WO2010094666A2 - Fungicidal n-(phenylcycloalkyl)carboxamide, n-(benzylcycloalkyl)carboxamide and thiocarboxamide derivatives - Google Patents

Fungicidal n-(phenylcycloalkyl)carboxamide, n-(benzylcycloalkyl)carboxamide and thiocarboxamide derivatives Download PDF

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WO2010094666A2
WO2010094666A2 PCT/EP2010/051886 EP2010051886W WO2010094666A2 WO 2010094666 A2 WO2010094666 A2 WO 2010094666A2 EP 2010051886 W EP2010051886 W EP 2010051886W WO 2010094666 A2 WO2010094666 A2 WO 2010094666A2
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substituted
halogen atoms
alkyl
different
same
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PCT/EP2010/051886
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French (fr)
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WO2010094666A3 (en
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Jürgen BENTING
Peter Dahmen
Philippe Desbordes
Stéphanie Gary
Marie-Claire Grosjean-Cournoyer
Philippe Rinolfi
Ulrike Wachendorff-Neumann
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Bayer Cropscience Ag
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Priority to US13/201,616 priority Critical patent/US8372982B2/en
Priority to JP2011549594A priority patent/JP5728735B2/en
Priority to BRPI1006006-5A priority patent/BRPI1006006B1/en
Priority to CN201080008786.1A priority patent/CN102317259B/en
Priority to EP10703890.3A priority patent/EP2398770B1/en
Publication of WO2010094666A2 publication Critical patent/WO2010094666A2/en
Publication of WO2010094666A3 publication Critical patent/WO2010094666A3/en

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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
    • C07D207/36—Oxygen or sulfur atoms
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered 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
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members

Definitions

  • the present invention relates to fungicidal N-(Phenylcycloalkyl)carboxamide or N- (Benzylcycloalkyl)carboxamide or its thiocarboxamide derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.
  • R 2 can represent a substituted aryl group or a substituted aralkyl group and n can be 1.
  • this document does not disclose compounds wherein the nitrogen atom of the carboxamide residue can be substituted by a cycloalkyl group.
  • A can represent a 5-membered heterocyclic ring
  • X can be an oxygen or sulfur atom
  • R 1 , R 2 , R 3 and R 4 can represent a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl, a cyano or a nitro group
  • B can represent a substituted phenyl group
  • R5 can represent various substituents among which a hydrogen atom or a Ci-C 4 -alkyl group.
  • this document does not disclose compounds wherein the nitrogen atom of the (thio)carboxamide residue can be substituted by a cycloalkyl group.
  • certain fungicidal N-(2-Pyridylcycloalkyl) carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
  • Het can represent a 5-membered heterocyclic ring
  • A can represent a Cs-Cycycloalkyl ring
  • R 1 and R 2 can represent various substituents among which a hydrogen atom or a C 1 -C 6 - alkyl group
  • R can represent various substituents among which a hydrogen atom, a Ci-C ⁇ -alkyl group or a Cs-Cycycloalkyl group
  • X and R a can represent various substituents among which a hydrogen atom, a halogen atom or a Ci-Cs-alkyl group.
  • this document does not disclose compounds wherein the 2-pyridine moeity can be replaced by a phenyl group.
  • Het can represent a 5-membered heterocyclic ring
  • A can represent a Cs-Cycycloalkyl ring
  • R 1 and R 2 can represent various substituents among which a hydrogen atom or a C 1 -C 6 - alkyl group
  • R can represent various substituents among which a hydrogen atom, a Ci-C ⁇ -alkyl group or a Cs-Cycycloalkyl group
  • R a represents a Ci-C ⁇ -halogenoalkyl group
  • X can represent a hydrogen atom, a halogen atom, a Ci-C ⁇ -alkyl group or a Ci-C ⁇ -halogenoalkyl group.
  • A can represent a 5-membered heterocyclic ring
  • R 1 , R 2 , R3 and R 4 can represent various substituents among which a hydrogen atom or a Ci-C 4 -alkyl group and Ri and R 3 together with the carbon to which they are linked can form a C 3 -Cy-cycloalkyl ring that can be substituted by one or more Ci-C ⁇ -alkyl groups
  • B can represent a substituted phenyl group
  • Ri 5 can be a hydrogen atom or a C 3 -Cy-cycloalkyl group.
  • this document does not disclose nor suggest compounds wherein the oxygen atom linking the B ring to the C 3 -Cy-cycloalkyl moeity can be replaced by a carbon atom.
  • the present invention provides a N-(Phenylcycloalkyl)carboxamide or N- (Benzylcycloalkyl)carboxamide or its thiocarboxamide derivative of formula (I)
  • A represents a carbo- linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R ;
  • T represents O or S ;
  • B represents a 3-, A-, 5-, 6- or 7-membered non aromatic carbocycle that can be substituted by one to four Ci-Cs-alkyl groups ; • n represents 0, 1, 2, 3, 4 or 5 ;
  • X represents a halogen atom ; nitro ; cyano ; isonitrile ; hydroxy ; amino ; sulfanyl ; pentafluoro- ⁇ 6 -sulfanyl ; formyl ; formyloxy ; formylamino ; substituted or non- substituted (hydroxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C 1 -C 8 - alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C2-Cs-alkenyloxyimino)-Ci-
  • Cs-alkyl substituted or non-substituted (C 2 -C 8 -alkynyloxyimino)-Ci-C 8 -alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; carboxy ; carbamoyl ; N- hydroxycarbamoyl ; carbamate ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs- halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkenyl ; C2-C8-halogenoalkenyl having 1 to 5 halogen atoms ; substituted or non-substituted C 2 -
  • Ci-Cs-halogenoalkylsulfanyl substituted or non-substituted Ci-Cs-alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfinyl ; Ci-Cs- halogenoalkylsulfinyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfinyl ; Ci-Cs- halogenoalkylsulfinyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs- alkylsulfonyl ; Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-Cls
  • Z 1 and Z 2 independently represent a hydrogen atom ; a halogen atom ; cyano ; a substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy; substituted or non-substituted Ci-Cs- alkylsulfanyl; or substituted or non-substituted Ci-Cs-alkoxycarbonyl ;
  • Z 3 represents a non-substituted C3-C7-cycloalkyl or a C3-C7-cycloalkyl substituted by up to 10 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkoxy, Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, Ci-Cs- alkoxycarbonyl, Ci-Cs-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkylaminocarbonyl and di-Ci-Cs-alkylamino- carbonyl ; • Z 4 and Z 5 independently represent a hydrogen atom ; a halogen
  • Ci-Cs-alkyl Ci-Cs-halogenoalkyl having 1 to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy having 1 to 9 halogen atoms that can be the same or different ; substituted or non- substituted C 1 - C 8 -alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 9 halogen atoms that can be the same or different ; substituted or non- substituted tri(Ci-C8)alkylsilyl ; substituted or non-substituted tri(Ci-C8)alkylsilyl-Ci-C8-alkyl ; substituted or non-substituted (C 1 -C 8 - alkoxyimino)-Ci-C 8 -alkyl ; substituted or non-substituted
  • R independently represents hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxy ; amino ; sulfanyl ; pentafluoro- ⁇ 6 -sulfanyl ; substituted or non-substituted (C 1 -C 8 - alkoxyimino)-Ci-C 8 -alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C 8 -alkyl ; substituted or non-substituted d-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted C 2 -Cs-alkenyl ; C 2 -Cs-halogenoalkenyl having 1 to 5 halogen atoms ; substituted or non-substituted C 2 -Cs-alkynyl ; C 2 -Cs-halogen
  • halogen means fluorine, bromine, chlorine or iodine.
  • SO represents a sulfoxyde group ; SO 2 represents a sulfone group ;
  • an alkyl group, an alkenyl group and an alkynyl group as well as moieties containing these terms, can be linear or branched;
  • the aryl moeity contained in an aryl group, an arylalkyl group, an arylalkenyl group and an arylalkynyl group as well as moieties containing these terms can be a phenyl group that can be substituted by up to 5 groups Q, a naphtyl group that can be substituted by up to 6 groups Q or a pyridyl group that can be substituted by up to 4 groups Q ;
  • heteroatom means sulphur, nitrogen or oxygen.
  • a group or a substituent that is substituted according to the invention can be substituted by one or more of the following groups or atoms: a halogen atom, a nitro group, a hydroxy group, a cyano group, an amino group, a sulfanyl group, a pentafluoro- ⁇ 6 -sulfanyl group, a formyl group, a formyloxy group, a formylamino group, a carbamoyl group, a N-hydroxycarbamoyl group, a carbamate group, a (hydroxyimino)- Ci-Ce-alkyl group, a Ci-C 8 -alkyl, a tri(Ci-C 8 -alkyl)silyl-Ci-C 8 -alkyl, Ci-C 8 -cycloalkyl, tri(Ci-C 8 -alkyl)silyl-Ci-C 8 -cycloalkyl, tri(Ci
  • any of the compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound.
  • the invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term "scalemic” denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions.
  • the diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.
  • Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound.
  • the invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
  • the geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art. Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents of ring B.
  • the invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions.
  • the syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
  • any of the compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group may be found in its tautomeric form resulting from the shift of the proton of said hydroxy, sulfanyl or amino group.
  • Such tautomeric forms of such compounds are also part of the present invention. More generally speaking, all tautomeric forms of compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group, as well as the tautomeric forms of the compounds which can optionally be used as intermediates in the preparation processes and which will be defined in the description of these processes, are also part of the present invention.
  • Preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of: - a heterocycle of formula (A 1 )
  • R 1 to R 3 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
  • R 7 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci- C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R 8 represents a hydrogen atom or a substituted or non-substituted Ci-Cs-alkyl ;
  • R 9 to R 11 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; amino ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted Ci-Cs-alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
  • R 12 and R 13 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; amino ; Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci- C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R 14 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; amino ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be
  • R , 15 represents a hydrogen atom ; a halogen atom ; a cyano ; substituted or non-substituted C 1 -C 5 - alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 16 and R 18 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or
  • Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 17 represent a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
  • R 19 represents a hydrogen atom or a Ci-C 5 -alkyl R 20 to R 22 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 23 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 24 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;
  • R 25 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 26 represents a hydrogen atom ; substituted or non-substituted Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R , 27 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R , 28 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C 1 -C 5 - halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non-substituted di(Ci-Cs- alkyl)amino ;
  • R 29 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 30 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C 1 -C 5 - halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non-substituted di(Ci-Cs- alkyl)amino ;
  • R 31 represents a hydrogen atom or a substituted or non-substituted Ci-Cs-alkyl
  • R 32 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different
  • R 33 represents a hydrogen atom ; a halogen atom ; a nitro ; substituted or non-substituted C 1 -C 5 - alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 34 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted C 3 -Cs-cycloalkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C2-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
  • R 35 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; a cyano ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C 1 -C 5 - alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non- substituted di(Ci-C5-alkyl)amino; R 36 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
  • R 37 and R 38 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci-Cs-alkoxy or a substituted or non- substituted C 1 -C 5 - alkylsulphanyl ; R , 39 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl
  • R 40 and R 41 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 44 and R 45 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 47 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 46 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or substituted or non- substituted Ci-Cs-alkylsulfanyl ;
  • R 49 and R 48 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; C 1 -C 5 - halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 50 and R 51 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; C 1 -C 5 - halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; -a heterocycle of formula (A 21 )
  • R 52 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
  • R 53 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
  • R 54 and R 56 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 55 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
  • R 57 and R 59 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 58 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
  • R 60 and R 61 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R 62 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
  • R 65 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Cs-Cs-cycloalkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C2-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
  • R 63 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; a cyano ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C 1 -C 5 - alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or di(Ci-C5-alkyl)amino; R 64 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl.
  • More preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of A 2 ; A 6 ; A 10 and A 13 as herein-defined. Even more preferred compounds according to the invention are compounds of formula (I) wherein A represents A 13 wherein R 34 represents a substituted or non-substituted Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci-Cs-alkoxy ; R 35 represents a hydrogen atom or a halogen atom and R 36 represents a substituted or non-substituted Ci-Cs-alkyl.
  • n 0, 1 or 2.
  • B is a 3-, 5-, 6- or 7-membered non aromatic carbocycle that can be substituted by one to four Ci- Cs-alkyl groups.
  • B is chosen from cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl carbocycle that can be substituted by one to four methyl groups.
  • X independently represents a halogen atom ; substituted or non-substituted d-Cg-alkyl ; Ci-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted tri(Ci-C8-alkyl)silyl ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non substituted 1,3-benzodioxolyl ; 1,2,3,4-tetrahydro-quinoxalinyl ; 3,4-dihydro-2H-l,4- benzoxazinyl ; 1 ,4-benzodioxany
  • Z 1 and Z 2 independently represent a hydrogen atom or a substituted or non- substituted Ci-Cs-alkyl.
  • Z represents a non- substituted C3-C7 cycloalkyl or a C3-C7 cycloalkyl substituted by up to 10 groups or atoms that can be the same or different and that can be selected in the list consisting of halogen atoms, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different. More preferably Z 3 represents a non-substituted C3-C7- cycloalkyl ; even more preferably Z 3 represents cyclopropyl.
  • Z 4 and Z 5 independently represent a hydrogen atom, a halogen atom or a substituted or non- substituted Ci-C 8 -alkyl.
  • R independently represents a hydrogen atom ; halogen atom ; cyano ; substituted or non-substituted Ci-Cs-alkylamino ; substituted or non-substituted di-Ci-Cs-alkylamino ; substituted or non- substituted tri(Ci-C8-alkyl)silyl ; substituted or non-substituted d-Cg-alkyl ; Ci-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkylsulfanyl ; amino ; hydroxyl ; nitro ; substituted or non-
  • T with preferred features of A, B, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , X, n, m and R;
  • n - preferred features of n with preferred features of A, B, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , X, T, m and R;
  • m preferred features of A, B, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , X, T, n and R;
  • the said preferred features can also be selected among the more preferred features of each of A, B, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 ' X, T, n, m and R, so as to form most preferred subclasses of compounds according to the invention.
  • the present invention also relates to a process for the preparation of the compound of formula
  • N-cycloalkylamine derivatives of formula (II) can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters (2006), 2014), or reduction of imines (Tetrahedron (2005), 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 3887).
  • Carboxylic acid derivatives of formula (III) can be prepared by known processes.
  • condensing agent may be selected in the non limited list consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous -pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl- chloride; carbodiimides, such as N,N'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, N,N'-carbonyl-diimidazole, 2-ethoxy-N- ethoxycarbonyl-l,2-di
  • acid halide former such as phosgene, phosphorous tribromide, phosphorous trichloride
  • Suitable catalyst may be selected in the list consisting of 4-dimethyl-aminopyridine, 1-hydroxy- benzotriazole or dimethylformamide.
  • L 1 represents a halogen atom
  • the process according to the present invention is conducted in the presence of an acid binder.
  • Suitable acid binders for carrying out process Pl according to the invention are in each case all inorganic and organic bases that are customary for such reactions.
  • alkaline earth metal alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide
  • alkali metal carbonates such as cesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetateand also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N- methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecen
  • DABCO di
  • X, n, m, B, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and A are as herein-defined, in the optional presence of a catalytic or stoechiometric or more, quantity of a base such as an inorganic and organic base.
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate
  • heterocyclic aromatic bases such as pyridine, picoline, lutidine, collidine
  • tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylaminopyridine or N-methylpiperidine.
  • Process P2 according to the invention is performed in the presence of a thionating agent.
  • Suitable thionating agents for carrying out process P2 according to the invention can be sulphur (S), sulfhydric acid (H 2 S), sodium sulfide (Na 2 S), sodium hydrosulf ⁇ de (NaHS), boron trisulf ⁇ de (B2S3), bis (diethylaluminium) sulfide ((AlEt 2 ) 2 S), ammonium sulfide ((NH 4 ) 2 S), phosphorous pentasulf ⁇ de (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-l,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in J.Chem.Soc.
