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WO2009016221A1 - Fungicide n-6-membered fused (hetero)aryl-methylene-n-cycloalkyl carboxamide derivatives - Google Patents

Fungicide n-6-membered fused (hetero)aryl-methylene-n-cycloalkyl carboxamide derivatives Download PDF

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Publication number
WO2009016221A1
WO2009016221A1 PCT/EP2008/060040 EP2008060040W WO2009016221A1 WO 2009016221 A1 WO2009016221 A1 WO 2009016221A1 EP 2008060040 W EP2008060040 W EP 2008060040W WO 2009016221 A1 WO2009016221 A1 WO 2009016221A1
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Prior art keywords
alkyl
different
same
halogen atoms
substituted
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PCT/EP2008/060040
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French (fr)
Inventor
Philippe Desbordes
Stéphanie Gary
Marie-Claire Grosjean-Cournoyer
Benoït HARTMANN
Philippe Rinolfi
Arounarith Tuch
Jean-Pierre Vors
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Bayer Cropscience Sa
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Priority to EP08786665A priority Critical patent/EP2185507B1/en
Priority to AT08786665T priority patent/ATE555090T1/en
Priority to AU2008281773A priority patent/AU2008281773B2/en
Priority to UAA201000538A priority patent/UA98652C2/en
Priority to CN200880101329XA priority patent/CN101772486B/en
Priority to JP2010518674A priority patent/JP5563453B2/en
Priority to US12/452,921 priority patent/US8226966B2/en
Priority to MX2010001005A priority patent/MX2010001005A/en
Priority to BRPI0813022A priority patent/BRPI0813022B1/en
Priority to PL08786665T priority patent/PL2185507T3/en
Priority to CA 2692696 priority patent/CA2692696A1/en
Priority to ES08786665T priority patent/ES2383571T3/en
Publication of WO2009016221A1 publication Critical patent/WO2009016221A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • 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
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/416—2,5-Pyrrolidine-diones 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 other ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D231/16—Halogen atoms or nitro radicals
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    • 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
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to N-(aronnatic,6-nnennbered, fused, (hetero)aryl-methylene)-N- cycloalkyl carboxamide derivatives, their thiocarboxamide or N-substituted carboximidamide analogues, their process of preparation, 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.
  • Ar can represent a 5- to 10-heterocycle
  • R 7 can represent a C 3 -C 7 -cycloalkyl while X, Y and Z can represent N or CR 1 , at least one representing N.
  • X, Y and Z can represent N or CR 1 , at least one representing N.
  • the present invention provides N-(aromatic, 6-membered, fused, (hetero)aryl- methylene)-N-cycloalkyl-carboxamide derivatives 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 a ;
  • o W 1 to W 5 independently represent N or CR b1 ; o Y 1 to Y 3 independently represent N, O, S, NR b2 or CR b3 ; o Y 1 to Y 3 together with the atoms W n to which they are linked, form an aromatic 5- or 6-membered, fused heterocyclyl ring comprising up to four heteroatoms, or an aromatic 6-membered fused carbocyclyl ring ; o p represents 1 or 2 ; • T represents O, S, N-R c , N-OR d , N-NR c R d or N-CN ;
  • Z 1 represents a non substituted C 3 -C 7 -cycloalkyl or a C 3 -C 7 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-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C 1 C 8 -alkoxy ; C 1 -C 8 - halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C-rC 8 -alkoxycarbonyl ; C-i-C 8 -halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C 8 -alkylaminocarbonyl ; CIi-(C 1 -C 8 - alkyl)
  • Z 2 and Z 3 independently represent a hydrogen atom ; a halogen atom ; C- ⁇ -C 8 -alkyl ; C 1 - C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C 2 -C 8 -alkenyl ; C 2 -C 8 -alkynyl ; cyano ; nitro ; C- ⁇ -C 8 -alkoxy ; C 2 -C 8 -alkenyloxy ; C 2 -C 8 - alkynyloxy ; C 3 -C 7 -cycloalkyl ; C- ⁇ -C 8 -alkylsulphenyl ; amino ; C 1 C 8 -alkylamino ; di-(C- ⁇ - ⁇ -
  • R a independently represents a hydrogen atom ; halogen atom ; cyano ; nitro ; amino ; sulfanyl ; hydroxyl ; pentafluoro- ⁇ -6-sulfanyl ; C- ⁇ -C 8 -alkylamino ; di-(C- ⁇ -C 8 -alkyl)amino ; tri(C 1 -C 8 -alkyl)silyl ; tri(C 1 -C 8 -alkyl)silyl-C 1 -C 8 -alkyl ; CrC 8 -alkylsulfanyl ; C 1 -C 8 - halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different ; C- ⁇ -C 8 -alkyl ; C- ⁇ -C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C 2 -C 8
  • R c and R d that can be the same or different, represent a hydrogen atom ; C- ⁇ -C 8 -alkyl ; d-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C- ⁇ -C 8 -alkoxy-C- ⁇ -C 8 -alkyl ; C 2 -C 8 -alkenyl ; C 2 -C 8 -halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C 2 -C 8 -alkynyl ; C 2 -C 8 - halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C 3 -C 7 -cycloalkyl ; C 3 -C 7 -cycloalkyl-Ci-C 8 -alkyl ; C 3 -C 7 -halogenocycloalkyl
  • C 8 -halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C 8 -alkylsulphonyl ; Ci-C 8 -halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; phenyl that can be substituted by up to 5 groups Q ; naphthyl that can be substituted by up to 6 groups Q ; phenylmethylene that can be substituted by up to 5 groups Q ; phenylsulphonyl that can be substituted by up to 5 groups Q ;
  • R b1 and R b3 independently represent a hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxyl ; sulphanyl ; amino ; pentafluoro- ⁇ 6-sulphanyl ; Ci-C 8 -alkyl ; Ci-C 8 - halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-
  • Ci-C 8 -alkyl)aminocarbonyl Ci-C 8 -alkylcarbonyloxy ; d-C 8 -halogenoalkylcarbonyloxy comprising up to 9 halogen atoms that can be the same or different ; Ci-C 8 - alkylcarbonylamino ; d-C 8 -alkylaminocarbonyloxy ; di-(d-C 8 -alkyl)aminocarbonyloxy ; d-C 8 -alkyloxycarbonyloxy ; d-C 8 -alkoxyimino ; (d-C 8 -alkoxyimino)-d-C 8 -alkyl ; (C 1 - C 8 -alkenyloxyimino)-d-C 8 -alkyl ; (d-C 8 -alkynyloxyimino)- d-C 8 -alkyl ;
  • R b2 represents a hydrogen atom ; d-C 8 -alkyl ; d-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d-C 8 -alkoxy-d-C 8 -alkyl ; C 2 -C 8 - alkenyl ; C 2 -C 8 -halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C 2 -C 8 -alkynyl ; C 2 -C 8 -halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C 3 -C 7 -cycloalkyl ; C 3 -C 7 -cycloalkyl-d-C 8 -alkyl ; C 3 - d-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • Q that can be the same or different, represents a halogen atom ; cyano ; nitro ; Ci-C 8 - alkyl ; Ci-C 8 -alkoxy ; Ci-C 8 -alkylsulfanyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C 8 -halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; tri(C 1 -C 8 )alkylsilyl and tri(d- C 8 )alkylsilyl-Ci-C 8 -alkyl ; C-i-C 8 -alkoxyimino ; (C-i-C 8 -alkoxyimino)- Ci-C 8 -alkyl ;
  • any of the compounds according to the invention can exist as one or more stereoisomers depending on the number of stereogenic units (as defined by the IUPAC rules) in the compound.
  • the invention thus relates equally to all the stereoisomers, and to the mixtures of all the possible stereoisomers, in all proportions.
  • the stereoisomers can be separated according to the methods that are known per se by the man ordinary skilled in the art.
  • halogen means fluorine, chlorine, bromine or iodine ;
  • heteroatom can be nitrogen, oxygen or sulphur ;
  • halogenated groups notably haloalkyl, haloalkoxy and cycloalkyl groups, can comprise up to nine identical or different a halogen atoms ;
  • any alkyl, alkenyl or alkynyl group can be linear or branched ; • the term "aryl” means phenyl or naphthyl, optionally substituted by one to five groups selected in the list consisting of halogen, [d-C 6 ]-alkyl, [d-C 6 ]-haloalkyl, [C 2 -C 6 ]-alkenyl, [C 2 -C 6 ]-haloalkenyl, [C 2 -C 6 ]-alkynyl, [C 2 -C 6 ]-haloalkynyl, [Ci-C 6 ]-alkoxy, [d-C 4 ]-alkoxy- [d-C 4 -alkyl, [d-C 4 ]-alkoxy-[d-C 4 ]-alkoxy, [d-C 6 ]-haloalkoxy and [d-C 4 ]-haloalkoxy- [d-C 4 ]-alky
  • V 1 represents O, S or NR a1 ;
  • R a1 represents a hydrogen atom ; Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d-C 8 -alkoxy-d-C 8 -alkyl ;
  • R a2 and R a3 that can be the same or different represent a hydrogen atom ; a halogen atom ; cyano ; Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C 8 -alkoxy or Ci-C 8 -halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C 3 -C 7 -cycloalkyl ;
  • R a4 represents a hydrogen atom, a halogen atom ; cyano ; Ci-C 8 -alkyl ; Ci-C 8 - halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d- C 8 -alkoxy or Ci-C 8 -halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C 3 -C 7 -cycloalkyl ; Ci-C 8 -alkylsulfanyl ; amino ; Ci-C 8 -alkylamino ; di- (Ci-C 8 -alkyl)amino ; d-C 8 -alkyloxycarbonyl.
