 MHz, CDCIs) δ ppm: 7.95 (d, 2H), 7.64 (d, 2H), 7.29 (d, 2H), 5.38 (s, 2H), 4.29 (q, 2H), 1.33 (t, 3H). Step 2: ethyl 1-[[4-(N-hvdroxycarbamimidoyl)phenyllmethyllpyrazole-4-carboxylate
Figure imgf000077_0003
To a suspension of ethyl 1-[(4-cyanophenyl)methyl]pyrazole-4-carboxylate (20 g, 74.0 mmol) in ethanol (200 mL) at room temperature was added hydroxylamine hydrochloride (6.3 g, 88.0 mmol), triethylamine (12.4 mL, 88.8 mmol). The reaction mixture was heated at 80°C for 2 hours. The mixture was cooled to room temperature and volatiles were then removed under reduced pressure. The contents were filtered, washed with water, and dried under vacuum to afford 21 g of the title compound that was used directly in the next transformation without further purification.
Ή NMR (400 MHz, DMSO-c/6) δ ppm: 9.67 (s, 1 H), 8.47 (s, 1 H), 7.88 (s, 1 H), 7.67 (d, 2H), 7.27 (d, 2H), 5.81 (brs, 2H), 5.38 (s, 2H), 4.19 (q, 2H), 1.25 (t, 3H).
Step 3: ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpyrazole-4-carboxylate
Figure imgf000078_0001
To a solution of ethyl 1-[[4-(A/-hydroxycarbamimidoyl)phenyl]nriethyl]pyrazole-4-carboxylate (10.0 g, 33.3 mol) in 2-methyltetrahydrofuran (100 mL) was added TFAA (5.1 1 mL, 35.5 mmol). The reaction mixture was stirred for 6 hours then poured into 100 mL of ice water and basified by slow addition of aqueous saturated NaHCCh solution. The reaction mixture was extracted with ethyl acetate, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 1 1.8 g of the title compound as a white solid, mp: 120-125°C
Ή NMR (400 MHz, CDCIs) δ ppm: 8.1 1 (d, 2H), 7.96 (d, 2H), 7.37 (d, 2H), 5.39 (s, 2H), 4.30 (q, 2H), 1.34 (t, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.32 (s).
Step 4: 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpyrazole-4-carboxylic acid To a solution of ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4- carboxylate (5.0 g, 13.7 mmol) dissolved in 37% hydrochloric acid (130 mL) was added trifluoroacetic acid (52 mL). The reaction was heated at 55°C for 50 hours, cooled to room temperature and poured into ice water (400 mL), and basified by slow addition of aqueous saturated NaHCCh solution. The reaction mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99:1 to 9: 1 ) to afford 4.62 g of the title compound as an off-white solid, mp: 182-192°C.
Ή NMR (400 MHz, CDCI3) δ ppm: 8.05 (d, 2H), 7.60 (d, 2H), 7.39 (d, 2H), 5.39 (d, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.39 (s).
Example 2: This example illustrates the preparation building block 1-[1-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]eth l]pyrazole-4-carboxylic acid
Figure imgf000078_0002
Step 1 : Preparation of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzoyl chloride
Figure imgf000079_0001
4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzoic acid (4.00 g, 15.0 mmol) was suspended in dichloromethane (90 mL) and DMF (0.01 mL, 0.150 mmol) then oxalyl chloride (1.46 mL, 16.5 mmol) was added. The reaction mixture was heated at reflux for 2 hours then evaporated under reduced pressure to afford 4.15 g of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzoyl chloride as a yellow solid that was used directly in the next transformation without further purification.
Step 2: Preparation of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzamide
Figure imgf000079_0002
A solution of crude 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzoyl chloride (4.15 g, 14.6 mmol) in dichloromethane (20 mL) was added drop wise at room temperature to a stirred solution of N- methoxymethanamine (1.10 g, 17.5 mmol) and triethylamine (3.10 ml, 21.8 mmol) in dichloromethane (80 mL). The mixture was stirred at room temperature for 18 hours then poured into water and extracted twice with dichloromethane. The combined organic layers was washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (heptane: EtOAc eluent gradient 9: 1 to 65:35) to afford 4.12 g of the title compound as a solid. LC/MS (Method A) retention time = 0.97 minutes, 302 (M+H).
Ή NMR (400 MHz, CDCIs) δ ppm: 8.18 (d, 2H), 7.84 (d, 2H), 3.56 (s, 3H), 3.40 (s, 3H). Step 3: Preparation of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzaldehyde
Figure imgf000079_0003
To a 75-mL multi neck flask equipped with stirrer and thermometer at -78°C under argon,
DIBAL-H, 1.0M in toluene (16 mL, 16.0 mmol) was added drop-wise a solution of A/-methoxy-A/-methyl- 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (4.10 g, 13.3 mmol) in 2-methyltetrahydrofuran (90 mL). The mixture was stirred for two hours at -78°C and for one hour temperature was increase to 0°C via ice bath. The mixture was quenched by drop-wise addition of a saturated ammonium chloride solution. Precipitation of a white solid resulted and 4M HCI was added until full solubilisation occurred. The mixture was extracted with ethyl acetate and the combined organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The crude residue was subject to combiflash chromatography over silica gel (heptane: EtOAc eluent gradient 99:1 to 90: 10) to afford 2.93 g of the title compound as a white solid, mp: 40-50°C.
Ή NMR (400 MHz, CDCIs) δ ppm: 10.12 (s, 1 H), 8.31 (d, 2H), 8.05 (d, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.29 (s).
Step 4: Preparation of 1-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethanol
Figure imgf000080_0001
In a 50 mL flask dried and under argon, 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yljbenzaldehyde (1.36 mol) was dissolved in THF (10 mL) and cooled to -78°C via a dry ice acetone bath. To this solution was introduced dropwise methyl magnesium bromide (0.70 mL, 2.0 M in diethyl ether). The mixture was stirred for 1 hour at -78°C then quenched with a saturated aqueous ammonium chloride solution. The dry ice bath was removed and the reaction was stirred at room temperature for 5 minutes then extracted with ethyl acetate. The total combined organic layer was dried over sodium sulfate and concentrated under reduced pressure. The resultant crude residue was subject to combiflash chromatography over silicagel (heptane: EtOAc eluent gradient 99:1 to 1 : 1 ) to afford the title compound as a white solid.
Ή NMR (400 MHz, CDCI3) δ ppm: 8.12 (d, 2H), 7.54 (d, 2H), 5.00 (s, 1 H), 1.54 (d, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.31 (s).
Step 5: Preparation of 1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllethanone
Figure imgf000080_0002
In a 50 mL flask dried and under argon, 1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]ethanol (1.36 mol) was dissolved in dichloromethane (10 mL). To this solution was introduced manganese oxide (40.6 mmol) and the heterogenous mixture was stirred overnight at room temperature. The reaction solution was filtered over a pad of celite, rinsed with dichloromethane, and the total combined organic layer was concentrated under reduced pressure to afford the title compound as a white solid which was used directly without further purification.
Ή NMR (400 MHz, CDCIs) δ ppm: 8.24 (d, 2H), 8.12 (d, 2H), 2.67 (d, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.39 (s).
Step 6: Preparation of 3-[4-(1-bromoethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
Figure imgf000081_0001
To a solution of 1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethanol (1.15 g, 4.45 mmol) in dichloromethane (15 mL) cooled to 0°C via an ice bath was added tribromophosphane (0.465 mL, 4.90 mmol) over 30 minutes and the reaction mixture was stirred for 1.5 hours. Then, a 10% sodium metabisulphite (50 ml) was introduced and after 15 minutes the aqueous layer was extracted with dichloromethane. The total combined organic layer was washed with water, dried over Na2S04, filtered and concentrated under reduced pressure. The resultant crude residue was purified by combiflash chromatography over silica gel using cyclohexane as eluent to afford 1.0 g of the title compound pure as white solid.
