WO2015162268A1 - Dérivés microbiocides d'imidazole - Google Patents

Dérivés microbiocides d'imidazole Download PDF

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WO2015162268A1
WO2015162268A1 PCT/EP2015/058965 EP2015058965W WO2015162268A1 WO 2015162268 A1 WO2015162268 A1 WO 2015162268A1 EP 2015058965 W EP2015058965 W EP 2015058965W WO 2015162268 A1 WO2015162268 A1 WO 2015162268A1
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substituted
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alkyl
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Pulakesh MAITY
Julien Daniel Henri GAGNEPAIN
Stephane André Marie JEANMART
Clemens Lamberth
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to microbiocidal imidazole derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to preparation of these imidazole derivatives, to imidazole derivatives used as intermediates in the preparation of these imidazole derivatives, to preparation of these intermediates, to agrochemical compositions which comprise at least one of the imidazole derivatives, to preparation of these compositions and to use of the imidazole 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.
  • the present invention provides compounds of formula (I):
  • X and Y are independently O, S or NR 4 ;
  • R 5 is independently hydrogen, halogen, cyano, hydroxyl, amino, nitro, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-C 6 alkylsulfinyl, d- dalkylsulfonyl, d-C 6 alkylcarbonyl, C 2 -dalkenyl, C 2 -C 6 haloalkenyl, d-C 6 alkenyloxy, C 2 - dhaloalkenyloxy, d-C 6 alkynyl, C 2 -dalkynyloxy, d-C 6 cycloalkyl-d-C 6 alkynyl, unsubstituted aryl or aryl substituted by 1 to 3
  • R 6 is independently hydroxyl, amino, nitro, cyano, halogen, d-C 6 alkyl, d-C 6 alkoxy d-C 6 haloalkyl, d- dhaloalkoxy, aryl, aryloxy, or aryld-C 6 alky, in which the alkyl, alkoxy and aryl groups can be substituted by halogen, cyano, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy or a salt or a N-oxide thereof.
  • substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g. one to three substituents. Normally not more than three such optional substituents are present at the same time.
  • substituents are indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio. The same applies for the cycloalkyl, aryl, alkenyl, alkynyl and heteroaryl groups.
  • the number of substituents does not exceed the number of available C-H and N-H bonds, for example in the group Ci-C 8 alkyl substituted by one or more substituents has only one to three substituents if dalkyl thus methyl is meant.
  • halogen refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Alkyl substituents may be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.
  • Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkenyl substituents can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configu ration. Examples are vinyl and allyl.
  • the alkenyl groups are preferably C 2 -C 6 , more preferably C 2 -C 4 and most preferably C 2 -C 3 alkenyl groups.
  • Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl.
  • the alkynyl groups are preferably C 2 -C 6 , more preferably C 2 -C 4 and most preferably C 2 - C 3 alkynyl groups.
  • Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may stand for CH 2 CI, CHCI 2 , CCI 3 , CH 2 F, CHF 2 , CF 3 , CF 3 CH 2 , CH 3 CF 2 , CF 3 CF 2 or CCI 3 CCI 2 .
  • Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2-difluorovinyl or 1 ,2-dichloro-2-fluoro- vinyl.
  • Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above.
  • Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1 -methylethoxy, propoxy, butoxy, 1 -methylpropoxy and 2- methylpropoxy.
  • Haloalkoxy means a radical -OR, where R is haloalkyl, e.g. is described above.
  • Haloalkloxy groups include, but are not limited to, CH 2 CIO, CHCI 2 0, CCI 3 0, CH 2 FO, CHF 2 0-, CF 3 0-, CF 3 CH 2 0-, CH 3 CF 2 0 or CCI 3 CCI 2 0-.
  • Cyano means a -CN group.
  • Amino means an -NH 2 group.
  • Hydroxyl or hydroxy stands for a -OH group.
  • Aryl means a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
  • Preferred optional substituents for aryl are halogen, cyano, hydroxyl, amino, nitro, Ci-C 6 alkyl, d- C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, d- C 6 alkylsulfinyl, Ci-C 6 alkylsulfonyl, Ci-C 6 alkylcarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyl and C 2 -C 6 alkynyloxy.
  • Heteroaryl stands for aromatic heterocyclic ring systems, which can be mono-, bi- or tricyclic and wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member, which can be accompanied by other oxygen, nitrogen, sulphur atoms as ring members.
  • Monocyclic and bicyclic aromatic ring systems are preferred.
  • monocyclic heteroaryl may be a 5- or 6-membered ring containing one to three heteroatoms selected from oxygen, nitrogen and sulfur, more preferably selected from nitrogen and sulfur.