  • More preferred compounds of formula (I) according to the invention are those wherein A is selected in the list consisting of: wherein:
  • V 1 represents O, S or NR a1 ; • R a1 represents a hydrogen atom ; Ci-C 8 -alkyl ; Ci C 8 -alkoxy-C 1 -C 8 -alkyl ;
  • R a2 represents Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C 8 -alkoxy ;
  • R a3 represents a hydrogen atom ; a halogen atom ; C- ⁇ -C 8 -alkyl ;
  • R a4 represents a hydrogen atom, a halogen atom ; Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
  • V 1 represents NR a1 ; • R a1 represents d-C 8 -alkyl ;
  • R a2 and R a3 that can be the same or different represent a hydrogen atom ; a halogen atom ; Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; or
  • A represents A 4 ;
  • V 1 represents S ;
  • R a2 represents a C- ⁇ -C 8 -alkyl ;
  • C-i-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
  • R a4 represents a hydrogen atom ; Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
  • W 1 to W 5 , Y 1a , Y 2a , Y 3a and Y 3b independently represent NR b2 or CR b3 ;
  • Y /D represents O, S or NR b2.
  • B represent B 1 or B 2 ; W 1 to W 5 , Y 1a , Y 2a , Y 3a and Y 3b independently represent CR b3 ; or B represent B 5 or B 6 ;W 1 to W 5 , Y 1a and Y 3a independently represent CR b1 ; Y 2b represents S.
  • Other preferred compounds of formula (I) according to the invention are those wherein Z 2 and Z 3 independently represent a hydrogen atom or C 1 -C 8 alkyl.
  • Other preferred compounds of formula (I) according to the invention are those wherein Q represents a halogen atom ; Ci-C 8 -alkyl ; Ci-C 8 -alkoxy ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C 8 -halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
  • T with preferred features of one or more A, Z 1 to Z 3 , R a , R b , V 1 and Q ;
  • R a with preferred features of one or more A, T, Z 1 to Z 3 , R b , V 1 and Q ;
  • R b preferred features of R b with preferred features of one or more A, T, Z 1 to Z 3 , R a , V 1 and Q ;
  • V 1 with preferred features of one or more A, T, Z 1 to Z 3 , R a , R b and Q ;
  • the said preferred features can also be selected among the more preferred features of each of A, T, Z 1 to Z 3 , R a , R b , V 1 and Q ; 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 compounds of formula (I).
  • U 1 represents a halogen atom or a leaving group.
  • step 1 can be performed if appropriate in the presence of a solvent and if appropriate in the presence of an acid binder.
  • N-cycloalkyl-amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters, 2006, p 2014 synthesis of compounds 7 and 8), or reduction of imines (Tetrahedron, 2005, p 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry, 2002, p 3887 preparation of intermediate for compound 28).
  • Carboxylic acid derivatives of formula (III) are known or can be prepared by known processes (WO-93/11117 ; EP-545 099 ; Nucleosides & Nucleotides, 1987, p737-759, Bioorg. Med. Chem., 2002, p2105-2108).
  • Suitable acid binders for carrying out process P1 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 acetate, and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N methylpiperidine, N,N-dimethylaminopyridine, diazabic
  • Suitable solvents for carrying out process P1 according to the invention are in each case all customary inert organic solvents.
  • reaction temperatures can independently be varied within a relatively wide range.
  • processes according to the invention are carried out at temperatures between O 0 C and 16O 0 C, preferably between 1O 0 C and 12O 0 C.
  • a way to control the temperature for the processes according to the invention is to use micro-wave technology.
  • Process P1 according to the invention is generally independently carried out under atmospheric pressure. However, in each case, it is also possible to operate under elevated or reduced pressure.
  • step 1 of process P1 When carrying out step 1 of process P1 according to the invention, generally 1 mol or other an excess of the acid derivative of formula (III) and from 1 to 3 mol of acid binder are employed per mole of amine of formula (II). It is also possible to employ the reaction components in other ratios.
  • reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that can still be present.
  • Process P2 can be 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 hydrosulfide (NaHS), boron trisulfide (B 2 S 3 ), bis (diethylaluminium) sulfide ((AIEt 2 ) 2 S), ammonium sulfide ((NH 4 ) 2 S), phosphorous pentasulfide (P 2 S 5 ), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1 ,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in J.Chem.Soc. Perkin 1, (2001), 358.
  • S sulphur
  • H 2 S sulfhydric acid
  • Na 2 S sodium sulfide
  • a catalytic or stoechiometric or more, quantity of a base such as an inorganic and organic base.
  • 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-dimethyl- aminopyridine or N-methylpiperidine.
  • Suitable solvents for carrying out process P2 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane or 1 ,2-diethoxyethane ; nitriles, such as acetonitrile, pro
  • reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from O 0 C to 16O 0 C, preferably from 1O 0 C to 12O 0 C.
  • a way to control the temperature for the processes according to the invention is to use micro-wave technology.
  • Process P2 according to the invention is generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
  • reaction components in other ratios. Work-up is carried out by known methods.
  • reaction mixture is concentrated under reduced pressure.
  • residue that remains can be freed by known methods, such as chromatography or recrystallization, from any impurities that can still be present.
  • step 2 can be performed in the presence of an acid binder and in the presence of a solvent.
  • N-cycloalkyl-amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters, 2006, p 2014 synthesis of compounds 7 and 8), or reduction of imines (Tetrahedron, 2005, p 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry, 2002, p 3887 preparation of intermediate for compound 28).
  • N-substituted carboximidoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Houben-Weyl, “Methoden der organischen Chemie” (1985), E5/1 , p 628-633 and Patai, "The chemistry of amidines and imidates” (1975), p 296-301.
  • N-substituted or N,N-disubstituted hydrazonoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Tetrahedron, 1991 , 47, p 447 and Journal of Heterocyclic Chemistry, 1983, 20, p 225
  • N-cyano carboximidoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Tetrahedron Letters, 1968, p 5523 and Bioorganic and Medicinal Chemistry, 2006, p 4723.
  • Suitable acid binders for carrying out process P3 according to the invention can be inorganic and organic bases that are customary for such reactions.
  • alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives ; alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate ; alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate ; alkaline earth metal or alkali metal hydrides, such as sodium hydride or potassium hydride ; alkaline earth metal or alkali metal 440ates, such as sodium methylate, sodium ethylate, sodium propylate or potassium t-butylate ;and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine,
  • Suitable solvents for carrying out process P3 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole ; nitriles, such as acetonit
  • reaction temperatures can be varied within a relatively wide range.
  • these processes are carried out at temperatures from O 0 C to 16O 0 C, preferably from 1 O 0 C to 12O 0 C.
  • a way to control the temperature for the processes according to the invention is to use micro-wave technology.
  • Process P3 according to the invention is generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
  • the amine derivative of formula (III) can be employed as its salt, such as chlorhydate or any other convenient salt.
  • reaction components in other ratios. Work-up is carried out by known methods.
  • reaction mixture is concentrated under reduced pressure.
  • residue that remains can be freed by known methods, such as chromatography or recrystallization, from any impurities that can still be present.
  • 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 crops, and 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.
  • 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.
  • 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.
  • 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 emulsifier, 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.
  • 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, emulsifiable 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 nucleic acid synthesis for example benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolinic acid.
  • Inhibitors of the mitosis and cell division for example benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate, thiophanate- methyl and zoxamide.
  • Inhibitors of the respiration for example diflumetorim as Cl-respiration inhibitor; bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (9R- component), isopyrazam (9S-component), mepronil, oxycarboxin, penthiopyrad, thifluzamide as Cll-respiration inhibitor; amisulbrom, azoxystrobin, cyazofamid, dimoxystrobin, enestroburin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin as Clll-respiration inhibitor.
  • diflumetorim as Cl-respiration inhibitor
  • Inhibitors of the ATP production for example fentin acetate, fentin chloride, fentin hydroxide, and silthiofam.
  • Inhibitors of the amino acid and/or protein biosynthesis for example andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil.
  • Inhibitors of the signal transduction for example fenpiclonil, fludioxonil and quinoxyfen.
  • Inhibitors of the lipid and membrane synthesis for example biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride, pyrazophos, tolclofos-m ethyl and vinclozolin.
  • Inhibitors of the ergosterol biosynthesis for example aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutra
  • Inhibitors of the cell wall synthesis for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, prothiocarb, validamycin A, and valiphenal.
  • Inhibitors of the melanine biosynthesis for example carpropamid, diclocymet, fenoxanil, phthalide, pyroquilon and tricyclazole.
  • 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.
  • the plants that may becan be protected by the method according to the invention mention may becan be made of cotton; flax; vine; fruit or vegetable crops such as Rosaceae sp.
  • Solanaceae sp. for instance tomatoes
  • Liliaceae sp. for instance lettuces
  • Umbelliferae sp. for instance lettuces
  • Umbelliferae sp. for instance lettuces
  • Cilionaceae 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.