  • the present invention relates to compounds of formula (II) useful as intermediate compounds or materials for the process of preparation according to the invention.
  • the present invention thus provides compounds of formula (II) :
  • the present invention also relates to a fungicide composition
  • a fungicide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).
  • an effective and non-phytotoxic amount means an amount of composition according to the invention that is sufficient to control or destroy the fungi present or liable to appear on the cropsand that does not entail any appreciable symptom of phytotoxicity for the said crops.
  • Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
  • a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler.
  • support denotes a natural or synthetic, organic or inorganic compound with that the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant.
  • This support is thus generally inert and should be agriculturally acceptable.
  • the support can be a solid or a liquid.
  • suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.
  • composition according to the invention can also comprise additional components.
  • the composition can further comprise a surfactant.
  • the surfactant can be an emulsif ⁇ er, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants.
  • the presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water.
  • surfactant content can be comprised from 5% to 40% by weight of the composition.
  • additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents.
  • the active compounds can be combined with any solid or liquid additive, that complies with the usual formulation techniques.
  • composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight.
  • compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsif ⁇ able concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure),gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder.
  • These compositions include not only compositions that are ready to be applied to the plant or seed to
  • the compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity.
  • the mixtures thus obtained have normally a broadened spectrum of activity.
  • the mixtures with other fungicide compounds are particularly advantageous.
  • fungicide mixing partners can be selected in the following lists:
  • Inhibitors of the ergosterol biosynthesis for example (1.1) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325- 08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16)
  • inhibitors of the respiratory chain at complex I or II for example (2.1) bixafen (581809-46- 03), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68-4), (2.4) difiumetorim (130339-07-0), (2.5) fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) furametpyr (123572-88-3), (2.9) furmecyclox (60568-05-0), (2.10) isopyrazam (mixture of syn- epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR) (881685-58-1), (2.11) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.12) isopyrazam (anti-epimeric enantiomer 1R,4S,9
  • inhibitors of the respiratory chain at complex III for example (3.1) amisulbrom (348635-87- 0), (3.2) azoxystrobin (131860-33-8), (3.3) cyazofamid (120116-88-3), (3.4) dimoxystrobin (141600-52-4), (3.5) enestroburin (238410-11-2) (known from WO 2004/058723), (3.6) famoxadone (131807-57-3) (known from WO 2004/058723), (3.7) fenamidone (161326-34-7) (known from WO 2004/058723), (3.8) fiuoxastrobin (361377-29-9) (known from WO 2004/058723), (3.9) kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.10) metominostrobin (133408-50-1) (known from WO 2004/058723), (3.11) orysastrobin (1898
  • Inhibitors of the mitosis and cell division for example (4.1) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7) fuberidazole (3878-19- 1), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5) and (4.13) 5- chloro-7-(4-methylpiperidin- 1 -yl)-6-(2,4,6-trifluorophenyl)[ 1 ,2,4]triazolo [ 1 ,5-a]pyrimidine (214706-)
  • Inhibitors of the amino acid and/or protein biosynthesis for example (7.1) andoprim (23951- 85-1), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980- 18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7) and (7.7) pyrimethanil (53112-28-0).
  • Inhibitors of the ATP production for example (8.1) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide (76-87-9), (8.4) and silthiofam (175217-20-6).
  • Inhibitors of the cell wall synthesis for example (9.1) benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7) polyoxorim (22976-86- 9), (9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0).
  • Inhibitors of the lipid and membrane synthesis for example (10.1) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb (25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11) prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18- 6), (10.13) quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15) tolclofos-methyl (57018-04-9).
  • Inhibitors of the melanine biosynthesis for example (11.1) carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3) fenoxanil (115852-48-7), (11.4) phthalide (27355-22-2), (11.5) pyroquilon (57369-32-1) and (11.6) tricyclazole (41814-78-2).
  • Inhibitors of the nucleic acid synthesis for example (12.1) benalaxyl (71626-11-4), (12.2) benalaxyl-M (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-85-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30-7), (12.8) hymexazol (10004-44-1), (12.9) metalaxyl (57837-19-1), (12.10) metalaxyl-M (70630-17- 0), (12.11) ofurace (58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4).
  • Inhibitors of the signal transduction for example (13.1) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fiudioxonil (131341-86-1), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7) vinclozolin (50471-44-8).
  • composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous.
  • suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • the compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.
  • a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.
  • the method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots.
  • the method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
  • cotton Among the plants that can be protected by the method according to the invention, mention can be made of cotton; flax; vine; fruit or vegetable crops such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp. for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches
  • Rosaceae sp. for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches
  • Rubiaceae sp. for instance banana trees and plantins
  • Rubiaceae sp. Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons oranges and grapefruit); Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); major crops such as Graminae sp.
  • GMOs genetically modified organisms
  • plants or seeds for instance maize, lawn or cereals such as wheat, rye, rice, barley and triticale
  • Asteraceae sp. for instance sunflower
  • Cruciferae sp. for instance colza
  • Fabacae sp. for instance peanuts
  • Papilionaceae sp. for instance soybean
  • Solanaceae sp. for instance potatoes
  • Chenopodiaceae sp. for instance beetroots
  • Elaeis sp. for instance oil palm
  • the method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds.
  • GMOs genetically modified organisms
  • heterologous gene essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, co suppression technology or RNA interference - RNAi - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • the treatment according to the invention may also result in superadditive (“synergistic") effects.
  • superadditive for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
  • the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted phytopathogenic fungi and/ or microorganisms and/or viruses. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, for example against fungi.
  • Plant-strengthening (resistance- inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted phytopathogenic fungi and/ or microorganisms and/or viruses, the treated plants display a substantial degree of resistance to these unwanted phytopathogenic fungi and/ or microorganisms and/or viruses.
  • unwanted phytopathogenic fungi and/ or microorganisms and/or viruses are to be understood as meaning phytopathogenic fungi, bacteria and viruses.
  • the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment.
  • the period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
  • Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechno logical means).
  • Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
  • Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozon exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which may also be treated according to the invention are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation.
  • Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stress factors. Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male- fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome.
  • Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering.
  • a particularly useful means of obtaining male-sterile plants is described in WO 1989/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 1991/002069).
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
  • Herbicide-tolerant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means.
  • glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5 -enolpyruvylshikimate-3 -phosphate synthase (EPSPS).
  • EPSPS 5 -enolpyruvylshikimate-3 -phosphate synthase
  • Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al, Science (1983), 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.
  • Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido -reductase enzyme as described in US 5,776,760 and US 5,463,175.
  • Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyl transferase enzyme as described in for example WO 2002/036782, WO 2003/092360, WO 2005/012515 and WO 2007/024782.
  • Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally-occurring mutations of the above-mentioned genes, as described in for example WO 2001/024615 or WO 2003/013226.
  • herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate.
  • Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition.
  • One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species).
  • Plants expressing an exogenous phosphinothricin acetyltransferase are for example described in US 5,561,236; US 5,648,477; US 5,646,024; US 5,273,894; US 5,637,489; US 5,276,268; US 5,739,082; US 5,908,810 and US 7,112,665.
  • Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD).
  • Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate.
  • Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated HPPD enzyme as described in WO 1996/038567, WO 1999/024585 and WO 1999/024586. Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native
  • HPPD enzyme by the HPPD-inhibitor.
  • Such plants and genes are described in WO 1999/034008 and WO 2002/36787.
  • Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate dehydrogenase in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928.
  • Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors.
  • ALS acetolactate synthase
  • ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides.
  • Different mutations in the ALS enzyme also known as acetohydroxyacid synthase, AHAS
  • AHAS acetohydroxyacid synthase
  • WO 2004/106529 WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO 2006/060634.
  • Further sulfonylurea- and imidazolinone-tolerant plants are also described in for example WO 2007/024782.
  • plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in US 5,084,082, for rice in WO 1997/41218, for sugar beet in US 5,773,702 and WO 1999/057965 , for lettuce in US 5,198,599, or for sunflower in WO 2001/065922.
  • Plants or plant cultivars which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • An "insect-resistant transgenic plant”, as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:
  • an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal portion thereof such as the insecticidal crystal proteins listed by Crickmore et al, Microbiology and Molecular Biology Reviews (1998), 62, 807-813, updated by Crickmore et al. (2005) at the Bacillus thuringiensis toxin nomenclature, online at: http://www.lifesci. Hampshire. ac.uk/Home/Neil_Crickmore/Bt/), or insecticidal portions thereof, e.g., proteins of the Cry protein classes CrylAb, CrylAc, CrylF, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof; or
  • a crystal protein from Bacillus thuringiensis or a portion thereof which is insecticidal in the presence of a second other crystal protein from Bacillus thuringiensis or a portion thereof, such as the binary toxin made up of the Cry34 and Cry35 crystal proteins
  • a hybrid insecticidal protein comprising parts of different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, e.g., the CrylA.105 protein produced by corn event MON98034 (WO 2007/027777); or
  • VIP vegetative insecticidal
  • a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin made up of the VIPlA and VIP2A proteins (WO 1994/21795); or
  • a hybrid insecticidal protein comprising parts from different secreted proteins from Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1) above or a hybrid of the proteins in 2) above; or 8) a protein of any one of 1) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT 102.
  • an insect-resistant transgenic plant also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 8.
  • an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 8, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include:
  • plants which contain a transgene capable of reducing the expression and/or the activity of poly(ADP-ribose)polymerase (PARP) gene in the plant cells or plants as described in WO 2000/004173 or WO2006/045633 or PCT/EP07/004142.
  • PARP poly(ADP-ribose)polymerase
  • plants which contain a stress tolerance enhancing transgene coding for a plant- functional enzyme of the nicotinamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide phosphoribosyltransferase as described e.g. in WO2006/032469 or WO 2006/133827 or PCT/EP07/002433.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as :
  • transgenic plants which synthesize a modified starch, which in its physical-chemical characteristics, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscosity behaviour, the gelling strength, the starch grain size and/or the starch grain morphology, is changed in comparison with the synthesised starch in wild type plant cells or plants, so that this is better suited for special applications.
  • Said transgenic plants synthesizing a modified starch are disclosed, for example, in EP 0571427, WO 1995/004826, EP
  • WO 2006/063862 WO 2006/072603, WO 2002/034923, EP 06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP 07090009.7, WO 2001/14569, WO 2002/79410, WO 2003/33540, WO 2004/078983, WO 2001/19975, WO 1995/26407, WO 1996/34968, WO 1998/20145, WO 1999/12950, WO 1999/66050, WO 1999/53072, US 6,734,341, WO 2000/11192, WO 1998/22604, WO 1998/32326, WO 2001/98509,
  • transgenic plants which synthesize non starch carbohydrate polymers or which synthesize non starch carbohydrate polymers with altered properties in comparison to wild type plants without genetic modification.
  • Examples are plants producing polyfructose, especially of the inulin and levan-type, as disclosed in EP 0663956, WO 1996/001904, WO 1996/021023, WO 1998/039460, and WO 1999/024593, plants producing alpha 1,4 glucans as disclosed in WO 1995/031553, US 2002/031826, US 6,284,479, US 5,712,107, WO 1997/047806, WO 1997/047807, WO 1997/047808 and WO 2000/014249, plants producing alpha- 1,6 branched alpha- 1,4-glucans, as disclosed in WO 2000/73422, plants producing alternan, as disclosed in WO 2000/047727, EP 06077301.7, US 5,908,975 and EP 0728213,
  • transgenic plants which produce hyaluronan, as for example disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/039316, JP 2006/304779, and WO 2005/012529.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include: a) Plants, such as cotton plants, containing an altered form of cellulose synthase genes as described in WO 1998/000549 b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO2004/053219 c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO 2001/017333 d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO02/45485 e) Plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fiber cell is altered, e.g.
  • Plants such as cotton plants, having fibers with altered reactivity, e.g. through the expression of N-acteylglucosaminetransferase gene including nodC and chitinsynthase genes as described in WO2006/136351
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics.
  • Such plants can be obtained by genetic transformation or by selection of plants contain a mutation imparting such altered oil characteristics and include: a) Plants, such as oilseed rape plants, producing oil having a high oleic acid content as described e.g.
  • transgenic plants which may be treated according to the invention are plants which comprise one or more genes which encode one or more toxins, such as the following which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), BiteGard® (for example maize), Bt-Xtra® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B®(cotton), NatureGard® (for example maize), Protecta® and NewLeaf® (potato).
  • YIELD GARD® for example maize, cotton, soya beans
  • KnockOut® for example maize
  • BiteGard® for example maize
  • Bt-Xtra® for example maize
  • StarLink® for example maize
  • Bollgard® cotton
  • Nucotn® cotton
  • Nucotn 33B® cotton
  • NatureGard® for example maize
  • herbicide-tolerant plants examples include maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize).
  • Herbicide-resistant plants plants bred in a conventional manner for herbicide tolerance
  • Clearf ⁇ eld® for example maize.
  • transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).