  • Bicyclic heteroaryl may be a 9- or 10-membered bicyclic ring containing one to five heteroatoms, preferably one to three heteroatoms, selected from oxygen, nitrogen and sulfur.
  • heteroaryl examples include furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.
  • Heteroaryl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms.
  • Preferred optional substituents for heteroaryl are halogen, cyano, hydroxyl, amino, nitro, Ci-C 6 alkyl, d- C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, d- C 6 alkylsulfinyl, Ci-C 6 alkylsulfonyl, Ci-C 6 alkylcarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyl and C 2 -C 6 al
  • asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond.
  • 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.
  • 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 a N-oxide or in salt form, e.g. an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • X and Y are independently O, S or NR 5 .
  • X and Y are independently O or S, more preferably S.
  • Z , Z 2 , Z 3 , Z 4 and Z 5 are independently CR 5 or N and that at least two out of Z , Z 2 , Z 3 , Z 4 and Z 5 are N.
  • two or three out of Z , Z 2 , Z 3 , Z 4 and Z 5 are N, more preferably two out of Z , Z 2 , Z 3 , Z 4 and Z 5 are N.
  • the ring formed by Z , Z 2 , Z 3 , Z 4 and Z 5 are selected from pyridazinyl, cinnolinyl, pyrimidinyl, pyrazinyl, triazinyl each of the pyridazinyl, cinnolinyl, pyrimidinyl, pyrazinyl, triazinyl can be substituted by F, CI, Br, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl-C 2 -C 6 alkynyl, unsubstituted phenox or substituted phenoxy substituted by F, CI, unsubstituted phenylthio or substituted phenylthio substituted by F.
  • the ring formed by Z , Z 2 , Z 3 , Z 4 and Z 5 are selected from pyrimidinyl, pyrazinyl each of the from pyrimidinyl, pyrazinyl can be substituted by F, CI, Br, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl- C 2 -C 6 alkynyl, unsubstituted phenoxy or phenoxy substituted by F, CI, unsubstituted phenylthio or substituted phenylthio substituted by F.
  • R , R 2 and R 3 are independently hydrogen, halogen, CrC 6 alkyl, Ci-C 6 haloalkyl, d-C 6 alkoxy or Ci-C 6 haloalkoxy.
  • R , R 2 and R 3 are independently hydrogen, halogen, Ci-C 6 alkyl or Ci-C 6 haloalkyl; more preferably hydrogen or Ci-C 6 alkyl; even more preferably hydrogen or methyl. Most preferably R , R 2 and R 3 are all hydrogen.
  • R 5 is independently hydrogen, halogen, cyano, hydroxyl, amino, nitro, Ci-C 6 alkyl, d- C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, d- C 6 alkylsulfinyl, Ci-C 6 alkylsulfonyl, Ci-C 6 alkylcarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally
  • R 5 is independently hydrogen, halogen, cyano, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 - C 6 cycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryloxy or optionally substituted heteroaryloxy; more preferably hydrogen, halogen, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, optionally substituted aryl or optionally substituted aryloxy; even more preferably hydrogen, halogen, d-C 6 alkyl, d-C 6 haloalkyl or optionally substituted aryloxy.
  • R 6 is independently hydroxyl, amino, nitro, halogen, d-C 6 alkyl, d-C 6 alkoxy, d-
  • R 6 is independently halogen, d-C 6 alkyl, d-C 6 haloalkyl or unsubstituted aryl or substituted aryl which can be substituted by CI or F.
  • the compounds are of formula (I) wherein
  • X and Y are independently O or S;
  • Z , Z 2 , Z 3 , Z 4 and Z 5 are independently CR 5 or N and at least two out of Z Z 2 , Z 3 , Z 4 and Z 5 are N;
  • R , R 2 and R 3 are independently hydrogen, halogen, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy or d- C 6 haloalkoxy;
  • R 5 is independently hydrogen, halogen, cyano, hydroxyl, amino, nitro, d-C 6 alkyl, d-C 6 haloalkyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, d-C 6 alkylthio, d-C 6 alkylsulfinyl, d- C 6 alkylsulfonyl, d-C 6 alkylcarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkenyloxy, C 2 - C 6 haloalkenyloxy, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy C 3 -C 6 cycloalkyl-C 2 -C 6 alkynyl, unsubstituted
  • R 6 is independently hydroxyl, amino, nitro, cyano, halogen, d-C 6 alkyl, d-C 6 alkoxy d-C 6 haloalkyl, d- C 6 haloalkoxy, aryl, aryloxy, or arylCi-C 6 alky, in which the alkyl, alkoxy and aryl groups can be independently substituted by one to three substituents selected from halogen, cyano, Ci-C 6 alkyl, d- C 6 haloalkyl, d-C 6 alkoxy or Ci-C 6 haloalkoxy.