  • 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 Sphaerotheca fuliginea; Uncinula diseases caused for example by Uncinula necator;
  • Gymnosporangium diseases caused for example by Gymnosporangium sabinae
  • Hemileia diseases caused for example by Hemileia vastatrix
  • Phakopsora diseases caused for example by Phakopsora pachyrhizi and Phakopsora meibomiae;
  • Puccinia diseases caused for example by Puccinia recondita, 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 and Peronospora 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 and Pseudo- peronospora cubensis;
  • Leaf spot, Leaf blotch and Leaf Blight Diseases such as
  • Alternaria diseases caused for example by Alternaria solani;
  • Cercospora diseases caused for example by Cercospora beticola
  • Cladiosporium 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 lindemuthianum;
  • Cycloconium diseases caused for example by Cycloconium oleaginum
  • Diaporthe diseases caused for example by Diaporthe citri;
  • Elsinoe diseases caused for example by Elsinoe fawcettii; Gloeosporium diseases caused for example by Gloeosporium laeticolor;
  • Glomerella diseases caused for example by Glomerella cingulata caused for example by Glomerella cingulata
  • Guignardia diseases caused for example by Guignardia bidwellii;
  • Leptosphaeria diseases caused for example by Leptosphaeria maculans and Leptosphaeria nodorum;
  • Magnaporthe diseases caused for example by Magnaporthe grisea;
  • Mycosphaerella diseases caused for example by Mycosphaerella graminicola, Mycosphaerella arachidicola and 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 and Septoria lycopersici
  • 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 including Maize cob such as Alternaria diseases caused for example by Alternaria spp.; Aspergillus diseases caused for example by Aspergillus flavus; Cladosporium diseases caused for example by Cladiosporium cladosporioides; 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;
  • 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;
  • Aspergillus diseases caused for example by Aspergillus flavus
  • Botrytis diseases caused for example by Botrytis cinerea
  • Penicillium diseases caused for example by Penicillium expansum and Penicillium purpurogenum;
  • Rhizopus diseases caused by example by Rhizopus stolonifer Sclerotinia diseases caused for example by Sclerotinia sclerotiorum; Verticillium diseases caused for example by Verticillium alboatrum;
  • 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
  • Cochliobolus diseases caused for example by Cochliobolus sativus;
  • Colletotrichum diseases caused for example by Colletotrichum coccodes
  • Macrophomina diseases caused for example by Macrophomina phaseolina
  • Microdochium diseases caused for example by Microdochium nivale
  • Penicillium diseases caused for example by Penicillium expansum
  • Phoma diseases caused for example by Phoma lingam
  • Phomopsis diseases caused for example by Phomopsis sojae
  • Pyrenophora diseases caused for example by Pyrenophora graminea 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 caused for example by Septoria nodorum
  • Typhula diseases caused for example by Typhula incarnata caused for example by Typhula incarnata
  • Verticillium diseases caused for example by Verticillium dahliae
  • Nectria diseases caused for example by Nectria galligena caused for example by Nectria galligena
  • Esca disease caused for example by Phaeomoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea;
  • Ganoderma diseases caused by example by Ganoderma boninense
  • Botrytis diseases caused for example by Botrytis cinerea
  • Rhizoctonia diseases caused for example by Rhizoctonia solani
  • Helminthosporium diseases caused for example by Helminthosporium solani
  • Plasmodiophora diseases cause for example by Plamodiophora brassicae.
  • Xanthomanas species for example Xanthomonas campestris pv. oryzae; Pseudomonas species for example Pseudomonas syringae pv. lachrymans; Erwinia species for example Erwinia amylovora.
  • the fungicide composition according to the invention can 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 15O g per 100 kg of seed in the case of seed treatment.
  • the fungicide composition according to the invention can also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention.
  • Genetically modified plants are plants into genome of that a heterologous gene encoding a protein of interest has been stably integrated.
  • the expression "heterologous gene encoding a protein of interest” essentially means genes that give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the modified plant.
  • 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.
  • M+H means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass unit) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy.
  • the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below : Temperature: 4O 0 C , Mobile phases : 0.1 % aqueous formic acid and acetonitrile linear gradient from 10% acetonitrile to 90% acetonitrile.
  • Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones).
  • the lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 190nm to 400nm.
  • the active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
  • Barley plants (Express variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 12 0 C, are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
  • Pyrenophora teres spores (12,000 spores per ml).
  • the spores are collected from a 15-day-old culture.
  • the contaminated barley plants are incubated for 24 hours at about 2O 0 C and at 100% relative humidity, and then for 12 days at 80% relative humidity.
  • Efficacy example B in vivo preventive test on Sphaerotheca fuliginea (cucurbit powdery mildew)
  • the active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
  • 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 2 first leaves stage by spraying with the aqueous suspension described above Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water 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 11-12 days after the contamination, in comparison with the control plants.
  • the active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, and 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 0 C, are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water 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 0 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.
  • Efficacy example D in vivo test on Puccinia recondita f. Sp. tritici (wheat brown rust).
  • the active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
  • Wheat plants (Scipion variety) in starter cups, sown on 50/50 peat soil-pozzolana substrate and grown at 12 0 C, are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water 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/l of tween 80 10%.
  • the contaminated wheat plants are incubated for 24 hours at 2O 0 C and at 100% relative humidity, and then for 10 days at 2O 0 C and at 70% relative humidity. Grading is carried out 10 days after the contamination, in comparison with the control plants.
  • Example E 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 18-2O 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.
  • 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 0 C, under a humid atmosphere.
  • Example F in vivo test on Botrytis cinerea (Grey mould)
  • 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), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 18- 2O 0 C, are treated at the cotyledon Z11 stage by spraying with the active ingredient prepared as 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 depositing drops of an aqueous suspension of Botrytis cinerea spores (150,000 spores per ml) on upper surface of the leaves. The spores are collected from a 15-day-old culture and are suspended in a nutrient solution composed of : - 20 g/L of gelatin;
  • the contaminated cucumber plants are settled for 5-7 days in a climatic room at 15-11 0 C (day/night) and at 80% relative humidity.
  • Example G In vivo test on Peronospora parasitica (Crucifer downy mildew)
  • 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.
  • Cabbage plants (Eminence variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-2O 0 C, are treated at the cotyledon 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 Peronospora parasitica spores (50 000 spores per ml). The spores are collected from infected plant. The contaminated cabbage plants are incubated for 5 days at 2O 0 C, under a humid atmosphere. Grading is carried out 5 days after the contamination, in comparison with the control plants.

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Abstract

The present invention relates N-(aromatic, 6-membered, fused, (hetero)aryl-methylene)-N-cycloalkyl carboxamide derivatives, their thiocarboxamide or N-substituted carboximidamide analogues, all of formula (I) wherein A represents a carbo-linked 5-mennbered heterocyclyl group; T represents O, S, N-Rc, N-ORd, N-NRcRd or N-CN; Z1 to Z3 and B represents an aromatic, 6-membered, fused, (hetero)aryl; their process of preparation; 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

FUNGICIDE N-6-MEMBERED FUSED (HETERO)ARYL-METHYLENE-N-CYCLOALKYL CARBOXAMIDE
DERIVATIVES
DESCRIPTION
The present invention relates to N-(aronnatic,6-nnennbered, fused, (hetero)aryl-methylene)-N- cycloalkyl carboxamide derivatives, their thiocarboxamide or N-substituted carboximidamide analogues, their process of preparation, 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.
International patent application WO-2001/11966 generically mentions certain haloalkyl-2- pyridyl-methylene-heterocyclyl-amide derivatives. However, there is no disclosure in this document of any such derivative substituted by any cycloalkyl group. International patent application WO-2004/074259 discloses GABAA receptor-bondable compounds of the following formula:
Figure imgf000002_0001
wherein Ar can represent a 5- to 10-heterocycle, R7 can represent a C3-C7-cycloalkyl while X, Y and Z can represent N or CR1, at least one representing N. However, there is no disclosure in this document of any compound including a 5-membered heterocycle or a cycloalkyl linked to the nitrogen atom.
International patent application WO-2006/120224 discloses 2-pyridyl-methylene-carboxamide derivatives of the following formula:
Figure imgf000002_0002
there was no hint in this document to prepare the fungicide bicyclic derivatives according to the invention.
International patent application WO-2007/117778 discloses quinoline derivatives useful as inducible nitric oxide synthase inhibitors, including N-cyclopropyl-N-((7,8-fluoro-2-oxo-l,2- dihydroquinolin-4-yl)methyl)-4-methylthiazole-5-carboxamide and N-cyclopropyl-N-((8-fluoro-2- oxo-l, 2-dihydroquinolin-4-yl)methyl)-4-nnethylthiazole-5- carboxamide. These compounds do not form part of the present invention.
It is always of high-interest in agriculture to use novel pesticide compounds in order to avoid or to control the development of resistant strains to the active ingredients. It is also of high-interest to use novel compounds being more active than those already known, with the aim of decreasing the amounts of active compound to be used, whilst at the same time maintaining effectiveness at least equivalent to the already known compounds. We have now found a new family of compounds that possess the above mentioned effects or advantages.
