WO2007124907A2 - Nouveaux microbiocides - Google Patents

Nouveaux microbiocides Download PDF

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WO2007124907A2
WO2007124907A2 PCT/EP2007/003653 EP2007003653W WO2007124907A2 WO 2007124907 A2 WO2007124907 A2 WO 2007124907A2 EP 2007003653 W EP2007003653 W EP 2007003653W WO 2007124907 A2 WO2007124907 A2 WO 2007124907A2
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hydrogen
alkyl
halo
together form
formula
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PCT/EP2007/003653
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WO2007124907A3 (fr
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Hans Tobler
Camilla Corsi
Josef Ehrenfreund
Harald Walter
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • the present invention relates to novel tricyclic amine derivatives which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to the preparation of these compounds, to novel intermediates used in their preparation, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the agrochemical compositions and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, especially fungi.
  • the preparation and microbiocidal use of certain tricyclic amine derivatives are described in WO 04/35589.
  • the present invention is concerned with the provision of alternative tricyclic amine derivatives having microbiocidal activity.
  • the present invention provides a compound of formula (I):
  • Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, the ring being substituted by the groups R 10 , R 1 ' and R 12 ;
  • R 1 is hydrogen, Ci -4 alkyl, Ci -4 haloalkyl, Cj -4 alkoxy, Ci -4 haloalkoxy, CH 2 C ⁇ CR 13 ,
  • R and R are each, independently, hydrogen, halo, Ci -4 alkyl, C) -4 alkoxy, Ci -4 haloalkyl or Ci -4 haloalkoxy;
  • R 4 and R 5 are each, independently, hydrogen, halo or Ci -6 alkyl
  • R 6 and R 7 are each, independently, hydrogen, halo, Ci -6 alkyl, Cj -6 haloalkyl, Cj -4 alkoxy or C i-4 haloalkoxy, or R 6 and R 7 together form a Cj -6 alkylidene group optionally substituted by halo, cyano or nitro, or together form a alkyl group;
  • R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is other than hydrogen, that when R 4 is methyl neither R 6 nor R 7 is methyl and that when R 5 is methyl neither R 8 nor R 9 is methyl;
  • R 10 , R 1 1 and R 12 are each, independently, hydrogen, halo, cyano, nitro, Ci -4 alkyl, Ci -4 haloalkyl, Ci-4 alkoxy(Ci- 4 )alkyl, Ci. 4 haloalkoxy(Ci.
  • R 10 , R 1 ' and R 12 are other than hydrogen
  • R 13 , R 14 and R 15 are each, independently, hydrogen, halo, Ci -4 alkyl, Ci -4 haloalkyl or Ci -4 alkoxy(Ci- 4 )alkyl
  • R 16 is hydrogen, Ci -6 alkyl, C ]-6 haloalky], Ci -4 alkoxy(Ci. 4 )alkyl, Ci -4 alkyl, Ci -4 alkoxy or aryl.
  • Halo either as a lone substituent or in combination with another substituent (e.g. haloalkyl) is generally fluoro, chloro, bromo or iodo, and usually fluoro, chloro or bromo.
  • Each alkyl moiety (or alkyl moiety of alkoxy, alkylthio, etc.) is a straight or branched chain and, depending on whether it contains 1 to 4 or 1 to 6 carbon atoms, is, for example, methyl, ethyl, n-propyl, /z-butyl, ⁇ -pentyl, rc-hexyl, iso-propy ⁇ , sec-butyl, iso-buty ⁇ , tert-buty], neo-penty ⁇ or 1,3-dimethylbutyl, and usually methyl or ethyl.
  • Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1-fluoroethyl, 2- chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, /s ⁇ -propoxy, / ⁇ -butoxy, iso- butoxy, sec-butoxy and tert-bxAoxy, and usually methoxy or ethoxy.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2- difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, /s ⁇ -propylthio, n- butylthio, /s ⁇ -butylthio, sec-butyl thio or terf-butylthio, and usually methylthio or ethylthio.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, /i-propoxyethyl, ⁇ r ⁇ propoxymethy] or /sopropoxyethyl.
  • Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl, but is usually phenyl.
  • the compounds of formula (I) may exist as different geometric or optical isomers or in different tautomeric forms. These may be separated and isolated by well-known (usually chromatographic) techniques, and all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms, such as deuterated compounds, are part of the present invention.
  • R 10 , R 11 and R 12 are each, independently, hydrogen, halo, cyano, nitro, C 1.4 alky], C ⁇ haloalkyl, Ci -4 a]koxy(Ci -4 )alkyl or Ci -4 haloalkoxy(C ]-4 )alkyl, provided that at least one of R 10 , R 11 and R 12 is other than hydrogen.
  • R 1 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above and R 2 and R 3 are each, independently, hydrogen, halo (especially fluoro, chloro or bromo), Ci_ 4 alky] (especially methyl) or C 1 ⁇ alkoxy (especially methoxy).
  • R 2 and R 3 is hydrogen and the other is fluoro, chloro, bromo or methyl (for example, 7-fluoro, 7-chloro, 6-bromo or 7-methyl) or R 2 and R 3 are both hydrogen, both - A -
  • R 2 and R 3 are hydrogen.
  • Het, R 1 , R 2 , R 3 , R 6 , R 7 , R 8 and R 9 are as defined above and R 4 and R 5 are each, independently, hydrogen or Ci -6 alkyl. Usually both are hydrogen or one is Ci -6 alkyl and the other is hydrogen. Typically both R 4 and R 5 are hydrogen.
  • R 6 and R 7 are each, independently, hydrogen, halo or Ci -6 alkyl or R 6 and R 7 together form a C 1-6 alkylidene group optionally substituted by halo, cyano or nitro.
  • R 6 and R 7 are hydrogen or halo, or one is halo or Ci -6 alkyl and the other is hydrogen, or R 6 and R 7 together form a C 1-4 alkylidene group optionally substituted by halo or cyano.
  • the Cj -4 alkylidene group is substituted, typically it is a dihalo-, monohalo- dicyano- or monocyano-methylidene group.
  • R 8 and R 9 are each, independently, hydrogen, halo or Ci -6 alkyl or R 8 and R 9 together form a C 1-6 alkylidene group optionally substituted by halo, cyano or nitro.
  • R 8 and R 9 are hydrogen or halo, or one is halo or C 1 -O alkyl and the other is hydrogen, or R 8 and R 9 together form a Ci -4 alkylidene group optionally substituted by halo or cyano.
  • the Ci -4 alkylidene group is substituted, typically it is a dihalo-, monohalo- dicyano- or monocyano-methylidene group.
  • Het, R 1 , R 2 and R 3 are as defined above and
  • R 6 , R 7 , R 8 and R 9 are all hydrogen and one of R 4 and R 5 is halo or C 1-6 alkyl and the other is hydrogen; or (b) R 4 , R 5 , R 8 and R 9 are all hydrogen and one of R 6 and R 7 is halo, C 1-6 alkyl,
  • R 6 and R 7 or R 8 and R 9 are both halo, they are suitably both fluoro, chloro or bromo, especially both fluoro or chloro.
  • R 1 , R 2 and R 3 are as defined above and one of R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is Cj -6 alkyl and the others are all hydrogen or, either R 6 and R 7 or R 8 and R 9 together form a C )-6 alkylidene group optionally substituted by halo, cyano or nitro, and the others are all hydrogen.
  • R 6 and R 7 or R 8 and R 9 together form an optionally substituted Ci -6 alkylidene group typically they form a dihalo-, monohalo- dicyano- or monocyano-methylidene group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above and Het is pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl, triazolyl, pyridyl, pyrimidinyl, pyridazinyl, 2,3-dihydro-[l,4]oxathiinyl, oxazinyl, thiazinyl or triazinyl, the rings being substituted by at least one of the groups R 10 , R 11 and R 12 as defined above.