  • Powdery mildew diseases such as :
  • Blumeria diseases caused for example by Blumeria graminis ;
  • Podosphaera diseases caused for example by Podosphaera leucotricha ;
  • Sphaerotheca diseases caused for example by Sphaerothecafuliginea ;
  • Uncinula diseases caused for example by Uncinula necator ; Rust diseases such as :
  • Gymnosporangium diseases caused for example by Gymnosporangium sabinae ; Hemileia diseases, caused for example by Hemileia vastatrix ; Phakopsora diseases, caused for example by Phakopsora pachyrhizi or Phakopsora meibomiae ; Puccinia diseases, caused for example by Puccinia recondite, Puccinia graminis or
  • Uromyces diseases caused for example by Uromyces appendiculatus ; Oomycete diseases such as :
  • Albugo diseases caused for example by Albugo Candida
  • Bremia diseases caused for example by Bremia lactucae
  • Peronospora diseases caused for example by Peronospora pisi or P. brassicae
  • Phytophthora diseases caused for example by Phytophthora infestans
  • Plasmopara diseases caused for example by Plasmopara viticola ;
  • Pseudoperonospora diseases caused for example by Pseudoperonospora humuli or Pseudoperonospora cubensis ;
  • Pythium diseases caused for example by Pythium ultimum ;
  • Leafspot, leaf blotch and leaf blight diseases such as : Alternaria diseases, caused for example by Alternaria solani ;
  • Cercospora diseases caused for example by Cercospora beticola ;
  • Cladiosporum diseases caused for example by Cladiosporium cucumerinum ;
  • Cochliobolus diseases caused for example by Cochliobolus sativus (Conidiaform:
  • Drechslera Syn: Helminthosporium) or Cochliobolus miyabeanus ; Colletotrichum diseases, caused for example by Colletotrichum lindemuthanium ;
  • Cycloconium diseases caused for example by Cycloconium oleaginum ;
  • Diaporthe diseases caused for example by Diaporthe citri ;
  • Elsinoe diseases caused for example by Elsinoefawcettii ;
  • Gloeosporium diseases caused for example by Gloeosporium laeticolor ;
  • Glomerella diseases caused for example by Glomerella cingulata ;
  • Guignardia diseases caused for example by Guignardia bidwelli ;
  • Leptosphaeria diseases caused for example by Leptosphaeria maculans ; Leptosphaeria nodorum ;
  • Magnaporthe diseases caused for example by Magnaporthe grisea ;
  • Mycosphaerella diseases caused for example by Mycosphaerella graminicola ;
  • Phaeosphaeria diseases caused for example by Phaeosphaeria nodorum ;
  • Pyrenophora diseases caused for example by Pyrenophora teres, or Pyrenophora tritici repentis
  • Ramularia diseases caused for example by Ramularia collo-cygni , or Ramularia areola;
  • Rhynchosporium diseases caused for example by Rhynchosporium secalis ;
  • Septoria diseases caused for example by Septoria apii or Septoria lycopercisi ;
  • Typhula diseases caused for example by Typhula incarnata ;
  • Venturia diseases caused for example by Venturia inaequalis ; Root, Sheath and stem diseases such as :
  • Corticium diseases caused for example by Corticium graminearum ;
  • Fusarium diseases caused for example by Fusarium oxysporum ;
  • Gaeumannomyces diseases caused for example by Gaeumannomyces graminis ;
  • Rhizoctonia diseases caused for example by Rhizoctonia solani ;
  • Sarocladium diseases caused for example by Sarocladium oryzae;
  • Sclerotium diseases caused for example by Sclerotium oryzae
  • Tapesia diseases caused for example by Tapesia acuformis ;
  • Thielaviopsis diseases caused for example by Thielaviopsis basicola ; Ear and panicle diseases such as : Alternaria diseases, caused for example by Alternaria spp. ; Aspergillus diseases, caused for example by Aspergillus flavus ;
  • Cladosporium diseases caused for example by Cladosporium spp. ;
  • Claviceps diseases caused for example by Claviceps purpurea ;
  • Fusarium diseases caused for example by Fusarium culmorum ; Gibberella diseases, caused for example by Gibberella zeae ;
  • Monographella diseases caused for example by Monographella nivalis ; Smut and bunt diseases such as :
  • Sphacelotheca diseases caused for example by Sphacelotheca reiliana ;
  • Tilletia diseases caused for example by Tilletia caries ;
  • Urocystis diseases caused for example by Urocystis occulta ;
  • Ustilago diseases caused for example by Ustilago nuda ;
  • Fruit rot and mould diseases such as :
  • Aspergillus diseases caused for example by Aspergillus flavus ;
  • Botrytis diseases caused for example by Botrytis cinerea ;
  • Penicillium diseases caused for example by Penicillium expansum ;
  • Rhizopus diseases caused by example by Rhizopus stolonifer
  • Sclerotinia diseases caused for example by Sclerotinia sclerotiorum ;
  • Verticilium diseases caused for example by Verticilium alboatrum ; Seed and soilborne decay, mould, wilt, rot and damping-off diseases : Alternaria diseases, caused for example by Alternaria brassicicola
  • Aphanomyces diseases caused for example by Aphanomyces euteiches
  • Ascochyta diseases caused for example by Ascochyta lentis
  • Cladosporium diseases caused for example by Cladosporium herbarum
  • Cochlio bolus diseases caused for example by Cochliobolus sativus
  • Colletotrichum diseases caused for example by Colletotrichum coccodes
  • Fusarium diseases caused for example by Fusarium culmorum
  • Gibberella diseases caused for example by Gibberella zeae
  • Macrophomina diseases caused for example by Macrophomina phaseolina
  • Monographella diseases caused for example by Monographella nivalis
  • Penicillium diseases caused for example by Penicillium expansum
  • Phoma diseases caused for example by Phoma lingam
  • Phomopsis diseases caused for example by Phomopsis sojae
  • Phytophthora diseases caused for example by Phytophthora cactorum
  • Pyrenophora diseases caused for example by Pyrenophora graminea
  • Pyricularia diseases caused for example by Pyricularia oryzae
  • Pythium diseases caused for example by Pythium ultimum
  • Rhizoctonia diseases caused for example by Rhizoctonia solani
  • Rhizopus diseases caused for example by Rhizopus oryzae
  • Sclerotium diseases caused for example by Sclerotium rolfsii;
  • Septoria diseases caused for example by Septoria nodorum
  • Typhula diseases caused for example by Typhula incarnata
  • Verticillium diseases caused for example by Verticillium dahliae ; Canker, broom and dieback diseases such as :
  • Nectria diseases caused for example by Nectria galligena ; Blight diseases such as :
  • Monilinia diseases caused for example by Monilinia laxa ;
  • Leaf blister or leaf curl diseases such as : Exobasidium diseases caused for example by Exobasidium vexans
  • Taphrina diseases caused for example by Taphrina deformans ; Decline diseases of wooden plants such as :
  • Esca diseases caused for example by Phaemoniella clamydospora ;
  • Eutypa dyeback caused for example by Eutypa lata ; Ganoderma diseases caused for example by Ganoderma boninense;
  • Rigidoporus diseases caused for example by Rigidoporus lignosus Diseases of Flowers and Seeds such as
  • Botrytis diseases caused for example by Botrytis cinerea
  • Diseases of Tubers such as Rhizoctonia diseases caused for example by Rhizoctonia solani;
  • Helminthosporium diseases caused for example by Helminthosporium solani; Club root diseases such as
  • Plasmodiophora diseases cause for example by Plamodiophora brassicae. Diseases caused by Bacterial Organisms such as Xanthomonas species for example Xanthomonas campestris pv. oryzae;
  • Pseudomonas species for example Pseudomonas syringae pv. lachrymans;
  • Erwinia species for example Erwinia amylovora.
  • the composition according to the invention may also be used against fungal diseases liable to grow on or inside timber.
  • the term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood.
  • the method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
  • the dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment.
  • the dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed in the case of seed treatment.
  • the compounds or mixtures according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
  • fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
  • Table 1 illustrates in a non- limiting manner examples of compounds of formula (I) according to the invention.
  • M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation.
  • Step 1 preparation of cis and trans-N-cyclopropyl-2-phenylcyclohexanamine
  • the cake is washed twice by 80 ml of methanol and the combined methanolic extracts are concentrated under vacuum. 100 ml of water are then added to the residue and the pH is ajusted to 12 with a 1 N solution of sodium hydroxyde. The watery layer is extracted with 100 ml of ethyl acetate. The organic layer is washed twice by brine and dried over magnesium sulfate to yield after concentration 3.52 g of a yellow oil.
  • Step 2 preparation of c ⁇ -N-cyclopropyl-5-fluoro-l,3-dimethyl-N-(2-phenylcyclohexyl)-lH- pyrazole-4-carboxamide
  • a solution of 180 mg (1.02 mmol) of 5-fluoro-l,3-dimethyl-lH- pyrazole-4-carbonyl chloride in 1 ml of tetrahydrofurane is added dropwise to a solution of 200 mg (0.93 mmol) of c ⁇ -N-cyclopropyl-2-phenylcyclohexanamine and 100 mg (1.02 mmol) of triethylamine in 5 ml of tetrahydrofurane.
  • the reaction mixture is stirred for 2 hrs at 70 0 C.
  • the solvent is removed under vacuum and 100 ml of water are then added to the residue.
  • the watery layer is extracted twice with ethyl acetate (2 x 50 ml) and the combined organic layers are successively washed by a 1 N solution of HCl, a saturated solution of potassium carbonate and brine and dried over a chemelutTM cartridge to yield after concentration 380 mg of a yellow oil.
  • Example A in vivo test on Puccinia recondita (Brown rust)
  • the active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material.
  • Wheat plants (Scipion variety) sown on 50/50 peat soil-pozzolana substrate in starter cups and grown at 12°C, are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
  • the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores (100,000 spores per ml).
  • the spores are collected from a 10-day-old contaminated wheat and are suspended in water containing 2.5 ml/1 of tween 80 10%.
  • the contaminated wheat plants are incubated for 24 hours at 20 0 C and at 100% relative humidity, and then for 10 days at 20 0 C and at 70% relative humidity.
  • Example B in vivo test on Mycosphaerella graminicola (Wheat Leaf Spot)
  • the active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
  • Wheat plants (Scipion variety), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 12°C, are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
  • the plants are contaminated by spraying them with an aqueous suspension of Mycosphaerella graminicola spores (500 000 spores per ml).
  • the spores are collected from a 7-day-old culture.
  • the contaminated wheat plants are incubated for 72 hours at 18°C and at 100% relative humidity, and then for 21 to 28 days at 90% relative humidity. Grading (% of efficacy) is carried out 21 to 28 days after the contamination, in comparison with the control plants.
  • Example C in vivo test on Alternaria brassicae (Leaf spot of crucifers)
  • the active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material. Radish plants (Pernot variety), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 18-20 0 C, are treated at the cotyledon stage by spraying with the active ingredient prepared as described above.
  • Plants, used as controls, are treated with the mixture of acetone/tween/water not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of
  • Alternaria brassicae spores (40,000 spores per cm3). The spores are collected from a 12 to 13 days-old culture.
  • the contaminated radish plants are incubated for 6-7 days at about 18°C, under a humid atmosphere. Grading is carried out 6 to 7 days after the contamination, in comparison with the control plants.
  • Example D in vivo test on Sphaerotheca fuliginea (cucurbits powdery mildew)
  • the active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material.
  • Gherkin plants (Vert petit de Paris variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 20°C/23°C, are treated at the cotyledon ZlO stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
  • the plants are contaminated by spraying them with an aqueous suspension of Sphaerotheca fuliginea spores (100 000 spores per ml).
  • the spores are collected from a contaminated plants .
  • the contaminated gherkin plants are incubated at about 20°C/25°C and at 60/70% relative humidity. Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.
  • Example E in vivo test on Pyrenophora teres (barley) / preventive Solvent: 49 parts by weight of N,N-dimethylformamide
  • Emulsif ⁇ er 1 part by weight of Alkylarylpolyglycolether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsif ⁇ er, and the concentrate is diluted with water to the desired concentration.
  • the test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the control while an efficacy of 100% means that no disease is observed.
  • Example F in vivo test on Venturia inaequalis (apple scab) / protective
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsif ⁇ er, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at approximately 21 0 C and a relative atmospheric humidity o f approximately 90 % .
  • the test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • Example G in vivo test on Septoria tritici (wheat) / preventive
  • Emulsif ⁇ er 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsif ⁇ er, and the concentrate is diluted with water to the desired concentration.
  • the plants are sprayed with a spore suspension of Septoria tritici.
  • the plants remain for 48 hours in an incubation cabinet at approximately 20 0 C and a relative atmospheric humidity of approximately 100% and then 60 hours at approximately 15°C in a translucent incubation cabinet at a relative atmospheric humidity of approximately 100%.
  • the plants are placed in a greenhouse at a temperature of approximately 15 0 C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 21 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • Example H In vivo comparative test on Leptosphaeria nodorum (wheat) / preventive
  • Emulsif ⁇ er 1 part by weight of alkylaryl polyglycol ether
  • a suitable preparation of active compound 1 part by weight of active compound or the compound combination is mixed with the stated amounts of solvent and emulsif ⁇ er, and the concentrate is diluted with water to the desired concentration.
  • young plants are sprayed with a preparation of active compound or active compound combination at the stated rate of application. After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabinet at 20 0 C and a relative atmospheric humidity of 100%. The plants are placed in a greenhouse at a temperature of approximately 15°C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. Under these conditions, good (at least 70% of disease control or higher) is observed at a dose of 500ppm with the following compounds : 7 and 32 according to the invention whereas weak protection (less than 10% of disease control) is observed at a dose of 500ppm with the compounds of example 1.001 disclosed in international patent application WO-2007/134799.
  • Example 1.001 disclosed in patent application WO-2007/134799 corresponds to the following compound : cis-N- [2-(4-chlorophenyl)cyclopropyl] -3 -(difluoro-methyl)- 1 -methyl- 1 H-pyrazo Ie- 4-carboxamide

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Abstract

The present invention relates to a N-(Phenylcycloalkyl)carboxamide or N- (Benzylcycloalkyl)carboxamide or its thiocarboxamide derivative of formula (I) wherein A represents a carbo-linked, unsaturated or partially saturated, substituted or non-substituted 5- membered heterocyclyl group, T represents an oxygen or a sulphur atom, B represents a non aromatic carbocycle that can be substituted by one to four C1-C8-alkyl groups, and X, Z1, Z2 and Z3 represent various substituents; their process of preparation; the preparation of intermediate compounds; their use as fungicide active agents, particularly in the form of fungicide compositions and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.

Description

FUNGICIDAL N-(PHENYLCYCLOALKYL)CARBOXAMIDE, N-
(BENZYLCYCLOALKYL)CARBOXAMIDE AND THIOCARBOXAMIDE DERIVATIVES
DESCRIPTION
The present invention relates to fungicidal N-(Phenylcycloalkyl)carboxamide or N- (Benzylcycloalkyl)carboxamide or its thiocarboxamide derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.
In international patent application WO- 1998/03495, certain fungicidal N- (Phenylcyclohexyl)carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000002_0001
wherein R2 can represent a substituted aryl group or a substituted aralkyl group and n can be 1. However, this document does not disclose compounds wherein the nitrogen atom of the carboxamide residue can be substituted by a cycloalkyl group.
In international patent application WO-2007/134799 certain fungicidal N-(Phenylcyclopropyl) (thio)carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000002_0002
wherein A can represent a 5-membered heterocyclic ring, X can be an oxygen or sulfur atom, R1, R2, R3 and R4 can represent a hydrogen atom, a halogen atom, a Ci-C4-alkyl, a cyano or a nitro group, B can represent a substituted phenyl group and R5 can represent various substituents among which a hydrogen atom or a Ci-C4-alkyl group. However, this document does not disclose compounds wherein the nitrogen atom of the (thio)carboxamide residue can be substituted by a cycloalkyl group. In international patent application WO-2006/122955 certain fungicidal N-(2-Pyridylcycloalkyl) carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000003_0001
wherein Het can represent a 5-membered heterocyclic ring, A can represent a Cs-Cycycloalkyl ring, R1 and R2 can represent various substituents among which a hydrogen atom or a C1-C6- alkyl group, R can represent various substituents among which a hydrogen atom, a Ci-Cβ-alkyl group or a Cs-Cycycloalkyl group, and, X and Ra, the same or different, can represent various substituents among which a hydrogen atom, a halogen atom or a Ci-Cs-alkyl group. However, this document does not disclose compounds wherein the 2-pyridine moeity can be replaced by a phenyl group. Furthermore, there is no explicit disclosure in this document of any compound including a cycloalkyl group linked to the nitrogen atom of the carboxamide residue.
In international patent application WO-2005/103006 certain fungicidal N-(2-Pyridylcycloalkyl) carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000003_0002
wherein Het can represent a 5-membered heterocyclic ring, A can represent a Cs-Cycycloalkyl ring, R1 and R2 can represent various substituents among which a hydrogen atom or a C1-C6- alkyl group, R can represent various substituents among which a hydrogen atom, a Ci-Cβ-alkyl group or a Cs-Cycycloalkyl group, Ra represents a Ci-Cβ-halogenoalkyl group and X can represent a hydrogen atom, a halogen atom, a Ci-Cβ-alkyl group or a Ci-Cβ-halogenoalkyl group.
However, this document does not disclose compounds wherein the 2-pyridine moeity can be replaced by a phenyl group. Furthermore, there is no explicit disclosure in this document of any compound including a cycloalkyl group linked to the nitrogen atom of the carboxamide residue.
In international patent application WO-2009/016218 certain fungicidal N-cycloalkyl-N-bicyclic amides are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000004_0001
wherein A can represent a 5-membered heterocyclic ring, T can be an oxygen or sulfur atom, Z1 can represent a Cs-Cycycloalkyl ring, Z2 can represent various substituents among which a hydrogen atom or a Ci-Cβ-alkyl group, L1 or L2 can represent various linkers among which a non-substituted or substituted CH2, m can represent 1, 2 or 3 and X can represent a non- substituted or substituted CH or N. However, this document does not disclose compounds wherein the phenyl or the 2-pyridinyl moeity can be detached from the 5-, 6- or 7-membered cycloalkyl moeity.
In international patent application WO-2009/012998 certain fungicidal N-Phenyloxy- cycloalkylcarboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000004_0002
wherein A can represent a 5-membered heterocyclic ring, R1, R2, R3 and R4 can represent various substituents among which a hydrogen atom or a Ci-C4-alkyl group and Ri and R3 together with the carbon to which they are linked can form a C3-Cy-cycloalkyl ring that can be substituted by one or more Ci-Cβ-alkyl groups, B can represent a substituted phenyl group and Ri 5 can be a hydrogen atom or a C3-Cy-cycloalkyl group. However, this document does not disclose nor suggest compounds wherein the oxygen atom linking the B ring to the C3-Cy-cycloalkyl moeity can be replaced by a carbon atom.
