WO2020070050A1 - Fungicidal 5-substituted imidazol-1-yl carbinol derivatives - Google Patents

Fungicidal 5-substituted imidazol-1-yl carbinol derivatives

Info

Publication number
WO2020070050A1
WO2020070050A1 PCT/EP2019/076410 EP2019076410W WO2020070050A1 WO 2020070050 A1 WO2020070050 A1 WO 2020070050A1 EP 2019076410 W EP2019076410 W EP 2019076410W WO 2020070050 A1 WO2020070050 A1 WO 2020070050A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
cycloalkyl
alkoxy
plants
methyl
Prior art date
Application number
PCT/EP2019/076410
Other languages
French (fr)
Inventor
David Bernier
Robert Alan WEBSTER
Ricarda MILLER
Pierre-Yves Coqueron
Pierre Genix
Stephane Brunet
Philippe Kennel
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Publication of WO2020070050A1 publication Critical patent/WO2020070050A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings 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
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • C07D405/06—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 carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to novel 5-substituted imidazol-l-yl carbinol derivatives, to processes and intermediates for preparing these compounds, to compositions comprising those, and to the use thereof as biologically active compounds and compositions, especially for control of harmful microorganisms in crop protection and in the protection of materials.
  • object of the invention is to serve this need by providing novel compounds useful for control of harmful microorganisms in crop protection and in the protection of materials, in particular compounds showing fungicidal efficacy.
  • R 1 represents hydrogen, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Cs-Cs-cycloalkyl or C6-Ci4-aryl,
  • R 2 represents hydrogen, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Cs-Cs-cycloalkyl or C6-Ci4-aryl, wherein the aliphatic moieties, excluding cycloalkyl moieties, of R 1 and R 2 may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, C 3 -Cs-cycloalkyl, C 6 -Ci 4 -aryl, Ci-C 4 -alkoxy and C 1 -C 4 - haloalkoxy, wherein the C 3 -Cs-cycloalkyl and C 6 -Ci 4 -aryl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently from each other from halogen, CN, nitro, Ci-C 4 -alkyl, C 1 -C 4 - alkoxy
  • R 3 represents halogen, hydroxyl, cyano, isocyano, nitro, amino, sulfanyl, pentafluoro ⁇ 6 -sulfanyl, carboxaldehyde, hydroxycarbonyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs-alkyloxy, Ci-C -haloalkyloxy, tri(Ci-Cs-alkyl)silyl, tri(Ci-C 8 -alkyl)silyl-Ci-C 8 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 - halocycloalkyl, C 3 -C 7 -cycloalkenyl, C 3 -C 7 -halocycloalkenyl, C 3 -C 7 -cycloalkyl-Ci-C 8 -alkyl, C 3 -C 7
  • R 4 represents a bicyclic moiety of formula (Q)
  • X 1 , X 2 , X 3 , and X 4 independently from each other represent hydrogen, halogen, nitro, cyano, sulfanyl, pentafluoroA 6 -sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C 3 -C 7 -cycloalkyl, C 3 -C 7 -halocycloalkyl having 1 to 5 halogen atoms, Ci-Cs-haloalkyl-C 3 -C 7 - cycloalkyl, C 3 -C 7 -cycloalkenyl, C 2 -Cs-alkenyl, C 2 -Cs-alkynyl, C 6 -Ci 2 -bicycloalkyl, C 3 -C 7 - cycloalkyl-C 2 -C 8 -alkenyl, C 3 -C 7 -cycloalkyl-
  • the salts or N-oxides of the compounds of formula (I) also have fungicidal properties.
  • Formula (I) provides a general definition of the compounds according to the invention. Preferred radical definitions for the formulae shown above and below are given below. These definitions apply to the end products of formula (I) and likewise to all educts and intermediates.
  • R 1 preferably represents hydrogen, Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl or phenyl, wherein the aliphatic moieties, excluding the cycloalkyl moieties, of R 1 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, C3-C6-cycloalkyl, phenyl, Ci-C4-alkoxy and C1-C4- haloalkoxy, wherein C3-C6-cycloalkyl and phenyl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently from each other from halogen, CN, nitro, Ci-C4-atkyl, Ci-C4-alkoxy, C1-C4- haloalkyl, Ci-C4-haloalkoxy, and wherein the cycl
  • R 1 more preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, allyl, CH2CoC-CH3, CH2CoCH, cyclopropyl or phenyl, wherein the aliphatic groups, excluding the cycloalkyl moieties, of R 1 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from fluorine, chlorine, bromine, iodine, CN or nitro, and wherein the cyclopropyl and phenyl group of R 1 may be substituted by 1, 2, 3, 4 or 5 substituents R b selected independently of one another from fluorine, chlorine, bromine, iodine, CN and nitro.
  • R 1 more preferably represents methyl, /c/7- butyl, cyclopropyl or phenyl, wherein the aliphatic groups, excluding the cycloalkyl moieties, of R 1 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from fluorine, chlorine and bromine, and wherein the cyclopropyl and phenyl group of R 1 may be substituted by 1 , 2 or 3 substituents R b selected independently of one another from fluorine, chlorine and bromine.
  • R 1 more preferably represents cyclopropyl or phenyl, wherein the cyclopropyl and phenyl group may be substituted by 1, 2 or 3, preferably 1 or 2 substituents R b selected independently of one another from fluorine, chlorine and bromine.
  • R 1 more preferably represents cyclopropyl, 1 -fluorocyclopropyl, 1 -chlorocyclopropyl, 1- bromocyclopropyl, phenyl, 2-fluorophenyl, 3 -fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-difluorophenyl,
  • R 1 more preferably represents 1 -fluorocyclopropyl, 1 -chlorocyclopropyl, 2,3-difluorophenyl, 2,4- difluorophenyl, 2,5-difluorophenyl or 2,6-difluorophenyl.