Ή NMR (400 MHz, DMSO-c/6) δ ppm: 8.07 (m, 2H), 7.75 (m, 2H), 5.59 (q, 1 H), 2.02 (d, 3H). Step 7: Preparation of ethyl 1-[1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllethyllpyrazole-4- carboxylate
Figure imgf000081_0002
Ethyl 1 H-pyrazole-4-carboxylate (0.061 g, 0.46 mmol), potassium carbonate (0.13 g, 0.93 mmol), 3-[4-(1-bromoethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.15 g, 0.47 mmol), and acetonitrile (1.5 mL) were reacted at room temperature overnight then concentrated under reduced pressure. Water was added and the organics were extracted twice with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, and filtered. Volatiles was removed under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 93:7) to afford 0.1 15 g of the title compound. LC/MS (Method C) retention time = 1.61 minutes, 385 (M+H). Ή NMR (400 MHz, CDCIs) δ ppm: 8.12 (d, 2H), 7.98 (d, 2H), 7.37 (d, 2H), 5.61 (q, 1 H), 4.31
(q, 2H), 1.97 (d, 3H), 1.35 (t, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.33 (s).
Step 8: Preparation of 1-[1-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethyllpyrazole-4- carboxylic acid
To a suspension of ethyl 1-[1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]pyrazole- 4-carboxylate (315 mg, 0.83 mmol) in MeOH (12.6 mL) was added barium hydroxide octahydrate (0.53 g, 1.66 mmol) in water (6.3 mL) at 0°C. The reaction mixture was stirred at room temperature for 12 hours. To the aqueous layer 10% aqueous HCI was added until the pH was acidic. The product was extracted thrice using ethyl acetate. The totoal combined organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was subjected to flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 50:50) to afford 0.036 g of the title compound.
Ή NMR (400 MHz, DMSO-c/6) δ ppm: 12.27 (brs, 1 H), 8.48 (s, 1 H), 8.05 (d, 2H), 7.86 (s, 1 H), 7.37 (d, 2H), 5.79 (q, 1 H), 1.86 (d, 3H), 1.35 (t, 3H).
9F NMR (400 MHz, DMSO-c/6) δ ppm: -64.70 (s).
Example 3: This example illustrates the preparation building block 1-[[3-fluoro-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phen l]methyl]pyrazole-4-carboxylic acid
Figure imgf000082_0001
Step 1 : Preparation of 2-fluoro-N'-hvdroxy-4-methyl-benzamidine
Figure imgf000082_0002
To a suspension of 2-fluoro-4-methylbenzonitrile (5 g, 37.0 mmol) in ethanol (125 mL) at 25°C was added hydroxylamine hydrochloride (7.7 g, 1 1 1 mmol) and triethylamine (15.5 mL, 1 1 1 mmol). The reaction mixture was heated at 80°C for 2 hours. After cooling to room temperature, volatiles were removed under reduced pressure thus affording a white solid that was used in the next step without any purification. LC/MS (Method A) retention time = 0.25 minutes, 169.2 (M+H). Ή NMR (400 MHz, CDCIs) δ ppm: 7.96 (t, 1 H), 7.1 1 (m, 2H), 2.45 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.26 (s), -108.12 (s).
Step 2: Preparation of 3-(2-fluoro-4-methyl-phenvn-5-(trifluoromethvn-1 ,2,4-oxadiazole
Figure imgf000083_0001
To a solution of 2-fluoro-/V-hydroxy-4-methyl-benzamidine (37 mmol) in tetrahydrofuran (122 mL) cooled via an ice bath to 0°C was added TFAA (7.7 mL, 55.5 mmol). The reaction mixture was stirred at 25°C overnight and then diluted with water. The organic layer was separated, washed successively with a saturated aqueous sodium bicarbonate solution, a saturated aqueous ammonium chloride solution, water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99: 1 to 1 :1 ) to afford 6.6 g of the title compound as an amorphous white solid. LC/MS (Method A) retention time = 1.14 minutes, 247 (M+H). Ή NMR (400 MHz, CDCI3) δ ppm: 8.00 (d, 1 H), 7.32 (d, 2H), 2.45 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.3 (s), 108.1 (s).
Step 3a: Preparation of 3-[4-(bromomethyl)-2-fluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000083_0002
A mixture of 3-(2-fluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (4.2 g, 17.1 mmol) and NBS (3.1 1 g, 17.1 mmol) in tetrachloromethane (34.3 mL) was heated to 70°C. AIBN (0.29 g, 1.71 mmol) was introduced and the reaction mixture stirred at 65°C for 18 hours. The contents were cooled to 25°C, diluted with dichloromethane and water, and the layers were separated. A succinimide by-product was filtrated off the organic fraction and the solvent was removed under reduced pressure to afford a brown gum. The crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 100:0 to 4: 1 ) to afford 1.7 g of the title compound as a white solid. LC/MS (Method A) retention time = 1.13 minutes, (M+H) not detected.
Ή NMR (400 MHz, CDCI3) δ ppm: 8.09 (t, 1 H), 7.34 (m, 2H), 4.49 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.18 (s), -106.2 (s). 3-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole was isolated as byproduct in the form of a beige solid (4.0 g, 58% yield) LC/MS (Method A) retention time = 1 .20 minutes, (M+H) not detected. Ή NMR (400 MHz, CDCIs) δ ppm: 8.14 (d, 1 H), 7.52 (dd, 2H), 6.63 (s, 1 H).
Step 3b: Preparation of 3-[4-(bromomethvn-2-fluoro-phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole from 3-[4-(dibromomethvn-2-fluoro-phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
Figure imgf000084_0001
To a 1 :20 mixture of 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole and 3-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (4.0 g, 9.9 mmol) in acetonitrile (37 mL), water (0.8 mL) and DIPEA (2.59 mL, 14.8 mmol) cooled to 5°C was added diethylphosphite (2.0 mL, 14.8 mmol). The mixture was stirred at 5-10°C for 2 hours, then water and 1 M HCI were added and volatiles were removed under reduced pressure. The resultant white slurry was extracted with dichloromethane and the combined organic layer was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the resultant light orange colored crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 99: 1 to 1 :1 ) to afford 2.2 g of the title compound as a white solid. Ή NMR (400 MHz, CDCI3) δ ppm: 8.09 (t, 1 H), 7.34 (m, 2H), 4.49 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.18 (s), -106.2 (s).
Step 4: Preparation of2-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-4,4- dimethyl-isoxazolidin-3-one
Ethyl 1 H-pyrazole-4-carboxylate (0.066 g, 0.46 mmol), potassium carbonate (0.086 g, 0.62 mmol), 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.10 g, 0.31 mmol), and acetonitrile (1.5 mL) were sealed in a vial. The reaction contents were irradiated with microwaves and heated at 130°C for 0.5 hour. After cooling to 25°C, all solids were filtered off, rinsed with ethyl acetate, and the volatiles were removed under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99: 1 to 1 : 1 ) to afford 0.075 g of the title compound. LC/MS (Method C) retention time = 1.61 minutes, 381 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 8.19 (t, 1 H), 7.98 (d, 2H), 7.36 (m, 1 H), 7.18 (m, 1 H), 5.36 (s, 2H), 4.30 (q, 2H), 1.32 (t, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.18 (s), 105.62 (s). Step 5: Preparation of 1-[[3-fluoro-4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllmethyllpyrazole-4- carboxylic acid solution of 2-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-4,4- dimethyl-isoxazolidin-3-one (2.5 g, 6.5 mmol) dissolved in 37% hydrochloric acid (65 mL) was added trifluoroacetic acid (26 mL). The reaction was heated at 55°C for 50 hours, cooled to room temperature and poured into ice water (200 mL), and basified by slow addition of aqueous saturated NaHCCh solution. The reaction mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (cyclohexane:EtOAc 3:1 to EtOAc:EtOH 9: 1 eluent gradient) to afford 2.3 g of the title compound as an off-white solid, mp: 185-186°C.
Example 4: This example illustrates the preparation of building block ethyl 2-oxo-2-[1-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetate (Compound 4.1 of Table T4)
Figure imgf000085_0001
Ethyl 2-oxo-2-(1 H-pyrazol-4-yl)acetate (0.33 g, 1.95 mmol), potassium carbonate (0.36 g, 2.62 mmol), 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.40 g, 1.31 mmol), and acetonitrile (6.5 mL) were sealed in a vial. The reaction contents were irradiated with microwaves and heated at 1 10°C for 0.5 hour. After cooling to 25°C, all solids were filtered off, rinsed with ethyl acetate, and the volatiles were removed under reduced pressure. The resultant crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 1 : 1 ) to afford 0.32 g of the title compound. LC/MS (Method A) retention time = 1.08 minutes, 385 (M+H).