Accordingly, the present invention provides N-(aromatic, 6-membered, fused, (hetero)aryl- methylene)-N-cycloalkyl-carboxamide derivatives of formula (I)
Figure imgf000003_0001
wherein
• A represents a carbo-linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups Ra ;
• B represents
Figure imgf000003_0002
wherein o W1 to W5 independently represent N or CRb1 ; o Y1 to Y3 independently represent N, O, S, NRb2 or CRb3 ; o Y1 to Y3 together with the atoms Wn to which they are linked, form an aromatic 5- or 6-membered, fused heterocyclyl ring comprising up to four heteroatoms, or an aromatic 6-membered fused carbocyclyl ring ; o p represents 1 or 2 ; • T represents O, S, N-Rc, N-ORd, N-NRcRd or N-CN ;
• Z1 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-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1 C8-alkoxy ; C1-C8- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C-rC8-alkoxycarbonyl ; C-i-C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C8-alkylaminocarbonyl ; CIi-(C1-C8- alkyl)aminocarbonyl ;
• Z2 and Z3 independently represent a hydrogen atom ; a halogen atom ; C-ι-C8-alkyl ; C1- C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkenyl ; C2-C8-alkynyl ; cyano ; nitro ; C-ι-C8-alkoxy ; C2-C8-alkenyloxy ; C2-C8- alkynyloxy ; C3-C7-cycloalkyl ; C-ι-C8-alkylsulphenyl ; amino ; C1 C8-alkylamino ; di-(C-ι-
C8-alkyl)amino ; C-i-C8-alkoxycarbonyl ; C-i-C8-alkylcarbonyl ; C-i-C8-alkylcarbamoyl ; di- (C-ι-C8-alkyl)carbamoyl ; N-C-i-C8-alkyl-C-i-C8-alkoxycarbamoyl ; or
• Z2 and Z3 together with the carbon atom to which they are linked can form a substituted or non substituted C3-C7 cycloalkyl ;
• Ra independently represents a hydrogen atom ; halogen atom ; cyano ; nitro ; amino ; sulfanyl ; hydroxyl ; pentafluoro-λ-6-sulfanyl ; C-ι-C8-alkylamino ; di-(C-ι-C8-alkyl)amino ; tri(C1-C8-alkyl)silyl ; tri(C1-C8-alkyl)silyl-C1-C8-alkyl ; CrC8-alkylsulfanyl ; C1-C8- halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different ; C-ι-C8-alkyl ; C-ι-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C-ι-C8-alkoxy ; C1- C8-alkoxy-C-ι-C8-alkyl ; C-ι-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C2 C8-alkenyloxy ; C2-C8-alkynyloxy ; C3-C7-cycloalkyl ;
C3-C7-cycloalkyl- C-ι-C8-alkyl ; C-ι-C8-alkylsulphinyl ; C-ι-C8-alkylsulphonyl ; C1- C8alkoxyimino ; (C-i-C8-alkoxyimino^C-i-C8-alkyl ; (benzyloxyimino)-C-ι-C8-alkyl ; C1-C8- alkylcarbonyl ; C-i-C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C8-alkoxycarbonyl ; C-i-C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8- alkylaminocarbonyl ; di-(C1-C8-alkyl)aminocarbonyl ;
• Rc and Rd, that can be the same or different, represent a hydrogen atom ; C-ι-C8-alkyl ; d-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C-ι-C8-alkoxy-C-ι-C8-alkyl ; C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8- halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; C3-C7-cycloalkyl-Ci-C8-alkyl ; C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ; formyl ; d-C8-alkylcarbonyl ; d-
C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkylsulphonyl ; Ci-C8-halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; phenyl that can be substituted by up to 5 groups Q ; naphthyl that can be substituted by up to 6 groups Q ; phenylmethylene that can be substituted by up to 5 groups Q ; phenylsulphonyl that can be substituted by up to 5 groups Q ;
• Rb1 and Rb3 independently represent a hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxyl ; sulphanyl ; amino ; pentafluoro-λ6-sulphanyl ; Ci-C8-alkyl ; Ci-C8- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-
C8-alkylamino ; di-(Ci-C8-alkyl)amino ; Ci-C8-alkoxy ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxy-Ci-C8-alkyl ; Ci- C8-alkylsulphanyl ; Ci-C8-halogenoalkylsulphanyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkylsulphenyl, Ci-C8-halogenoalkylsulphenyl comprising up to 9 halogen atoms that can be the same or different, Ci-C8- alkylsulphinyl, Ci-C8-halogenoalkylsulphinyl comprising up to 9 halogen atoms that can be the same or different, Ci-C8-alkylsulphonyl, Ci C8-halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkenyl ; C2- C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkinyloxy ; C2-C8- halogenoalkinyloxy comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; C3-C7-cycloalkyl-Ci-C8-alkyl ; C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ; formyl ; formyloxy ; formylamino ; carboxy ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; (hydroxyimino)- Ci-C8-alkyl ; Ci-C8-alkylcarbonyl ; d-C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; N-Ci-C8-alkyl-Ci-C8- alkoxycarbamoyl ; Ci-C8-alkoxycarbonyl ; d-C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C8-alkylaminocarbonyl ; di-
(Ci-C8-alkyl)aminocarbonyl ; Ci-C8-alkylcarbonyloxy ; d-C8-halogenoalkylcarbonyloxy comprising up to 9 halogen atoms that can be the same or different ; Ci-C8- alkylcarbonylamino ; d-C8-alkylaminocarbonyloxy ; di-(d-C8-alkyl)aminocarbonyloxy ; d-C8-alkyloxycarbonyloxy ; d-C8-alkoxyimino ; (d-C8-alkoxyimino)-d-C8-alkyl ; (C1- C8-alkenyloxyimino)-d-C8-alkyl ; (d-C8-alkynyloxyimino)- d-C8-alkyl ;
(benzyloxyimino)-d-C8-alkyl ; tri(d-C8-alkyl)silyl ; tri(d-C8-alkyl)silyl- d-C8-alkyl ; phenyl that can be substituted by up to 5 groups Q ; benzyloxy that can be substituted by up to 5 groups Q ; benzylsulphanyl that can be substituted by up to 5 groups Q ; benzylamino that can be substituted by up to 5 groups Q ; phenoxy that can be substituted by up to 5 groups Q ; phenylamino that can be substituted by up to 5 groups
Q ; phenylsulphanyl that can be substituted by up to 5 groups Q ; benzyl that can be substituted by up to 5 groups Q ; pyridinyl that can be substituted by up to four groups Q and pyridinyloxy that can be substituted by up to four groups Q ;
• Rb2 represents a hydrogen atom ; d-C8-alkyl ; d-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d-C8-alkoxy-d-C8-alkyl ; C2-C8- alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; C3-C7-cycloalkyl-d-C8-alkyl ; C3- d-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ; formyl, Ci-C8-alkylcarbonyl ; d-C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkylsulphonyl ; Ci-C8- halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; phenylsulfonyl can be substituted by up to 5 groups Q ; benzyl that can be substituted by up to 5 groups Q ;
• Q, that can be the same or different, represents a halogen atom ; cyano ; nitro ; Ci-C8- alkyl ; Ci-C8-alkoxy ; Ci-C8-alkylsulfanyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; tri(C1-C8)alkylsilyl and tri(d- C8)alkylsilyl-Ci-C8-alkyl ; C-i-C8-alkoxyimino ; (C-i-C8-alkoxyimino)- Ci-C8-alkyl ;
as well as salts, N-oxides, metallic complexes, metalloidic complexes and optically active or geometric isomers thereof provided that compound of formula (I) differs from N-cyclopropyl-N-
((6,8-dimethyl-2-oxo-1 ,2-dihydroquinolin-3-yl)methyl)-furane-2-carboxamide, N-cyclopropyl-N-
((6-ethoxy-2-oxo-1 ,2-dihydroquinolin-3-yl)methyl)-furane-2-carboxamide, N-cyclopropyl-N-((6- methyl-2-oxo-1 ,2-dihydroquinolin-3-yl)methyl)-furane-2-carboxamide, N-cyclopropyl-N-((7,8- difluoro-2-oxo-1 ,2-dihydroquinolin-4-yl)methyl)-4-methylthiazole-5-carboxamide and from N- cyclopropyl-N-((8-fluoro-2-oxo-1 ,2-dihydroquinolin-4-yl)methyl)-4-methylthiazole-5-carboxamide.
Any of the compounds according to the invention can exist as one or more stereoisomers depending on the number of stereogenic units (as defined by the IUPAC rules) in the compound. The invention thus relates equally to all the stereoisomers, and to the mixtures of all the possible stereoisomers, in all proportions. The stereoisomers can be separated according to the methods that are known per se by the man ordinary skilled in the art.
According to the invention, the following generic terms are generally used with the following meanings: • halogen means fluorine, chlorine, bromine or iodine ;
• heteroatom can be nitrogen, oxygen or sulphur ;
• halogenated groups, notably haloalkyl, haloalkoxy and cycloalkyl groups, can comprise up to nine identical or different a halogen atoms ;
• Any alkyl, alkenyl or alkynyl group can be linear or branched ; • the term "aryl" means phenyl or naphthyl, optionally substituted by one to five groups selected in the list consisting of halogen, [d-C6]-alkyl, [d-C6]-haloalkyl, [C2-C6]-alkenyl, [C2-C6]-haloalkenyl, [C2-C6]-alkynyl, [C2-C6]-haloalkynyl, [Ci-C6]-alkoxy, [d-C4]-alkoxy- [d-C4-alkyl, [d-C4]-alkoxy-[d-C4]-alkoxy, [d-C6]-haloalkoxy and [d-C4]-haloalkoxy- [d-C4]-alkyl ; • 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. Preferred compounds of formula (I) according to the invention are those wherein A is selected in the list consisting of:
Figure imgf000008_0001
wherein: • -* represents the attachment point to the carbonyl moiety ;
• V1 represents O, S or NRa1 ;
• Ra1 represents a hydrogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d-C8-alkoxy-d-C8-alkyl ;
• Ra2 and Ra3, that can be the same or different represent a hydrogen atom ; a halogen atom ; cyano ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxy or Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ;
• Ra4 represents a hydrogen atom, a halogen atom ; cyano ; Ci-C8-alkyl ; Ci-C8- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d- C8-alkoxy or Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; Ci-C8-alkylsulfanyl ; amino ; Ci-C8-alkylamino ; di- (Ci-C8-alkyl)amino ; d-C8-alkyloxycarbonyl.