  • R 1 more preferably represents 1 -chlorocyclopropyl, or 2,4-difluorophenyl.
  • R 1 represents in one particular preferred embodiment 1 -chlorocyclopropyl.
  • R 1 represents in a further particular preferred embodiment 2,4-difluorophenyl.
  • R 1 most preferably represents 1 -chlorocyclopropyl.
  • R 2 preferably represents hydrogen, Ci-C4-alkyl, allyl or propargyl, wherein the aliphatic moieties of R 2 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, wherein the phenyl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently of one another from halogen, CN, nitro, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy.
  • R 2 more preferably represents hydrogen, methyl, ethyl, isopropyl or allyl, wherein the aliphatic groups R 2 may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, phenyl, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy, wherein the phenyl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently of one another from halogen, CN, nitro, Ci-C 4 -alkyl, Ci- C 4 -alkoxy, Ci-C 4 -haloalkyl, Ci-C 4 -haloalkoxy.
  • R 2 more preferably represents hydrogen or methyl, ethyl, isopropyl or allyl.
  • R 2 more preferably represents hydrogen or methyl.
  • R 2 most preferably represents hydrogen.
  • R 3 preferably represents halogen, hydroxyl, cyano, isocyano, nitro, carboxaldehyde, hydroxycarbonyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs-alkyloxy, Ci-Cs-haloalkyloxy, C 3 -C 7 - cycloalkyl, C 3 -C 7 -halocycloalkyl, C 2 -Cs-alkenyl, C 2 -Cs-alkynyl, C 2 -Cs-alkenyloxy, C 2 -C 8 - haloalkenyloxy, C 3 -C 8 -alkynyloxy, C 3 -C 8 -halooalkynyloxy, Ci-Cs-alkylsulfanyl, Ci-Cs- haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci
  • R 3 more preferably represents halogen, cyano, nitro, carboxaldehyde, hydroxycarbonyl, Ci-C 4 -alkyl, Ci- C 4 -haloalkyl, Ci-C 4 -cyanoalkyl, Ci-C 4 -alkyloxy, Ci-C 4 -haloalkyloxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halocycloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, Ci-C 4 -atkylsulfanyl, Ci-C 4 -haloalkylsulfanyl, C 1 -C 4 - alkylcarbonyl, Ci-C 4 -haloalkylcarbonyl, aminothiocarbonyl, carbamoyl, Ci-C 4 -alkoxycarbonyl or Ci- C 4 -halogenoalkoxycarbonyl.
  • R 3 more preferably represents fluorine, chlorine, bromine, iodine, cyano, nitro, aminothiocarbonyl, Ci- C 4 -haloalkyl or carbamoyl.
  • R 3 more preferably represents fluorine, chlorine, bromine, iodine, cyano, aminothiocarbonyl or C 1 -C 4 - haloalkyl.
  • R 3 more preferably represents fluorine, chlorine, bromine, iodine, cyano, aminothiocarbonyl, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, l-chloroethyl, 1- bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
  • R 3 more preferably represents fluorine, cyano or CF 3 .
  • R 3 more preferably represents cyano or CF 3 .
  • R 3 most preferably represents cyano.
  • R 4 is a benzo fused at least partially saturated carbocycle or heterocycle which is represented by formula (Q)
  • dotted line A represents a single or double bond and the arrow depicts the bonding position of the shown moiety to the remainder of the molecule.
  • X 5 preferably represents -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -Y-CH 2 - or -Y-(CH 2 ) 2 -, wherein Y represents O, S or NY 1 , wherein Y 1 represents hydrogen or methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or fer/-butyl.
  • X 5 more preferably represents -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -O-CH 2 -, -0-(O3 ⁇ 4) 2 -, -S-CH 2 - or -S- (CH 2 ) 2 -.
  • X 5 more preferably represents -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -O-CH 2 - or -S-CH 2 -.
  • X 5 particularly preferred represents -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - or -O-CH 2 -.
  • R 4 particularly preferred represents a bicyclic moiety of formulae (Ql) to (Q8)
  • X 1 , X 2 , X 3 , and X 4 are defined as in formula (Q).
  • X 1 , X 2 , X 3 and X 4 preferably represent independently from each other hydrogen, halogen, nitro, cyano, sulfanyl, pentafluoro ⁇ 6 -sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C 3 -C 8 - cycloalkyl, Cs-Cs-halocycloalkyl having 1 to 5 halogen atoms, Ci-Cs-haloalkyl-C 3 -C 7 -cycloalkyl, C 3 - C 7 -cycloalkenyl, C 2 -Cs-alkenyl, C 2 -Cs-alkynyl, C 6 -Ci 2 -
  • X 1 , X 2 , X 3 and X 4 more preferably represent independently from each other hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C 2 -Cs-alkenyl, C 2 -Cs-alkynyl, C 3 -C 8 - cycloalkyl-C 2 -C 8 -alkenyl, C 3 -C 8 -cycloalkyl-C 2 -C 8 -alkynyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy having 1 to 5 halogen atoms, Ce-C aryl, or C 6 -Ci 4 -aryloxy, wherein the C 6 -Ci 4 -aryl and C 6 -Ci 4 -aryloxy is non-substituted or substituted by one or more group(s) selected from halogen, Ci-Cs-
  • X 1 , X 2 , X 3 and X 4 more preferably represent independently from each other hydrogen, fluorine, chlorine, bromine, cyano, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl having 1 to 5 halogen atoms, C 2 -C 4 -alkenyl, C 2 -C 4 - alkynyl, C 3 -C 6 -cycloalkyl-C 2 -C 4 -alkenyl, C 3 -C 6 -cycloatkyl-C 2 -C 4 -atkynyl, Ci-C 4 -alkoxy, C 1 -C 4 - haloalkoxy having 1 to 5 halogen atoms, phenyl, or phenyloxy, wherein the phenyl and phenyloxy is non-substituted or substituted by one or more group(s) selected from fluorine, chlorine, bromine, Ci- C 4 -alkyl,
  • X 1 , X 2 , X 3 and X 4 more preferably represent independently from each other hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, CF 3 , vinyl, cyclopropyl-C 2 -C 4 -alkynyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert- butoxy, OCF3, phenyl, or phenyloxy, wherein the phenyl and phenyloxy is non-substituted or substituted by one or more group(s) selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, fer/-butyl, and CF3.