  • the compounds are of formula (I) wherein
  • X and Y are both S;
  • Z Z 2 , Z 3 , Z 4 and Z 5 are independently CR 5 or N with the proviso, that at least two out of Z Z 2 , Z 3 , Z 4 and Z 5 are N;
  • R , R 2 and R 3 are independently hydrogen, Ci-C 6 alkyl, d-C 6 alkoxy or C 3 -C 6 cycloalkyl;
  • R 5 is hydrogen, halogen, cyano, hydroxyl, amino, nitro, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, d-C 6 alkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, Ci-C 6 alkylcarbonyl, d-C 6 alkenyl, d-C 6 haloalkenyl, C 2 -dalkenyloxy, d-C 6 haloalkenyloxy, C 2 - dalkynyl, d-C 6 alkynyloxy, C 3 -dcycloalkyl-C 2 -dalkynyl, unsubstituted aryl or aryl substituted by 1 to
  • R 6 is is hydroxyl, amino, nitro, cyano, halogen, d-C 6 alkyl, d-C 6 alkoxy d-C 6 haloalkyl, d- dhaloalkoxy, aryl, aryloxy, or aryld-C 6 alky, in which the alkyl, alkoxy and aryl groups can be independently substituted by one to three substituents selected from halogen, cyano, d-C 6 alkyl, d- Cehaloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy.
  • the compounds are of formula (I) wherein
  • X and Y are both S;
  • Z Z 2 , Z 3 , Z 4 and Z 5 are independently CR 5 or N with the proviso, that at least two out of Z Z 2 , Z 3 , Z 4 and Z 5 are N;
  • R , R 2 and R 3 are independently hydrogen or d-C 6 alkyl
  • R 5 is hydrogen, halogen, cyano, hydroxyl, amino, nitro, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl, C 3 - dhalocycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, d-C 6 alkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, Ci-C 6 alkylcarbonyl, d-C 6 alkenyl, C 2 -dhaloalkenyl, d-C 6 alkenyloxy, d-C 6 haloalkenyloxy, C 2 - dalkynyl, C 2 -dalkynyloxy, d-C 6 cycloalkyl-d-C 6 alkynyl, unsubstituted aryl or aryl substituted by 1 to 3
  • R 6 is is hydroxyl, amino, nitro, cyano, halogen, d-C 6 alkyl, d-C 6 alkoxy d-C 6 haloalkyl, d- dhaloalkoxy, aryl, aryloxy, or aryld-C 6 alky, in which the alkyl, alkoxy and aryl groups can be independently substituted by one to three substituents selected from halogen, cyano, d-C 6 alkyl, d- dhaloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy.
  • substituents selected from halogen, cyano, d-C 6 alkyl, d- dhaloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy.
  • X and Y are independently O or S;
  • Z , Z 2 , Z 3 , Z 4 and Z 5 are independently CR 5 or N with the proviso, that two or three out of Z , Z 2 , Z 3 , Z 4 and Z 5 are N;
  • R , R 2 and R 3 each hydrogen
  • R 5 is hydrogen, halogen, cyano, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy, d- C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C3-C 6 cycloalkyl-C 2 -C 6 alkynyl, unsubstituted aryl or aryl substituted by 1 to 3 substituents R 6 , unsubstituted heteroaryl or heteroaryl substituted by 1 to 3 substituents R 6 , unsubstituted aryloxy or aryloxy substituted by 1 to 3 substituents R 6 , unsubstituted phenylthio or phenylthio substituted by 1 to 3 substituents R 6 , unsubstituted heteroaryloxy or heteroaryloxy substituted by 1 to 3 substituents R 6 , un
  • R 6 is independently hydroxyl, amino, nitro, cyano, halogen, Ci-C 6 alkyl, d-C 6 alkoxy Ci-C 6 haloalkyl, d- C 6 haloalkoxy, aryl, aryloxy, or arylCi-C 6 alky, in which the alkyl, alkoxy and aryl groups can be independently substituted by one to three substituents selected from halogen, cyano, Ci-C 6 alkyl, d- Cehaloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy.
  • the compounds are of formula (I) wherein
  • X and Y are both S;
  • Z Z 2 , Z 3 , Z 4 and Z 5 are independently CR 5 or N with the proviso, that two or three out of Z Z 2 , Z 3 , Z 4 and Z 5 are N;
  • R , R 2 and R 3 are all hydrogen
  • R 5 is F, CI, Br, d-C 6 haloalkyl, d-C 6 cycloalkyl-d-C 6 alkynyl, unsubstituted phenoxy or substituted phenoxy substituted by F, CI, unsubstituted phenylthio or substituted phenylthio substituted by F, CI.