  • Het is pyrrolyl (especially pyrrol-3-yl), pyrazolyl (especially pyrazol-4-yl), thiazolyl (especially thiazol-5-yl), oxazolyl (especially oxazol-5-yl), 1,2,3 triazolyl, pyridyl (especially pyrid-3-yl) or 2,3-dihydro-[l,4]oxathiinyl (especially 2,3-dihydro- [l,4]oxathiin-5-yl), typically pyrrol-3-yl, pyrazol-4-yl, thiazol-5-yl or pyrid-3-yl and preferably pyrazol-4-yl.
  • the substiuents of Het are usually hydrogen, fluoro, chloro, bromo, Cj -4 alkyl (especially methyl and ethyl), Ci -4 haloalkyl (especially trifluoromethyl, difluoromethyl, monofluoromethyl and chloro- difluoromethyl) and Ci -4 ) alkoxy(Ci -4 )alkyl (especially methoxymethyl).
  • Het Typical values of Het are the pyrrol-3-yl of the general formula (Het 1 ) and the pyrazol-4-yl of the general formula (Het 2 ):
  • R 10 is Ci -4 alkyl or Ci -4 alkoxy(Ci -4 )alkyl (especially methyl, ethyl or methoxymethyl)
  • R 11 is Ci -4 alkyl or Ci -4 haloalkyl (especially methyl, trifluoromethyl, difluoromethyl, monofluoromethyl or chlorodifluoromethyl)
  • R 12 is hydrogen or halo (especially hydrogen, fluoro or chloro); the thiazol-5-yl and oxazol-5-yl of the general formula (Her 3 ):
  • R 10 is Ci -4 alkyl (especially methyl) and R 11 is Ci -4 alkyl or Ci -4 haloalkyl (especially methyl or trifluoromethyl); the l,2,3-triazol-4-yl of the general formula (Het 4 ):
  • R 10 is Cj. 4 alkyl (especially methyl) and R 11 is Ci -4 haloalkyl (especially trifluoromethyl, difluoromethyl or monfluoromethyl); the pyrid-3-yl of the general formula (Het 5 ):
  • R 10 is halo or C ]-4 haloalkyl (especially chloro, bromo or trifluoromethyl); or the 2,3-dihydro[l,4]oxathiin-5-yl of the general formula (Het 6 ):
  • R 10 is Ci -4 alkyl or Cj -4 haloalkyl (especially methyl or trifluoromethyl).
  • R 2 and R 3 are both hydrogen, halo or methoxy or one of R 2 and R 3 is halo, methyl or methoxy and the other is hydrogen;
  • R 6 , R 7 , R 8 and R 9 are all hydrogen and one of R 4 and R 5 is halo or Ci. 6 alkyl and the other is hydrogen;
  • R 2 and R 3 are both hydrogen, halo or methoxy or one of R and R is halo, methyl or methoxy and the other is hydrogen;
  • R 4 , R 5 , R 8 and R 9 are all hydrogen and one of R 6 and R 7 is halo or Ci -6 alkyl and the other is hydrogen, or both of R 6 and R 7 are halo, or R 6 and R 7 together form a Ci- 4 alkylidene group optionally substituted by halo or cyano; and
  • R 2 and R 3 are both hydrogen, halo or methoxy or one of R 2 and R 3 is halo, methyl or methoxy and the other is hydrogen;
  • R 4 , R 5 , R 6 and R 7 are all hydrogen and one of R 8 and R 9 is halo or C 1-6 alkyl and the other is hydrogen, or both of R 8 and R 9 are halo, or R 8 and R 9 together form a C] -4 alkylidene group optionally substituted by halo or cyano.