  • X 1 , X 2 , X 3 and X 4 more preferably represent independently from each other hydrogen, fluorine, chlorine, bromine, cyano, methyl, CF 3 , vinyl, cyclopropyl-ethynyl, methoxy, OCF 3 , phenyl, or phenyloxy, wherein the phenyl and phenyloxy is non-substituted or substituted by one or more group(s) selected from fluorine, and chlorine.
  • X 1 , X 2 , X 3 and X 4 more preferably represent independently from each other hydrogen, fluorine, chlorine, methyl or methoxy.
  • X 1 most preferably represents hydrogen.
  • X 2 most preferably represents hydrogen, fluorine or methyl.
  • X 3 most preferably represents hydrogen or methoxy.
  • X 4 most preferably represents hydrogen, fluorine, chlorine, methyl or methoxy.
  • X 1 , X 2 , X 3 and X 4 all represent hydrogen.
  • X 1 represents hydrogen
  • X 2 represents hydrogen or methyl
  • X 3 and/or X 4 represent fluorine or chlorine.
  • radical definitions and explanations given above in general terms or stated within preferred ranges can, however, also be combined with one another as desired, i.e. including between the particular ranges and preferred ranges. They apply both to the end products and correspondingly to precursors and intermediates. In addition, individual definitions may not apply.
  • R 1 represents 1 -fluorocyclopropyl, l-chlorocyclopropyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5- difluorophenyl or 2,6-difluorophenyl;
  • R 2 represents hydrogen
  • R 3 represents fluorine, cyano or CF 3 , preferably cyano
  • R 4 represents a bicyclic moiety of formulae (Ql) to (Q8)
  • X 1 , X 2 , X 3 and X 4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci- C4-alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X 1 represents hydrogen, X 2 represents hydrogen, fluorine or methyl, X 3 represents hydrogen or methoxy and X 4 represents hydrogen, fluorine, chlorine, methyl or methoxy.
  • X 1 , X 2 , X 3 and X 4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci- C4-alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X 1 represents hydrogen, X 2 represents hydrogen, fluorine or methyl, X 3 represents hydrogen or methoxy and X 4 represents hydrogen, fluorine, chlorine, methyl or methoxy.
  • R 1 represents 1 -chlorocyclopropyl or 2,4-difluorophenyl
  • R 2 represents hydrogen
  • R 3 represents cyano
  • R 4 represents a bicyclic moiety of formulae (Ql) to (Q8)
  • X 1 , X 2 , X 3 and X 4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci- C4-alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X 1 represents hydrogen, X 2 represents hydrogen, fluorine or methyl, X 3 represents hydrogen or methoxy and X 4 represents hydrogen, fluorine, chlorine, methyl or methoxy.
  • R 1 represents 1 -chlorocyclopropyl
  • R 2 represents hydrogen
  • R 3 represents cyano; and R 4 represents a bicyclic moiety of formulae (Ql) to (Q8)
  • X 1 , X 2 , X 3 and X 4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci-
  • C 4 -alkyl or Ci-C 4 -alkoxy preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X 1 represents hydrogen, X 2 represents hydrogen, fluorine or methyl, X 3 represents hydrogen or methoxy and X 4 represents hydrogen, fluorine, chlorine, methyl or methoxy.
  • X 1 represents hydrogen
  • X 2 represents hydrogen, fluorine or methyl
  • X 3 represents hydrogen or methoxy
  • X 4 represents hydrogen, fluorine, chlorine, methyl or methoxy.
  • Halogen fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Halogen- substitution is generally indicated by the prefix halo, halogen or halogeno.
  • Alkyl saturated, straight-chain or branched hydrocarbyl radical having 1 to 8, preferably 1 to 6, and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C 6 -alkyl such as methyl, ethyl, propyl (n-propyl), 1 -methylethyl (iso-propyl), butyl (n-butyl), l-methylpropyl (sec-butyl), 2-methylpropyl (iso butyl), l,l-dimethylethyl (tert-butyl), pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, l-ethylpropyl, l,l-dimethylpropyl, l,2-dimethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3 -methylpentyl, 4-methylpentyl,
  • Ci- C4-alkyl group e.g. a methyl, ethyl, propyl, 1 -methylethyl (isopropyl), butyl, l-methylpropyl (sec-butyl), 2- methylpropyl (iso-butyl) or l, l-dimethylethyl (tert-butyl) group.
  • alkyl as part of a composite substituent, for example cycloalkylalkyl, hydroxyalkyl etc., unless defined elsewhere like, for example, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, haloalkyl or haloalkylsulfanyl.