More preferred compounds of formula (I) according to the invention are those wherein A is selected in the list consisting of:
Figure imgf000009_0001
wherein:
• -* represents the attachment point to the carbonyl group ;
• V1 represents O, S or NRa1 ; • Ra1 represents a hydrogen atom ; Ci-C8-alkyl ; Ci C8-alkoxy-C1-C8-alkyl ;
• Ra2 represents Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxy ;
• Ra3 represents a hydrogen atom ; a halogen atom ; C-ι-C8-alkyl ;
• Ra4 represents a hydrogen atom, a halogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
Other more preferred compounds of formula (I) according to the invention are those wherein
• A represents A5 ;
• V1 represents NRa1 ; • Ra1 represents d-C8-alkyl ;
• Ra2 and Ra3, that can be the same or different represent a hydrogen atom ; a halogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; or
• A represents A4 ; • V1 represents S ; Ra2 represents a C-ι-C8-alkyl ; C-i-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
Ra4 represents a hydrogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
Other preferred compounds of formula (I) according to the invention are those wherein B is selected in the list consisting of :
Figure imgf000010_0001
wherein
W1 to W5, Y1a, Y2a, Y3aand Y3b independently represent NRb2 or CRb3 ;
• Y/D represents O, S or NR b2.
Other more preferred compounds of formula (I) according to the invention are those wherein B represent B1 or B2 ; W1 to W5, Y1a, Y2a, Y3a and Y3b independently represent CRb3 ; or B represent B5 or B6 ;W1 to W5, Y1a and Y3a independently represent CRb1 ; Y2b represents S.
Other preferred compounds of formula (I) according to the invention are those wherein T represents O or S.
Other preferred compounds of formula (I) according to the invention are those wherein Z1 represents cyclopropyl.
Other preferred compounds of formula (I) according to the invention are those wherein Z2 and Z3 independently represent a hydrogen atom or C1-C8 alkyl. Other preferred compounds of formula (I) according to the invention are those wherein Q represents a halogen atom ; Ci-C8-alkyl ; Ci-C8-alkoxy ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
The above mentioned preferences with regard to the substituents of the compounds of formula (I) according to the invention can be combined in various manners, either individually, partially or entirely. 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 combine:
- preferred features of A with preferred features of one or more T, Z1 to Z3, Ra, Rb, T, V1 and Q ;
- preferred features of T with preferred features of one or more A, Z1 to Z3, Ra, Rb, V1 and Q ;
- preferred features of Z1 with preferred features of one or more A, T, Z2, Z3, Ra, Rb, V1 and Q ;
- preferred features of Z2 with preferred features of one or more A, T, Z1, Z3, Ra, Rb, V1 and Q ; - preferred features of Z3 with preferred features of one or more A, T, Z1, Z2, Ra, Rb, V1 and Q ;
- preferred features of Ra with preferred features of one or more A, T, Z1 to Z3, Rb, V1 and Q ;
- preferred features of Rb with preferred features of one or more A, T, Z1 to Z3, Ra, V1 and Q ;
- preferred features of V1 with preferred features of one or more A, T, Z1 to Z3, Ra, Rb and Q ;
- preferred features of Q with preferred features of one or more A, T, Z1 to Z3, Ra, Rb and V1 ; 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, T, Z1 to Z3, Ra, Rb, V1 and Q ; 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 compounds of formula (I).
Thus according to a further aspect of the present invention, there is provided a process P1 for the preparation of a compound of formula (I) wherein T represents O, as illustrated by the following reaction scheme:
Figure imgf000011_0001
wherein • A, Z1 to Z3, W1 to W5 and B are as herein-defined ;
• U1 represents a halogen atom or a leaving group.
In process P1 according to the invention, step 1 can be performed if appropriate in the presence of a solvent and if appropriate in the presence of an acid binder.
N-cycloalkyl-amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters, 2006, p 2014 synthesis of compounds 7 and 8), or reduction of imines (Tetrahedron, 2005, p 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry, 2002, p 3887 preparation of intermediate for compound 28).
Carboxylic acid derivatives of formula (III) are known or can be prepared by known processes (WO-93/11117 ; EP-545 099 ; Nucleosides & Nucleotides, 1987, p737-759, Bioorg. Med. Chem., 2002, p2105-2108).
Suitable acid binders for carrying out process P1 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 acetate, and 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.
Suitable solvents for carrying out process P1 according to the invention are in each case all customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile ; amides, such as N, N- dimethylformannide, N,N-dimethylacetannide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or sulphones, such as sulpholane.
When carrying out process P1 according to the invention, the reaction temperatures can independently be varied within a relatively wide range. Generally, processes according to the invention are carried out at temperatures between O0C and 16O0C, preferably between 1O0C and 12O0C. A way to control the temperature for the processes according to the invention is to use micro-wave technology.
Process P1 according to the invention is generally independently carried out under atmospheric pressure. However, in each case, it is also possible to operate under elevated or reduced pressure.
When carrying out step 1 of process P1 according to the invention, generally 1 mol or other an excess of the acid derivative of formula (III) and from 1 to 3 mol of acid binder are employed per mole of amine of formula (II). It is also possible to employ the reaction components in other ratios.
Work-up is carried out by customary methods. Generally, the reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that can still be present.
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, and illustrated according to the following reaction scheme :
Figure imgf000013_0001
wherein A, Z1 to Z3, W1 to W5 and B are as herein-defined. Process P2 can be performed in the presence of a thionating agent.
Starting amide derivatives of formula (I) can be prepared according to process P1.
Suitable thionating agents for carrying out process P2 according to the invention can be sulphur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), boron trisulfide (B2S3), bis (diethylaluminium) sulfide ((AIEt2)2S), ammonium sulfide ((NH4)2S), phosphorous pentasulfide (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1 ,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in J.Chem.Soc. Perkin 1, (2001), 358.
in the presence or in the absence, 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-dimethyl- aminopyridine or N-methylpiperidine.
Suitable solvents for carrying out process P2 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane or 1 ,2-diethoxyethane ; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile ; sulphurous solvents, such as sulpholane or carbon disufide.
When carrying out process P2 according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from O0C to 16O0C, preferably from 1O0C to 12O0C. A way to control the temperature for the processes according to the invention is to use micro-wave technology. Process P2 according to the invention is generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
When carrying out process P2 according to the invention, 1 mole or an excess of the sulphur equivalent of the thionating agent and from 1 to 3 moles of the base can be employed per mole of the amide derivative (I).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
In general, the reaction mixture is concentrated under reduced pressure. The residue that remains can be freed by known methods, such as chromatography or recrystallization, from any impurities that can still be present.
According to a further aspect according to the invention, there is provided a process P3 for the preparation of a compound of formula (I), wherein T represents N-Rc, N-ORd, N-NRcRd or N-CN, and illustrated according to the following reaction scheme :
(I)
Figure imgf000015_0001
wherein
• A, Z1 to Z3, W1 to W5 and B are as herein-defined ; • U2 represents a chlorine atom or a methylsulfanyl goup,
In process P3 according to the invention, step 2 can be performed in the presence of an acid binder and in the presence of a solvent.
N-cycloalkyl-amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters, 2006, p 2014 synthesis of compounds 7 and 8), or reduction of imines (Tetrahedron, 2005, p 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry, 2002, p 3887 preparation of intermediate for compound 28). N-substituted carboximidoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Houben-Weyl, "Methoden der organischen Chemie" (1985), E5/1 , p 628-633 and Patai, "The chemistry of amidines and imidates" (1975), p 296-301.
N-substituted or N,N-disubstituted hydrazonoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Tetrahedron, 1991 , 47, p 447 and Journal of Heterocyclic Chemistry, 1983, 20, p 225
N-cyano carboximidoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Tetrahedron Letters, 1968, p 5523 and Bioorganic and Medicinal Chemistry, 2006, p 4723.
Suitable acid binders for carrying out process P3 according to the invention can be inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives ; alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate ; alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate ; alkaline earth metal or alkali metal hydrides, such as sodium hydride or potassium hydride ; alkaline earth metal or alkali metal alcoolates, such as sodium methylate, sodium ethylate, sodium propylate or potassium t-butylate ;and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethyl- aminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diaza- bicycloundecene (DBU) ; or a polymer-supported acid scavenger (for example as detailed in http://www.iris-biotech.de/downloads/scavengers.pdf).
It is also possible to work in the absence of any additional acid binder.
Suitable solvents for carrying out process P3 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile ; amides, such as N, N- dimethylformannicle, N,N-dimethylacetannide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or sulphones, such as sulpholane.
When carrying out process P3 according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from O0C to 16O0C, preferably from 1 O0C to 12O0C. A way to control the temperature for the processes according to the invention is to use micro-wave technology.
Process P3 according to the invention is generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
When carrying out process P3 according to the invention, the amine derivative of formula (III) can be employed as its salt, such as chlorhydate or any other convenient salt.