  • a compound of the general formula (I) wherein Het is pyrrol-3-yl substituted at the 1-position by C 1-4 alkyl or C 1-4 alkoxy(Ci-4)alkyl (especially methyl, ethyl or methoxymethyl), substituted at the 4-position by C 1-4 alkyl or Ci -4 haloalkyl (especially methyl, difluoromethyl, monofluoromethyl or chloro-difluoromethyl) and optionally substituted at the 2-position by halo (especially fluoro or chloro), pyrazolyl-4-yl substituted at the 1-position by C 1-4 alkyl or C 1-4 alkoxy(Ci -4 )alkyl (especially methyl, ethyl or methoxymethyl), substituted at the 3-position by Ci -4 alkyl or Ci -4 haloalkyl (especially methyl, difluoromethyl, monofluoromethyl or chloro-difluoromethyl) and optional
  • R 2 and R 3 are both hydrogen, halo or methoxy or one of R 2 and R 3 is halo, methyl or methoxy and the other is hydrogen, and
  • R 6 , R 7 , R 8 and R 9 are all hydrogen and one of R 4 and R 5 is halo or Ci_ 6 alkyl and the other is hydrogen; or
  • R 4 , R 5 , R 8 and R 9 are all hydrogen and one of R 6 and R 7 is halo or Ci -6 alkyl and the other is hydrogen, or both of R 6 and R 7 are fluoro or chloro, or R 6 and R 7 together form a C] . 4 alkylidene group optionally substituted by halo or cyano; or
  • R 4 , R 5 , R 6 and R 7 are all hydrogen and one of R 8 and R 9 is halo or Ci -6 alkyl and the other is hydrogen, or both of R 8 and R 9 are fluoro or chloro, or R 8 and R 9 together form a Ci -4 alkylidene group optionally substituted by halo or cyano.
  • Tables 1 to 30 Each of Tables 1 to 30, which follow the Table X below, comprises 206 compounds of the formula (I) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 have the values given in Table X and Het has the value given in the relevant Table 1 to 30.
  • Table 1 corresponds to Table X when X is 1 and Het has the value given under the Table 1 heading
  • Table 2 corresponds to Table X when X is 2 and Het has the value given under the Table 2 heading, and so on for Tables 3 to 30.
  • Table 1 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 2 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 3 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 4 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 6 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 7 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 8 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 9 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 10 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 11 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 12 provides 216 compounds of formula (I) where Het is
  • Table 13 provides 216 compounds of formula (I) where Het is and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 14 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 15 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 17 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 18 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 19 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 20 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 21 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 23 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 24 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 25 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 26 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 27 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 28 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 29 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 30 provides 216 compounds of formula (I) where Het is
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined in Table X.
  • Table 32 shows selected melting point and selected NMR data, all with CDCl 3 as the solvent, unless otherwise stated, for compounds of Tables 1 to 31. No attempt is made to list all characterising data in all cases.
  • the compounds of formula (I) may be prepared as described below with reference to reaction Schemes 1 to 6.
  • a compound of formula (I), where R 1 is hydrogen and Het, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above, may be synthesized by reacting a compound of formula (II), where Het is as defined above and R' is Ci -5 alkyl, with an aniline of formula (HI), where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above, in the presence of NaN(TMS) 2 at -1O 0 C to ambient temperature, preferably in dry tetrahydrofuran, as described by J.Wang et al. Synlett, 2001, 1485.
  • a compound of formula (I), where R 1 is hydrogen and Het, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above may be prepared by reacting a compound of formula (H'), where Het is as defined above and R' is hydrogen, with an aniline of formula (EI), where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above, in the presence of an activating agent, such as BOP-Cl (bis-(2-oxo-3- oxazolidinyl)-phosphinic acid chloride), and two equivalents of a base, such as triethylamine, in a solvent, such as dichloromethane (as described, for example, by J.
  • an activating agent such as BOP-Cl (bis-(2-oxo-3- oxazolidinyl)-phosphinic acid chloride)
  • a base
  • the compound of formula (U") is obtained from a compound of formula (H') by treatment with a halogenating agent such as thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, SF 4 ZHF, DAST ((diethylamino)sulphur trifluoride), or Deoxo-Fluor ® ([bis(2-methoxyethyl)amino]sulphur trifluoride) in a solvent such as toluene, dichloromethane or acetonitrile.