  • Alkenyl unsaturated, straight-chain or branched hydrocarbyl radicals having 2 to 8, preferably 2 to 6, and more preferably 2 to 4 carbon atoms and one double bond in any position, for example (but not limited to) C2-C6-alkenyl such as vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, isopropenyl, homoallyl, (E)-but-2- enyl, (Z)-but-2-enyl, (E)-but- 1 -enyl, (Z)-but-l-enyl, 2-methylprop-2-enyl, 1 -methylprop-2-enyl, 2- methylprop- 1 -enyl, (E)-l-methylprop-l-enyl, (Z)-l-methylprop-l-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)- pent-3-enyl, (E)-pent-2
  • Alkynyl straight-chain or branched hydrocarbyl groups having 2 to 8, preferably 2 to 6, and more preferably 2 to 4 carbon atoms and one triple bond in any position, for example (but not limited to) Ck-CV r alkynyl, such as ethynyl, prop-l-ynyl, prop-2 -ynyl, but-l-ynyl, but-2-ynyl, but-3-ynyl, 1 -methylprop-2-ynyl, pent-l-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, 2-methylbut-3-ynyl, 1 -methylbut-3-ynyl, l-methylbut-2-ynyl, 3- methylbut-l-ynyl, 1 -ethylprop-2-ynyl, hex-l-ynyl, hex-2-ynyl, hex-3-
  • said alkynyl group is ethynyl, prop-l-ynyl, or prop-2-ynyl.
  • This definition also applies to alkynyl as part of a composite substituent, for example haloalkynyl etc., unless defined elsewhere.
  • Alkoxy saturated, straight-chain or branched alkoxy radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C 6 -alkoxy such as methoxy, ethoxy, propoxy, 1 -methylethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1- methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1- dimethylpropoxy, 1,2-dimethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4- methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-
  • Alkylsulfanyl saturated, straight-chain or branched alkylsulfanyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C 6 -alkylsulfanyl such as methylsulfanyl, ethylsulfanyl, propylsulfanyl, 1-methylethylsulfanyl, butylsulfanyl, 1-methylpropyl- sulfanyl, 2-methylpropylsulfanyl, l,l-dimethylethylsulfanyl, pentylsulfanyl, l-methylbutylsulfanyl, 2- methylbutylsulfanyl, 3-methylbutylsulfanyl, 2,2-dimethylpropylsulfanyl, 1 -ethylpropylsulfanyl, 1,1- dimethylpropylsulfanyl, 1
  • Alkylsulfinyl saturated, straight-chain or branched alkylsulfinyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C 6 -alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1 -methylethylsulfinyl, butylsulfinyl, l-methylpropylsulfinyl, 2-methylpropylsulfinyl, l,l-dimethylethylsulfinyl, pentylsulfinyl, 1 -methylbutylsulfinyl, 2- methylbutylsulfinyl, 3 -methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1 -ethylpropyls
  • Alkylsulfonyl saturated, straight-chain or branched alkylsulfonyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C 6 -alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropyl- sulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1 -methylbutylsulfonyl, 2- methylbutylsulfonyl, 3 -methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1 -ethylpropylsulfony
  • Monoalkylamino represents an amino radical having one alkyl residue with 1 to 4 carbon atoms attached to the nitrogen atom.
  • Non-limiting examples include methylamino, ethylamino, n-propylamino, isopropyl- amino, n-butylamino and tert-butylamino.
  • Dialkylamino represents an amino radical having two independently selected alkyl residues with 1 to 4 carbon atoms each attached to the nitrogen atom.
  • Non-limiting examples include /V, /V- d i m c t h y 1 a m i n o , /V,/V- diethyl ami no, /V, /V- d i i s o p ro py 1 a m i n o , /V- c t h y 1 - /V- m c t h y 1 a m i n o , /V- m c t h y 1 - /V- n - p o py 1 a m i n o , /V-iso- p ro p y 1 - /V- n - p ro p y 1 a m i n o and /V- 1 c rt - b u t y 1 - -
  • Cycloalkyl monocyclic, saturated hydrocarbyl groups having 3 to 10, preferably 3 to 8 and more preferably
  • Cycloalkenyl monocyclic, partially unsaturated hydrocarbyl groups having 3 to 10, preferably 3 to 8 and more preferably 3 to 6 carbon ring members, for example (but not limited to) cyclopropenyl, cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as part of a composite substituent, for example cycloalkenylalkyl etc., unless defined elsewhere.
  • Cycloalkoxy monocyclic, saturated cycloalkyloxy radicals having 3 to 10, preferably 3 to 8 and more preferably 3 to 6 carbon ring members, for example (but not limited to) cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as part of a composite substituent, for example cycloalkoxyalkyl etc., unless defined elsewhere.
  • Haloalkyl straight-chain or branched alkyl groups having 1 to 8, preferably 1 to 6 and more preferably 1 to
  • Ci-C3-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and l,
  • Ci-C3-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro
  • Haloalkenyl and haloalkynyl are defined analogously to haloalkyl except that, instead of alkyl groups, alkenyl and alkynyl groups are present as part of the substituent.
  • Haloalkoxy straight-chain or branched alkoxy groups having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms (as specified above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as specified above, for example (but not limited to) Ci-C3-haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-flu
  • Haloalkylsulfanyl straight-chain or branched alkylsulfanyl groups having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms (as specified above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as specified above, for example (but not limited to) Ci-C3-haloalkylsulfanyl such as chloromethylsulfanyl, bromomethylsulfanyl, dichloromethylsulfanyl, trichloromethylsulfanyl, fluoromethylsulfanyl, difluoromethylsulfanyl, trifluoromethylsulfanyl, chlorofluoromethylsulfanyl, dichlorofluoromethylsulfanyl, chlorodifluoromethylsulfanyl, 1 -chloroethylsulfanyl, 1 -bromoethylsulfanyl, l-fluoroe
  • Aryl mono-, bi- or tricyclic aromatic or partially aromatic group having 6 to 14 carbon atoms, for example (but not limited to) phenyl, naphthyl, tetrahydronapthyl, indenyl and indanyl.
  • the binding to the superordinate general structure can be carried out via any possible ring member of the aryl residue.