  • X and Y are both S;
  • the ring framed by Z Z 2 , Z 3 , Z 4 and Z 5 is selected from pyridazinyl, cinnolinyl, pyrimidinyl, pyrazinyl, triazinyl each of them can be substituted by hydrogen, halogen, cyano, d-C 6 alkyl, d-C 6 haloalkyl, C 3 - C 6 cycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C3-C 6 cycloalkyl-C 2 -C 6 alkynyl, unsubstituted aryl or aryl substituted by 1 to 3 substituents R 6 , unsubstituted heteroaryl or heteroaryl substituted by 1 to 3 substituents R 6 , unsubstituted aryloxy or aryloxy substituted by 1 to 3 substituent
  • R 6 is is hydroxyl, amino, nitro, cyano, halogen, d-C 6 alkyl, d-C 6 alkoxy d-C 6 haloalkyl, d- C 6 haloalkoxy, aryl, aryloxy, or arylCi-C 6 alky, in which the alkyl, alkoxy and aryl groups can be independently substituted by one to three substituents selected from halogen, cyano, d-C 6 alkyl, d- C 6 haloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy.
  • X and Y are both S;
  • the ring fromed by Z , Z 2 , Z 3 , Z 4 and Z 5 is selected from pyridazinyl, cinnolinyl, pyrimidinyl, pyrazinyl, triazinyl each of them can be substituted by F, CI, Br, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl-C 2 -C 6 alkynyl, unsubstituted phenoxy or substituted phenoxy substituted by F, CI, unsubstituted phenylthio or substituted phenylthio substituted by F, CI;
  • R , R 2 and R 3 are each is hydrogen.
  • X and Y are both S;
  • the ring fromed by Z , Z 2 , Z 3 , Z 4 and Z 5 is selected from pyrimidinyl, pyrazinyl, each of can be substituted by F, CI, Br, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl-C 2 -C 6 alkynyl, unsubstituted phenoxy or substituted phenoxy substituted by F, CI, unsubstituted phenylthio or substituted phenylthio substituted by F, CI;
  • R , R 2 and R 3 are all hydrogen.
  • the invention also relates to compounds of formula (1-1 ):
  • Z , Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 have the definitions as described for formula (I).
  • Preferred definitions of Z , Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I).
  • the invention also relates to compounds of formula (I-2):
  • X, Y, Z , Z 2 , Z 3 , Z 4 and Z 5 have the definition as described for formula (I).
  • Preferred definitions of X, Y, Z Z 2 , Z 3 , Z 4 and Z 5 are as defined for formula (I).
  • the invention also relates to compounds of formula (I-3):
  • X, Y, R , R 2 and R 3 are as defined for formula (I).
  • the compounds of the present invention are selected from the formula (l.b), (l.c), (l.d), (l.e), (l.f), (l.g), (l.h), (l.i), (l.j), (l.k), (l.m), (l.n), (l.o), (l.p), (l.q), (l.r), (l.s), (l.t), (l.u), (l.v), (l.w), (l.x), (l.y), (l.z), (l.aa), (l.ab), (l.ac), (l.ad), (l.ae), (l.af), (Lag), (l.ah), (Lai), (l.aj), (l.ak), (Lam), (l.an), (l.ao), (Lap), (l.aq), (l.ar), (
  • the compounds of the present invention are selected from the formula (l.k), (l.r), (l.v), (l.aa), (l.ae), (l.ao), and (l.bb) wherein X and Y are both S and R , R 2 and R 4 are independently hydrogen or methyl more preferably R , R 2 and R 4 are each hydrogen.
  • embodiment E-I.a is represented by the compounds of formula (La)
  • Embodiments E-I.b to E-I.ba are defined accordingly and the substituents X, Y, R , R 2 and R 3 have the meanings as definded above or one of the meanings 1 to 28 given in the corresponding Table 1.
  • the invention further relates to a process for the preparation of a compound of formula (I) and to compounds obtainable by this process
  • the reaction is carried out in a polar aprotic solvent, preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).
  • the invention further relates to a process for the preparation of a compound of formula (I) and to compounds obtainable by this process
  • R 7 is a sulfonyl group, and Hal is halogen.
  • the base is sodium hydroxide or potassium hydroxide.
  • R 7 is sodium hydroxide or potassium hydroxide.
  • the reaction is carried out in a polar aprotic solvent, preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).
  • a polar aprotic solvent preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).
  • the compounds of formula (I), wherein X, Y, Z , Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I), can be obtained by transformation of imidazol-1 -yl-acetonitrile (II), a compound of formula (I II), wherein Z , Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I) and Hal is halogen, and a compound of formula (IV), wherein X and Y are as defined for formula (I), with a base, such as sodium hydroxide or potassium hydroxide. This is shown in Scheme 1 .