  • a halogenating agent such as thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, SF 4 ZHF, DAST ((diethylamino)sulphur trifluoride), or Deoxo-Fluor ® ([bis(2-methoxyethyl)amino]sulphur trifluoride
  • a compound of formula (I), where R 1 is other than hydrogen and Het, R 2 , R 3 , R 4 , R 5 , R , R 7 , R and R 9 are as defined above, may be prepared by reacting a compound of fomula (I), where R 1 is hydrogen and Het, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above, with a species Z-R 1 , where R 1 is as defined above but is not hydrogen and Z is preferably chloro, bromo or iodo or Z is such that Z-R 1 is an anhydride (that is, when R 1 is COR 16 , Z is OCOR 16 ) in the presence of a base, for example sodium hydride, sodium or potassium hydroxide, NaN(TMS) 2 , triethylamine, sodium bicarbonate or potassium carbonate, in an appropriate solvent, such as ethyl acetate, or in a biphasic mixture
  • the compounds (II) and (H') are generally known compounds and may be prepared as described in the chemical literature or obtained from commercial sources.
  • the compound (III) is a novel compound and may be prepared as described with reference to Schemes 4, 5 and 6.
  • Useful catalysts include palladium catalysts such as Pd/C, rhodium catalysts such as Rh/C, platinum catalysts such Pt/C or PtO 2 , and nickel catalysts such Raney Nickel.
  • Useful solvents include ethers such as tetrahydrofuran, ethyl acetate, alcohols such as ethanol and methanol, and toluene.
  • ethers such as tetrahydrofuran, ethyl acetate
  • alcohols such as ethanol and methanol
  • toluene toluene.
  • the ratio of the aniline (IQ) where R 6 is R" and R 7 is H (endo epimer) to the aniline (HI) where R 6 is H and R 7 is R" (exo-epimer) and the ratio of the aniline (HI) where R 8 is R" and R 9 is H (endo epimer) to the aniline (m) where R 8 is H and R 9 is R" (exo-epimer) are catalyst- and solvent-dependent.
  • exhaustive hydrogenation of the mixture C with Pd/C in MeOH yields the aniline (HI) with predominantly the endo- epimers.
  • the mixture of regio-isomers C may be obtained by the [4+2]cycloaddition of an in situ generated benzyne A to an alkyl cyclopentadiene (B) according to or by analogy with one of the procedures described by R. Muneyuki and H. Tanida, J. Org. Chem. 31, 1988 (1966), P. Knochel et al, Angew. Chem. 116, 4464 (2004), J.W. Coe et al, Organic Letters 6, 1589 (2004), L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), R.N. Warrener et al, Molecules, 6, 353 (2001) and R.N.
  • Suitable aprotic solvents for this process include diethyl ether, butyl methyl ether, ethyl acetate, dichloromethane, acetone, tetrahydrofuran, toluene, 2-butanone and dimethoxyethane.
  • Reaction temperatures range from room temperature to 100 0 C, preferably 35-80 0 C.
  • the benzyne A may be obtained, for example, from a 6-nitro- anthranilic acid of formula AA, as described by L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), or from other suitable precursors (see H.
  • 6-Nitroanthranilic acids of formula AA are generally known compounds and may be prepared as described in the chemical literature or obtained from commercial sources.
  • Alkyl cyclopentadienes of formula B may be prepared according to or by analogy to the procedure described by Asahi Corporation in JP 2003055272. Under the reaction conditions, B exists as an equilibrium of tautomers Bi, B 2 and
  • the regi ⁇ -isomers of the benzonorbornadiene C, of the aniline (HI) or of the final compound (I) may be separated by established methods such as chromatography (LC, MPLC, HPLC, TLC), distillation or crystallization.