  • Aryl is preferably selected from phenyl, 1 -naphthyl and 2-naphthyl. Phenyl is particularly preferred.
  • Heteroaryl 5 or 6-membered cyclic aromatic group containing at least 1, if appropriate also 2, 3, 4 or 5 heteroatoms, wherein the heteroatoms are each selected independently of one another from the group S, N and O, and which group can also be part of a bi- or tricyclic system having up to 14 ring members, wherein the ring system can be formed with one or two further cycloalkyl, cycloalkenyl, heterocyclyl, aryl and/or heteroaryl residues and wherein benzofused 5 or 6-membered heteroaryl groups are preferred.
  • the binding to the superordinate general structure can be carried out via any possible ring member of the heteroaryl residue.
  • Examples of 5-membered heteroaryl groups which are attached to the skeleton via one of the carbon ring members are fur-2-yl, fur-3-yl, thien-2-yl, thien-3-yl, pyrrol-2-yl, pyrrol-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, imidazol-2-yl, imidazole-4-yl, l,2,4-oxadiazol-3-yl, l,2,4-
  • Examples of 5- membered heteroaryl groups which are attached to the skeleton via a nitrogen ring member are pyrrol- 1-yl, pyrazol-l-yl, 1,2,4-triazol-l-yl, imidazol-l-yl, 1,2,3-triazol-l-yl and 1,3,4-triazol-l-yl.
  • 6- membered heteroaryl groups are pyridine-2-yl, pyridine-3 -yl, pyridine-4-yl, pyridazin-3-yl, pyridazin-4- yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazine-2-yl, l,3,5-triazin-2-yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl.
  • benzofused 5-membered heteroaryl groups are indol-l-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-l-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-l-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1 -benzofuran-2-yl, l-benzofuran-3-yl, l-benzofuran-4-yl, l-benzofuran-5-yl, 1- benzofuran-6-yl, l-benzofuran-7-y
  • benzofused 6-membered heteroaryl groups are quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-l-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-
  • Further examples of 5- or 6-membered heteroaryls which are part of a bicyclic ring system are l,2,3,4-tetrahydroquinolin-l-yl, 1 ,2,3,4- tetrahydroquinolin-2-yl, l,2,3,4-tetrahydroquinolin-7-yl, 1 ,2,3,4-tetrahydroquinolin-8-yl, 1 ,2,3,4- tetrahydroisoquinolin-l-yl, l,2,3,4-tetrahydroisoquinolin-2-yl, l,2,3,4-tetrahydroisoquinolin-5-yl, 1 ,2,3,4- tetrahydroisoquinolin-6-yl and l,2,3,4-tetrahydroisoquinolin-7-y
  • the binding to the superordinate general structure can be carried out via a ring carbon atom or, if possible, via a ring nitrogen atom of the heterocyclic group.
  • Saturated heterocyclic groups in this sense are for example (but not limited to) oxiranyl, aziridinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin- 5-yl, oxazolidin-2-yl, oxazolidin-4-yl, oxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-4-yl, thi
  • Partially unsaturated heterocyclic groups in this sense are for example (but not limited to) 2,3 -dihydro fur-2-yl, 2,3 -dihydro fur- 3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4- dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4- yl, 2-isoxazolin-5-yl, 3-is
  • benzofused heterocyclic groups are indolin-l- yl, indolin-2-yl, indolin-3-yl, isoindolin-l-yl, isoindolin-2-yl, 2,3-dihydrobenzofuran-2-yl and 2,3- dihydrobenzofuran-3-yl.
  • This definition also applies to heterocyclyl as part of a composite substituent, for example heterocyclylalkyl etc., unless defined elsewhere.
  • Oxo represents a doubly bonded oxygen atom.
  • Thiooxo represents a doubly bonded sulfur atom.
  • Optionally substituted groups may be mono- or polysubstituted, where the substituents in the case of polysubstitutions may be identical or different.
  • Ring structures having three or more adjacent oxygen atoms, for example, are excluded.
  • the compounds of the invention may be present in the form of different stereoisomers. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixture of these isomers. Where a compound can be present in two or more tautomer forms in equilibrium, reference to the compound by means of one tautomeric description is to be considered to include all tautomer forms.
  • the present invention is furthermore related to processes for preparing compounds of formula (I).
  • the present invention furthermore relates to intermediates such as compounds of formula (VI) and the preparation thereof.
  • the compounds (I) can be obtained by various routes in analogy to prior art processes known (see e.g. J. Agric. Food Chem. (2009) 57, 4854-4860; EP-A 0 275 955; DE-A 40 03 180; EP-A 0 1 13 640; EP-A 0 126 430; WO-A 2013/007767; WO 2016/156290 Al ; and references cited in those documents) and by synthesis routes shown schematically below and in the experimental part of this application.
  • the radicals X 1 , X 2 , X 3 , X 4 , X 5 , R 1 , R 2 , R 3 and R 4 and the bond A have the meanings given above for the compounds of formula (I). These definitions apply not only to the end products of the formula (I) but likewise to all intermediates. If individual compounds (I) cannot be obtained by those routes, they can be prepared by derivatization of other compounds (I).
  • ketones (II) which are either commercially available or prepared using methods known to a person skilled in the art, can be converted to vinyl halides (III) using methods described in the literature (see: ./. Org. Chern. 2007, 72, 2216-2219; Org. Lett. 2015, 17, 18-21), including classical methods such as the reaction with PBr3 or POCI3 in a suitable inert solvent, including but not limited to: dichloromethane, 1,2- dichloroethane or toluene (Scheme 1 ).
  • the vinyl halides (III) can be reacted either with metals (e.g.