  • the compounds of formula (I II), wherein Z Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I) and Hal is halogen can be obtained by transformation of a compound of formula (V), wherein Z Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I) and Hal is halogen, with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide. This is shown in Scheme 2.
  • the compounds of formula (I II), wherein Z Z 2 , Z 3 , Z 4 , Z 5 , R and R 2 are as defined for formula (I) and Hal is halogen can be obtained by transformation of a compound of formula (VI), wherein, Z Z 2 , Z 3 , Z 4 , Z 5 , R and R 2 are as defined for formula (I), with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide. This is shown in Scheme 3.
  • a halogenation reagent such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • the compounds of formula (VII), wherein Z , Z 2 , Z 3 , Z 4 , Z 5 , R and R 2 are as defined for formula (I) and Hal is halogen, can be obtained by transformation of a compound of formula (VIII), wherein Z , Z 2 , Z 3 , Z 4 , Z 5 , R and R 2 are as defined for formula (I), with a halogenation reagent, such as chlorine or bromine. This is shown in Scheme 5.
  • the compounds of formula (V), wherein Z Z 2 , Z 3 , Z 4 , Z 5 , R and R 2 are as defined for formula (I), R 3 is hydrogen and Hal is halogen can be obtained by transformation of a compound of formula (IX), wherein Z Z 2 , Z 3 , Z 4 and Z 5 are as defined for formula (I), with a compound of formula (X), wherein R and R 2 are as defined for formula (I) and Hal is halogen, preferably chloro or bromo, and a base. This is shown in Scheme 6.
  • the compounds of formula (I), wherein X, Y, Z Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I) can be obtained by transformation of imidazol-1-yl-acetonitrile (II), a compound of formula (XI), wherein X, Y, Z Z 2 , Z 3 , Z 4 , Z 5 , R 1 , R 2 and R 3 are as defined for formula (I), R 6 is a sulfonyl group, such as methylsulfonyl or p-tolylsulfonyl, and Hal is halogen, and a compound of formula (IV), wherein X and Y are as defined for formula (I), with a base, such as sodium hydroxide or potassium hydroxide.
  • a base such as sodium hydroxide or potassium hydroxide.
  • the compounds of formula (XI), wherein Z Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I), R 7 is a sulfonyl group, such as methylsulfonyl or p-tosylsulfonyl, and Hal is halogen, can be obtained by transformation of a compound of formula (V), wherein Z Z 2 , Z 3 , Z 4 , Z 5 , R , R 2 and R 3 are as defined for formula (I) and Hal is halogen, with a sulfonyl halide, such as mesyl chloride or tosyl chloride. This is shown in Scheme 8.
  • Embodiments E-I.b to E-I.bb are defined accordingly and the substituents X, Y, R , R 2 and R 4 have the meanings as definded above or one of the meanings 1 to 28 given in the corresponding Table 1.
  • the invention further relates to a process for the preparation of a compound of formula (I) and to compounds obtainable by this process
  • a base wherein X, Y, R , R 2 , R 3 and R 4 are as defined as in any of the claims 1 to 7 and Hal is halogen.
  • the base is sodium hydroxide or potassium hydroxide.
  • the reaction is carried out in a polar aprotic solvent, preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).
  • the invention further relates to a process for the preparation of a compound of formula (I) and to compounds obtainable by this process
  • R 7 is a sulfonyl group, and Hal is halogen.
  • the base is sodium hydroxide or potassium hydroxide.
  • R 7 is sodium hydroxide or potassium hydroxide.
  • the reaction is carried out in a polar aprotic solvent, preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).
  • a polar aprotic solvent preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).
  • the compounds of formula (I), wherein X, Y, R , R 2 , R 3 and R 4 are as defined for formula (I), can be obtained by transformation of imidazol-1-yl-acetonitrile (II), a compound of formula (III), wherein R , R 2 , R 3 and R 4 are as defined for formula (I) and Hal is halogen, and a compound of formula (IV), wherein X and Y are as defined for formula (I), with a base, such as sodium hydroxide or potassium hydroxide.
  • a base such as sodium hydroxide or potassium hydroxide
  • the compounds of formula (III), wherein R , R 2 , R 3 and R 4 are as defined for formula (I) and Hal is halogen can be obtained by transformation of a compound of formula (V), wherein R , R 2 , R 3 and R 4 are as defined for formula (I) and Hal is halogen, with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide. This is shown in Scheme 2.