Ή NMR (400 MHz, CDCIs) δ ppm: 8.38 (s, 1 H), 8.25 (s, 1 H), 8.15 (d, 2H), 7.18 (m, 1 H), 5.42
(s, 2H), 4.30 (q, 2H), 1.32 (t, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.34 (s).
Example 5: This example illustrates the preparation of building block 2-oxo-2-[1-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetic acid
Figure imgf000085_0002
To a solution of 2-oxo-2-[1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4- yl]acetate (1.50 g, 13.7 mmol) dissolved in tetrahydofuran (1 1.9 mL) and water (1.9 mL) was added lithium hydroxide (0.02 g, 0.76 mmol) and stirred overnight. The reaction mixture was then acidified with 1 M HCI to pH =1 and extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 0.125 g of the title compound as an off-white solid.
Ή NMR (400 MHz, CDCIs) δ ppm: 8.70 (s, 1 H), 8.35 (s, 1 H), 8.15 (d, 2H), 7.45 (d, 2H), 5.43 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.33 (s).
Example 6: This example illustrates the preparation of 2-oxo-2-[1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phen l]methyl]pyrazol-4-yl]acetyl chloride (Compound 4.5 of Table T4)
Figure imgf000086_0001
To a solution of 2-oxo-2-[1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4- yl]acetic acid (0.055 g, 0.15 mmol) dissolved in dichloromethane (0.8 mL) and dimethylamide (2 drops) was added oxalyl dichloride (3.46 mL, 39 mmol). The mixture was heated at reflux (33-38°C) for 1 hour and then propanol (0.013g, 0.22 mmol) was slowly added. After the contents stirred for 2 hours, the contents were concentrated under reduced pressure to afford 0.033 mg of the title compound as a white solid, mp: 94 - 99°C. LC/MS (Method A) retention time = 1.12 minutes, 409 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 8.36 (s, 1 H), 8.25 (s, 1 H), 8.15 (d, 2H), 7.42 (d, 2H), 5.41 (s, 2H), 4.28 (q, 2H), 1.72 (m, 2H), 1.02 (t, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.38 (s).
Example 7: This example illustrates the preparation of N-methyl-2-oxo-2-[1-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetamide (Compound 4.3 of Table T4)
Figure imgf000086_0002
2-Oxo-2-[1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazol-4-yl]acetic acid (0.05 g, 0.14 mmol) and N-ethyl-N-isopropyl-propan-2-amine (0.09 mL, 0.55 mmol) in N,N- dimethylformamide (0.68 mL), were stirred at room temperature for 10 min. Then methanamine hydrochloride (0.014 g, 0.205 mmol) was added followed by [dimethylamino(triazolo[4,5-b]pyridin-3- yloxy)methylene]-dimethyl-ammonium hexafluorophosphate (0.078 g, 0.205 mmol) and the reaction was stirred 2 hours at room temperture. EtOAc (10 mL) and H2O (5 mL) were added, the layers were separated, and the aqueous layer was extractedwith EtOAc. The combined organic layers were washed with water, dried with Na2S04, filtered, and evaporated, to get a beige solid of crude. The crude residue was purified by flash chromatography over silica gel (cyclohexane:ethyl acetate eluent gradient 99:1 to 1 : 1 ) to afford 0.028 g of the title compound as a white solid.
Ή NMR (400 MHz, CDCI3) δ ppm: 8.76 (s, 1 H), 8.32 (s, 1 H), 8.12 (d, 2H), 7.42 (d, 2H), 5.41 (s, 2H), 2.98 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.40 (s).
Example 8: This example illustrates the preparation of methyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]pyrazole-3-carboxylate (Compound 5.1 of Table T5)
Figure imgf000087_0001
A mixture of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (5.0 g, 16.3 mmol), methyl 1 H-pyrazole-3-carboxylate (3.08 g, 24.4 mmol) and potassium carbonate (3.29 g, 32.5 mmol) in acetonitrile (81 mL) was heated at 25°C for 4 hours. The white suspension was filtered to remove the solids and the filtrate solution was then concentrated under reduced pressure. The resultant crude residue was purified by flash chromatography on silica gel (cyclohexane:ethyl acetate eluent gradient 99:1 to 35:65) to afford 3.90 g of the title compound as a white solid. LC/MS (Method A) retention time = 1.02 minutes, 353 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 8.12 (d, 2H), 7.49 (d, 1 H), 7.39 (d, 2H), 6.89 (s, 1 H), 5.51 (s, 2H), 3.98 (s, 3H). methyl 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-3-carboxylate (Compound 5.2 of Table T5) was isolated as a byproduct in form of a white solid (1.53 g). LC/MS (Method A) retention time = 1 .1 1 minutes, 353 (M+H).
Figure imgf000087_0002
Ή NMR (400 MHz, CDCIs) δ ppm: 8.05 (d, 2H), 7.55 (s, 1 H), 7.40 (d, 2H), 6.95 (s, 1 H), 5.35 (s, 2H), 3.85 (s, 3H).
Example 9: This example illustrates the preparation of N,N-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l]pyrazole-3-carboxamide (Compound 5.19 of Table T5)
Figure imgf000088_0001
To a clear solution of N-methylmethanamine hydrochloride (0.046 g, 0.57 mmol) in toluene (2 mL) was introduced dropwise diethylaluminum chloride (1 M in toluene, 0.57 mL, 0.57 mmol). After 10 minutes, methyl 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-3-carboxylate (0.10 mg, 0.28 mmol) was added and the mixture was heated for 12 hours at 90°C. The heat source was then removed, and the reaction media was allowed to reach room temperature reaction then quenched with water (ca. 0.030 mL). The suspension was concentrated under reduced pressure and the resultant residue was purified by flash chromatography on silica gel using a cyclohexane/ethyl acetate gradient to afford the title compound (0.08 g, 77% yield) as a yellow gum. LC/MS (Method A) retention time = 0.98 minutes, 366 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 8.05 (d, 2H), 7.55 (s, 1 H), 7.40 (d, 2H), 6.40 (s, 1 H), 5.61 (s, 2H), 3.05 (s, 3H), 2.91 (s, 3H).
The following procedures (protocol A and protocol B) were made in a combinatorial fashion and used appropriate building blocks (compounds (IB) and (XIII)) to provide compounds of Formula (IA), wherein R -Nu-H is HN R7a)R7b, HN(R7c)R7d, HN(R9a)R9b, HN(R 0a)R 0b, HOR7c, HOR9c, or HOR 0c:
Figure imgf000088_0002
analyzed using LC/MS Method B. Protocol A: A stock solution of the 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- azole-carboxylic acid derivative of formula (IB) (600 mg) wherein Z is Z\ Z2, or Z was prepared in N,N- dimethylacetamide (9.6 mL). This solution (48 times 0.2 mL) was dispensed to a deep well plate containing 48 amines of formula (XIII), wherein R -Nu is HN(R7a)R7b, HN(R7c)R7d, HN(R9a)R9b, HN(R 0a)R 0b (each 2 equivalents), and dissolved in N,N-dimethylacetamide (48 times 0.3 mL). Then, N-ethyl-N-(1-methylethyl)-2-propanamine (3 equivalents) was added to each position of the plate, followed by a solution of 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (1.2 equivalents) in N,N-dimethylacetamide (48 times 0.3 mL). The plate was sealed and reaction mixtures were stirred at ambient temperature for 24 hours. Then the solvent was evaporated and each of the crude products was purified by preparative reversed phase HPLC. Thus, the compounds of Formula (IA) were obtained (0.6 to 8 mg each) in pure form.
Protocol B: A stock solution of the 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- azole-carboxylic acid derivative of formula (IB) (24 times 0.04 mmol) wherein Z is Z , Z2, or Z was prepared in 24 portions of DMF (each 0.3 mL) in a deep well plate. Then, a stock solution of O- (benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate (24 times 1.7 equivalents) and 2,3,4,6,7,8,9, 10-octahydropyrimido[1 ,2-a]azepine (24 times 3.35 equivalents) was prepared in 24 portions. This was diluted with Ν,Ν-dimethylformamide (each 0.3 mL), dispensed to each position of the plate, and stirred for 30 minutes at ambient temperature. Then 24 alcohols of formula (XIII), wherein R -Nu-H is HOR7c, HOR9c, or HOR 0c (each between 8 and 40 equivalents) were dispensed to each position, the plate was sealed, and the reaction mixtures stirred at ambient temperature for 24 hours. The solvent was evaporated and each of the crude products was purified by preparative reversed phase HPLC. Thus, the compounds of Formula (IA) were obtained (1 to 4 mg each) in pure form.