  • aniline of formula (HI) may be obtained according to Scheme 5 in which R 6 , R 7 , R 8 , R 9 , R * and R ** are as defined in Scheme 5, and R 2 and R 3 are as defined above.
  • the aniline of formula (DT) may be prepared by catalytic hydrogenation or by a Bechamp reduction of the nitro-compounds F, G, H and J.
  • Mono- or dihalides F ang G are prepared by reacting ketones D and E or their precursors DD and EE with halogenating agents such as DAST, SF 4 /HF, CCl 4 ZPh 3 P, CBr 4 ZPh 3 P or PBr 3 according to standard procedures.
  • halogenating agents such as DAST, SF 4 /HF, CCl 4 ZPh 3 P, CBr 4 ZPh 3 P or PBr 3 according to standard procedures.
  • anilines of formula (IH) may be obtained according to Scheme 6 in which R 2 and R 3 are as defined above.
  • the reaction of ketones D and E with a 0-Ci -6 alkyl- hydroxylamine under standard conditions affords oximes K and L, each as an E/Z- mixture.
  • the invention includes a compound of the formula (UI):
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above.
  • R 6 , R 7 , R 8 and R 9 are all hydrogen and one of R 4 and R 5 is C )-6 alkyl and the other is hydrogen; or
  • R 6 and R 7 or R 8 and R 9 are both halo, they are suitably both fluoro, chloro or bromo, especially both fluoro or both chloro.
  • R 6 and R 7 or R 8 and R 9 are suitably both fluoro, chloro or bromo, especially both fluoro or both chloro.
  • R 2 and R 3 are both hydrogen
  • R 4 , R 5 , R 6 , R 7 , R 8 and R 9 have the meanings given in the table
  • * indicates an exo/endo- ⁇ xlure
  • ** indicates an EIZ mixture.
  • Table 34 shows selected melting point and selected NMR data, all with CDCl 3 as the solvent, unless otherwise stated, for compounds of Table 33. No attempt is made to list all characterising data in all cases. The abbreviations used are the same as those used in Table 32 earlier.
  • the invention also includes a compound of the formula (IV), which embraces the compounds of the formulae F, G, H, J, K and L shown in Schemes 5 and 6:
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are as defined above.
  • R 6 , R 7 , R 8 and R 9 are all hydrogen and one of R 4 and R 5 is Ci -6 alky] and the other is hydrogen; or
  • R 6 and R 7 or R 8 and R 9 are both halo, they are suitably both fluoro, chloro or bromo, especially both fluoro or both chloro.
  • R 2 and R 3 are both hydrogen
  • R 4 , R 5 , R 6 , R 7 , R 8 and R 9 have the meanings given in the table
  • * indicates an exo/endo- ⁇ nixtme
  • ** indicates an EIZ mixture
  • Table 36 shows selected melting point and selected NMR data, all with CDCl 3 as the solvent, unless otherwise stated, for compounds of Table 35. No attempt is made to list all characterising data in all cases. The abbreviations used are the same as those used in Table 32 earlier.
  • Table 37 shows selected melting point and selected NMR data, all with CDCl 3 as the solvent, unless otherwise stated, for compounds of Table 36. No attempt is made to list all characterising data in all cases. The abbreviations used are the same as those used in Table 31 earlier.
  • the invention relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as acitve ingredient to the plants, to parts thereof or the locus thereof.
  • the compounds of formula (I) according to the invention 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 are used for protecting numerous useful plants.
  • the compounds of formula (I) can be used to inhibit or destroy the diseases 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.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds of formula (I) according to the invention may 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 or in hygiene management.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria
  • Basidiomycetes e.g. Rhizoctonia, Hemileia, Puccinia
  • novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
  • useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco
  • useful plants is to be understood as including also 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 including also 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.
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-O 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • 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 may 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 may 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) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation. Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.
  • compounds of formula (I) and inert carriers are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula (I) or compositions, comprising a compound of formula (I) as acitve ingredient and an inert carrier can be applied to the locus of the plant 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 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.