When carrying out process P3 according to the invention, 1 mole or an excess of the amine derivative of formula (II) and from 1 to 3 moles of the acid binder can be employed per mole of the N-substituted carboximidoyl chloride of formula (IV).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
In general, the reaction mixture is concentrated under reduced pressure. The residue that remains can be freed by known methods, such as chromatography or recrystallization, from any impurities that can still be present.
Compounds according to the invention can be prepared according to the above described process. 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 these processes according to the specifics of each of the compounds according to the invention that is desired to be synthesized.
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 crops, and 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 emulsifier, 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 polyols, and derivatives of the above compounds comprising 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, emulsifiable 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 nucleic acid synthesis, for example benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolinic acid.
(2) Inhibitors of the mitosis and cell division, for example benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate, thiophanate- methyl and zoxamide.
(3) Inhibitors of the respiration, for example diflumetorim as Cl-respiration inhibitor; bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (9R- component), isopyrazam (9S-component), mepronil, oxycarboxin, penthiopyrad, thifluzamide as Cll-respiration inhibitor; amisulbrom, azoxystrobin, cyazofamid, dimoxystrobin, enestroburin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin as Clll-respiration inhibitor. (4) Compounds capable to act as an uncoupler, like for example binapacryl, dinocap, fluazinam and meptyldinocap. (5) Inhibitors of the ATP production, for example fentin acetate, fentin chloride, fentin hydroxide, and silthiofam.
(6) Inhibitors of the amino acid and/or protein biosynthesis, for example andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil.
(7) Inhibitors of the signal transduction, for example fenpiclonil, fludioxonil and quinoxyfen. (8) Inhibitors of the lipid and membrane synthesis, for example biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride, pyrazophos, tolclofos-m ethyl and vinclozolin.
(9) Inhibitors of the ergosterol biosynthesis, for example aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazol, pefurazoate, penconazole, piperalin, prochloraz, propiconazole, prothioconazole, pyributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafine, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, triforine, triticonazole, uniconazole, viniconazole and voriconazole.
(10) Inhibitors of the cell wall synthesis, for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, prothiocarb, validamycin A, and valiphenal. (11 ) Inhibitors of the melanine biosynthesis, for example carpropamid, diclocymet, fenoxanil, phthalide, pyroquilon and tricyclazole.
(12) Compounds capable to induce a host defence, like for example acibenzolar-S-methyl, probenazole, and tiadinil.
(13) Compounds capable to have a multisite action, like for example bordeaux mixture, captafol, captan, chlorothalonil, copper naphthenate, copper oxide, copper oxychloride, copper preparations such as copper hydroxide, copper sulphate, dichlofluanid, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zinc, oxine-copper, propamidine, propineb, sulphur and sulphur preparations including calcium polysulphide, thiram, tolylfluanid, zineb and ziram. (14) Further compounds like for example 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one, ethyl (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, N-[2-(1 ,3-dimethylbutyl)phenyl]-5-fluoro-1 ,3- dimethyl-1 H-pyrazole-4-carboxamide, N-{2-[1 , 1 '-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)- 1-methyl-1 H-pyrazole-4-carboxamide, (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5- fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide, (2E)-2-{2-[({[(2E,3E)-4- (2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N- methylethanamide, 2-chloro-N-(1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl)pyridine-3- carboxamide, N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide, 5- methoxy-2-methyl-4-(2-{[({(1 E)-1-[3- (trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1 ,2,4-triazol-3-one, (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1 E)-1-[3-
(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide, (2E)-2-
(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3- (trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide, (2E)-2-{2-[({[(1 E)-1-(3-{[(E)-1- fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N- methylethanamide, 1-(4-chlorophenyl)-2-(1 H-1 ,2,4-triazol-1-yl)cycloheptanol, methyl 1-(2,2- dimethyl-2,3-dihydro-1 H-inden-1-yl)-1 H-imidazole-5-carboxylate, N-ethyl-N-methyl-N'-{2-methyl- 5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide, N'-{5-(difluoromethyl)-2- methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, O-{1-[(4- methoxyphenoxy)methyl]-2,2-dimethylpropyl} 1 H-imidazole-1-carbothioate, N-[2-(4-{[3-(4- chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2-(methylsulfonyl)valinamide, 5- chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1 ,2,4]triazolo[1 ,5-a]pyrimidine, 5- amino-1 ,3,4-thiadiazole-2-thiol, propamocarb-fosetyl, 1-[(4-methoxyphenoxy)methyl]-2,2- dimethylpropyl 1 H-imidazole-1-carboxylate, 1-methyl-N-[2-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl]-3- (trifluoromethyl)-i H-pyrazole-4-carboxamide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 2- butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-phenylphenol and salts, 3-(difluoromethyl)-1- methyl-N-[2-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl]-1 H-pyrazole-4-carboxamide, 3,4,5- trichloropyridine-2,6-dicarbonitrile, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine, 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, 4-(4-chlorophenyl)-5- (2,6-difluorophenyl)-3,6-dimethylpyridazine, quinolin-8-ol, quinolin-8-ol sulfate (2:1 ) (salt), benthiazole, bethoxazin, capsimycin, carvone, chinomethionat, chloroneb, cufraneb, cyflufenamid, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomezine, dicloran, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomate, ferimzone, flumetover, fluopicolide, fluoroimide, flusulfamide, fosetyl-aluminium, fosetyl-calcium, fosetyl- sodium, hexachlorobenzene, irumamycin, isotianil, methasulfocarb, methyl (2E)-2-{2- [({cyclopropyl[(4-methoxyphenyl)innino]nnethyl}thio)nnethyl]phenyl}-3-nnethoxyacrylate, methyl isothiocyanate, metrafenone, (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6- methylphenyl)nnethanone, mildiomycin, tolnifanide, N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2- yn-1-yloxy)phenyl]propanamide, N-[(4-chlorophenyl)(cyano)methyl]-3-[3-nnethoxy-4-(prop-2-yn- 1-yloxy)phenyl]propanamide, N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3- carboxamide, N-[ 1-(5-bromo-3-chloropyridin2-yl)ethyl]-2,4 -dichloropyridine-3-carboxamide, N- [1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxannide, N-{(Z)-
[(cyclopropylmethoxy)innino][6-(difluoronnethoxy)-2,3-difluorophenyl]nnethyl}-2-phenylacetannide, N-{(E)-[(cyclopropylmethoxy)innino][6-(difluoronnethoxy)-2,3-difluorophenyl]nnethyl}-2- phenylacetamide, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and salts, phenazine-1-carboxylic acid, phenothrin, phosphorous acid and its salts, propamocarb fosetylate, propanosine-sodium, proquinazid, pyrrolnitrine, quintozene, S-prop-2-en-1-yl 5-amino-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo- 2,3-dihydro-1 H-pyrazole-1-carbothioate, tecloftalam, tecnazene, triazoxide, trichlamide, 5- chloro-N'-phenyl-N'-prop-2-yn-1-ylthiophene-2-sulfonohydrazide and zarilamid.
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 may becan be protected by the method according to the invention, mention may becan 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.
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 Sphaerotheca fuliginea; 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 and Phakopsora meibomiae;
Puccinia diseases caused for example by Puccinia recondita, 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 and Peronospora 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 and Pseudo- peronospora cubensis;
Pythium diseases caused for example by Pythium ultimum;
Leaf spot, Leaf blotch and Leaf Blight Diseases such as
Alternaria diseases caused for example by Alternaria solani;
Cercospora diseases caused for example by Cercospora beticola;
Cladiosporium 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 lindemuthianum;
Cycloconium diseases caused for example by Cycloconium oleaginum;
Diaporthe diseases caused for example by Diaporthe citri;
Elsinoe diseases caused for example by Elsinoe fawcettii; Gloeosporium diseases caused for example by Gloeosporium laeticolor;
Glomerella diseases caused for example by Glomerella cingulata;
Guignardia diseases caused for example by Guignardia bidwellii;
Leptosphaeria diseases caused for example by Leptosphaeria maculans and Leptosphaeria nodorum; Magnaporthe diseases caused for example by Magnaporthe grisea;
Mycosphaerella diseases caused for example by Mycosphaerella graminicola, Mycosphaerella arachidicola and 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 and Septoria lycopersici;
Typhula diseases caused for example by Thyphula 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 including Maize cob such as Alternaria diseases caused for example by Alternaria spp.; Aspergillus diseases caused for example by Aspergillus flavus; Cladosporium diseases caused for example by Cladiosporium cladosporioides; 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 and Penicillium purpurogenum;
Rhizopus diseases caused by example by Rhizopus stolonifer Sclerotinia diseases caused for example by Sclerotinia sclerotiorum; Verticillium diseases caused for example by Verticillium 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;
Cochliobolus 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;
Microdochium diseases caused for example by Microdochium nivale;
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 including deformation of blooms and fruits such as Exobasidium diseases caused for nexample by Exobasidium vexans. Taphrina diseases caused for example by Taphrina deformans;
Decline Diseases of Wooden Plants such as
Esca disease caused for example by Phaeomoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea;
Ganoderma diseases caused by example by Ganoderma boninense;
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
Xanthomanas species for example Xanthomonas campestris pv. oryzae; Pseudomonas species for example Pseudomonas syringae pv. lachrymans; Erwinia species for example Erwinia amylovora.
The fungicide composition according to the invention can 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 15O 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 fungicide composition according to the invention can also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention. Genetically modified plants are plants into genome of that a heterologous gene encoding a protein of interest has been stably integrated. The expression "heterologous gene encoding a protein of interest" essentially means genes that give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the modified plant. 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 examples.