Table T1 : Melting point (mp) data and/or retention times (T.R) for compounds 1.1 to 1.28 according to
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
_
96
Table T2: Melting point (mp) data and/or retention times HR) for compounds 2.1 to 2.107 according to Formula (I):
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Table T3: Melting point (mp) data and/or retention times HR) for compounds 3.1 to 3.81 according to
Formula (I):
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Table T4: Melting point (mp) data and/or retention times HR) for compounds 4.1 to 4.9 according to
Formula (I):
Figure imgf000148_0001
Figure imgf000149_0001
Table T5: Melting point (mp) data and/or retention times HR) for compounds 5.1 to 5.26 according to Formula (I):
Figure imgf000149_0002
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
BIOLOGICAL EXAMPLES
General examples of leaf disk tests in well plates:
Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse. The cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar. The leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation. Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying. The inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated. General examples of liquid culture tests in well plates:
Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth. DMSO solutions of the test compound (max. 10 mg/ml) are diluted with 0.025% Tween20 by a factor of 50 and 10 μΙ of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound. The test plates are incubated in the dark at 24°C and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check is calculated.
Example 1 : Fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)
Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 C and 75% relative humidity (rh) under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 to 9 days after application).
The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Compounds (from Table T1 ) 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.1 1 , 1.12, 1.13,
1.14, 1 .15, 1.16, 1.17, 1 .18, 1.19, 1.20, 1 .21 , 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, and 1.28.
Compounds (from Table T2) 2.1 , 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.1 1 , 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.19, 2.20, 2.21 , 2.22, 2.23, 2.24, 2.25, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 , 2.32, 2.33, 2.34, 2.35, 2.36, 2.37, 2.38, 2.39, 2.40, 2.41 , 2.42, 2.43, 2.44, 2.45, 2.46, 2.47, 2.48, 2.49, 2.50, 2.52, 2.53, 2.54, 2.55, 2.57, 2.58, 2.59, 2.60, 2.61 , 2.62, 2.64, 2.65, 2.66, 2.67, 2.68, 2.69, 2.70, 2.71 , 2.72, 2.73, 2.74, 2.75, 2.76, 2.77, 2.78, 2.79, 2.80, 2.81 , 2.82, 2.83, 2.84, 2.85, 2.86, 2.87, 2.88, 2.89, 2.90, 2.91 , 2.92, 2.93, 2.94, 2.95, 2.96, 2.97, 2.98, 2.99, 2.100, 2.101 , 2.102, 2.103, 2.104, 2.105, 2.106, and 2.107.
Compounds (from Table T3) 3.1 , 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.10, 3.1 1 , 3.12, 3.13, 3.15, 3.16, 3.17, 3.18, 3.19, 3.20, 3.21 , 3.22, 3.23, 3.24, 3.25, 3.26, 3.27, 3.28, 3.29, 3.30, 3.31 , 3.33, 3.34, 3.35, 3.36, 3.38, 3.39, 3.40, 3.42, 3.44, 3.45, 3.46, 3.47, 3.49, 3.50, 3.51 , 3.52, 3.54, 3.55, 3.56, 3.57, 3.59, 3.60, 3.61 , 3.62, 3.63, 3.65, 3.66, 3.67, 3.68, 3.69, 3.71 , 3.72, 3.73, 3.74, 3.75, 3.77, 3.78, 3.79, 3.80, and 3.81.
Compounds (from Table T4) 4.1 , 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, and 4.9.
Compounds (from Table T5) 5.1 , 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.1 1 , 5.12, 5.13, 5.14, 5.15,
5.16, 5.17, 5.18, 5.19, 5.20, 5.22, 5.23, 5.24, 5.25, and 5.26.
Example 2: Fungicidal activity against Puccinia recondita f. sp. triticil wheat / leaf disc curative (Brown rust)
Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 to 8 days after application).
The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Compounds (from Table T1 )_1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.1 1 , 1.12, 1.13,
1.14, 1 .15, 1.16, 1 .17, 1.18, 1.19, 1.20, 1 .21 , 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, and 1.28.
Compounds (from Table T2).2.1 , 2.2, 2.3, 2.4, 2.6, 2.7, 2.8, 2.9, 2.10, 2.1 1 , 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.21 , 2.22, 2.23, 2.24, 2.25, 2.31 , 2.32, 2.33, 2.34, 2.36, 2.38, 2.39, 2.41 , 2.42, 2.43, 2.46, 2.47, 2.48, 2.49, 2.50, 2.54, 2.57, 2.58, 2.60, 2.61 , 2.62, 2.64, 2.67, 2.69, 2.72, 2.73, 2.74, 2.75, 2.80, 2.83, 2.84, 2.85, 2.86, 2.87, 2.88, 2.90, 2.91 , 2.93, 2.94, 2.95, 2.96, 2.97, 2.98, 2.99, 2.100, 2.103, and 2.104.
Compounds (from Table T3) 3.2, 3.5, 3.8, 3.1 1 , 3.13, 3.16, 3.17, 3.18, 3.22, 3.27, 3.30, 3.31 , 3.35, 3.39, 3.40, 3.46, 3.49, 3.51 , 3.55, 3.60, 3.61 , 3.62, 3.63, 3.64, 3.67, 3.68, 3.70, 3.72, 3.75, 3.77, 3.78, 3.80, and 3.81.
Compounds (from Table T4) 4.1 , 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, and 4.9.
Compounds (from Table T5) 5.1 , 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 5.10, 5.1 1 , 5.13, 5.14,
5.15, 5.16, 5.17, 5.18, 5.19, 5.20, 5.22, 5.23, 5.24, 5.25, and 5.26.
Example 3: Fungicidal activity against Phakopsora pachyrhizi I soybean / leaf disc preventative (Asian soybean rust)
Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20°C and 75% rh leaf disc are kept at 20°C with 12 h light/day and 75% rh. The activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 to 14 days after application).
The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Compounds (from Table T1 ) 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1 .12, 1.13, 1.14, 1.15, 1.16,
1.17, 1.18, 1 .19, 1.20, 1.21 , 1.22, 1 .25, 1.26, 1.27, and 1.28.
Compounds (from Table T2) 2.1 , 2.2, 2.3, 2.6, 2.7, 2.8, 2.9, 2.10, 2.1 1 , 2.12, 2.13, 2.15, 2.16,
2.17, 2.18, 2.19, 2.20, 2.21 , 2.22, 2.23, 2.24, 2.25, 2.26, 2.27, 2.30, 2.31 , 2.32, 2.33, 2.36, 2.37,
2.38, 2.39, 2.40, 2.41 , 2.42, 2.43, 2.44, 2.45, 2.46, 2.47, 2.48, 2.49, 2.50, 2.51 , 2.52, 2.53, 2.55, 2.56, 2.57, 2.58, 2.59, 2.62, 2.63, 2.64, 2.65, 2.66, 2.67, 2.68, 2.69, 2.71 , 2.72, 2.73, 2.74, 2.75,
2.76, 2.77, 2.78, 2.79, 2.82, 2.83, 2.84, 2.85, 2.88, 2.90, 2.91 , 2.92, 2.94, 2.95, 2.97, 2.98, 2.99,
2.100, 2.102, 2.104, and 2.107.
Compounds (from Table T3) 3.2, 3.4, 3.5, 3.6, 3.8, 3.12, 3.13, 3.14, 3.16, 3.18, 3.21 , 3.22,
3.24, 3.27, 3.28, 3.29, 3.30, 3.34, 3.35, 3.39, 3.41 , 3.42, 3.44, 3.45, 3.47, 3.49, 3.51 , 3.52, 3.54, 3.55, 3.57, 3.58, 3.59, 3.60, 3.62, 3.63, 3.64, 3.65, 3.66, 3.67, 3.68, 3.69, 3.70, 3.72, 3.73, 3.75,
3.78, 3.80, and 3.81.
Compounds (from Table T4) 4.1 , 4.2, 4.3, 4.4, 4.5, 4.7, and 4.8.