  • a preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as acitve ingredient and an inert carrier is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • 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 i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is 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).
  • the agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 1Og to lkg a.i./ha, most preferably from 2Og to 600g a.i./ha.
  • convenient rates of application are from lOmg to Ig of active substance per kg of seeds.
  • the rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.
  • the compounds of formula (I), or a pharmaceutical salt thereof, described above may also an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal.
  • Animal can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human.
  • Treatment means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection.
  • prevention means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
  • a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal.
  • a compound of formula (I) as a pharmaceutical agent.
  • a compound of formula (I) as an antimicrobial agent in the treatment of an animal.
  • a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier.
  • This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal.
  • This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs.
  • this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion.
  • this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection.
  • this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
  • the compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal. Examples of such microbial species are those causing Aspergillosis such as Aspergillus fiimigatus, A. ⁇ avus, A. terras, A. nidulans and A.
  • Blastomycosis such as Blastomyces dermatitidis
  • Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C. lusitaniae
  • Coccidioidomycosis such as
  • Coccidioides immitis those causing Cryptococcosis such as Cryptococcus neoformans; those causing Histoplasmosis such as Histoplasma capsulatum and those causing Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizus.
  • Fusarium Spp such as Fusarium oxysporum and Fusarium solani
  • Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans.
  • Microsporum Spp Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.
  • Example 1 illustrates the above-described invention in more detail.
  • This Example illustrates the preparation of a mixture of 1 -/-propyl-, 2-/-propyl-, 3-i- propyl- and 4-/-propyl-5-nitro-benzonorbornadiene (Compound No 36.04)
  • Example 2 This Example illustrates the preparation of 1- ⁇ -propyl- (Compound No. 32.11), 2-endo-i- propyl- (Compound No. 32.27) and the mixture of 3-era/ ⁇ -/-propyl- (Compound No. 32.19) and 4-/-propyl-5-amino-benzonorbornene (Compound No. 32.03)
  • Example 1 The product mixture of Example 1 (17.44g, 76mmol) in methanol (300ml) was exhaustively hydrogenated in the presence of 3.5g 5% Pd/C at 30-35 0 C and ambient pressure for 18 hours.
  • the crude was fractionally chromatographed on silica gel (2kg) in ethyl acetate-hexane (1:6) to give the mixture of anilines 32.19 and 32.03 (6.89g), aniline 32.27 (2.184g) and aniline 32.11 (1.846g), each as a brown viscous oil, in a total yield of 10.92g (71%).
  • the combined fractions of minor components accounted for 527mg and were not identified.
  • the structures were assigned by established 1 H and 13 C- NMR techniques.
  • Example 5 This Example illustrates the preparation of 3-methylene-5-nitro-benzonorbornene (Compound No. 34.07)
  • Example 6 This Example illustrates the preparation of 3-(e;e ⁇ /emfo)-ethyl-5-amino-benzonor- bornene (Compound No. 32.18)
  • Example 9 This Example illustrates the preparation of 2,2-difluoro-5-amino-benzonorbornene (Compound No. 32.42)
  • Example B-2 Action against Podosphaera leucotricha / apple (Powdery mildew on apple)
  • Example B-4 Action against Erysiphe graminis / barley (Powdery mildew on barley) 1 week old barley plants cv. Regina are treated with the formulated test compound
  • Example B-5 Action against Botrytis cinerea / grape (Botrytis on grapes)
  • Example B-8 Action against Helminthosporium teres / barley (Net blotch on barley)
  • Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber.
  • the tomato plants are inoculated by spraying a spore suspension (2xl0 5 conidia/ml) on the test plants. After an incubation period of 3 days at 2O 0 C and 95% r.h. in a growth chamber the disease incidence is assessed.
  • the formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application barley seeds (cv.Express) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80% r.h. One week after sowing barley plants were inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days the disease incidence was assessed. The efficacy of each test compound is used as an indicator for systemic activity.