It is always of high-interest in the field of agrochemicals to use pesticidal compounds more active than the compounds already known by the man ordinary skilled in the art whereby reduced amounts of compound can be used whilst retaining equivalent efficacy. Furthermore, the provision of new pesticidal compounds with a higher efficacy strongly reduces the risk of appearance of resistant strains in the fungi to be treated.
We have now found a new family of compounds which show enhanced fungicidal activity over the general known family of such compounds. Accordingly, the present invention provides a N-(Phenylcycloalkyl)carboxamide or N- (Benzylcycloalkyl)carboxamide or its thiocarboxamide derivative of formula (I)
Figure imgf000005_0001
wherein • A represents a carbo- linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R ;
• T represents O or S ;
• B represents a 3-, A-, 5-, 6- or 7-membered non aromatic carbocycle that can be substituted by one to four Ci-Cs-alkyl groups ; • n represents 0, 1, 2, 3, 4 or 5 ;
• m represents 0 or 1 ;
• X represents a halogen atom ; nitro ; cyano ; isonitrile ; hydroxy ; amino ; sulfanyl ; pentafluoro-λ6-sulfanyl ; formyl ; formyloxy ; formylamino ; substituted or non- substituted (hydroxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C1-C8- alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C2-Cs-alkenyloxyimino)-Ci-
Cs-alkyl ; substituted or non-substituted (C2-C8-alkynyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; carboxy ; carbamoyl ; N- hydroxycarbamoyl ; carbamate ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs- halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkenyl ; C2-C8-halogenoalkenyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-
C8-alkynyl ; C2-Cs-halogenoalkynyl having 1 to 5 halogen atoms ; substituted or non- substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfinyl ; Ci-Cs- halogenoalkylsulfinyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs- alkylsulfonyl ; Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylamino ; substituted or non-substituted di-Ci-Cs-alkylamino ; substituted or non-substituted C2-Cs-alkenyloxy ; C2-Cs-halogenoalkenyloxy having 1 to 5 halogen atoms ; substituted or non-substituted Cs-Cs-alkynyloxy ; C2-C8- halogenoalkynyloxy having 1 to 5 halogen atoms ; substituted or non-substituted C3-C7- cycloalkyl ; C3-C7-halogenocycloalkyl having 1 to 5 halogen atoms ; substituted or non- substituted (C3-C7-cycloalkyl)-Ci-C8-alkyl ; substituted or non-substituted (C3-C7- cycloalkyl)-C2-C8-alkenyl ; substituted or non-substituted (C3-C7-cycloalkyl)-C2-Cs- alkynyl ; substituted or non- substituted tri(Ci-C8)alkylsilyl ; substituted or non- substituted tri(Ci-C8)alkylsilyl-Ci-C8-alkyl ; substituted or non-substituted Ci-Cs- alkylcarbonyl ; Ci-Cs-halogenoalkylcarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylcarbonyloxy ; Ci-Cs-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylcarbonylamino ; Ci-Cs- halogenoalkyl- carbonylamino having 1 to 5 halogen atoms ; substituted or non- substituted Ci-Cs-alkoxycarbonyl ; Ci-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkyloxycarbonyloxy ; Ci-Cs- halogenoalkoxycarbonyloxy having 1 to 5 halogen atoms ; substituted or non-substituted Ci-C8-alkylcarbamoyl ; substituted or non-substituted di-Ci-Cs-alkylcarbamoyl ; substituted or non-substituted Ci-Cs-alkylaminocarbonyloxy ; substituted or non- substituted di-Ci-Cs-alkylaminocarbonyloxy ; substituted or non-substituted N-(C1-C8- alkyl)hydroxy carbamoyl ; substituted or non-substituted Ci-Cs-alkoxycarbamoyl ; substituted or non-substituted N-(Ci-Cs-alkyl)-Ci-Cs-alkoxycarbamoyl ; aryl that can be susbtituted by up to 6 groups Q ; Ci-Cs-arylalkyl that can be susbtituted by up to 6 groups Q ; C2-C8-arylalkenyl that can be susbtituted by up to 6 groups Q ; C2-Cs-arylalkynyl that can be susbtituted by up to 6 groups Q ; aryloxy that can be susbtituted by up to 6 groups Q ; arylsulfanyl that can be susbtituted by up to 6 groups Q ; arylamino that can be susbtituted by up to 6 groups Q ; Ci-Cs-arylalkyloxy that can be susbtituted by up to 6 groups Q ; Ci-Cs-arylalkylsulfanyl that can be susbtituted by up to 6 groups Q ; or Ci-Cs- arylalkylamino that can be susbtituted by up to 6 groups Q ; • two substituents X together with the consecutive carbon atoms to which they are linked can form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which can be substituted by up to four groups Q which can be the same or different ;
• Z1 and Z2 independently represent a hydrogen atom ; a halogen atom ; cyano ; a substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy; substituted or non-substituted Ci-Cs- alkylsulfanyl; or substituted or non-substituted Ci-Cs-alkoxycarbonyl ;
• Z3 represents a non-substituted C3-C7-cycloalkyl or a C3-C7-cycloalkyl substituted by up to 10 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkoxy, Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, Ci-Cs- alkoxycarbonyl, Ci-Cs-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkylaminocarbonyl and di-Ci-Cs-alkylamino- carbonyl ; • Z4 and Z5 independently represent a hydrogen atom ; a halogen atom ; cyano ; a substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy; substituted or non-substituted Ci-Cs- alkylsulfanyl ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; or Z4 and Z5 are a C2-C5-alkylene group that can be substituted by one to four d-Cg-alkyl groups ; • Q independently represents a halogen atom ; cyano ; nitro ; substituted or non- substituted
Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy having 1 to 9 halogen atoms that can be the same or different ; substituted or non- substituted C1- C8-alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 9 halogen atoms that can be the same or different ; substituted or non- substituted tri(Ci-C8)alkylsilyl ; substituted or non-substituted tri(Ci-C8)alkylsilyl-Ci-C8-alkyl ; substituted or non-substituted (C1-C8- alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ;
• R independently represents hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxy ; amino ; sulfanyl ; pentafluoro-λ6-sulfanyl ; substituted or non-substituted (C1-C8- alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted d-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkenyl ; C2-Cs-halogenoalkenyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkynyl ; C2-Cs-halogenoalkynyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy ; C1-C8- halogenoalkoxy having 1 to 5 halogen atoms ; substituted or non-substituted C1-C8- alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfmyl ; Ci-Cs-halogenoalkylsulfinyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfonyl ; Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylamino ; substituted or non-substituted di-Ci-Cs-alkylamino ; substituted or non-substituted C2-C8- alkenyloxy ; substituted or non-substituted Cs-Cs-alkynyloxy ; substituted or non- substituted C3-C7-cycloalkyl ; d-d-halogenocycloalkyl having 1 to 5 halogen atoms ; substituted or non-substituted tri(d-C8)alkylsilyl ; substituted or non-substituted C1-C8- alkylcarbonyl ; Ci-Cs-halogenoalkylcarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; Ci-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylcarbamoyl ; substituted or non- substituted di-Ci-Cs-alkylcarbamoyl ; phenoxy ; phenylsulfanyl ; phenylamino ; benzyloxy ; benzylsulfanyl ; or benzylamino ; as well as its salts, N-oxydes, metallic complexes, metalloidic complexes and optically active isomers.
For the compounds according to the invention, the following generic terms are generally used with the following meanings:
• halogen means fluorine, bromine, chlorine or iodine. carboxy means -C(=O)OH ; carbonyl means -C(=O)- ; carbamoyl means -Q=O)NH2 ; N-hydroxycarbamoyl means -C(=O)NHOH ; SO represents a sulfoxyde group ; SO2 represents a sulfone group ;
• an alkyl group, an alkenyl group and an alkynyl group as well as moieties containing these terms, can be linear or branched;
• the aryl moeity contained in an aryl group, an arylalkyl group, an arylalkenyl group and an arylalkynyl group as well as moieties containing these terms, can be a phenyl group that can be substituted by up to 5 groups Q, a naphtyl group that can be substituted by up to 6 groups Q or a pyridyl group that can be substituted by up to 4 groups Q ;
• and, heteroatom means sulphur, nitrogen or oxygen.
• in the case of an amino group or the amino moiety of any other amino-comprising group, substituted by two substituents that can be the same or different, the two substituents together with the nitrogen atom to which they are linked can form a heterocyclyl group, preferably a 5- to 7-membered heterocyclyl group, that can be substituted or that can include other hetero atoms, for example a morpholino group or piperidinyl group.
• unless indicated otherwise, a group or a substituent that is substituted according to the invention can be substituted by one or more of the following groups or atoms: a halogen atom, a nitro group, a hydroxy group, a cyano group, an amino group, a sulfanyl group, a pentafluoro-λ6-sulfanyl group, a formyl group, a formyloxy group, a formylamino group, a carbamoyl group, a N-hydroxycarbamoyl group, a carbamate group, a (hydroxyimino)- Ci-Ce-alkyl group, a Ci-C8-alkyl, a tri(Ci-C8-alkyl)silyl-Ci-C8-alkyl, Ci-C8-cycloalkyl, tri(Ci-C8-alkyl)silyl-Ci-C8-cycloalkyl, a Ci-C8-halogenoalkyl having 1 to 5 halogen atoms, a Ci-Cs-halogenocycloalkyl having 1 to 5 halogen atoms, a C2-Cs-alkenyl, a C2- Cg-alkynyl, a C2-Cs-alkenyloxy, a C2-Cs-alkynyloxy, a Ci-Cs-alkylamino, a di-d-Cg- alkylamino, a Ci-Cs-alkoxy, a Ci-Cs-halogenoalkoxy having 1 to 5 halogen atoms, a Ci- C8-alkylsulfanyl, a Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms, a C2-Cs- alkenyloxy, a C2-C8-halogenoalkenyloxy having 1 to 5 halogen atoms, a C3-C8- alkynyloxy, a Cs-Cs-halogenoalkynyloxy having 1 to 5 halogen atoms, a Ci-Cs- alkylcarbonyl, a Ci-Cs-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a Ci-Cs- alkylcarbamoyl, a di-Ci-Cs-alkylcarbamoyl, a N-Ci-Cs-alkyloxycarbamoyl, a Ci-Cs- alkoxycarbamoyl, a N-Ci-Cs-alkyl-Ci-Cs-alkoxycarbamoyl, a Ci-Cs-alkoxycarbonyl, a Ci-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a Ci-Cs-alkylcarbonyloxy, a
Ci-Cs-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, a Ci-Cs- alkylcarbonylamino, a Ci-Cs-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a Ci-Cs-alkylaminocarbonyloxy, a di-Ci-Cs-alkylaminocarbonyloxy, a Ci-Cs- alkyloxycarbonyloxy, a Ci-Cs-alkylsulfmyl, a Ci-Cs-halogenoalkylsulfinyl having 1 to 5 halogen atoms, a Ci-Cs-alkylsulfonyl, a Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms, a Ci-Cs-alkylaminosulfamoyl, a di-Ci-Cs-alkylaminosulfamoyl, a (C1-C6- alkoxyimino)-Ci-C6-alkyl, a (Ci-C6-alkenyloxyimino)-Ci-C6-alkyl, a (C1-C6- alkynyloxyimino)-C1-C6-alkyl, a 2-oxopyrrolidin-l-yl, (benzyloxyimino)-Ci-C6-alkyl, d-Cg-alkoxyalkyl, Ci-Cs-halogenoalkoxyalkyl having 1 to 5 halogen atoms, benzyloxy, benzylsulfanyl, benzylamino, phenoxy, phenylsulfanyl, or phenylamino.
Any of the compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term "scalemic" denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art. Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art. Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents of ring B. The invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions. The syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art. Any of the compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group may be found in its tautomeric form resulting from the shift of the proton of said hydroxy, sulfanyl or amino group. Such tautomeric forms of such compounds are also part of the present invention. More generally speaking, all tautomeric forms of compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group, as well as the tautomeric forms of the compounds which can optionally be used as intermediates in the preparation processes and which will be defined in the description of these processes, are also part of the present invention.
Preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of: - a heterocycle of formula (A1)
Figure imgf000010_0001
wherein :
R1 to R3 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A2)
Figure imgf000010_0002
wherein :
R > 4 t -o„ r R> 6 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A )
Figure imgf000011_0001
wherein :
R7 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci- C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R8 represents a hydrogen atom or a substituted or non-substituted Ci-Cs-alkyl ;
- a heterocycle of formula (A4)
Figure imgf000011_0002
wherein :
R9 to R11 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; amino ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted Ci-Cs-alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A5)
Figure imgf000011_0003
wherein : R12 and R13 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; amino ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci- C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R14 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; amino ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A6)
Figure imgf000012_0001
wherein
R , 15 represents a hydrogen atom ; a halogen atom ; a cyano ; substituted or non-substituted C1-C5- alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R16 and R18 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or
Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R17 represent a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
- a heterocycle of formula (A7)
Figure imgf000012_0002
wherein :
R19 represents a hydrogen atom or a Ci-C5 -alkyl R20 to R22 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A8)
Figure imgf000013_0001
wherein :
R23 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R24 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;
- a heterocycle of formula (A9)
Figure imgf000013_0002
wherein :
R25 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R26 represents a hydrogen atom ; substituted or non-substituted Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A 10\ )
Figure imgf000013_0003
wherein
R , 27 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R , 28 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non-substituted di(Ci-Cs- alkyl)amino ;
- a heterocycle of formula (A I h )
Figure imgf000014_0001
wherein :
R29 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R30 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non-substituted di(Ci-Cs- alkyl)amino ;
- a heterocycle of formula (A12)
Figure imgf000014_0002
wherein :
R31 represents a hydrogen atom or a substituted or non-substituted Ci-Cs-alkyl R32 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R33 represents a hydrogen atom ; a halogen atom ; a nitro ; substituted or non-substituted C1-C5- alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A13)
Figure imgf000015_0001
wherein :
R34 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted C3-Cs-cycloalkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C2-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R35 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; a cyano ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C1-C5- alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non- substituted di(Ci-C5-alkyl)amino; R36 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A14)
Figure imgf000015_0002
wherein : R37 and R38 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci-Cs-alkoxy or a substituted or non- substituted C1-C5- alkylsulphanyl ; R , 39 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl
- a heterocycle of formula (A 15\ )
Figure imgf000016_0001
wherein :
R40 and R41 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A 16Λ )
Figure imgf000016_0002
wherein :
R > 42 and i r R> 43 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or amino ;
-a heterocycle of formula (A 17\ )
Figure imgf000016_0003
wherein :
R44 and R45 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A 18Λ )
Figure imgf000017_0001
wherein :
R47 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R46 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or substituted or non- substituted Ci-Cs-alkylsulfanyl ;
- a heterocycle of formula (A 19\ )
Figure imgf000017_0002
wherein :
R49 and R48 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
a heterocycle of formula (A 2(k )
Figure imgf000017_0003
wherein :
R50 and R51 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; -a heterocycle of formula (A21)
Figure imgf000018_0001
wherein : R52 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A22)
Figure imgf000018_0002
wherein :
R53 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A23)
Figure imgf000018_0003
wherein :
R54 and R56 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R55 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A24)
Figure imgf000019_0001
wherein :
R57 and R59 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R58 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A 25x )
Figure imgf000019_0002
wherein :
R60 and R61 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R62 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A26)
Figure imgf000019_0003
wherein :
R65 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Cs-Cs-cycloalkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C2-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R63 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; a cyano ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C1-C5- alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or di(Ci-C5-alkyl)amino; R64 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl.
More preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of A2 ; A6 ; A10 and A13 as herein-defined. Even more preferred compounds according to the invention are compounds of formula (I) wherein A represents A 13 wherein R34 represents a substituted or non-substituted Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci-Cs-alkoxy ; R35 represents a hydrogen atom or a halogen atom and R36 represents a substituted or non-substituted Ci-Cs-alkyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein T represents O.
Other preferred compounds according to the invention are compounds of formula (I) wherein n represents 0, 1 or 2.