Compounds (from Table T5) 5.2, 5.3, 5.4, 5.6, 5.7, 5.8, 5.9, 5.10, 5.1 1 , 5.12, 5.13, 5.14, 5.15, 5.16,
5.17, 5.18, 5.19, 5.20, 5.21 , 5.23, 5.24, 5.25, and 5.26.
Example 4: Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liguid culture / cucumber / preventative (Anthracnose)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB - potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96- well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is measured photometrically 3 to 4 days after application.
The following compounds at 20 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.
Compounds (from Table T1 )_1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.1 1 , 1.12, 1.13, 1.14, 1 .15, 1.16, 1.17, 1.18, 1.19, 1 .20, 1.21 , 1.22, 1.23, 1.24, 1 .25, 1.26, 1.27, and 1.28.
Compounds (from Table T2) 2.1 , 2.2, 2.3, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.1 1 , 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.19, 2.20, 2.21 , 2.22, 2.23, 2.25, 2.27, 2.29, 2.31 , 2.32, 2.33, 2.34, 2.35, .38, 2.39, 2.41 , 2.42, 2.43, 2.45, 2.46, 2.47, 2.48, 2.50, 2.51 , 2.52, 2.53, 2.55, 2.57, 2.58, .60, 2.61 , 2.62, 2.64, 2.65, 2.66, 2.67, 2.68, 2.69, 2.70, 2.71 , 2.72, 2.73, 2.74, 2.76, 2.78,.83, 2.84, 2.85, 2.86, 2.87, 2.88, 2.90, 2.91 , 2.92, 2.93, 2.94, 2.95, 2.97, 2.98, 2.99, 2.100, 2.104, 2.105, 2.106, and 2.107.
Compounds (from Table T33.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.1 1 , 3.12, 3.13, .15, 3.16, 3.17, 3.18, 3.19, 3.20, 3.21 , 3.22, 3.23, 3.24, 3.25, 3.26, 3.27, 3.28, 3.29, 3.30, .32, 3.33, 3.34, 3.35, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41 , 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, .49, 3.50, 3.51 , 3.52, 3.53, 3.54, 3.55, 3.56, 3.57, 3.58, 3.59, 3.60, 3.61 , 3.62, 3.63, 3.64,.66, 3.67, 3.68, 3.69, 3.70, 3.71 , 3.72, 3.73, 3.74, 3.75, 3.76, 3.77, 3.78, 3.79, 3.80, and 3.81. Compounds (from Table T4) 4.1 , 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, and 4.9.
Compounds (from Table T5) 5.1 , 5.2, 5.3, 5.9, 5.10, 5.1 1 , 5.12, 5.13, 5.14, 5.15, 5.16, 5.17,.19, 5.20, 5.21 , 5.23, 5.24, 5.25, and 5.26.

Claims

CLAIMS:
1. A compound of formula (I):
Figure imgf000159_0001
wherein R\ R2, R3, R4 are independently selected from hydrogen or fluoro and wherein 0, 1 or 2 of R\ R2, R3 and R4 are fluoro;
R5 and R6 are independently selected from hydrogen or methyl;
Z represents Z1, Z2, or Z3, wherein:
Figure imgf000159_0002
(Z1) (Z2) (Z3) wherein, when Z is Z1, Rz is R7, wherein
(i) R7 represents -C(0)N(R7a)(R7b), wherein
R7a is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC2-4alkyl, C2- 3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, hydroxyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl-, C3-scycloalkyl, or C3-5cycloalkylCi-2alkyl, and
R7b is Ci-4alkyl, Ci-4haloalkyl or cyclopropyl, or
R7a and R7b together with the nitrogen atom to which they are bonded , form a cycle selected from azetidinyl, pyrrolidinyl, isoxazolidinyl or oxazolidinyl, or
R7a and R7b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8, wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or
(ii) R7 represents -C(0)N(R7c)(R7d), wherein:
R7c is C3-5alkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyC3-4alkyl, C2- 3alkoxyethyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C4-salkynyl, hydroxyl, aminoCi-4alkyl, N,N-diCi- 2alkylamino, N-formyl-N-Ci-2alkyl-amino, N-Ci-2alkylcarbonyl-N-Ci-2alkylamino, pyrroldin-1 -amino, piperdin-1-amino, morpholin-4-amino, N-Ci-4alkylaminoCi-4alkyl, formyl, C2-salkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy, (Ci-4alkyl)-0-N=C(H)Ci-4alkyl-; or
R7c is C4-6cycloalkyl, C3-6cycloalkylC2alkyl, phenyl, phenylCi-2alkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, heterocyclyl, phenyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 oxo (=0) group, and
R7d is hydrogen; or (iii) R7 represents -C(0)OR7e, wherein:
R7e is n-butyl, iso-butyl, sec-butyl, n-pentyl, 2,2-dimethylpropyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, C2-3alkoxyC2-4alkyl, Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-4haloalkenyl, or C3- 5alkynyl, or
R7e is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroarylCi-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0); or wherein, when Z is Z2 or Z3, Rz is R9, wherein
R9 is hydroxyl, cyano, methyl, difluoromethyl, Ν,Ν-dimethylamino, methoxy, ethoxy, or difluoromethoxy, or
(i) R9 represents -C(0)N(R9a)(R9b), wherein: R9a is hydrogen, d-salkyl, Ci-4haloalkyl, cyanoCi-4alkyl, hydroxyCi-4alkyl, Ci-2alkoxyCi-4alkyl,
Ci-2haloalkoxyCi-4alkyl, C3-salkenyl, C3-salkynyl, aminoCi-4alkyl, amino, N,N-diCi-2alkylamino, N-Ci- 2alkylaminoCi-4alkyl, N,N-diCi-2alkylaminoCi-4alkyl, hydroxyl, Ci-4alkoxy, C3-4alkenyloxy, C3- 4haloalkyloxy, C3-4alkynyloxy, cyclopropylCi-2alkoxy; or R9a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyl, phenyl, heterocyclyl, or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0);
R9b is hydrogen, Ci-4alkyl, Ci-4haloalkyl, cyclopropyl, or R9a and R9b together with the nitrogen atom to which they are bonded, form a 4- to 6-membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR8, or R9a and R9b together with the nitrogen atom to which they are bonded, form a 5- to 8-membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8, wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or
(ii) R9 represents -C(0)OR9c, wherein: R9c is hydrogen, d-salkyl, d-4haloalkyl, cyanod-4alkyl, hydroxyd-4alkyl, d-2alkoxyd-4alkyl,
Ci-2alkoxyCi-2alkoxyCi-4alkyl, d-2haloalkoxyd-4alkyl, d-salkenyl, d-salkynyl, d-4haloalkenyl, N-d- 3alkylaminoCi-4alkyl, N,N-di-d-3alkylaminod-4alkyl; or
R9c is d ecycloalkyl, d-6cycloalkyld-2alkyl, phenyl, phenyld-2alkyl, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the groups consisting of O, S, N or S(0)2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl or heteroaryld-2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the cycloalkyi, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyi or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0); or wherein, when Z is Z1, Z2, or Z3, Rz is R 0, wherein (i) R 0 represents -C(O)C(O)-N(R 0a)(R 0b), wherein
R 0a is hydrogen, d-salkyl, d-4haloalkyl, cyanod-4alkyl, hydroxyd-4alkyl, d-3alkoxyd-4alkyl, Ci-2haloalkoxyCi-4alkyl, d-salkenyl, d-salkynyl, hydroxyl, aminod-4alkyl, N-d-4alkylaminod-4alkyl, N,N-diCi-2alkylamino, pyrroldin-1-amino, piperdin-1-amino, morpholin-4-amino, d-salkoxy, d- 4haloalkyloxy, d-4alkenyloxy, d-4alkynyloxy, cyclopropyld-2alkoxy, (d-4alkyl)-0-N=C(H)d-4alkyl-, or R 0a is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2, or 3 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, wherein the cycloalkyl, phenyl, heterocyclyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, formyl, acyl, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy, or the cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups which are oxo (=0);
R 0b is hydrogen, Ci-4alkyl, Ci-4fluoroalkyl, cyclopropyl, cyclopropylmethyl, or R 0a and R 0b together with the nitrogen atom to which they are bonded , form a 4- to 6- membered monocyclic ring optionally containing an additional heteroatom or group selected from O, S, S(0)2, C(O) and NR8, or
R 0a and R 0b together with the nitrogen atom to which they are bonded , form a 5- to 8- membered spirobicyclic ring system optionally containing an additional heteroatom or group selected from O, C(O), and NR8, wherein R8 is hydrogen, methyl, methoxy, formyl or acyl; or
(ii) R 0 represents -C(O)C(O)-OR 0c, wherein:
R 0c is hydrogen, d-salkyl, Ci-4haloalkyl, C3-salkenyl, C3-salkynyl, or
R 0c is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 ring members independently selected from the group consisting of O, S, N, SO2, with the proviso that the heterocycle cannot contain 2 contiguous atoms selected from O and S, or heteroaryl wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, or
(iii) R 0 represents -C(O)C(O)-R 0d, wherein R 0d is hydrogen, d-salkyl, or cyclopropyl; or a salt or an N-oxide thereof.