  • a conidia suspension of F. culmorum (7xl0 5 conidia/ml) is mixed with the formulated test compound (0.002% active ingredient).
  • the mixture is applied into a pouch which was previously equipped with a filter paper.
  • wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper.
  • the prepared pouches are then incubated for 11 days at ca.l ⁇ -18° C and 100% r.h. with a daily light period of 14 hours.
  • the evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.
  • a defined amount of mycelium of G. graminis is mixed with water.
  • the formulated test compound (0.002% active ingredient) is added to the mycelium suspension.
  • the mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper.
  • the prepared pouches are then incubated for 14 days at 18°C/16°C (day/night) and 80% r.h. with a daily light period of 14 hours. The evaluation is made by assessing the degree of root browning.
  • Formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv. Arina) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80% r.h. One week after sowing, the wheat plants were inoculated by spraying a spore suspension (lxl0 5 uredospores/ml) on the test plants. After an incubation period of 1 day at 23°C and 95% r.h. the plants were kept for 9 days at 20°C/18°C (day/night) and 80% r.h . The disease incidence was assessed 10 days after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.
  • Example B-15 Action against Rhizoctonia solani / rice (Sheath blight on rice) (Pouch test)
  • a defined amount of mycelium of R. solani is mixed with water.
  • the formulated test compound (0.002% active ingredient) is added to the mycelium suspension.
  • the mixture is applied into a pouch which was previously equipped with a filter paper.
  • rice seeds cv.Koshihikari
  • the prepared pouches are then incubated for 10 days at 23°C/21°C (day/night) and 100% r.h. with a daily light period of 14 hours.
  • the evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.
  • Example B- 16 Action against Septoria nodorum / wheat (Septoria leaf spot on wheat) (Pouch test)
  • the formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application, wheat seeds (cv. Arina) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80% r.h. One week after sowing, the wheat plants are inoculated by spraying a spore suspension (5xl0 5 conidia/ml) on the test plants. After an incubation period of 1 day at 23°C and 95% r.h. the plants are kept for 9 days at 20°C/18°C (day/night) and 80% r.h. The disease incidence is assessed 8 days after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.

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Abstract

La présente invention a pour objet des composés à activité fongicide de formule (I) : où Het, R1, R2, R3, R4, R5, R6, R7, R8 et R9 sont tels que définis dans la revendication 1, la synthèse de ces composés, les nouveaux intermédiaires employés dans la synthèse de ces composés, les compositions agrochimiques qui comprennent au moins l'un des nouveaux composés au titre de principe actif, l'élaboration des compositions mentionnées et l'emploi des principes actifs ou des compositions en agriculture ou en horticulture pour la maîtrise ou la prévention d'une infestation des plantes par des micro-organismes phytopathogènes, de préférence des champignons.
PCT/EP2007/003653 2006-04-27 2007-04-25 Nouveaux microbiocides WO2007124907A2 (fr)

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WO2011131545A1 (fr) * 2010-04-20 2011-10-27 Syngenta Participations Ag Procédé de synthèse d'amides d'acide pyrazolecarboxylique
WO2011131546A1 (fr) * 2010-04-20 2011-10-27 Syngenta Participations Ag Procédé d'élaboration d'amides d'acides carboxyliques de pyrazoles
JP2013529225A (ja) * 2010-06-07 2013-07-18 ダウ アグロサイエンシィズ エルエルシー 殺真菌剤としてのピラジニルカルボキサミド
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EA018967B1 (ru) * 2008-02-05 2013-12-30 Басф Се Способ повышения выхода и/или повышения жизнеспособности и/или увеличения устойчивости или сопротивления к факторам абиотического стресса и фунгицидные смеси
WO2009098218A2 (fr) * 2008-02-05 2009-08-13 Basf Se Composition phytosanitaire
WO2009098223A3 (fr) * 2008-02-05 2010-08-12 Basf Se Composition phytosanitaire
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