Other preferred compounds according to the invention are compounds of formula (I) wherein B is a 3-, 5-, 6- or 7-membered non aromatic carbocycle that can be substituted by one to four Ci- Cs-alkyl groups.
Even more preferably, B is chosen from cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl carbocycle that can be substituted by one to four methyl groups.
Other preferred compounds according to the invention are compounds of formula (I) wherein X independently represents a halogen atom ; substituted or non-substituted d-Cg-alkyl ; Ci-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted tri(Ci-C8-alkyl)silyl ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non substituted 1,3-benzodioxolyl ; 1,2,3,4-tetrahydro-quinoxalinyl ; 3,4-dihydro-2H-l,4- benzoxazinyl ; 1 ,4-benzodioxanyl ; indanyl ; 2,3-dihydrobenzofuranyl ; or indolinyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein Z1 and Z2 independently represent a hydrogen atom or a substituted or non- substituted Ci-Cs-alkyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein Z represents a non- substituted C3-C7 cycloalkyl or a C3-C7 cycloalkyl substituted by up to 10 groups or atoms that can be the same or different and that can be selected in the list consisting of halogen atoms, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different. More preferably Z3 represents a non-substituted C3-C7- cycloalkyl ; even more preferably Z3 represents cyclopropyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein Z4 and Z5 independently represent a hydrogen atom, a halogen atom or a substituted or non- substituted Ci-C8-alkyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein R independently represents a hydrogen atom ; halogen atom ; cyano ; substituted or non-substituted Ci-Cs-alkylamino ; substituted or non-substituted di-Ci-Cs-alkylamino ; substituted or non- substituted tri(Ci-C8-alkyl)silyl ; substituted or non-substituted d-Cg-alkyl ; Ci-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkylsulfanyl ; amino ; hydroxyl ; nitro ; substituted or non- substituted Ci-Cs-alkoxycarbonyl ; substituted or non- substituted C2- C8-alkynyloxy.
The above mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention can be combined: - preferred features of A with preferred features of B, Z1, Z2, Z3, Z4, Z5, X, T, n, m and R; - preferred features of B with preferred features of A, Z1, Z2, Z3, Z4, Z5, X, T, n, m and R;
- preferred features of Z1 with preferred features of A, B, Z2, Z3, Z4, Z5, X, T, n, m and R;
- preferred features of Z2 with preferred features of A, B, Z1, Z3, Z4, Z5, X, T, n, m and R;
- preferred features of Z3 with preferred features of A, B, Z1, Z2, Z4, Z5, X, T, n, m and R; - preferred features of Z4 with preferred features of A, B, Z1, Z2, Z3, Z5, X, T, n, m and R;
- preferred features of Z5 with preferred features of A, B, Z1, Z2, Z3, Z4, X, T, n, m and R;
- preferred features of X with preferred features of A, B, Z1, Z2, Z3, Z4, Z5, T, n, m and R;
- preferred features of T with preferred features of A, B, Z1, Z2, Z3, Z4, Z5, X, n, m and R;
- preferred features of n with preferred features of A, B, Z1, Z2, Z3, Z4, Z5, X, T, m and R; - preferred features of m with preferred features of A, B, Z1, Z2, Z3, Z4, Z5, X, T, n and R;
- preferred features of R with preferred features of A, B, Z1, Z2, Z3, Z4, Z5, X, T, n and m;
In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of A, B, Z1, Z2, Z3, Z4, Z5' X, T, n, m and R, so as to form most preferred subclasses of compounds according to the invention.
The present invention also relates to a process for the preparation of the compound of formula
(I)- Thus, according to a further aspect of the present invention there is provided a process Pl for the preparation of a compound of formula (I) as herein-defined and wherein T represents O and that comprises reacting a 2-phenylcycloalkylamine or 2-benzylcycloalkylamine derivative of formula (II) or one of its salts:
Figure imgf000022_0001
wherein X, n, m, B, Z1, Z2, Z3, Z4 and Z5 are as herein-defined; with a carboxylic acid derivative of formula (III):
Figure imgf000022_0002
wherein A is as herein-defined and L1 represents a leaving group selected in the list consisting of a halogen atom, a hydroxyl group, -ORa, -OC(=O)Ra, Ra being a substituted or non-substituted Ci-Cβ-alkyl, a substituted or non- substituted Ci-Cβ-haloalkyl, a benzyl, 4-methoxybenzyl or pentafluorophenyl group, or a group of formula O-C(=O)A ; in the presence of a catalyst and in the presence of a condensing agent in case L1 represents a hydroxyl group, and in the presence of an acid binder in case L1 represents a halogen atom.
N-cycloalkylamine derivatives of formula (II) can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters (2006), 2014), or reduction of imines (Tetrahedron (2005), 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 3887).
Carboxylic acid derivatives of formula (III) can be prepared by known processes.
In case L1 represents a hydroxy group, the process according to the present invention is conducted in the presence of condensing agent. Suitable condensing agent may be selected in the non limited list consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous -pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl- chloride; carbodiimides, such as N,N'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, N,N'-carbonyl-diimidazole, 2-ethoxy-N- ethoxycarbonyl-l,2-dihydroquinoline (EEDQ), triphenylphosphine/tetrachloro-methane, 4-(4,6- dimethoxy[1.3.5]triazin-2-yl)-4-methylmorpholinium chloride hydrate or bromo-tripyrrolidino- phosphonium-hexafluorophosphate.
The process according to the present invention is conducted in the presence of a catalyst. Suitable catalyst may be selected in the list consisting of 4-dimethyl-aminopyridine, 1-hydroxy- benzotriazole or dimethylformamide.
In case L1 represents a halogen atom, the process according to the present invention is conducted in the presence of an acid binder. Suitable acid binders for carrying out process Pl according to the invention are in each case all inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as cesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetateand also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N- methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
It is also possible to work in the absence of an additional condensing agent or to employ an excess of the amine component, so that it simultaneously acts as acid binder agent.
According to a further aspect according to the invention, there is provided a process P2 for the preparation of a compound of formula (I) wherein T represents S, starting from a compound of formula (I) wherein T represents O and illustrated according to the following reaction scheme :
Figure imgf000024_0001
wherein X, n, m, B, Z1, Z2, Z3, Z4, Z5 and A are as herein-defined, in the optional presence of a catalytic or stoechiometric or more, quantity of a base such as an inorganic and organic base.
Preference is given to using alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate ; heterocyclic aromatic bases, such as pyridine, picoline, lutidine, collidine ; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylaminopyridine or N-methylpiperidine.
Process P2 according to the invention is performed in the presence of a thionating agent.
Starting amide derivatives of formula (I) can be prepared according to processes Pl.
Suitable thionating agents for carrying out process P2 according to the invention can be sulphur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfϊde (NaHS), boron trisulfϊde (B2S3), bis (diethylaluminium) sulfide ((AlEt2)2S), ammonium sulfide ((NH4)2S), phosphorous pentasulfϊde (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-l,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in J.Chem.Soc. Perkin 1, (2001), 358. The compound according to the present invention can be prepared according to the general processes of preparation described above. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesize.
Still in a further aspect, the present invention relates to compounds of formula (II) useful as intermediate compounds or materials for the process of preparation according to the invention. The present invention thus provides compounds of formula (II) :
Figure imgf000025_0001
wherein X, n, m, Z1, Z2, Z3, Z4 and Z5 are as herein-defined, and B represents a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl group with the exclusion of N-cyclopropyl-2- pheny lcyclo hexanamine . On the basis of the present description and his general knowledge and of available publications as for example the international patent application WO-2006/122955, the skilled person can prepare intermediate compound of formula (II) according to the present invention.
In a further aspect, the present invention also relates to a fungicide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).
The expression "effective and non-phytotoxic amount" means an amount of composition according to the invention that is sufficient to control or destroy the fungi present or liable to appear on the cropsand that does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
Thus, according to the invention, there is provided a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler. According to the invention, the term "support" denotes a natural or synthetic, organic or inorganic compound with that the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.
The composition according to the invention can also comprise additional components. In particular, the composition can further comprise a surfactant. The surfactant can be an emulsifϊer, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention can be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyolsand derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content can be comprised from 5% to 40% by weight of the composition.
Optionally, additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, that complies with the usual formulation techniques.
In general, the composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight.
Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifϊable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure),gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions that are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions that must be diluted before application to the crop.
The compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity. The mixtures thus obtained have normally a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous.
Examples of suitable fungicide mixing partners can be selected in the following lists:
(1) Inhibitors of the ergosterol biosynthesis, for example (1.1) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325- 08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin (67306-00-7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20) fiurprimidol (56425- 91-3), (1.21) fiusilazole (85509-19-9), (1.22) flutriafol (76674-21-0), (1.23) furconazole (112839-33-5), (1.24) furconazole-cis (112839-32-4), (1.25) hexaconazole (79983-71-4), (1.26) imazalil (60534-80-7), (1.27) imazalil sulfate (58594-72-2), (1.28) imibenconazole (86598-92- 7), (1.29) ipconazole (125225-28-7), (1.30) metconazole (125116-23-6), (1.31) myclobutanil (88671-89-0), (1.32) naftifme (65472-88-0), (1.33) nuarimol (63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) paclobutrazol (76738-62-0), (1.36) pefurazoate (101903-30-4), (1.37) penconazole (66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747-09-5), (1.40) propiconazole (60207-90-1), (1.41) prothioconazole (178928-70-6), (1.42) pyributicarb (88678- 67-5), (1.43) pyrifenox (88283-41-4), (1.44) quinconazole (103970-75-8), (1.45) simeconazole (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole (107534-96-3), (1.48) terbinafϊne (91161-71-6), (1.49) tetraconazole (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol (89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole (68694-11- 1), (1.54) triforine (26644-46-2), (1.55) triticonazole (131983-72-7), (1.56) uniconazole (83657- 22-1), (1.57) uniconazole-p (100761-65-7), (1.58) viniconazole (77174-66-4), (1.59) voriconazole (137234-62-9), (1.60) l-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-yl)cycloheptanol (129586-32-9), (1.61) methyl l-(2,2-dimethyl-2,3-dihydro-lH-inden-l-yl)-lH-imidazole-5- carboxylate (111323-95-0), (1.62) N'-{5-(difluoromethyl)-2-methyl-4-[3-
(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, (1.63) N-ethyl-N-methyl- N'- {2-methyl-5 -(trifluoromethyl)-4- [3 -(trimethylsilyl)propoxy]phenyl} imido formamide and (1.64) O-{l-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl} lH-imidazole-1-carbothioate (111226-71-2).
(2) inhibitors of the respiratory chain at complex I or II, for example (2.1) bixafen (581809-46- 03), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68-4), (2.4) difiumetorim (130339-07-0), (2.5) fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) furametpyr (123572-88-3), (2.9) furmecyclox (60568-05-0), (2.10) isopyrazam (mixture of syn- epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR) (881685-58-1), (2.11) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.12) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.13) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.14) isopyrazam (syn epimeric racemate 1RS,4SR,9RS), (2.15) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.16) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.17) mepronil (55814-41- 0), (2.18) oxycarboxin (5259-88-1), (2.19) penfiufen (494793-67-8), (2.20) penthiopyrad (183675-82-3), (2.21) sedaxane (874967-67-6), (2.22) thifiuzamide (130000-40-7), (2.23) 1- methyl-N- [2-( 1 , 1 ,2,2-tetrafluoroethoxy)phenyl] -3 -(trifluoromethyl)- 1 H-pyrazo le-4-carboxamide, (2.24) 3-(difluoromethyl)-l-methyl-N-(3',4',5'-trifluorobiphenyl-2-yl)-lH-pyrazole-4- carboxamide, (2.25) 3-(difluoromethyl)-l-methyl-N-[2-(l,l,2,2-tetrafluoroethoxy)phenyl]-lH- pyrazole-4-carboxamide, (2.26) 3-(difluoromethyl)-N-[4-fluoro-2-(l,l,2,3,3,3- hexafluoropropoxy)phenyl]-l -methyl- lH-pyrazole-4-carboxamide and salts thereof.
(3) inhibitors of the respiratory chain at complex III, for example (3.1) amisulbrom (348635-87- 0), (3.2) azoxystrobin (131860-33-8), (3.3) cyazofamid (120116-88-3), (3.4) dimoxystrobin (141600-52-4), (3.5) enestroburin (238410-11-2) (known from WO 2004/058723), (3.6) famoxadone (131807-57-3) (known from WO 2004/058723), (3.7) fenamidone (161326-34-7) (known from WO 2004/058723), (3.8) fiuoxastrobin (361377-29-9) (known from WO 2004/058723), (3.9) kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.10) metominostrobin (133408-50-1) (known from WO 2004/058723), (3.11) orysastrobin (189892- 69- 1 ) (known from WO 2004/058723), (3.12) picoxystrobin ( 117428-22-5) (known from WO 2004/058723), (3.13) pyraclostrobin (175013-18-0) (known from WO 2004/058723), (3.14) pyrametostrobin (915410-70-7) (known from WO 2004/058723), (3.15) pyraoxystrobin (862588-11-2) (known from WO 2004/058723), (3.16) pyribencarb (799247-52-2) (known from WO 2004/058723), (3.17) trifioxystrobin (141517-21-7) (known from WO 2004/058723), (3.18) (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2- (methoxyimino)-N-methylethanamide (known from WO 2004/058723), (3.19) (2E)-2- (methoxyimino)-N-methyl-2-(2-{[({(lE)-l-[3-
(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide (known from WO 2004/058723) and salts thereof, (3.20) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({l-[3- (trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide (158169-73-4), (3.21) (2E)-2- {2-[({[(lE)-l-(3-{[(E)-l-fluoro-2- phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N- methylethanamide (326896-28-0), (3.22) (2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en- 2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide, (3.23) 2-chloro- N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)pyridine-3-carboxamide (119899-14-8), (3.24) 5- methoxy-2-methyl-4-(2-{[({(lE)-l-[3-
(trifluoromethyl)phenyl]ethylidene} amino)oxy]methyl}phenyl)-2,4-dihydro-3H- 1 ,2,4-triazol-3- one, (3.25) methyl 2-{2-[({cyclopropyl[(4- methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3-methoxyacrylate (149601-03-6), (3.26) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide (226551- 21-9) and salts thereof.
(4) Inhibitors of the mitosis and cell division, for example (4.1) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7) fuberidazole (3878-19- 1), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5) and (4.13) 5- chloro-7-(4-methylpiperidin- 1 -yl)-6-(2,4,6-trifluorophenyl)[ 1 ,2,4]triazolo [ 1 ,5-a]pyrimidine (214706-53-3).
(5) Compounds capable to have a multisite action, like for example (5.1) bordeaux mixture (8011-63-0), (5.2) captafol (2425-06-1), (5.3) captan (133-06-2) (known from WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copper hydroxide (20427-59-2), (5.6) copper naphthenate (1338-02-9), (5.7) copper oxide (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9) copper(2+) sulfate (7758-98-7), (5.10) dichlofluanid (1085-98-9), (5.11) dithianon (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free base, (5.14) ferbam (14484-64-1), (5.15) fluorofolpet (719-96-0), (5.16) folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18) guazatine acetate, (5.19) iminoctadine (13516-27-3), (5.20) iminoctadine albesilate (169202-06- 6), (5.21) iminoctadine triacetate (57520-17-9), (5.22) mancopper (53988-93-5), (5.23) mancozeb (2234562), (5.24) maneb (12427-38-2), (5.25) metiram (9006-42-2), (5.26) metiram zinc (9006-42-2), (5.27) oxine-copper (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb (12071-83-9), (5.30) sulphur and sulphur preparations including calcium polysulphide (7704-34-9), (5.31) thiram (137-26-8), (5.32) tolylfluanid (731-27-1), (5.33) zineb (12122-67-7), (5.34) ziram (137-30-4) and salts thereof.
(6) Compounds capable to induce a host defence, like for example (6.1) acibenzolar-S-methyl (135158-54-2), (6.2) isotianil (224049-04-1), (6.3) probenazole (27605-76-1) and (6.4) tiadinil (223580-51-6).