2. A compound according to claim 1 , wherein R to R4 are hydrogen; R is fluoro and R2 to R4 are hydrogen; R3 is fluoro and R\ R2 and R4 are hydrogen; or R and R3 are fluoro and R2 and R4 are hydrogen.
3. A compound according to claim 1 or claim 2, wherein R5 and R6 are hydrogen.
4. A compound according to any one of claims 1 to 3, wherein Z is Z .
5. A compound according to claim 4, wherein R7 is -C(0)N(R7a)(R7b) and R7a is C3-salkyl.
6. A compound according to claim 4 or claim 5, wherein R7 is -C(0)N(R7a)(R7b) and R7b is methyl or cyclopropyl.
7. A compound according to claim 4, wherein R7 is -C(0)N(R7c)(R7d) and R7c is C3-salkyl, Ci- 2fluoroalkyl, C3-4alkenyl, C4-salkynyl or C2-4alkoxy.
8. A compound according to claim 4, wherein R7 is -C(0)OR7e and R7e is n-butyl, iso-butyl, sec- butyl, n-pentyl, 2,2-dimethylpropyl, Ci-2fluoroalkyl, C3-4alkenyl or C3-4alkynyl.
9. A compound according to any one of claims 1 to 3, wherein Z is Z2 or Z3.
10. A compound according to claim 9, wherein R9 is -C(0)N(R9a)(R9b), R9a is Ci-5alkyl, Ci- 2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl, Ci-2fluoroalkoxyCi-2alkyl, C3-4alkenyl, C3-4alkynyl, hydroxyl or Ci-2alkoxy, and R9b is hydrogen, methyl or cyclopropyl.
11. A compound according to claim 9, wherein R9 is -C(0)OR9c, and R9c is d-salkyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyC2alkyl, C3-4alkenyl or C3-4alkynyl.
12. An agrochemical composition comprising a fungicidally effective amount of a compound of Formula (I) according to any one of claims 1 to 11.
13. The composition according to claim 12, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of Formula (I) according to any of claims 1 to 1 1 , or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
15. Use of a compound of Formula (I) according to any one of claims 1 to 1 1 as a fungicide.
PCT/EP2018/068688 2017-07-11 2018-07-10 Microbiocidal oxadiazole derivatives WO2019011926A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020016180A1 (en) * 2018-07-16 2020-01-23 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2021033133A1 (en) 2019-08-19 2021-02-25 Pi Industries Ltd. Novel oxadiazole compounds containing 5- membered heteroaromatic ring for controlling or preventing phytopathogenic fungi

Citations (82)

* 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 (en) 1988-09-02 1990-03-07 Sankyo Company Limited 13-Substituted milbemycin derivatives, their preparation and use
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0382173A2 (en) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. PF 1022 substance, method of producing same and anthelmintic composition containing same
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0444964A1 (en) 1990-03-01 1991-09-04 Sankyo Company Limited Milbemycin ether derivatives, their preparation and their anthelmintic uses
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0503538A1 (en) 1991-03-08 1992-09-16 Meiji Seika Kaisha Ltd. Medicinal composition containing an anthelmintic cyclic depsipeptide
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1993019053A1 (en) 1992-03-17 1993-09-30 Fujisawa Pharmaceutical Co., Ltd. Depsipeptide derivative, production thereof and use thereof
WO1993025543A2 (en) 1992-06-11 1993-12-23 Bayer Aktiengesellschaft Enniatines and enniatine derivates used to control endoparasites
EP0594291A1 (en) 1992-09-01 1994-04-27 Sankyo Company Limited Novel processes for the production of 13-ether derivatives of milbemycins, and novel intermediates therefor
WO1994015944A1 (en) 1993-01-18 1994-07-21 Pfizer Limited New antiparasitic agents related to the milbemycins and avermectins
WO1994019334A1 (en) 1993-02-19 1994-09-01 Meiji Seika Kaisha, Ltd. Pf1022 derivative, cyclic depsipeptide
EP0626375A1 (en) 1993-05-26 1994-11-30 Bayer Ag Octacyclodepsipeptides having endoparasiticidal activity
WO1995019363A1 (en) 1994-01-14 1995-07-20 Pfizer Inc. Antiparasitic pyrrolobenzoxazine compounds
WO1995022552A1 (en) 1994-02-16 1995-08-24 Pfizer Limited Antiparasitic agents
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
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 (en) 1994-10-18 1996-04-25 Bayer Aktiengesellschaft Cyclic depsipeptide sulfonylation, sulfenylation and phosphorylation process
WO1996015121A1 (en) 1994-11-10 1996-05-23 Bayer Aktiengesellschaft Use of dioxomorpholines to combat endoparasites, novel dioxomorpholines and process for their production
DE19520936A1 (en) 1995-06-08 1996-12-12 Bayer Ag Ectoparasiticides means
WO1997033890A1 (en) 1996-03-11 1997-09-18 Novartis Ag Pyrimidin-4-one derivatives as pesticide
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003028729A2 (en) 2001-10-03 2003-04-10 Pharmacia Corporation Prodrugs of substituted polycyclic compounds useful for selective inhibition of the coagulation cascade
WO2003035617A2 (en) 2001-10-23 2003-05-01 Dow Agrosciences Llc Patent Department Derivatives of uk-2a
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2004072086A2 (en) 2003-02-14 2004-08-26 Pfizer Limited Antiparasitic terpene alkaloids
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2005070917A1 (en) 2004-01-23 2005-08-04 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
WO2005121104A1 (en) 2004-06-09 2005-12-22 Sumitomo Chemical Company, Limited Pyridazine compound and use thereof
WO2006087343A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Pyrazole carboxylic acid anilides, method for the production thereof and agents containing them for controlling pathogenic fungi
WO2007031513A1 (en) 2005-09-13 2007-03-22 Bayer Cropscience Ag Pesticide thiazolyloxy substituted phenylamidine derivatives
WO2007048556A1 (en) 2005-10-25 2007-05-03 Syngenta Participations Ag Heterocyclic amide derivatives useful as microbiocides
WO2007072999A1 (en) 2005-12-22 2007-06-28 Nihon Nohyaku Co., Ltd Pyrazinecarboxamide derivatives and plant disease controlling agents containing the same
US20070155739A1 (en) 2005-12-30 2007-07-05 Alantos Pharmaceuticals, Inc. Substituted bis-amide metalloprotease inhibitors
WO2007129454A1 (en) 2006-05-08 2007-11-15 Kumiai Chemical Industry Co., Ltd. 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent
US20080196127A1 (en) 2005-04-11 2008-08-14 Bayer Bioscience N.V. Elite Event A5547-127 and Methods and Kits For Identifying Such Event in Biological Samples
US20080312082A1 (en) 2006-10-31 2008-12-18 Kinney Anthony J Soybean event dp-305423-1 and compositions and methods for the identification and/or detection thereof
US20080320616A1 (en) 2005-04-08 2008-12-25 Bayer Bioscience N.V. Elite Event A2407-12 and Methods and Kits for Identifying Such Event in Biological Samples
WO2009022746A1 (en) 2007-08-10 2009-02-19 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and pest control agent
US7632985B2 (en) 2005-05-27 2009-12-15 Monsanto Technology Llc Soybean event MON89788 and methods for detection thereof
WO2010000841A1 (en) 2008-07-04 2010-01-07 Bayer Cropscience Sa Fungicide hydroximoyl-tetrazole derivatives
WO2010045251A2 (en) 2008-10-17 2010-04-22 Xenon Pharmaceuticals, Inc. Spiro-oxindole compounds and their use as therapeutic agents
WO2010080829A1 (en) 2009-01-07 2010-07-15 Basf Agrochemical Products B.V. Soybean event 127 and methods related thereto
US20100184079A1 (en) 2006-06-28 2010-07-22 Pioneer Hi-Bred International, Inc. Soybean event 3560.4.3.5 and compositions and methods for the identification and detection thereof