The following table illustrates in a non-limiting manner examples of compounds according to the invention.
In the following table, M+H (or M-H) means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass unit) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy.
In the following table, the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below : Temperature: 4O0C , Mobile phases : 0.1 % aqueous formic acid and acetonitrile linear gradient from 10% acetonitrile to 90% acetonitrile.
Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 190nm to 400nm.
The following examples illustrate in a non-limiting manner the preparation of the compounds of formula (I) according to the invention.
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
General preparation example 1 : preparation of an amide derivative of formula (I) on Optimizer™ micro-waves apparatus
In a 8 ml Optimizer™ vial is weighted 1.7 mmole of amine (II). 2 ml of a 1 molar solution of the acyl chloride (III) (2 mmoles) in acetonitrile are added followed by 1 ml of triethylamine. The vial is sealed, pre-stirred 10 s at ambient temperature then heated at 180 0C for 60 s under microwaves. After cooling, the vial is opened and poured onto 10 ml of a saturated solution of potassium carbonate. The watery layer is extracted twice by 5 ml of dichloromethane. The organic phases are dried over magnesium sulfate. The solvents are removed and the crude amide is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS.
General preparation example 2 thionation of an amide derivative of formula (I) on Chemspeed™ apparatus In a 13 ml Chemspeed™ vial is weighted 0.27 mmole of phosphorous pentasulfide (P2S5). 3 ml of a 0.18 molar solution of the amide (I) (0.54 mmole) 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 is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS.
Efficacy example A : in vivo preventive test on Pyrenophora teres (Barley net blotch)
The active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
Barley plants (Express variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 120C, are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of
Pyrenophora teres spores (12,000 spores per ml). The spores are collected from a 15-day-old culture. The contaminated barley plants are incubated for 24 hours at about 2O0C and at 100% relative humidity, and then for 12 days at 80% relative humidity.
Grading 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 500 ppm with the following compounds:. 1 , 2, 3, 6, 8, 9, 11 , 12, 16, 18, 24, 25, 26, 27, 33, 36, 40, 42, 47, 50, 54, 55, 57, 58, 59, 64, 65, 66, 67, 69, 71 , 72, 75, 79, 80, 81 , 82, 83, 85, 86, 87, 88, 89,
100, 109, 116, 119, 120, 145, 149, 166, 167, 168, 176, 177, 178, 204, 213, 214, 222, 226, 227,
228, 240, 241 and 242.
Efficacy example B : in vivo preventive test on Sphaerotheca fuliginea (cucurbit powdery mildew) The active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
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 2 first leaves stage by spraying with the aqueous suspension described above Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water 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 11-12 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 500 ppm with the following compounds:. 2, 6, 8, 11 , 12, 17, 18, 22, 23, 25, 26, 36, 40, 41 , 42, 47, 49, 50, 51 , 53, 55, 56, 57, 58, 59, 63, 64, 65, 66, 67, 69, 70, 71 , 72, 74, 75, 79, 80, 81 , 82, 83, 85, 86, 87, 88, 89, 100, 105, 109, 120, 128, 129, 136, 137, 138, 149, 157, 158, 159, 166, 167, 168, 176, 177, 178, 180, 185, 194, 195, 196, 198, 204, 205, 221 , 222, 240, 241 and 242.
Efficacy example C : in vivo preventive test on Mycosphaerella graminicola (wheat leaf spot)
The active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, and 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 120C, are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water 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 180C 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 500 ppm with the following compounds: 1 , 2, 5, 6, 7, 8, 9, 11 , 17, 18, 22, 23, 24, 26, 27, 32, 33, 34, 36, 40, 41 , 47, 48, 49, 50, 51 , 53, 54, 55, 56, 57, 58, 59, 63, 64, 65, 67, 69, 70, 71 , 74, 75, 79, 80, 81 , 83, 84, 85, 86, 87, 88, 89, 94, 96, 97, 100, 105, 109, 115, 116, 119, 120, 128, 129, 134, 136, 137, 138, 140, 145, 146, 147, 149, 155, 157, 158, 161 , 164, 166, 167, 168, 170, 172, 174, 176, 177, 178, 180, 183, 185, 186, 187, 190, 192, 194, 195, 221 , 225, 226, 227, 228, 229, 240, 241 and 242. Efficacy example D : in vivo test on Puccinia recondita f. Sp. tritici (wheat brown rust). The active ingredients tested are prepared by homogenisation in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration.
Wheat plants (Scipion variety) in starter cups, sown on 50/50 peat soil-pozzolana substrate and grown at 120C, are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water 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/l of tween 80 10%. The contaminated wheat plants are incubated for 24 hours at 2O0C and at 100% relative humidity, and then for 10 days at 2O0C 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 500 ppm with the following compounds: 1 , 2, 9, 16, 24, 25, 26, 36, 47, 49, 54, 57, 58, 63, 64, 65, 66, 67, 80, 83, 85, 87, 88, 89, 94, 100, 109, 119, 120, 134, 136, 137, 138, 140, 149, 158, 167, 176, 177, 178, 240 and 242.
Example E: 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 18-2O0C, 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 180C, 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: 2, 6, 12, 16, 18, 26, 47, 49, 57, 65, 66, 67, 69, 79, 80, 83, 166, 167, 176, 204, 213, 214 and 240.
Example F: in vivo test on Botrytis cinerea (Grey mould)
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), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 18- 2O0C, are treated at the cotyledon Z11 stage by spraying with the active ingredient prepared as 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 depositing drops of an aqueous suspension of Botrytis cinerea spores (150,000 spores per ml) on upper surface of the leaves. The spores are collected from a 15-day-old culture and are suspended in a nutrient solution composed of : - 20 g/L of gelatin;
- 50 g/L of D-fructose;
- 2 g/L of NH4NO3; - 1 g/L of KH2PO4.
The contaminated cucumber plants are settled for 5-7 days in a climatic room at 15-110C (day/night) and at 80% relative humidity.
Grading is carried out 5/7 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 70%) protection is observed at a dose of 500ppm with the following compounds: 36, 64, 65, 67,80 and 89.
Example G: In vivo test on Peronospora parasitica (Crucifer downy mildew)
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.
Cabbage plants (Eminence variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-2O0C, are treated at the cotyledon 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 Peronospora parasitica spores (50 000 spores per ml). The spores are collected from infected plant. The contaminated cabbage plants are incubated for 5 days at 2O0C, under a humid atmosphere. Grading is carried out 5 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm with the following compounds : 2, 6, 8, 19, 27, 48, 49, 57, 73, 75, 83, 84, 87, 88, 94, 99, 108, 109, 129, 134, 135, 136, 149, 155, 164, 169, 174, 176, 179, 183, 198, 219 and 240 according to the invention whereas weak protection (less than 30% of disease control) to no protection at all is observed at a dose of 500 ppm with the compounds of examples 5, 45 and 50 disclosed in patent application WO-2006/120224
Examples 5, 45 and 50 disclosed in patent application WO-2006/120224 correspond, respectively, to following compounds :
N-cyclopropyl-N-[(3-Chloro-5-trifluoromethyl-pyridin-2-yl)-methylene]-2,5-dimethyl-furane-3- carboxamide;
N-cyclopropyl-N-[(3-Chloro-5-trifluoromethyl-pyridin-2-yl)-methylene]-5-fluoro-1 ,3-dimethyl-IH- pyrazole-4-carboxamide; N-cyclopropyl-N-[(3-Chloro-5-trifluoromethyl-pyridin-2-yl)-methylene]-5-fluoro-3-(trifluoromethyl)-1- methyl -1 H-pyrazole-4-carboxamide;
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2006/120224

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 Ra ;
• B represents
Figure imgf000060_0002
wherein o W1 to W5 independently represent N or CRb1 ; o Y1 to Y3 independently represent N, O, S, NRb2 or CRb3 ; o Y1 to Y3 together with the atoms Wn to which they are linked, form an aromatic 5- or 6-membered, fused heterocyclyl ring comprising up to four heteroatoms, or an aromatic 6-membered fused carbocyclyl ring ; o p represents 1 or 2 ;
• T represents O, S, N-Rc, N-0Rd, N-NRcRd or N-CN ;
• Z1 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 ; C-ι-C8-alkyl ; C-ι-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci C8-alkoxy ; Ci-C8- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxycarbonyl ; d-C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C8-alkylaminocarbonyl ; di-(d-C8- alkyl)aminocarbonyl ; • Z2 and Z3 independently represent a hydrogen atom ; a halogen atom ; C-ι-C8-alkyl ; C1- C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkenyl ; C2-C8-alkynyl ; cyano ; nitro ; C1--8-alkoxy ; C2-C8-alkenyloxy ; C2-C8- alkynyloxy ; C3-C7-cycloalkyl ; d-C8-alkylsulphenyl ; amino ; C1 C8-alkylamino ; di-(C-ι-