  • lithium, magnesium or zinc in an appropriate form such as metallic powder or turnings
  • alkylmetal reagents such as e.g. solutions of methyllithium, n-butyllithium, phenyllithium, s-butyllithium, ter/.-butyllithium or isopropylmagnesium halide, with or without added salts such as lithium chloride
  • ketones (IV) optionally in the presence of added salts such as lithium chloride preferably under anhydrous conditions to obtain compounds of the general formula (I-Ha).
  • trialkoxyzirconium(IV) or trialkoxytitanium(IV) chloride [see e.g. Weidmann, Seebach, Angew. Chem. Int. Ed. 1983, 22(1), 31-45], cerium(III) trichloride [see e.g. Imamoto el al., J. Am. Chem. Soc. 1989, 1 11 (12), pp 4392-4398], lanthanum(III) trichloride [see e.g. Krasovskiy et al, Angew. Chem. Int. Ed. 2006, 45(3), 497-500], magnesium(II) dichloride [see e.g. Metzger et al, Angew. Chem.
  • ethers such as e.g. diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran
  • dichloromethane or mixtures thereof
  • the reaction can be effected in mixtures of two or more of these solvents.
  • the reaction is preferably performed at temperatures between -78 °C and refluxing temperature of the solvent, more preferably between -78 °C and 25 °C.
  • LG 1 is a replaceable group as listed in scheme 1 above, particularly preferred Br, I and methylsulfonyloxy.
  • Hydrazones of the general structure (VI) can be prepared by reacting ketones (II) and hydrazines (V) in an inert reaction solvent, preferably alcohols such as methanol, ethanol or isopropanol, or hydrocarbon solvents such as benzene or toluene, in analogy to various known methods, optionally in the presence of a dehydrating agent and/or acid, including but not limited to: activated molecular sieves, anhydrous inorganic salts such as magnesium sulphate or sodium sulphate, titanium(IV) oxides, such as titanium tetraethoxide or titanium tetraisopropoxide, toluenesulphonic acid, phosphoric acid or thionyl chloride.
  • an inert reaction solvent preferably alcohols such as methanol, ethanol or isopropanol, or hydrocarbon solvents such as benzene or toluene
  • a dehydrating agent and/or acid including but not limited
  • a reaction apparatus able to sequester water may also be used, such as a Dean Stark trap or a Soxhlet apparatus.
  • the hydrazones (VI) can be reacted with an appropriate base, such as an alkyllithium (see: Org. Lett. 2013, 15, 3894-3897, including methyllithium, n-butyllithium, s-butyllithium, fer/.-butyllithium, phenyllithium, lithium amides such as lithium diisopropyl amide, lithium tetramethylpiperidine, alkylmagnesium reagents (see: Org. Lett.
  • Grignard reagents such as isopropylmagnesium halides, using methods known to a person skilled in the art as the Shapiro Reaction, with or without added salts such as lithium chloride) and subsequently reacted with ketones (IV), optionally in the presence of added salts such as lithium chloride, preferably under anhydrous conditions to obtain compounds of the general formula (I-Ha).
  • ketones (IV) optionally in the presence of added salts such as lithium chloride, preferably under anhydrous conditions to obtain compounds of the general formula (I-Ha).
  • the solvent all common solvents inert under the reaction conditions, such as for example ethers (such as e.g. diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran), dichloromethane, or mixtures thereof can be used and the reaction can be e
  • reaction is preferably performed at temperatures between -78 °C and refluxing temperature of the solvent, more preferably between -78 °C and 25 °C.
  • R 2a -LG' compounds of the general formula (la) can be obtained as described above for process A (scheme 1).
  • Vinyl alcohols (I-Ha) may be converted to alcohols (I-Hb) using methods known to a person skilled in the art for carbon-carbon double bond reduction, such as hydrogenation using a metal catalyst, including palladium, platinum, rhodium, iridium, cobalt metals or salts thereof, optionally under pressure of hydrogen, or using a transfer hydrogenation reagent, such as cyclohexadiene, an alkyl silane such as triethylsilane or polymethylhydrosiloxane or similar, or by reaction with diimidc (sec: .!. Org. Chem. 2009, 74, 3186-3188; Org. Lett. 2010, 12, 5418-5421) or by hydroboration and subsequent deboronation.
  • a metal catalyst including palladium, platinum, rhodium, iridium, cobalt metals or salts thereof, optionally under pressure of hydrogen
  • a transfer hydrogenation reagent such as cyclohexadiene, an
  • ethers such as e.g. diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran
  • ethyl acetate or mixtures thereof
  • the reaction can be effected in mixtures of two or more of these solvents.
  • the reaction is preferably performed at temperatures between 0 °C and refluxing temperature of the solvent, more preferably between 25 °C and 100 °C.
  • the processes A to C according to the invention are optionally performed using one or more reaction auxiliaries.
  • Useful reaction auxiliaries are, as appropriate, inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogencarbonates, hydrides, hydroxides or alkoxides, for example sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or calcium hydrogencarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxid
  • Useful reaction auxiliaries are, as appropriate, inorganic or organic acids. These preferably include inorganic acids, for example hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulphuric acid, phosphoric acid and nitric acid, and acidic salts such as NaHSCri and KHSO4, or organic acids, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono- or diunsaturated C6-C20 fatty acids, alkylsulphuric monoesters, alkylsulphonic acids (sulphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulphonic acids or ary
  • diluents are virtually all inert organic solvents. Unless otherwise indicated for the above described processes, these preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether, dibutyl ether and methyl tert-butyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl
  • reaction temperatures can be varied within a relatively wide range.
  • the temperatures employed are between -78°C and 250°C, preferably temperatures between -78°C and 150°C.
  • the reaction time varies as a function of the scale of the reaction and of the reaction temperature, but is generally between a few minutes and 48 hours.