WO2010093059A1 (en) 2009-02-16 2010-08-19 住友化学株式会社 Method for producing phenylacetamide compound
WO2010130767A2 (en) 2009-05-15 2010-11-18 Bayer Cropscience Ag Fungicide pyrazole carboxamides derivatives
WO2010146031A2 (en) 2009-06-16 2010-12-23 Basf Se Fungicidal mixtures
WO2011022469A2 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Aad-1 event das-40278-9, related transgenic corn lines, and event-specific identification thereof
WO2011022470A1 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Control of aad-1 monocot volunteers in fields of dicot crops
WO2011022471A1 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Detection of aad-1 event das-40278-9
US20110067134A1 (en) 2009-09-17 2011-03-17 Brinker Ronald J Soybean transgenic event mon 87708 and methods of use thereof
WO2011081174A1 (en) 2010-01-04 2011-07-07 日本曹達株式会社 Nitrogen-containing heterocyclic compound and agricultural/horticultural germicide
US8049071B2 (en) 2007-11-15 2011-11-01 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event MON87701 and methods for detection thereof
WO2011138281A2 (en) 2010-05-06 2011-11-10 Bayer Cropscience Ag Process for the preparation of dithiine tetracarboxydiimides
WO2011162397A1 (en) 2010-06-24 2011-12-29 Sumitomo Chemical Company, Limited Plant disease control composition and method of controlling plant disease
WO2012020774A1 (en) 2010-08-10 2012-02-16 住友化学株式会社 Plant disease control composition and application for same
WO2012025557A1 (en) 2010-08-25 2012-03-01 Bayer Cropscience Ag Heteroarylpiperidine and -piperazine derivatives as fungicides
WO2012031061A2 (en) 2010-09-01 2012-03-08 E. I. Du Pont De Nemours And Company Fungicidal pyrazoles and their mixtures
WO2012084812A1 (en) 2010-12-20 2012-06-28 Isagro Ricerca S.R.L. Aminoindanes amides having a high fungicidal activity and their phytosanitary compositions
WO2012092115A1 (en) 2010-12-29 2012-07-05 E. I. Du Pont De Nemours And Company Mesoionic pyrido [1,2 -a] pyrimidine pesticides
WO2013024082A1 (en) 2011-08-15 2013-02-21 Basf Se Fungicidal substituted 1-{2-cyclyloxy-2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-ethyl}-1h-[1,2,4]triazole compounds
WO2013066838A1 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013132253A1 (en) 2012-03-07 2013-09-12 Institute Of Cancer Research: Royal Cancer Hospital (The) 3-aryl-5-substituted-isoquinolin-1-one compounds and their therapeutic use
WO2013162072A1 (en) 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Tetrazolinone compounds and its use as pesticides
US8632978B2 (en) 2011-07-26 2014-01-21 Dow Agrosciences, Llc. Soybean event pDAB9582.814.19.1 detection method
WO2014013842A1 (en) 2012-07-20 2014-01-23 住友化学株式会社 Composition for controlling plant disease and application therefor
WO2014020350A1 (en) 2012-08-01 2014-02-06 Proximagen Limited Par2 receptor antagonists
WO2014051165A1 (en) 2012-09-28 2014-04-03 Sumitomo Chemical Company, Limited Tetrazolinone compounds and their use as pesticides
WO2014095675A1 (en) 2012-12-19 2014-06-26 Bayer Cropscience Ag Difluoromethyl-nicotinic-indanyl carboxamides as fungicides
US20140201860A1 (en) 2010-12-15 2014-07-17 Syngenta Participations Ag Soybean event syht0h2 and compositions and methods for detection thereof
WO2014170327A1 (en) 2013-04-19 2014-10-23 Bayer Cropscience Ag Method for combating pests
WO2016139189A1 (en) 2015-03-05 2016-09-09 Bayer Cropscience Aktiengesellschaft Fungicidally active compound combinations
WO2017076740A1 (en) * 2015-11-04 2017-05-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017093348A1 (en) * 2015-12-02 2017-06-08 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017118689A1 (en) * 2016-01-08 2017-07-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives

Patent Citations (82)

* 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 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0357460A2 (en) 1988-09-02 1990-03-07 Sankyo Company Limited 13-Substituted milbemycin derivatives, their preparation and use
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
EP0382173A2 (en) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. PF 1022 substance, method of producing same and anthelmintic composition containing same
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0444964A1 (en) 1990-03-01 1991-09-04 Sankyo Company Limited Milbemycin ether derivatives, their preparation and their anthelmintic uses
EP0503538A1 (en) 1991-03-08 1992-09-16 Meiji Seika Kaisha Ltd. Medicinal composition containing an anthelmintic cyclic depsipeptide
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1993019053A1 (en) 1992-03-17 1993-09-30 Fujisawa Pharmaceutical Co., Ltd. Depsipeptide derivative, production thereof and use thereof
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 (en) 1992-06-11 1993-12-23 Bayer Aktiengesellschaft Enniatines and enniatine derivates used to control endoparasites
EP0594291A1 (en) 1992-09-01 1994-04-27 Sankyo Company Limited Novel processes for the production of 13-ether derivatives of milbemycins, and novel intermediates therefor
WO1994015944A1 (en) 1993-01-18 1994-07-21 Pfizer Limited New antiparasitic agents related to the milbemycins and avermectins
WO1994019334A1 (en) 1993-02-19 1994-09-01 Meiji Seika Kaisha, Ltd. Pf1022 derivative, cyclic depsipeptide
EP0626375A1 (en) 1993-05-26 1994-11-30 Bayer Ag Octacyclodepsipeptides having endoparasiticidal activity
WO1995019363A1 (en) 1994-01-14 1995-07-20 Pfizer Inc. Antiparasitic pyrrolobenzoxazine compounds
WO1995022552A1 (en) 1994-02-16 1995-08-24 Pfizer Limited Antiparasitic agents
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO1996011945A2 (en) 1994-10-18 1996-04-25 Bayer Aktiengesellschaft Cyclic depsipeptide sulfonylation, sulfenylation and phosphorylation process
WO1996015121A1 (en) 1994-11-10 1996-05-23 Bayer Aktiengesellschaft Use of dioxomorpholines to combat endoparasites, novel dioxomorpholines and process for their production
DE19520936A1 (en) 1995-06-08 1996-12-12 Bayer Ag Ectoparasiticides means
WO1997033890A1 (en) 1996-03-11 1997-09-18 Novartis Ag Pyrimidin-4-one derivatives as pesticide
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003028729A2 (en) 2001-10-03 2003-04-10 Pharmacia Corporation Prodrugs of substituted polycyclic compounds useful for selective inhibition of the coagulation cascade
WO2003035617A2 (en) 2001-10-23 2003-05-01 Dow Agrosciences Llc Patent Department Derivatives of uk-2a
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2004072086A2 (en) 2003-02-14 2004-08-26 Pfizer Limited Antiparasitic terpene alkaloids
WO2005070917A1 (en) 2004-01-23 2005-08-04 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
WO2005121104A1 (en) 2004-06-09 2005-12-22 Sumitomo Chemical Company, Limited Pyridazine compound and use thereof
WO2006087343A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Pyrazole carboxylic acid anilides, method for the production thereof and agents containing them for controlling pathogenic fungi
US20080320616A1 (en) 2005-04-08 2008-12-25 Bayer Bioscience N.V. Elite Event A2407-12 and Methods and Kits for Identifying Such Event in Biological Samples
US20080196127A1 (en) 2005-04-11 2008-08-14 Bayer Bioscience N.V. Elite Event A5547-127 and Methods and Kits For Identifying Such Event in Biological Samples
US7632985B2 (en) 2005-05-27 2009-12-15 Monsanto Technology Llc Soybean event MON89788 and methods for detection thereof