C8-alkyl)amino ; C-i-C8-alkoxycarbonyl ; C-i-C8-alkylcarbonyl ; C-i-C8-alkylcarbamoyl ; di- (C-ι-C8-alkyl)carbamoyl ; N-C-i-C8-alkyl-C-i-C8-alkoxycarbamoyl ; or
• Z2 and Z3 together with the carbon atom to which they are linked can form a substituted or non substituted C3-C7 cycloalkyl ;
• Ra independently represents a hydrogen atom ; halogen atom ; cyano ; nitro ; amino ; sulfanyl ; hydroxyl ; pentafluoro-λ-6-sulfanyl ; C-ι-C8-alkylamino ; di-(C-ι-C8-alkyl)amino ; tri(C1-C8-alkyl)silyl ; tri(C1-C8-alkyl)silyl-C1-C8-alkyl ; CrC8-alkylsulfanyl ; C1-C8- halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different ; C-ι-C8-alkyl ; C-ι-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C-ι-C8-alkoxy ; C1- C8-alkoxy-C-ι-C8-alkyl ; C-ι-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C2 C8-alkenyloxy ; C2-C8-alkynyloxy ; C3-C7-cycloalkyl ;
C3-C7-cycloalkyl- C-ι-C8-alkyl ; C-ι-C8-alkylsulphinyl ; C-ι-C8-alkylsulphonyl ; C1- C8alkoxyimino ; (C-i-C8-alkoxyimino)-C1- C8-alkyl ; (benzyloxyimino)-C-ι-C8-alkyl ; C1-C8- alkylcarbonyl ; C-i-C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C8-alkoxycarbonyl ; C-i-C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; C1-C8- alkylaminocarbonyl ; di-(C-ι-C8-alkyl)aminocarbonyl ;
• Rc and Rd, that can be the same or different, represent a hydrogen atom ; C-ι-C8-alkyl ; C-ι-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C-i-C8-alkoxy-C-i-C8-alkyl ; C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8- halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; C3-C7-cycloalkyl-C-ι-C8-alkyl ; C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ; formyl ; C-i-C8-alkylcarbonyl ; C1- C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkylsulphonyl ; Ci-C8-halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; phenyl that can be substituted by up to 5 groups Q ; naphthyl that can be substituted by up to 6 groups Q ; phenylmethylene that can be substituted by up to 5 groups Q ; phenylsulphonyl that can be substituted by up to 5 groups Q ;
Rb1 and Rb3 independently represent a hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxyl ; sulphanyl ; amino ; pentafluoro-λ6-sulphanyl ; Ci-C8-alkyl ; Ci-C8- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d- C8-alkylamino ; di-(d-C8-alkyl)amino ; d-C8-alkoxy ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; d-C8-alkoxy-Ci-C8-alkyl ; d- C8-alkylsulphanyl ; Ci-C8-halogenoalkylsulphanyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkylsulphenyl, Ci-C8-halogenoalkylsulphenyl comprising up to 9 halogen atoms that can be the same or different, Ci-C8- alkylsulphinyl, Ci-C8-halogenoalkylsulphinyl comprising up to 9 halogen atoms that can be the same or different, Ci-C8-alkylsulphonyl, Ci C8-halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkenyl ; C2- C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkinyloxy ; C2-C8- halogenoalkinyloxy comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; C3-C7-cycloalkyl-d-C8-alkyl ; C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ; formyl ; formyloxy ; formylamino ; carboxy ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; (hydroxyimino)-
Ci-C8-alkyl ; Ci-C8-alkylcarbonyl ; Ci-C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; N-Ci-C8-alkyl-Ci-C8- alkoxycarbamoyl ; Ci-C8-alkoxycarbonyl ; Ci-C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkylaminocarbonyl ; di- (Ci-C8-alkyOaminocarbonyl ; Ci-C8-alkylcarbonyloxy ; Ci-C8-halogenoalkylcarbonyloxy comprising up to 9 halogen atoms that can be the same or different ; Ci-C8- alkylcarbonylamino ; Ci-C8-alkylaminocarbonyloxy ; di-(Ci-C8-alkyl)aminocarbonyloxy ; Ci-C8-alkyloxycarbonyloxy ; Ci-C8-alkoxyimino ; (Ci-C8-alkoxyimino)-Ci-C8-alkyl ; (Ci- C8-alkenyloxyimino)-Ci-C8-alkyl ; (Ci-C8-alkynyloxyimino)- Ci-C8-alkyl ; (benzyloxyimino)-Ci-C8-alkyl ; tri(Ci-C8-alkyl)silyl ; tri(Ci-C8-alkyl)silyl- Ci-C8-alkyl ; phenyl that can be substituted by up to 5 groups Q ; benzyloxy that can be substituted by up to 5 groups Q ; benzylsulphanyl that can be substituted by up to 5 groups Q ; benzylamino that can be substituted by up to 5 groups Q ; phenoxy that can be substituted by up to 5 groups Q ; phenylamino that can be substituted by up to 5 groups Q ; phenylsulphanyl that can be substituted by up to 5 groups Q ; benzyl that can be substituted by up to 5 groups Q ; pyridinyl that can be substituted by up to four groups Q and pyridinyloxy that can be substituted by up to four groups Q ;
• Rb2 represents a hydrogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxy-Ci-C8-alkyl ; C2-C8- alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; C3-C7-cycloalkyl-Ci-C8-alkyl ; C3- C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different ; formyl, d-C8-alkylcarbonyl ; d-C8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; d-C8-alkylsulphonyl ; C1-C8- halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different ; phenylsulfonyl can be substituted by up to 5 groups Q ; benzyl that can be substituted by up to 5 groups Q ;
• Q, that can be the same or different, represents a halogen atom ; cyano ; nitro ; Ci-C8- alkyl ; d-C8-alkoxy ; d-C8-alkylsulfanyl ; d-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; tri(d-C8)alkylsilyl and tri(d- C8)alkylsilyl-d-C8-alkyl ; d-C8-alkoxyimino ; (d-C8-alkoxyimino)- d-C8-alkyl ;
as well as salts, N-oxides, metallic complexes, metalloidic complexes and optically active or geometric isomers thereof provided that compound of formula (I) differs from N-cyclopropyl-N- ((6,8-dimethyl-2-oxo-1 ,2-dihydroquinolin-3-yl)methyl)-furane-2-carboxamide, N-cyclopropyl-N- ((6-ethoxy-2-oxo-1 ,2-dihydroquinolin-3-yl)methyl)-furane-2-carboxamide, N-cyclopropyl-N-((6- methyl-2-oxo-1 ,2-dihydroquinolin-3-yl)methyl)-furane-2-carboxamide, N-cyclopropyl-N-((7,8- difluoro-2-oxo-1 ,2-dihydroquinolin-4-yl)methyl)-4-methylthiazole-5-carboxamide and from N- cyclopropyl-N-((8-fluoro-2-oxo-1 ,2-dihydroquinolin-4-yl)methyl)-4-methylthiazole-5-carboxamide.
2. A compound according to claim 1 wherein A is selected in the list consisting of:
Figure imgf000064_0001
wherein:
• -* represents the attachment point to the carbonyl moiety ;
• V1 represents O, S or NRa1 ; • Ra1 represents a hydrogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1-C8-alkoxy-C1-C8-alkyl ;
• Ra2 and Ra3, that can be the same or different represent a hydrogen atom ; a halogen atom ; cyano ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxy or Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ;
• Ra4 represents a hydrogen atom, a halogen atom ; cyano ; d-C8-alkyl ; C1-C8- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; d- C8-alkoxy or Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; C3-C7-cycloalkyl ; Ci-C8-alkylsulfanyl ; amino ; Ci-C8-alkylamino ; di- (Ci-C8-alkyl)amino ; d-C8-alkyloxycarbonyl.
3. A compound according to claims 1or 2 wherein A is selected in the list consisting of:
Figure imgf000065_0001
wherein:
• -* represents the attachment point to the carbonyl group ;
• V1 represents O, S or NRa1 ; • Ra1 represents a hydrogen atom ; Ci-C8-alkyl ; Ci C8-alkoxy-C1-C8-alkyl ;
• Ra2 represents Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-alkoxy ;
• Ra3 represents a hydrogen atom ; a halogen atom ; C-ι-C8-alkyl ;
• Ra4 represents a hydrogen atom, a halogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
4. A compound according to claims 1 to 3 wherein
• A represents A5 ;
• V1 represents NRa1 ; • Ra1 represents d-C8-alkyl ;
• Ra2 and Ra3, that can be the same or different represent a hydrogen atom ; a halogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; or
• A represents A4 ; • V1 represents S ; Ra2 represents a C-ι-C8-alkyl ; C-i-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
Ra4 represents a hydrogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
5. A compound according to claims 1 to 4 wherein B is selected in the list consisting of :
Figure imgf000066_0001
wherein
• W1 to W5, Y1a, Y2a, Y3a and Y3b independently represent NRb2 or CRb3 ;
• Y2b represents O, S or NRb2.
6. A compound according to claim 5 wherein
• B represent B1 or B2 ;
• W1 to W5, Y1a, Y2a, Y3a and Y3b independently represent CRb3 ; or
• B represent B5 or B6 ;
• W1 to W5, Y1a and Y3a independently represent CRb1 ;
• Y2b represents S.
7. A compound according to claims 1 to 6 wherein T represents O or S.
8. A compound according to claims 1 to 7 wherein Z1 represents cyclopropyl.
9. A compound according to claims 1 to 8 wherein Z2 and Z3 independently represent a hydrogen atom or C1-C8 alkyl.
10. A compound according to claims 1 to 9 wherein Q represents a halogen atom ; Ci-C8- alkyl ; Ci-C8-alkoxy ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
11. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claims 1 to 10 and an agriculturally acceptable support, carrier or filler.
12. 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 10 or a composition according to claim 11 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/EP2008/060040 2007-07-31 2008-07-31 Fungicide n-6-membered fused (hetero)aryl-methylene-n-cycloalkyl carboxamide derivatives WO2009016221A1 (en)

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