  • the processes are generally performed under standard pressure. However, it is also possible to work under elevated or reduced pressure.
  • the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the components used in each case in a relatively large excess.
  • the compounds are optionally separated from the reaction mixture by one of the customary separation techniques. If necessary, the compounds are purified by recrystallization or chromatography.
  • X 1 , X 2 , X 3 , X 4 and X 5 are defined as in formula (I) and
  • R 5 represents Ci-Cs-alkyl, C6-Ci4-aryl or 5- or 6-membered heteroaryl, wherein the Ci-Cs-alkyl may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a as defined in formula (I), and the C6-Ci4-aryl and 5- or 6-membered heteroaryl groups may carry 1, 2, 3, 4, 5 or up to the maximum number of groups R b as defined in formula (I).
  • R 5 preferably represents Ci-C4-alkyl or C6-Ci4-aryl, wherein the Ci-C4-alkyl group may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, C3-C6-cycloalkyl, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and wherein the C6-Ci4-aryl moiety may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups R b which independently of one another are selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
  • R 5 more preferably represents Ci-C4-alkyl or phenyl, wherein the Ci-C4-alkyl group may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, C3-C6-cycloalkyl, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and wherein the phenyl moiety may carry 1 , 2, 3, 4, 5 or up to the maximum number of identical or different groups R b which independently of one another are selected from halogen, CN, nitro, Ci- C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
  • R 5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups R b which independently of one another are selected from halogen, CN, nitro, C 1 -C 4 - alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
  • R 5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups R b which independently of one another are selected from fluorine, chlorine, bromine, iodine, CN, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
  • R 5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2 or 3 identical or different groups R b which independently of one another are selected from fluorine, chlorine, bromine, iodine, CN, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
  • R 5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2 or 3 identical or different groups R b which independently of one another are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
  • R 5 more preferably represents phenyl, substituted by 1 , 2 or 3, preferably 3, identical or different groups R b which independently of one another are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
  • R 5 more preferably represents phenyl, substituted by 1 , 2 or 3, preferably 3, identical or different groups R b which independently of one another are selected from methyl, ethyl, n-propyl and isopropyl.
  • R 5 most preferably represents 2,4,6-triisopropylphenyl.
  • X 5 represents -CH 2 -, -CH2-CH2-, -CH 2 -CH 2 -CH 2 -, -O-CH2-, -0-(CH 2 ) 2 -, -S-CH 2 - or -S-(CH 2 ) 2 -, preferably -CH 2 -, -CH2-CH2-, -CH 2 -CH 2 -CH 2 -, -O-CH2- or -S-CH 2 -, more preferably -CH 2 -, -CH2-CH2-, -CH 2 -CH 2 -CH 2 -CH 2 - or -O-CH2-,
  • X 1 , X 2 , X 3 and X 4 represent independently from each other hydrogen, fluorine, chlorine, bromine, C1-C4- alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X 1 represents hydrogen, X 2 represents hydrogen, fluorine or methyl, X 3 represents hydrogen or methoxy and X 4 represents hydrogen, fluorine, chlorine, methyl or methoxy, and
  • R 5 represents phenyl, substituted by 1, 2 or 3, preferably 3, identical or different groups R b which independently of one another are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert.
  • -butyl preferably represents phenyl, substituted by 1, 2 or 3, preferably 3, identical or different groups R b which independently of one another are selected from methyl, ethyl, n-propyl and isopropyl, more preferably represents 2,4,6-triisopropylphenyl.
  • the compounds of the invention and intermediates thereof may be present in the form of the free compound and/or an agriculturally acceptable salt thereof.
  • agriculturally acceptable salt refers to a salt of a compound of the invention with acids or bases which are agriculturally acceptable.
  • the compounds of formula (I) and intermediates thereof may have acidic or basic properties and can form salts, if appropriate also inner salts, or adducts with inorganic or organic acids or with bases or with metal ions. If the compounds carry amino, alkylamino or other groups which induce basic properties, these compounds can be reacted with acids to give salts, or they are directly obtained as salts in the synthesis. If the compound carries hydroxyl, carboxyl or other groups which induce acidic properties, these compounds can be reacted with bases to give salts.
  • Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines having (Ci-C4)-alkyl groups, mono-, di- and trialkanolamines of (Ci-C4)-alkanols, choline and also chlorocholine.
  • the salts obtainable in this manner also have fungicidal properties.
  • inorganic acids examples include hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulphuric acid, phosphoric acid and nitric acid, and acidic salts, such as NaHS04 and KHSO4.
  • Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, maleic acid, fumaric acid, tartaric acid, sorbic acid oxalic acid, alkylsulphonic acids (sulphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulphonic acids or aryldisulphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulphonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as
  • Suitable metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminium, tin and lead, and also of the first to eighth transition group, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to the metal ions of the elements of the fourth period.
  • the metals can be present in various valencies that they can assume.
  • the acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary methods for forming salts, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and be isolated in a known manner, for example by filtration, and, if required, be purified by washing with an inert organic solvent.
  • Suitable anions of the salts are those which are preferably derived from the following acids: hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulphuric acid.
  • the metal salt complexes of compounds of the formula (1) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (1).
  • Metal salt complexes can be isolated in a known manner, for example by filtration, and, if required, be purified by recrystallization.
  • Salts of the intermediates can also be prepared according to the processes mentioned above for the salts of compounds of formula (1).
  • N-oxides of compounds of the formula (1) or intermediates thereof can be obtained in a simple manner by customary processes, for example by N-oxidation with hydrogen peroxide (H2O2), peracids, for example peroxy sulfuric acid or peroxy carboxylic acids, such as meta-chloroperoxybenzoic acid or peroxymonosulfuric acid (Caro's acid).