WO2007031513A1 (en) 2005-09-13 2007-03-22 Bayer Cropscience Ag Pesticide thiazolyloxy substituted phenylamidine derivatives
WO2007048556A1 (en) 2005-10-25 2007-05-03 Syngenta Participations Ag Heterocyclic amide derivatives useful as microbiocides
WO2007072999A1 (en) 2005-12-22 2007-06-28 Nihon Nohyaku Co., Ltd Pyrazinecarboxamide derivatives and plant disease controlling agents containing the same
US20070155739A1 (en) 2005-12-30 2007-07-05 Alantos Pharmaceuticals, Inc. Substituted bis-amide metalloprotease inhibitors
WO2007129454A1 (en) 2006-05-08 2007-11-15 Kumiai Chemical Industry Co., Ltd. 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent
US20100184079A1 (en) 2006-06-28 2010-07-22 Pioneer Hi-Bred International, Inc. Soybean event 3560.4.3.5 and compositions and methods for the identification and detection thereof
US20080312082A1 (en) 2006-10-31 2008-12-18 Kinney Anthony J Soybean event dp-305423-1 and compositions and methods for the identification and/or detection thereof
WO2009022746A1 (en) 2007-08-10 2009-02-19 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and pest control agent
US8049071B2 (en) 2007-11-15 2011-11-01 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event MON87701 and methods for detection thereof
WO2010000841A1 (en) 2008-07-04 2010-01-07 Bayer Cropscience Sa Fungicide hydroximoyl-tetrazole derivatives
WO2010045251A2 (en) 2008-10-17 2010-04-22 Xenon Pharmaceuticals, Inc. Spiro-oxindole compounds and their use as therapeutic agents
WO2010080829A1 (en) 2009-01-07 2010-07-15 Basf Agrochemical Products B.V. Soybean event 127 and methods related thereto
WO2010093059A1 (en) 2009-02-16 2010-08-19 住友化学株式会社 Method for producing phenylacetamide compound
WO2010130767A2 (en) 2009-05-15 2010-11-18 Bayer Cropscience Ag Fungicide pyrazole carboxamides derivatives
WO2010146031A2 (en) 2009-06-16 2010-12-23 Basf Se Fungicidal mixtures
WO2011022469A2 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Aad-1 event das-40278-9, related transgenic corn lines, and event-specific identification thereof
WO2011022470A1 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Control of aad-1 monocot volunteers in fields of dicot crops
WO2011022471A1 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Detection of aad-1 event das-40278-9
US20110067134A1 (en) 2009-09-17 2011-03-17 Brinker Ronald J Soybean transgenic event mon 87708 and methods of use thereof
WO2011081174A1 (en) 2010-01-04 2011-07-07 日本曹達株式会社 Nitrogen-containing heterocyclic compound and agricultural/horticultural germicide
WO2011138281A2 (en) 2010-05-06 2011-11-10 Bayer Cropscience Ag Process for the preparation of dithiine tetracarboxydiimides
WO2011162397A1 (en) 2010-06-24 2011-12-29 Sumitomo Chemical Company, Limited Plant disease control composition and method of controlling plant disease
WO2012020774A1 (en) 2010-08-10 2012-02-16 住友化学株式会社 Plant disease control composition and application for same
WO2012025557A1 (en) 2010-08-25 2012-03-01 Bayer Cropscience Ag Heteroarylpiperidine and -piperazine derivatives as fungicides
WO2012031061A2 (en) 2010-09-01 2012-03-08 E. I. Du Pont De Nemours And Company Fungicidal pyrazoles and their mixtures
US20140201860A1 (en) 2010-12-15 2014-07-17 Syngenta Participations Ag Soybean event syht0h2 and compositions and methods for detection thereof
WO2012084812A1 (en) 2010-12-20 2012-06-28 Isagro Ricerca S.R.L. Aminoindanes amides having a high fungicidal activity and their phytosanitary compositions
WO2012092115A1 (en) 2010-12-29 2012-07-05 E. I. Du Pont De Nemours And Company Mesoionic pyrido [1,2 -a] pyrimidine pesticides
US8632978B2 (en) 2011-07-26 2014-01-21 Dow Agrosciences, Llc. Soybean event pDAB9582.814.19.1 detection method
WO2013024082A1 (en) 2011-08-15 2013-02-21 Basf Se Fungicidal substituted 1-{2-cyclyloxy-2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-ethyl}-1h-[1,2,4]triazole compounds
WO2013066838A1 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013132253A1 (en) 2012-03-07 2013-09-12 Institute Of Cancer Research: Royal Cancer Hospital (The) 3-aryl-5-substituted-isoquinolin-1-one compounds and their therapeutic use
WO2013162072A1 (en) 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Tetrazolinone compounds and its use as pesticides
WO2014013842A1 (en) 2012-07-20 2014-01-23 住友化学株式会社 Composition for controlling plant disease and application therefor
WO2014020350A1 (en) 2012-08-01 2014-02-06 Proximagen Limited Par2 receptor antagonists
WO2014051165A1 (en) 2012-09-28 2014-04-03 Sumitomo Chemical Company, Limited Tetrazolinone compounds and their use as pesticides
WO2014095675A1 (en) 2012-12-19 2014-06-26 Bayer Cropscience Ag Difluoromethyl-nicotinic-indanyl carboxamides as fungicides
WO2014170327A1 (en) 2013-04-19 2014-10-23 Bayer Cropscience Ag Method for combating pests
WO2016139189A1 (en) 2015-03-05 2016-09-09 Bayer Cropscience Aktiengesellschaft Fungicidally active compound combinations
WO2017076740A1 (en) * 2015-11-04 2017-05-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017093348A1 (en) * 2015-12-02 2017-06-08 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017118689A1 (en) * 2016-01-08 2017-07-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives

Non-Patent Citations (20)

* Cited by examiner, † Cited by third party
Title
"The Pesticide Manual - A World Compendium", THE BRITISH CROP PROTECTION COUNCIL
"The Pesticide Manual", 2009, BRITISH CROP PROTECTION COUNCIL
A. ALBINI; S. PIETRA: "Heterocyclic N-oxides", 1991, CRC PRESS
A. WOOD: "Compendium of Pesticide Common Names"
CRICH, D.; ZOU, Y., J. ORG. CHEM., vol. 70, 2005, pages 3309
GARCIA, M. ET AL., ORG. BIOMOL. CHEM., vol. 11, 2004, pages 1633
KITAMURA, S. ET AL., CHEM. PHARM. BULL., vol. 49, 2001, pages 268
KLOSOWSKI AC ET AL.: "Competitive fitness of Phakopsora pachyrhizi isolates with mutations in the CYP51 and CYTB genes", PHYTOPATHOLOGY, vol. 106, 2016, pages 1278 - 1284
KLOSOWSKI AC ET AL.: "Detection of the F129L mutation in the cytochrome b gene in Phakopsora pachyrhizi", PEST MANAG SCI, vol. 72, 2016, pages 1211 - 1215
KOMPELLA, A. ET AL., BIOORG. MED. CHEM. LETT., vol. 1, 2001, pages 3161
KOMPELLA, A. ET AL., ORG. PROC. RES. DEV., vol. 16, 2012, pages 1794
LANGENBACH C ET AL.: "Fighting Asian Soybean Rust", FRONT PLANT SCIENCE, vol. 7, 2016, pages 797
LIU, H. ET AL., BIOORG. MED. CHEM., vol. 16, 2008, pages 10013
LIU, S. ET AL., SYNTHEIS, vol. 14, 2001, pages 2078
LIU, S. ET AL., SYNTHESIS, vol. 14, 2001, pages 2078
NELSON, T. D ET AL., TETRAHEDRON LETT., vol. 45, 2004, pages 8917
PROC. BCPC, INT. CONGR., vol. 1, 2003, pages 93
SCHMITZ HK ET AL.: "Sensitivity of Phakopsora pachyrhizi towards quinone-outside-inhibitors and demethylation-inhibitors, and corresponding resistance mechanisms", PEST MANAG SCI, vol. 70, 2014, pages 378 - 388
SENTHIL, K. ET AL., PEST. RES. JOURNAL, vol. 21, 2009, pages 133
SIMÕES K ET AL.: "First detection of a SDH variant with reduced SDHI sensitivity in Phakopsora pachyrhizl", J PLANT DIS PROT, vol. 125, 2018, pages 21 - 2

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020016180A1 (en) * 2018-07-16 2020-01-23 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2021033133A1 (en) 2019-08-19 2021-02-25 Pi Industries Ltd. Novel oxadiazole compounds containing 5- membered heteroaromatic ring for controlling or preventing phytopathogenic fungi

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