  • a halogenation reagent such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • the compounds of formula (III), wherein R , R 2 , R 3 and R 4 are as defined for formula (I) and Hal is halogen can be obtained by transformation of a compound of formula (VI), wherein R , R 2 , R 3 and R 4 are as defined for formula (I), with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide. This is shown in Scheme 3.
  • a halogenation reagent such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide.
  • the compounds of formula (V), wherein R , R 2 and R 3 are as defined for formula (I), R 4 is hydrogen and Hal is halogen can be obtained by transformation of a compound of formula (IX), wherein R 3 is as defined for formula (I), with a compound of formula (X), wherein R and R 2 are as defined for formula (I) and Hal is halogen, preferably chloro or bromo, and a base. This is shown in Scheme 6.
  • the compounds of formula (I), wherein X, Y, R , R 2 , R 3 and R 4 are as defined for formula (I) can be obtained by transformation of imidazol-1-yl-acetonitrile (II), a compound of formula (XI), wherein R , R 2 , R 3 and R 4 are as defined for formula (I), R 6 is a sulfonyl group, such as methylsulfonyl or p-tolylsulfonyl, and Hal is halogen, and a compound of formula (IV), wherein X and Y are as defined for formula (I), with a base, such as sodium hydroxide or potassium hydroxide.
  • a base such as sodium hydroxide or potassium hydroxide.
  • the compounds of formula (XI), wherein R , R 2 , R 3 and R 4 are as defined for formula (I), R 7 is a sulfonyl group, such as methylsulfonyl or p-tosylsulfonyl, and Hal is halogen, can be obtained by transformation of a compound of formula (V), wherein R , R 2 , R 3 and R 4 are as defined for formula (I) and Hal is halogen, with a sulfonyl halide, such as mesyl chloride or tosyl chloride. This is shown in Scheme 8.
  • the compounds of formula (I) of this invention are useful as plant disease control agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.
  • Compounds of formula (I) and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete,
  • pathogens may include:
  • Oomycetes including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Br
  • Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva,
  • Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva,
  • Ophiobolus graminis Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium
  • Mycosphaerella fijiensis Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp.
  • Valsa ceratosperma and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp.
  • Phyllactinia guttata and Oidium arachidis molds for example those caused by Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola,
  • Macrophomina phaseolina Phyllosticta cucurbitacearum
  • anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola
  • wilts or blights for example those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae,
  • Gliocladium spp. Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae.
  • Basidiomycetes including smuts for example those caused by Ustilaginales such as
  • Ustilaginoidea virens Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,
  • Pucciniastrum coryli or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi- viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Ent
  • Blastocladiomycetes such as Physoderma maydis.
  • Mucoromycetes such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus,
  • the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
  • Compounds of formula (I) may be mixed with one or more of compounds selected from those in the following chemical or functional classes:- 1 ,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines, aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides, anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones, benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles, benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles, benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids, chloronitriles, cinnamic acid amides, copper containing compounds, cyanoacetamideoximes, cyanoacrylates,
  • cyanoimidazoles cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides, dicarboximides, dimethylsulphamates, dinitrophenol carbonates, dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiino compounds, dithiocarbamates, dithioethers, dithiolanes, ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furan carboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles, guanidines, herbicides/plant growth regulatosr, hexopyranosyl antibiotics, hydroxy(2- amino)pyrimidines, hydroxyanilides, hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growth regulators, isobenzofuranones, isoxazolidiny
  • phosphorothioates pyridyl carboxamides, pyridyl furfuryl ethers, pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.