(7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.1) andoprim (23951- 85-1), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980- 18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7) and (7.7) pyrimethanil (53112-28-0).
(8) Inhibitors of the ATP production, for example (8.1) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide (76-87-9), (8.4) and silthiofam (175217-20-6).
(9) Inhibitors of the cell wall synthesis, for example (9.1) benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7) polyoxorim (22976-86- 9), (9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0).
(10) Inhibitors of the lipid and membrane synthesis, for example (10.1) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb (25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11) prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18- 6), (10.13) quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15) tolclofos-methyl (57018-04-9). (11) Inhibitors of the melanine biosynthesis, for example (11.1) carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3) fenoxanil (115852-48-7), (11.4) phthalide (27355-22-2), (11.5) pyroquilon (57369-32-1) and (11.6) tricyclazole (41814-78-2).
(12) Inhibitors of the nucleic acid synthesis, for example (12.1) benalaxyl (71626-11-4), (12.2) benalaxyl-M (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-85-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30-7), (12.8) hymexazol (10004-44-1), (12.9) metalaxyl (57837-19-1), (12.10) metalaxyl-M (70630-17- 0), (12.11) ofurace (58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4).
(13) Inhibitors of the signal transduction, for example (13.1) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fiudioxonil (131341-86-1), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7) vinclozolin (50471-44-8).
(14) Compounds capable to act as an uncoupler, like for example (14.1) binapacryl (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone (89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5) meptyldinocap (131-72-6).
(15) Further compounds like for example (15.1) l-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5- dihydro- 1 ,2-oxazol-3-yTJ- 1 ,3-thiazol-2-yl}piperidin- 1 -yl)-2-[5-methyl-3-(trifluoromethyl)- IH- pyrazol-l-yl]ethanone, (15.2) l-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl lH-imidazole- 1-carboxylate (111227-17-9), (15.3) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52- 6), (15.4) 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7), (15.5) 2-[5- methyl-3-(trifluoromethyl)- lH-pyrazol- 1 -yl]- 1 -(4- {4-[(5R)-5-phenyl-4,5-dihydro- 1 ,2-oxazol-3- yl]- 1 ,3-thiazol-2-yl}piperidin- 1 -yl)ethanone, (15.6) 2-butoxy-6-iodo-3-propyl-4H-chromen-4- one, (15.7) 2-phenylphenol and salts (90-43-7), (15.8) 3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.9) 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine, (15.10) 3- chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.11) 4-(4- chlorophenyl)-5-(2,6-difluorophenyl)-3 ,6-dimethylpyridazine, (15.12) 5-amino- 1,3,4- thiadiazole-2-thiol, (15.13) 5-chloro-N'-phenyl-N'-prop-2-yn-l-ylthiophene-2-sulfonohydrazide (134-31-6), (15.14) 5-methyl-6-octyl-3,7-dihydro[l,2,4]triazolo[l,5-a]pyrimidin-7-amine, (15.15) ametoctradin (865318-97-4), (15.16) benthiazole (21564-17-0), (15.17) bethoxazin (163269-30-5), (15.18) capsimycin (70694-08-5), (15.19) carvone (99-49-0), (15.20) chinomethionat (2439-01-2), (15.21) chlazafenone (688046-61-9), (15.22) cufraneb (11096-18- 7), (15.23) cyflufenamid (180409-60-3), (15.24) cymoxanil (57966-95-7), (15.25) cyprosulfamide (221667-31-8), (15.26) dazomet (533-74-4), (15.27) debacarb (62732-91-6), (15.28) dichlorophen (97-23-4), (15.29) diclomezine (62865-36-5), (15.30) difenzoquat (43222- 48-6), (15.31) difenzoquat methylsulphate (43222-48-6), (15.32) diphenylamine (122-39-4),
(15.33) ecomate, (15.34) ethyl (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.35) flumetover (154025-04-4), (15.36) fluoroimide (41205-21-4), (15.37) fiusulfamide (106917-52-6), (15.38) flutianil (304900-25-2), (15.39) fosetyl-aluminium (39148-24-8), (15.40) fosetyl-calcium, (15.41) fosetyl-sodium (39148-16-8), (15.42) hexachlorobenzene (118-74-1), (15.43) irumamycin (81604-73-1), (15.44) methasulfocarb (66952-49-6), (15.45) methyl isothiocyanate (556-61-6), (15.46) metrafenone (220899-03-6), (15.47) mildiomycin (67527-71-3), (15.48) N- (4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn- 1 -yloxy)phenyl]propanamide, (15.49) N- [(4- chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn- 1 -yloxy)phenyl]propanamide, (15.50) N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide, (15.51) N-[I- (5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, (15.52) N-[l-(5- bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide, (15.53) N- ((E)- [(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2- phenylacetamide, (15.54) N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3- difiuorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.55) natamycin (7681-93-8), (15.56) nickel dimethyldithiocarbamate (15521-65-0), (15.57) nitrothal-isopropyl (10552-74-6), (15.58) N-methyl-2-( 1 - { [5 -methyl-3 -(trifluoromethyl)- 1 H-pyrazo 1- 1 -yl] acetyl} piperidin-4-yl)- N-( 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl)- 1 ,3 -thiazo le-4-carboxamide, (15.59) N-methyl-2-( 1 - { [5 - methyl-3 -(trifluoromethyl)- 1 H-pyrazo 1- 1 -yl]acetyl}piperidin-4-yl)-N-[(l R)- 1 ,2,3,4- tetrahydronaphthalen-l-yl]-l,3-thiazole-4-carboxamide, (15.60) octhilinone (26530-20-1), (15.61) oxamocarb (917242-12-7), (15.62) oxyfenthiin (34407-87-9), (15.63) pentachlorophenol and salts (87-86-5), (15.64) pentyl {6-[({[(l-methyl-lH-tetrazol-5- yl)(phenyl)methylidene] amino} oxy)methyl]pyridin-2-yl} carbamate, (15.65) phenazine- 1 - carboxylic acid, (15.66) phenothrin, (15.67) phosphorous acid and its salts (13598-36-2), (15.68) propamocarb-fosetylate, (15.69) propanosine-sodium (88498-02-6), (15.70) proquinazid (189278-12-4), (15.71) pyrrolnitrine (1018-71-9) (known from EP-A 1 559 320), (15.72) quinolin-8-ol (134-31-6), (15.73) quinolin-8-ol sulfate (2:1) (salt) (134-31-6), (15.74) fenpyrazamine (473798-59-3), (15.75) tebufloquin (376645-78-2), (15.76) tecloftalam (76280- 91-6), (15.77) tolnifanide (304911-98-6), (15.78) triazoxide (72459-58-6), (15.79) trichlamide (70193-21-4), (15.80) zarilamid (84527-51-5) and salts thereof. The composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous. Examples of suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
The compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.
Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.
The method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
Among the plants that can be protected by the method according to the invention, mention can be made of cotton; flax; vine; fruit or vegetable crops such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons oranges and grapefruit); Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); major crops such as Graminae sp. (for instance maize, lawn or cereals such as wheat, rye, rice, barley and triticale), Asteraceae sp. (for instance sunflower), Cruciferae sp. (for instance colza), Fabacae sp. (for instance peanuts), Papilionaceae sp. (for instance soybean), Solanaceae sp. (for instance potatoes), Chenopodiaceae sp. (for instance beetroots), Elaeis sp. (for instance oil palm); horticultural and forest crops; as well as genetically modified homologues of these crops. The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The expression "heterologous gene" essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, co suppression technology or RNA interference - RNAi - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
At certain application rates, the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted phytopathogenic fungi and/ or microorganisms and/or viruses. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, for example against fungi. Plant-strengthening (resistance- inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted phytopathogenic fungi and/ or microorganisms and/or viruses, the treated plants display a substantial degree of resistance to these unwanted phytopathogenic fungi and/ or microorganisms and/or viruses. In the present case, unwanted phytopathogenic fungi and/ or microorganisms and/or viruses are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Thus, the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment. The period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechno logical means).
Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozon exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability. Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stress factors. Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male- fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants it is typically useful to ensure that male fertility in the hybrid plants is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male-sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) were for instance described in Brassica species (WO 1992/005251, WO 1995/009910, WO 1998/27806, WO 2005/002324, WO 2006/021972 and US 6,229,072). However, genetic determinants for male sterility can also be located in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful means of obtaining male-sterile plants is described in WO 1989/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 1991/002069).
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
Herbicide-tolerant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5 -enolpyruvylshikimate-3 -phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al, Science (1983), 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., Curr. Topics Plant Physiol. (1992), 7, 139-145), the genes encoding a Petunia EPSPS (Shah et al., Science (1986), 233, 478-481), a Tomato EPSPS (Gasser et al, J. Biol. Chem. (1988),263, 4280-4289), or an Eleusine EPSPS (WO 2001/66704). It can also be a mutated EPSPS as described in for example EP-A 0837944, WO 2000/066746, WO 2000/066747 or WO 2002/026995. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido -reductase enzyme as described in US 5,776,760 and US 5,463,175. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyl transferase enzyme as described in for example WO 2002/036782, WO 2003/092360, WO 2005/012515 and WO 2007/024782. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally-occurring mutations of the above-mentioned genes, as described in for example WO 2001/024615 or WO 2003/013226. Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition. One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinothricin acetyltransferase are for example described in US 5,561,236; US 5,648,477; US 5,646,024; US 5,273,894; US 5,637,489; US 5,276,268; US 5,739,082; US 5,908,810 and US 7,112,665. Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated HPPD enzyme as described in WO 1996/038567, WO 1999/024585 and WO 1999/024586. Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native
HPPD enzyme by the HPPD-inhibitor. Such plants and genes are described in WO 1999/034008 and WO 2002/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate dehydrogenase in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928. Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides. Different mutations in the ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides, as described for example in Tranel and Wright, Weed Science (2002), 50, 700-712, but also, in US 5,605,011, US 5,378,824, US 5,141,870, and US 5,013,659. The production of sulfonylurea- tolerant plants and imidazolinone-tolerant plants is described in US 5,605,011; US 5,013,659; US 5,141,870; US 5,767,361; US 5,731,180; US 5,304,732; US 4,761,373; US 5,331,107; US 5,928,937; and US 5,378,824; and international publication WO 1996/033270. Other imidazolinone-tolerant plants are also described in for example WO 2004/040012,
WO 2004/106529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO 2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants are also described in for example WO 2007/024782.
Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in US 5,084,082, for rice in WO 1997/41218, for sugar beet in US 5,773,702 and WO 1999/057965 , for lettuce in US 5,198,599, or for sunflower in WO 2001/065922.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance. An "insect-resistant transgenic plant", as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:
1) an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal portion thereof, such as the insecticidal crystal proteins listed by Crickmore et al, Microbiology and Molecular Biology Reviews (1998), 62, 807-813, updated by Crickmore et al. (2005) at the Bacillus thuringiensis toxin nomenclature, online at: http://www.lifesci. Sussex. ac.uk/Home/Neil_Crickmore/Bt/), or insecticidal portions thereof, e.g., proteins of the Cry protein classes CrylAb, CrylAc, CrylF, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof; or
2) a crystal protein from Bacillus thuringiensis or a portion thereof which is insecticidal in the presence of a second other crystal protein from Bacillus thuringiensis or a portion thereof, such as the binary toxin made up of the Cry34 and Cry35 crystal proteins
(Moellenbeck et al., Nat. Biotechnol. (2001), 19, 668-72; Schnepf et al., Applied Environm. Microbiol. (2006), 71, 1765-1774); or
3) a hybrid insecticidal protein comprising parts of different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, e.g., the CrylA.105 protein produced by corn event MON98034 (WO 2007/027777); or
4) a protein of any one of 1) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation, such as the Cry3Bbl protein in corn events MON863 or MON88017, or the Cry3A protein in corn event MIR604;
5) an insecticidal secreted protein from Bacillus thuringiensis or Bacillus cereus, or an insecticidal portion thereof, such as the vegetative insecticidal (VIP) proteins listed at: http://www.lifesci. Sussex. ac.uk/home/Neil_Crickmore/Bt/vip.html, e.g., proteins from the VIP3Aa protein class; or
6) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin made up of the VIPlA and VIP2A proteins (WO 1994/21795); or
7) a hybrid insecticidal protein comprising parts from different secreted proteins from Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1) above or a hybrid of the proteins in 2) above; or 8) a protein of any one of 1) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT 102.
Of course, an insect-resistant transgenic plant, as used herein, also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 8. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 8, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect. Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include:
a. plants which contain a transgene capable of reducing the expression and/or the activity of poly(ADP-ribose)polymerase (PARP) gene in the plant cells or plants as described in WO 2000/004173 or WO2006/045633 or PCT/EP07/004142.
b. plants which contain a stress tolerance enhancing transgene capable of reducing the expression and/or the activity of the PARG encoding genes of the plants or plants cells, as described e.g. in WO 2004/090140.
c. plants which contain a stress tolerance enhancing transgene coding for a plant- functional enzyme of the nicotinamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide phosphoribosyltransferase as described e.g. in WO2006/032469 or WO 2006/133827 or PCT/EP07/002433.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as :
1) transgenic plants which synthesize a modified starch, which in its physical-chemical characteristics, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscosity behaviour, the gelling strength, the starch grain size and/or the starch grain morphology, is changed in comparison with the synthesised starch in wild type plant cells or plants, so that this is better suited for special applications. Said transgenic plants synthesizing a modified starch are disclosed, for example, in EP 0571427, WO 1995/004826, EP
0719338, WO 1996/15248, WO 1996/19581, WO 1996/27674, WO 1997/11188, WO 1997/26362, WO 1997/32985, WO 1997/42328, WO 1997/44472, WO 1997/45545, WO 1998/27212, WO 1998/40503, WO99/58688, WO 1999/58690, WO 1999/58654, WO 2000/008184, WO 2000/008185, WO 2000/008175, WO 2000/28052, WO 2000/77229, WO 2001/12782, WO 2001/12826, WO 2002/101059, WO 2003/071860, WO 2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO 2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO 2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO 2000/22140,
WO 2006/063862, WO 2006/072603, WO 2002/034923, EP 06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP 07090009.7, WO 2001/14569, WO 2002/79410, WO 2003/33540, WO 2004/078983, WO 2001/19975, WO 1995/26407, WO 1996/34968, WO 1998/20145, WO 1999/12950, WO 1999/66050, WO 1999/53072, US 6,734,341, WO 2000/11192, WO 1998/22604, WO 1998/32326, WO 2001/98509,
WO 2001/98509, WO 2005/002359, US 5,824,790, US 6,013,861, WO 1994/004693, WO 1994/009144, WO 1994/11520, WO 1995/35026, WO 1997/20936.
2) transgenic plants which synthesize non starch carbohydrate polymers or which synthesize non starch carbohydrate polymers with altered properties in comparison to wild type plants without genetic modification. Examples are plants producing polyfructose, especially of the inulin and levan-type, as disclosed in EP 0663956, WO 1996/001904, WO 1996/021023, WO 1998/039460, and WO 1999/024593, plants producing alpha 1,4 glucans as disclosed in WO 1995/031553, US 2002/031826, US 6,284,479, US 5,712,107, WO 1997/047806, WO 1997/047807, WO 1997/047808 and WO 2000/014249, plants producing alpha- 1,6 branched alpha- 1,4-glucans, as disclosed in WO 2000/73422, plants producing alternan, as disclosed in WO 2000/047727, EP 06077301.7, US 5,908,975 and EP 0728213,
3) transgenic plants which produce hyaluronan, as for example disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/039316, JP 2006/304779, and WO 2005/012529.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include: a) Plants, such as cotton plants, containing an altered form of cellulose synthase genes as described in WO 1998/000549 b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO2004/053219 c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO 2001/017333 d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO02/45485 e) Plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fiber cell is altered, e.g. through downregulation of fiberselective β 1,3- glucanase as described in WO2005/017157 f) Plants, such as cotton plants, having fibers with altered reactivity, e.g. through the expression of N-acteylglucosaminetransferase gene including nodC and chitinsynthase genes as described in WO2006/136351
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation or by selection of plants contain a mutation imparting such altered oil characteristics and include: a) Plants, such as oilseed rape plants, producing oil having a high oleic acid content as described e.g. in US 5,969,169, US 5,840,946 or US 6,323,392 or US 6,063,947 b) Plants such as oilseed rape plants, producing oil having a low linolenic acid content as described in US 6,270828, US 6,169,190 or US 5,965,755 c) Plant such as oilseed rape plants, producing oil having a low level of saturated fatty acids as described e.g. in US 5,434,283
Particularly useful transgenic plants which may be treated according to the invention are plants which comprise one or more genes which encode one or more toxins, such as the following which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), BiteGard® (for example maize), Bt-Xtra® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B®(cotton), NatureGard® (for example maize), Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfϊeld® (for example maize).
Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).
Among the diseases of plants or crops that can be controlled by the method according to the invention, mention can be made of : Powdery mildew diseases such as :
Blumeria diseases, caused for example by Blumeria graminis ; Podosphaera diseases, caused for example by Podosphaera leucotricha ; Sphaerotheca diseases, caused for example by Sphaerothecafuliginea ;
Uncinula diseases, caused for example by Uncinula necator ; Rust diseases such as :
Gymnosporangium diseases, caused for example by Gymnosporangium sabinae ; Hemileia diseases, caused for example by Hemileia vastatrix ; Phakopsora diseases, caused for example by Phakopsora pachyrhizi or Phakopsora meibomiae ; Puccinia diseases, caused for example by Puccinia recondite, Puccinia graminis or
Puccinia striiformis;
Uromyces diseases, caused for example by Uromyces appendiculatus ; Oomycete diseases such as :
Albugo diseases caused for example by Albugo Candida; Bremia diseases, caused for example by Bremia lactucae ; Peronospora diseases, caused for example by Peronospora pisi or P. brassicae ; Phytophthora diseases, caused for example by Phytophthora infestans ; Plasmopara diseases, caused for example by Plasmopara viticola ;
Pseudoperonospora diseases, caused for example by Pseudoperonospora humuli or Pseudoperonospora cubensis ;
Pythium diseases, caused for example by Pythium ultimum ; Leafspot, leaf blotch and leaf blight diseases such as : Alternaria diseases, caused for example by Alternaria solani ; Cercospora diseases, caused for example by Cercospora beticola ;
Cladiosporum diseases, caused for example by Cladiosporium cucumerinum ;
Cochliobolus diseases, caused for example by Cochliobolus sativus (Conidiaform:
Drechslera, Syn: Helminthosporium) or Cochliobolus miyabeanus ; Colletotrichum diseases, caused for example by Colletotrichum lindemuthanium ;
Cycloconium diseases, caused for example by Cycloconium oleaginum ;
Diaporthe diseases, caused for example by Diaporthe citri ;
Elsinoe diseases, caused for example by Elsinoefawcettii ;
Gloeosporium diseases, caused for example by Gloeosporium laeticolor ; Glomerella diseases, caused for example by Glomerella cingulata ;
Guignardia diseases, caused for example by Guignardia bidwelli ;
Leptosphaeria diseases, caused for example by Leptosphaeria maculans ; Leptosphaeria nodorum ;
Magnaporthe diseases, caused for example by Magnaporthe grisea ; Mycosphaerella diseases, caused for example by Mycosphaerella graminicola ;
Mycosphaerella arachidicola ; Mycosphaerella fijiensis ;
Phaeosphaeria diseases, caused for example by Phaeosphaeria nodorum ;
Pyrenophora diseases, caused for example by Pyrenophora teres, or Pyrenophora tritici repentis; Ramularia diseases, caused for example by Ramularia collo-cygni , or Ramularia areola;
Rhynchosporium diseases, caused for example by Rhynchosporium secalis ;
Septoria diseases, caused for example by Septoria apii or Septoria lycopercisi ;
Typhula diseases, caused for example by Typhula incarnata ;
Venturia diseases, caused for example by Venturia inaequalis ; Root, Sheath and stem diseases such as :
Corticium diseases, caused for example by Corticium graminearum ;
Fusarium diseases, caused for example by Fusarium oxysporum ;
Gaeumannomyces diseases, caused for example by Gaeumannomyces graminis ;
Rhizoctonia diseases, caused for example by Rhizoctonia solani ; Sarocladium diseases caused for example by Sarocladium oryzae;
Sclerotium diseases caused for example by Sclerotium oryzae;
Tapesia diseases, caused for example by Tapesia acuformis ;
Thielaviopsis diseases, caused for example by Thielaviopsis basicola ; Ear and panicle diseases such as : Alternaria diseases, caused for example by Alternaria spp. ; Aspergillus diseases, caused for example by Aspergillus flavus ;
Cladosporium diseases, caused for example by Cladosporium spp. ;
Claviceps diseases, caused for example by Claviceps purpurea ;
Fusarium diseases, caused for example by Fusarium culmorum ; Gibberella diseases, caused for example by Gibberella zeae ;
Monographella diseases, caused for example by Monographella nivalis ; Smut and bunt diseases such as :
Sphacelotheca diseases, caused for example by Sphacelotheca reiliana ;
Tilletia diseases, caused for example by Tilletia caries ; Urocystis diseases, caused for example by Urocystis occulta ;
Ustilago diseases, caused for example by Ustilago nuda ; Fruit rot and mould diseases such as :
Aspergillus diseases, caused for example by Aspergillus flavus ;
Botrytis diseases, caused for example by Botrytis cinerea ; Penicillium diseases, caused for example by Penicillium expansum ;
Rhizopus diseases caused by example by Rhizopus stolonifer
Sclerotinia diseases, caused for example by Sclerotinia sclerotiorum ;
Verticilium diseases, caused for example by Verticilium alboatrum ; Seed and soilborne decay, mould, wilt, rot and damping-off diseases : Alternaria diseases, caused for example by Alternaria brassicicola
Aphanomyces diseases, caused for example by Aphanomyces euteiches
Ascochyta diseases, caused for example by Ascochyta lentis
Aspergillus diseases, caused for example by Aspergillus flavus
Cladosporium diseases, caused for example by Cladosporium herbarum Cochlio bolus diseases, caused for example by Cochliobolus sativus
(Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);
Colletotrichum diseases, caused for example by Colletotrichum coccodes;
Fusarium diseases, caused for example by Fusarium culmorum;
Gibberella diseases, caused for example by Gibberella zeae; Macrophomina diseases, caused for example by Macrophomina phaseolina
Monographella diseases, caused for example by Monographella nivalis;
Penicillium diseases, caused for example by Penicillium expansum
Phoma diseases, caused for example by Phoma lingam
Phomopsis diseases, caused for example by Phomopsis sojae; Phytophthora diseases, caused for example by Phytophthora cactorum; Pyrenophora diseases, caused for example by Pyrenophora graminea
Pyricularia diseases, caused for example by Pyricularia oryzae;
Pythium diseases, caused for example by Pythium ultimum;
Rhizoctonia diseases, caused for example by Rhizoctonia solani; Rhizopus diseases, caused for example by Rhizopus oryzae
Sclerotium diseases, caused for example by Sclerotium rolfsii;
Septoria diseases, caused for example by Septoria nodorum;
Typhula diseases, caused for example by Typhula incarnata;
Verticillium diseases, caused for example by Verticillium dahliae ; Canker, broom and dieback diseases such as :
Nectria diseases, caused for example by Nectria galligena ; Blight diseases such as :
Monilinia diseases, caused for example by Monilinia laxa ; Leaf blister or leaf curl diseases such as : Exobasidium diseases caused for example by Exobasidium vexans
Taphrina diseases, caused for example by Taphrina deformans ; Decline diseases of wooden plants such as :
Esca diseases, caused for example by Phaemoniella clamydospora ;
Eutypa dyeback, caused for example by Eutypa lata ; Ganoderma diseases caused for example by Ganoderma boninense;
Rigidoporus diseases caused for example by Rigidoporus lignosus Diseases of Flowers and Seeds such as
Botrytis diseases caused for example by Botrytis cinerea; Diseases of Tubers such as Rhizoctonia diseases caused for example by Rhizoctonia solani;
Helminthosporium diseases caused for example by Helminthosporium solani; Club root diseases such as
Plasmodiophora diseases, cause for example by Plamodiophora brassicae. Diseases caused by Bacterial Organisms such as Xanthomonas species for example Xanthomonas campestris pv. oryzae;
Pseudomonas species for example Pseudomonas syringae pv. lachrymans;
Erwinia species for example Erwinia amylovora.
The composition according to the invention may also be used against fungal diseases liable to grow on or inside timber. The term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed in the case of seed treatment.
It is clearly understood that the doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated.
The compounds or mixtures according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
The various aspects of the invention will now be illustrated with reference to the following table of compound examples and the following preparation or efficacy examples.
Table 1 illustrates in a non- limiting manner examples of compounds of formula (I) according to the invention.
In table 1, M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation.
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
The following examples illustrate in a non-limiting manner the preparation and efficacy of the compounds of formula (I) according to the invention.
Preparation example 1 : preparation of cώ-N-cyclopropyl-5-fluoro-l,3-dimethyl-N-(2 -phenyl cyclohexyl)-lH-pyrazole-4-carboxamide (compound 18)
Step 1 : preparation of cis and trans-N-cyclopropyl-2-phenylcyclohexanamine
To a cooled solution of 2.78 ml (40 mmol) of cyclopropylamine and 2.87 ml (50 mmol) of acetic acid, together with 5 g of 3A molecular sieves, in 50 ml of methanol, are added 3.5 g (20 mmol) of 2-phenylcyclohexanone. The reaction mixture is stirred for 3.5 hrs at reflux. The reaction mixture is then cooled to 00C and 3 g (50 mmol) of sodium cyanoborohydride are slowly added and the reaction mixture is further stirred for 2 hrs at reflux. The cooled reaction mixture is then filtered over a cake of diatomaceous earth. The cake is washed twice by 80 ml of methanol and the combined methanolic extracts are concentrated under vacuum. 100 ml of water are then added to the residue and the pH is ajusted to 12 with a 1 N solution of sodium hydroxyde. The watery layer is extracted with 100 ml of ethyl acetate. The organic layer is washed twice by brine and dried over magnesium sulfate to yield after concentration 3.52 g of a yellow oil. Column chromatography on silica gel (gradient heptane/ethyl acetate) yields 1.0 g (23% yield) of cis-N- cyclopropyl-2-phenylcyclo- hexanamine as a yellow oil (M+H = 216) and 1.9 g (44% yield) of trans-N-cyclopropyl-2-phenylcyclohexanamine as a colorless oil (M+H = 216).
Step 2 : preparation of cώ-N-cyclopropyl-5-fluoro-l,3-dimethyl-N-(2-phenylcyclohexyl)-lH- pyrazole-4-carboxamide At ambient temperature, a solution of 180 mg (1.02 mmol) of 5-fluoro-l,3-dimethyl-lH- pyrazole-4-carbonyl chloride in 1 ml of tetrahydrofurane is added dropwise to a solution of 200 mg (0.93 mmol) of cώ-N-cyclopropyl-2-phenylcyclohexanamine and 100 mg (1.02 mmol) of triethylamine in 5 ml of tetrahydrofurane. The reaction mixture is stirred for 2 hrs at 700C. The solvent is removed under vacuum and 100 ml of water are then added to the residue. The watery layer is extracted twice with ethyl acetate (2 x 50 ml) and the combined organic layers are successively washed by a 1 N solution of HCl, a saturated solution of potassium carbonate and brine and dried over a chemelut™ cartridge to yield after concentration 380 mg of a yellow oil. Column chromatography on silica gel (gradient heptane/ethyl acetate) yields 160 mg (46% yield) of cώ-N-cyclopropyl-5-fluoro-l,3-dimethyl-N-(2-phenylcyclohexyl)-lH-pyrazole-4- carboxamide as a colorless oil (M+H = 356).
General preparation example: thionation of amide of formula (I) on Chemspeed apparatus In a 13 ml Chemspeed vial is weighted 0.27mmole of phosphorous pentasulfide (P2S5). 3 ml of a 0.18 molar solution of the amide (I) (0.54mmole) in dioxane is added and the mixture is heated at reflux for two hours. The temperature is then cooled to 8O0C and 2.5 ml of water are added. The mixture is heated at 8O0C for one more hour. 2 ml of water are then added and the reaction mixture is extracted twice by 4 ml of dichloromethane. The organic phase is deposited on a basic alumina cardridge (2g) and eluted twice by 8 ml of dichloromethane. The solvents are removed and the crude thioamide derivative is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS.
Example A : in vivo test on Puccinia recondita (Brown rust) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material. Wheat plants (Scipion variety) sown on 50/50 peat soil-pozzolana substrate in starter cups and grown at 12°C, are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores (100,000 spores per ml). The spores are collected from a 10-day-old contaminated wheat and are suspended in water containing 2.5 ml/1 of tween 80 10%. The contaminated wheat plants are incubated for 24 hours at 200C and at 100% relative humidity, and then for 10 days at 200C and at 70% relative humidity.
Grading is carried out 10 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 70%) or total protection is observed at a dose of 500ppm with the following compounds: 13, 17 and 18.
Example B : in vivo test on Mycosphaerella graminicola (Wheat Leaf Spot)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
Wheat plants (Scipion variety), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 12°C, are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Mycosphaerella graminicola spores (500 000 spores per ml). The spores are collected from a 7-day-old culture. The contaminated wheat plants are incubated for 72 hours at 18°C and at 100% relative humidity, and then for 21 to 28 days at 90% relative humidity. Grading (% of efficacy) is carried out 21 to 28 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) or total protection is observed at a dose of 500ppm with the following compounds: 13, 15, 17, 18, 21 and 25.
Example C: in vivo test on Alternaria brassicae (Leaf spot of crucifers)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material. Radish plants (Pernot variety), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 18-200C, are treated at the cotyledon stage by spraying with the active ingredient prepared as described above.
Plants, used as controls, are treated with the mixture of acetone/tween/water not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of
Alternaria brassicae spores (40,000 spores per cm3). The spores are collected from a 12 to 13 days-old culture.
The contaminated radish plants are incubated for 6-7 days at about 18°C, under a humid atmosphere. Grading is carried out 6 to 7 days after the contamination, in comparison with the control plants.
Under these conditions, good protection (at least 70%) is observed at a dose of 500ppm with the following compounds: 12, 13, 15, 17, 21, 23 and 25.
Example D: in vivo test on Sphaerotheca fuliginea (cucurbits powdery mildew) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material. Gherkin plants (Vert petit de Paris variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 20°C/23°C, are treated at the cotyledon ZlO stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Sphaerotheca fuliginea spores (100 000 spores per ml). The spores are collected from a contaminated plants .The contaminated gherkin plants are incubated at about 20°C/25°C and at 60/70% relative humidity. Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) or total protection is observed at a dose of 500ppm with the following compounds: 12, 13, 17, 18, 21 and 25.
Example E: in vivo test on Pyrenophora teres (barley) / preventive Solvent: 49 parts by weight of N,N-dimethylformamide
Emulsifϊer: 1 part by weight of Alkylarylpolyglycolether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifϊer, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Pyrenophora teres. The plants remain for 48 hours in an incubation cabinet at 22°C and a relative atmospheric humidity of 100%. Then the plants are placed in a greenhouse at a temperature of approximately 200C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the control while an efficacy of 100% means that no disease is observed.
In this test the compounds according to the invention of the following structures showed efficacy of 70% or even higher at a concentration of 500ppm of active ingredient: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 16, 20, 27, 28, 32 and 33.
Example F: in vivo test on Venturia inaequalis (apple scab) / protective
Solvent: 24,5 parts by weight of acetone
24,5 parts by weight of N,N-dimethylacetamide Emulsifϊer: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifϊer, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 200C and a relative atmospheric humidity of 100 %.