  • fungicidal combinations include the following where "I” designates compounds of formula (I): I + (.+/-.)-cis-1-(4-chlorophenyl)-2-(1 H-1 ,2,4-triazol-1-yl)-cycloheptanol (huanjunzuo), I + (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonil), I + (E)-N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, (mandestrobin), I + 1 -(5-bromo- 2-pyridyl)-2-(2,4-difluorophenyl)-1 , 1-difluoro-3-(1 ,2,4-triazol-1-yl)propan-2-ol, I + 1- methylcyclopropene, I + 2-methyl-, [[4-methoxy-2-[
  • coumoxystrobin I + cresol, I + cuprous oxide, I + cyazofamid, I + cyclafuramid, I + cymoxanil, I + cyproconazole, I + cyprodinil, I + daracide, I + dichlofluanid, I + dichlorophen (dichlorophene), I + dichlorprop, I + diclomezine, I + dicloran, I + diethofencarb, I + difenoconazole, I + difenzoquat, I + diflumetorim, I + dimetachlone (dimethaclone), I + dimetconazole, I + dimethipin, I + dimethirimol, I + dimethomorph, I + dimoxystrobin, I + dingjunezuo (Jun Si Qi), I + diniconazole, I + diniconazole- M, I + , I + dinobuton, I +
  • fluoxastrobin I + fluquinconazole, I + flusilazole, I + flusulfamide, I + flutianil, I + flutolanil, I + flutriafol, I + fluxapyroxad, l + folpet, I + forchlorfenuron, I + fosetyl, I + fuberidazole, l + furalaxyl, I + furametpyr, I + gibberellic acid, I + gibberellins, I + guazatine, I + hexachlorobenzene, I + hexaconazole, I + hymexazol, I + hymexazole, hydroxyisoxazole I + imazalil, I + I + etridiazole, I + imazalil, I + imazalil sulphate, I + imibenconazole, I + iminoctadine, I + iminoctadine triacetate, I +
  • prohexadione-calcium I + propamidine, I + propamocarb, I + propiconazole, I + propineb, I + propionic acid, I + proquinazid, I + prothioconazole, I + pyraclostrobin, I + pyrametostrobin, l + pyraoxystrobin, I + pyrazophos, I + pyribencarb (KIF-7767), I + pyrifenox, I + pyrimethanil, I + pyriofenone (IKF-309), I + pyroquilon, I + quinoxyfen, I + quintozene, I + sedaxane, I + silthiofam, I + simeconazole, I + spiroxamine, I + streptomycin, I + sulphur, I + tebuconazole, I + tebufloquin, I + tecloftalam, I + tecn
  • Compounds of this invention can also be mixed with one or more further pesticides including insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants,
  • Insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap,
  • chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucyth
  • methamidophos methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulprofos, t
  • Bactericides such as streptomycin
  • Acaricides such as amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and
  • Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compounds may also be applied to seeds to protect the seeds and seedlings developing from the seeds.
  • the compounds may also be applied through irrigation water to treat plants.
  • the present invention envisages application of the compounds of the invention to plant propagation material prior to, during, or after planting, or any combination of these.
  • seed in a sufficiently durable state to incurr no damage during the treatment process.
  • seed would have been harvested from the field; removed from the plant; and separated from any cob, stalk, outer husk, and surrounding pulp or other non-seed plant material. Seed would preferably also be biologically stable to the extent that treatment would not cause biological damage to the seed. It is believed that treatment can be applied to seed at any time between seed harvest and sowing of seed including during the sowing process.
  • Methods for applying or treating active ingredients on to plant propagation material or to the locus of planting include dressing, coating, pelleting and soaking as well as nursery tray application, in furrow application, soil drenching, soil injection, drip irrigation, application through sprinklers or central pivot, or incorporation into soil (broad cast or in band).
  • active ingredients may be applied on a suitable substrate sown together with the plant propagation material.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 10g per kilogram of seed.
  • Crops of useful plants in which the composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), mille
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors.
  • herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors.
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola.
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
  • Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi. An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
  • VipCot® Surgera Seeds
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the
  • microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane,
  • perchloroethylene perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.
  • alcohols of higher molecular weight such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol est
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C 8 -C 2 2 fatty acids, especially the methyl derivatives of Ci 2 -Ci 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates are:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • rface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 95 %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether - 2 % -
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • 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)
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • 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 or 0.8 ppm.
  • Example 1 This example illustrates the preparation of (2E)-2-[4-(3-bromopyrazin-2-yl)-1 ,3-dithiolan-2- ylidene]-2-imidazol-1-yl-acetonitrile (Compound l.ao.25) a) Preparation of 2-bromo-1-(3-bromopyrazin-2-yl)ethanone
  • Methanesulfonyl chloride (128 ⁇ L ⁇ , 1.63 mmol) is added at 0 ° C to a solution of 2-bromo- 1 -(3- bromopyrazin-2-yl)ethanol (461 mg, 1.63 mmol) and triethylamine (0.25 mL, 1.8 mmol) in ethyl acetate (3 mL).
  • the resulting white suspension is stirred at 0 ° C for 30 minutes and is filtered.
  • the filtrate is diluted with H 2 0 (10 mL) and the biphasic mixture is decanted.
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is: (ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 ⁇ particle size (3 micrometer particle size), 1 10 Angstrom, 30 x 3 mm column, 1.7mL/min., 60 °C, H 2 0 + 0.05% HCOOH (95%) / CH 3 CN/MeOH 4:1 + 0.04% HCOOH (5%) - 2 min. - CH 3 CN/MeOH 4:1 + 0.04% HCOOH (5%) - 0.8 min., ACQUITY SQD Mass Spectrometer from Waters, ionization method:
  • EI electrospray
  • Polarity positive ions
  • Capillary (kV) 3.00 Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60,
  • Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf disks are incubated at 23 °C / 21°C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.
  • DMSO fetal sulfate
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • Gaeumannomyces graminis I liquid culture (Take-all of cereals)
  • Mycelial fragments of the fungus from cryogenic storage were 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 iss added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (Anthracnose)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Mycosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segmens are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).
  • Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth

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

Abstract

L'invention concerne des composés de formule (I), dans laquelle X et Y représentent, indépendamment, O, S ou NR4 ; Z1, Z2, Z3, Z4 et Z5 représentent, indépendamment, CR5 ou N ; éventuellement, Z1 et Z2, Z2 et Z3, Z3 et Z4 ou Z4 et Z5 peuvent également appartenir à un deuxième cycle annelé, saturé, partiellement insaturé ou aromatique, isocyclique ou hétérocyclique pour former un système de cycle bicyclique, à condition qu'au moins deux parmi Z1, Z2, Z3, Z4 et Z5 représentent N ; R1, R2 et R3 représentent, indépendamment, hydrogène, halogène, C1-C6 alkyle, C1-C6-halogénoalkyle, C1-C6-alcoxy ou C1-C6-halogénoalcoxy ; R5 représente hydrogène, halogène, cyano, hydroxyle, amino, nitro, C1-C6-alkyle, C1-C6-halogénoalkyle, C3-C6-cycloalkyle, C3-C6-halogénocycloalkyle, C1-C6-alcoxy, C1-C6-halogénoalcoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyle, C1-C6-alkylsulfonyle, C1-C6-alkylcarbonyle, C2-C6-alcényle, C2-C6-halogénoalcényle, C2-C6-alcényloxy, C2-C6-halogénoalcényloxy, C2-C6-alcynyle, C2-C6-alcynyloxy, C3-C6-cycloalkyl-C2-C6-alcynyle, aryle non substitué ou aryle substitué par 1 à 3 substituants R6, hétéroaryle non substitué ou hétéroaryle substitué, aryloxy non substitué ou aryloxy substitué, phénylthio non substitué ou phénylthio substitué, hétéroaryloxy non substitué ou hétéroaryloxy substitué, aryl-C1-C6-alkyle non substitué ou hétéroaryl-C1-C6-alkyle substitué, qui sont utiles en tant que pesticides, en particulier en tant que fongicide.
PCT/EP2015/058965 2014-04-25 2015-04-24 Dérivés microbiocides d'imidazole WO2015162268A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018167677A1 (fr) 2017-03-15 2018-09-20 Oat & Iil India Laboratories Private Limited Nouveau composé dithiolane, un sel ou un n-oxyde et utilisation associée
WO2019150311A1 (fr) * 2018-02-02 2019-08-08 Pi Industries Ltd. Composés de dithiol 1-3 et leur utilisation pour la protection de cultures contre des micro-organismes phytopathogènes
CN110468057A (zh) * 2019-09-02 2019-11-19 昆明理工大学 一株植物内生盘双端毛孢属真菌m7sb 41及其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218736A1 (fr) * 1985-10-10 1987-04-22 Nihon Nohyaku Co., Ltd. Dérivé de cétène-S,S-acétal, procédé pour sa préparation et méthode pour guérir la mycose utilisant ce dérivé
US4738976A (en) * 1985-10-10 1988-04-19 Nihon Nohyaku Co., Ltd. Antimycotic agent and fungicidal agent
WO2015003991A1 (fr) * 2013-07-12 2015-01-15 Syngenta Participations Ag Nouveaux microbiocides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218736A1 (fr) * 1985-10-10 1987-04-22 Nihon Nohyaku Co., Ltd. Dérivé de cétène-S,S-acétal, procédé pour sa préparation et méthode pour guérir la mycose utilisant ce dérivé
US4738976A (en) * 1985-10-10 1988-04-19 Nihon Nohyaku Co., Ltd. Antimycotic agent and fungicidal agent
WO2015003991A1 (fr) * 2013-07-12 2015-01-15 Syngenta Participations Ag Nouveaux microbiocides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018167677A1 (fr) 2017-03-15 2018-09-20 Oat & Iil India Laboratories Private Limited Nouveau composé dithiolane, un sel ou un n-oxyde et utilisation associée
WO2019150311A1 (fr) * 2018-02-02 2019-08-08 Pi Industries Ltd. Composés de dithiol 1-3 et leur utilisation pour la protection de cultures contre des micro-organismes phytopathogènes
CN110468057A (zh) * 2019-09-02 2019-11-19 昆明理工大学 一株植物内生盘双端毛孢属真菌m7sb 41及其应用
CN110468057B (zh) * 2019-09-02 2021-09-24 昆明理工大学 一株植物内生盘双端毛孢属真菌m7sb 41及其应用

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