The plants are then placed in a greenhouse at approximately 210C and a relative atmospheric humidity o f approximately 90 % .
The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of lOOppm of active ingredient : 14 and 19.
Example G: in vivo test on Septoria tritici (wheat) / preventive
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifϊer: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifϊer, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has dried on, the plants are sprayed with a spore suspension of Septoria tritici. The plants remain for 48 hours in an incubation cabinet at approximately 200C and a relative atmospheric humidity of approximately 100% and then 60 hours at approximately 15°C in a translucent incubation cabinet at a relative atmospheric humidity of approximately 100%.
The plants are placed in a greenhouse at a temperature of approximately 150C and a relative atmospheric humidity of approximately 80%. The test is evaluated 21 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
In this test the folio wing, compounds according to the invention showed an efficacy of 70% or even higher at a concentration of 500ppm of active ingredient 14, 16 and 19.
Example H : In vivo comparative test on Leptosphaeria nodorum (wheat) / preventive
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifϊer: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or the compound combination is mixed with the stated amounts of solvent and emulsifϊer, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with a preparation of active compound or active compound combination at the stated rate of application. After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabinet at 200C and a relative atmospheric humidity of 100%. The plants are placed in a greenhouse at a temperature of approximately 15°C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. Under these conditions, good (at least 70% of disease control or higher) is observed at a dose of 500ppm with the following compounds : 7 and 32 according to the invention whereas weak protection (less than 10% of disease control) is observed at a dose of 500ppm with the compounds of example 1.001 disclosed in international patent application WO-2007/134799. Example 1.001 disclosed in patent application WO-2007/134799 corresponds to the following compound : cis-N- [2-(4-chlorophenyl)cyclopropyl] -3 -(difluoro-methyl)- 1 -methyl- 1 H-pyrazo Ie- 4-carboxamide
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compound disclosed in WO-2007/134799.

Claims

1. A compound of formula (I)
Figure imgf000060_0001
wherein
• A represents a carbo-linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R ;
• T represents O or S ;
• B represents a 3-, A-, 5-, 6- or 7-membered non aromatic carbocycle that can be substituted by one to four Ci-Cs-alkyl groups ;
• n represents 0, 1, 2, 3, 4 or 5 ;
• m represents 0 or 1 ;
• X represents a halogen atom ; nitro ; cyano ; isonitrile ; hydroxy ; amino ; sulfanyl ; pentafluoro-λ6-sulfanyl ; formyl ; formyloxy ; formylamino ; substituted or non- substituted (hydroxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C1-C8- alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C2-C8-alkenyloxyimino)-Ci- Cs-alkyl ; substituted or non-substituted (C2-C8-alkynyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; carboxy ; carbamoyl ; N- hydroxycarbamoyl ; carbamate ; substituted or non-substituted Ci-Cs-alkyl ; C1-C8- halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkenyl
; C2-C8-halogenoalkenyl having 1 to 5 halogen atoms ; substituted or non-substituted C2- Cs-alkynyl ; C2-Cs-halogenoalkynyl having 1 to 5 halogen atoms ; substituted or non- substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfmyl ; C1-C8- halogenoalkylsulfinyl having 1 to 5 halogen atoms ; substituted or non-substituted C1-C8- alkylsulfonyl ; Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylamino ; substituted or non-substituted di-Ci-Cs-alkylamino ; substituted or non-substituted C2-Cs-alkenyloxy ; C2-C8-halogenoalkenyloxy having 1 to 5 halogen atoms ; substituted or non-substituted Cs-Cs-alkynyloxy ; C2-C8- halogenoalkynyloxy having 1 to 5 halogen atoms ; substituted or non-substituted C3-C7- cycloalkyl ; C3-Cy-halogenocycloalkyl having 1 to 5 halogen atoms ; substituted or non- substituted (C3-C7-cycloalkyl)-Ci-C8-alkyl ; substituted or non-substituted (C3-C7- cycloalkyl)-C2-C8-alkenyl ; substituted or non-substituted (C3-C7-cycloalkyl)-C2-Cs- alkynyl ; substituted or non- substituted tri(Ci-C8)alkylsilyl ; substituted or non- substituted tri(Ci-C8)alkylsilyl-Ci-C8-alkyl ; substituted or non-substituted Ci-Cs- alkylcarbonyl ; Ci-Cs-halogenoalkylcarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylcarbonyloxy ; Ci-Cs-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylcarbonylamino ; C1-C8- halogenoalkyl- carbonylamino having 1 to 5 halogen atoms ; substituted or non- substituted Ci-Cs-alkoxycarbonyl ; Ci-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkyloxycarbonyloxy ; Ci-Cs- halogenoalkoxycarbonyloxy having 1 to 5 halogen atoms ; substituted or non-substituted Ci-C8-alkylcarbamoyl ; substituted or non-substituted di-Ci-Cs-alkylcarbamoyl ; substituted or non-substituted Ci-Cs-alkylaminocarbonyloxy ; substituted or non- substituted di-Ci-Cs-alkylaminocarbonyloxy ; substituted or non-substituted N-(C1-C8- alkyl)hydroxy carbamoyl ; substituted or non-substituted Ci-Cs-alkoxycarbamoyl ; substituted or non-substituted N-(Ci-C8-alkyl)-Ci-C8-alkoxycarbamoyl ; aryl that can be susbtituted by up to 6 groups Q ; Ci-Cs-arylalkyl that can be susbtituted by up to 6 groups Q ; C2-C8-arylalkenyl that can be susbtituted by up to 6 groups Q ; C2-C8-arylalkynyl that can be susbtituted by up to 6 groups Q ; aryloxy that can be susbtituted by up to 6 groups Q ; arylsulfanyl that can be susbtituted by up to 6 groups Q ; arylamino that can be susbtituted by up to 6 groups Q ; Ci-Cs-arylalkyloxy that can be susbtituted by up to 6 groups Q ; Ci-Cs-arylalkylsulfanyl that can be susbtituted by up to 6 groups Q ; or C1-C8- arylalkylamino that can be susbtituted by up to 6 groups Q ;
• two substituents X together with the consecutive carbon atoms to which they are linked can form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which can be substituted by up to four groups Q which can be the same or different ;
• Z1 and Z2 independently represent a hydrogen atom ; a halogen atom ; cyano ; a substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy; substituted or non-substituted Ci-Cs- alkylsulfanyl; or substituted or non-substituted Ci-Cs-alkoxycarbonyl ;
• Z3 represents a non-substituted C3-C7-cycloalkyl or a C3-C7-cycloalkyl substituted by up to 10 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, d-C8-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkoxy, Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, Ci-Cs- alkoxycarbonyl, Ci-Cs-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkylaminocarbonyl and di-Ci-Cs-alkylamino- carbonyl ;
• Z4 and Z5 independently represent a hydrogen atom ; a halogen atom ; cyano ; a substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy; substituted or non-substituted Ci-Cs- alkylsulfanyl ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; or Z4 and Z5 are a C2-C5-alkylene group that can be substituted by one to four d-Cg-alkyl groups ;
• Q independently represents a halogen atom ; cyano ; nitro ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy having 1 to 9 halogen atoms that can be the same or different ; substituted or non- substituted C1- C8-alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 9 halogen atoms that can be the same or different ; substituted or non- substituted tri(Ci-C8)alkylsilyl ; substituted or non-substituted tri(Ci-C8)alkylsilyl-Ci-C8-alkyl ; substituted or non-substituted (C1-C8- alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ;
• R independently represents hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxy ; amino ; sulfanyl ; pentafluoro-λ6-sulfanyl ; substituted or non-substituted (C1-C8- alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted d-Cs-alkyl ; Ci-Cs-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkenyl ; C2-Cs-halogenoalkenyl having 1 to 5 halogen atoms ; substituted or non-substituted C2-Cs-alkynyl ; C2-Cs-halogenoalkynyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxy ; C1-C8- halogenoalkoxy having 1 to 5 halogen atoms ; substituted or non- substituted C1-C8- alkylsulfanyl ; Ci-Cs-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfmyl ; Ci-Cs-halogenoalkylsulfinyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylsulfonyl ; Ci-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylamino ; substituted or non-substituted di-Ci-Cs-alkylamino ; substituted or non-substituted C2-C8- alkenyloxy ; substituted or non-substituted Cs-Cs-alkynyloxy ; substituted or non- substituted C3-C7-cycloalkyl ; d-d-halogenocycloalkyl having 1 to 5 halogen atoms ; substituted or non-substituted In(C1 -C8)alkylsilyl ; substituted or non-substituted C1-C8- alkylcarbonyl ; Ci-Cs-halogenoalkylcarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; Ci-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms ; substituted or non-substituted Ci-Cs-alkylcarbamoyl ; substituted or non- substituted di-Ci-C8-alkylcarbamoyl ; phenoxy ; phenylsulfanyl ; phenylamino ; benzyloxy ; benzylsulfanyl ; or benzylamino ; as well as its salts, N-oxydes, metallic complexes, metalloidic complexes and optically active isomers.
2. A compound according to claim 1 wherein A is selected in the list consisting of: - a heterocycle of formula (A1)
Figure imgf000063_0001
wherein :
R1 to R3 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A2)
Figure imgf000063_0002
wherein :
R4 to R6 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A3)
Figure imgf000064_0001
wherein :
R7 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci- C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R8 represents a hydrogen atom or a substituted or non-substituted Ci-Cs-alkyl ;
- a heterocycle of formula (A4)
Figure imgf000064_0002
wherein :
R9 to R11 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; amino ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted Ci-Cs-alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A )
Figure imgf000064_0003
wherein :
R12 and R13 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; amino ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci- C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R , 14 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; amino ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A )
Figure imgf000065_0001
wherein : R15 represents a hydrogen atom ; a halogen atom ; a cyano ; substituted or non-substituted C1-C5- alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R16 and R18 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkoxycarbonyl ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R17 represent a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
- a heterocycle of formula (A7)
Figure imgf000065_0002
wherein :
R19 represents a hydrogen atom or a Ci-Cs-alkyl R20 to R22 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A8)
Figure imgf000066_0001
wherein :
R23 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or
Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R24 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;
- a heterocycle of formula (A )
Figure imgf000066_0002
wherein :
R25 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R26 represents a hydrogen atom ; substituted or non-substituted Ci-Cs-alkyl or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A l(k )
Figure imgf000066_0003
wherein :
R27 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R28 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non-substituted di(Ci-Cs- alkyl)amino ;
- a heterocycle of formula (A I h )
Figure imgf000067_0001
wherein :
R29 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R30 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ;
Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non-substituted di(Ci-Cs- alkyl)amino ;
- a heterocycle of formula (A 12\ )
Figure imgf000067_0002
wherein :
R > 31 represents a hydrogen atom or a substituted or non-substituted Ci-Cs-alkyl
R , 32 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R33 represents a hydrogen atom ; a halogen atom ; a nitro ; substituted or non-substituted C1-C5- alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A 13\ )
Figure imgf000068_0001
wherein : R34 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Cs-Cs-cycloalkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C2-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R35 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; a cyano ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C1-C5- alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or substituted or non- substituted di(Ci-C5-alkyl)amino;
R36 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A14)
Figure imgf000068_0002
wherein :
R37 and R38 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci-Cs-alkoxy or a substituted or non- substituted C1-C5- alkylsulphanyl ;
R39 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
- a heterocycle of formula (A15)
Figure imgf000069_0001
wherein :
R40 and R41 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A 16\ )
Figure imgf000069_0002
wherein :
R42 and R43 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or amino ;
-a heterocycle of formula (A 17\ )
Figure imgf000069_0003
wherein :
R44 and R45 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A 18\ )
Figure imgf000069_0004
wherein :
R47 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or
Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R46 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ;
Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or substituted or non- substituted Ci-Cs-alkylsulfanyl ;
- a heterocycle of formula (A19)
Figure imgf000070_0001
wherein :
R49 and R48 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
a heterocycle of formula (A20)
Figure imgf000070_0002
wherein :
R50 and R51 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; C1-C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1-C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
-a heterocycle of formula (A21)
Figure imgf000070_0003
wherein :
R52 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A22)
Figure imgf000071_0001
wherein : R53 represents a hydrogen atom ; a halogen atom ; substituted or non- substituted Ci-Cs-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A23)
Figure imgf000071_0002
wherein :
R54 and R56 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R55 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A24)
Figure imgf000071_0003
wherein : R57 and R59 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R58 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A25)
Figure imgf000072_0001
wherein : R60 and R61 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; R62 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl ;
-a heterocycle of formula (A26)
Figure imgf000072_0002
wherein :
R65 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; substituted or non-substituted Cs-Cs-cycloalkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C2-Cs-alkynyloxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R63 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; a cyano ; substituted or non-substituted Ci-Cs-alkoxy ; substituted or non-substituted C1-C5- alkylsulphanyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci-Cs-alkylamino or di(Ci-C5-alkyl)amino; R64 represents a hydrogen atom or substituted or non-substituted Ci-Cs-alkyl.
3. A compound according to claim 2 wherein A is selected in the list consisting of A2 ; A6 ; A10 and A13.
4. A compound according to claim 3 wherein A represents A13 wherein R34 represents a substituted or non-substituted Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; R35 represents a hydrogen atom or a halogen atom and R36 represents a substituted or non-substituted Ci-Cs-alkyl.
5. A compound according to claim 1 wherein T represents O.
6. A compound according to claim 1 wherein n represents 0, 1 or 2.
7. A compound according to claim 1 wherein B is a 3-, 5-, 6- or 7-membered non aromatic carbocycle that can be substituted by one to four d-Cg-alkyl groups.
8. A compound according to claim 7 wherein B represents cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl carbocycle that can be substituted by one to four methyl groups.
9. A compound according to claim 1 wherein X independently represents a halogen atom ; substituted or non-substituted d-Cg-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted tri(Ci-C8-alkyl)silyl ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non substituted 1,3-benzodioxolyl ; 1,2,3,4- tetrahydro-quinoxalinyl ; 3,4-dihydro-2H-l,4-benzoxazinyl ; 1 ,4-benzodioxanyl ; indanyl ; 2,3- dihydrobenzofuranyl ; or indolinyl.
10. A compound according to claim 1 wherein Z1 and Z2 independently represent a hydrogen atom or a substituted or non-substituted d-Cg-alkyl.
11. A compound according to claim 1 wherein Z3 represents a non-substituted C3-C7 cycloalkyl or a C3-C7 cycloalkyl substituted by up to 10 groups or atoms that can be the same or different and that can be selected in the list consisting of halogen atoms, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, Ci-Cs-alkoxy or Ci-Cs- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
12. A compound according to claim 1 wherein Z3 represents a non-substituted C3-Cy-cycloalkyl, preferably cyclopropyl.
13. A compound according to claim 1 wherein Z4 and Z5 independently represent a hydrogen atom, a halogen atom or a substituted or non-substituted Ci-Cs-alkyl.
14. A compound according to claim 1 wherein R independently represents a hydrogen atom ; halogen atom ; cyano ; substituted or non- substituted Ci-Cs-alkylamino ; substituted or non- substituted di-Ci-C8-alkylamino ; substituted or non-substituted tri(Ci-C8-alkyl)silyl ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci-Cs-alkylsulfanyl ; amino ; hydroxyl ; nitro ; substituted or non-substituted Ci-Cs- alkoxycarbonyl ; substituted or non-substituted C2-Cs-alkynyloxy.
15. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claims 1 to 14 and an agriculturally acceptable support, carrier or filler.
16. A compound of formula (II)
Figure imgf000074_0001
wherein X, n, m, Z1, Zz, Z3, Z4 and ZD are according to anyone of claims 1 to 14, and B represents a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl group with the exclusion of N-cyclopropyl-2-phenylcyclohexanamine.
17. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a compound according to claims 1 to 14 or a composition according to claim 15 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.
PCT/EP2010/051886 2009-02-17 2010-02-16 Fungicidal n-(phenylcycloalkyl)carboxamide, n-(benzylcycloalkyl)carboxamide and thiocarboxamide derivatives WO2010094666A2 (en)

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