  • H2O2 hydrogen peroxide
  • peracids for example peroxy sulfuric acid or peroxy carboxylic acids, such as meta-chloroperoxybenzoic acid or peroxymonosulfuric acid (Caro's acid).
  • Crystalline Form The compound of the invention may exist in multiple crystalline and/or amorphous forms. Crystalline forms include unsolvated crystalline forms, solvates and hydrates.
  • the present invention further relates to compositions for controlling harmful microorganisms, preferably for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I) and at least one carrier and/or surfactant.
  • compositions for controlling harmful microorganisms preferably for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I) and at least one carrier and/or surfactant.
  • the compositions may be applied to the microorganisms and/or in their habitat.
  • a carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert.
  • the carrier generally improves the application of the compounds, for instance, to plants, plants parts or seeds.
  • suitable solid carriers include, but are not limited to, ammonium salts, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates.
  • typically useful solid carriers for preparing granules include, but are not limited to crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks.
  • suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof.
  • suitable solvents include polar and nonpolar organic chemical liquids, for example from the classes of aromatic and nonaromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyols (which may optionally also be substituted, etherified and/or esterified, such as butanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N-alkylpyrrolidones) and lactones, sulf
  • the carrier may also be a liquefied gaseous extender, i.e. liquid which is gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide.
  • the amount of carrier typically ranges from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99% by weight of the composition.
  • the surfactant can be an ionic (cationic or anionic) or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s) and any mixtures thereof.
  • surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols and derivatives of compounds containing sulfates, sulfonates, phosphates (for example, alkylsulfonates, alkyl sulfates, arylsulfonates) and protein hydroly
  • composition may comprise at least one other suitable auxiliary.
  • auxiliaries include water repellents, siccatives, binders (adhesive, tackifier, fixing agent, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone and tylose), thickeners, stabilizers (e.g. cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability), dyes or pigments (such as inorganic pigments, e.g.
  • iron oxide, titanium oxide and Prussian Blue ; organic dyes, e.g. alizarin, azo and metal phthalocyanine dyes), antifoams (e.g. silicone antifoams and magnesium stearate), preservatives (e.g.
  • dichlorophene and benzyl alcohol hemiformal secondary thickeners (cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica), stickers, gibberellins and processing auxiliaries, mineral and vegetable oils, perfumes, waxes, nutrients (including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrants, sequestering agents and complex formers.
  • secondary thickeners cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica
  • stickers gibberellins and processing auxiliaries
  • mineral and vegetable oils perfumes
  • waxes including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc
  • protective colloids including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molyb
  • auxiliaries are related to the intended mode of application of the compound of the invention and/or on the physical properties. Furthermore, the auxiliaries may be chosen to impart particular properties (technical, physical and/or biological properties) to the compositions or use forms prepared therefrom. The choice of auxiliaries may allow customizing the compositions to specific needs.
  • composition of the invention may be in any customary form, such as solutions (e.g aqueous solutions), emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural or synthetic products impregnated with the compound of the invention, fertilizers and also microencapsulations in polymeric substances.
  • solutions e.g aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g., wettable powders, water- and oil-based suspensions
  • composition of the invention may be provided to the end user as ready-for-use formulation, i.e. the compositions may be directly applied to the plants or seeds by a suitable device, such as a spraying or dusting device.
  • a suitable device such as a spraying or dusting device.
  • the compositions may be provided to the end user in the form of concentrates which have to be diluted, preferably with water, prior to use.
  • composition of the invention can be prepared in conventional manners, for example by mixing the compound of the invention with one or more suitable auxiliaries, such as disclosed herein above.
  • the composition according to the invention contains generally from 0.01 to 99% by weight, preferably from 0.05 to 98% by weight, more preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80% by weight of the compound of the invention. It is possible that a composition comprises two or more compounds of the invention. In such case the outlined ranges refer to the total amount of compounds of the present invention.
  • the compound and the composition of the invention can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or semiochemicals. This may allow to broaden the activity spectrum or to prevent development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th Edition.
  • Inhibitors of the ergosterol biosynthesis for example (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.01 1) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) Pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) t
  • Inhibitors of the respiratory chain at complex I or II for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer lR,4S,9S), (2.011) isopyrazam (anti- epimeric enantiomer lS,4R,9R), (2.012) isopyrazam (anti-epimeric racemate lRS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate lRS,4SR,9RS and anti-epimeric racemate lRS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer lR,4S,9R),
  • Inhibitors of the respiratory chain at complex III for example (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2- ⁇ 2-[( ⁇ [(lE)-l-(3- ⁇ 2-[
  • Inhibitors of the amino acid and/or protein biosynthesis for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-l-yl)quinoline.
  • Inhibitors of the ATP production for example (8.001) silthiofam.
  • Inhibitors of the cell wall synthesis for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one, (9.009) (2Z)-3- (4-tert-butylphenyl)-3 -(2-chloropyridin-4-yl)- 1 -(morpholin-4-yl)prop-2-en- 1 -one. 10) Inhibitors of the lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
  • Inhibitors of the melanin biosynthesis for example (1 1.001) tricyclazole, (1 1.002) 2,2,2-trifluoroethyl ⁇ 3-methyl- l-[(4-methylbenzoyl)amino]butan-2-yl ⁇ carbamate.
  • Inhibitors of the nucleic acid synthesis for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
  • Inhibitors of the signal transduction for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
  • the compound and the composition of the invention may also be combined with one or more biological control agents.
  • biological control agents which may be combined with the compound and the composition of the invention are:
  • Antibacterial agents selected from the group of:
  • (A1 ) bacteria such as (A1 A) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRU Accession No. B2166 land described in U.S. Patent No. 6,060,051); (A1.2) Bacillus amyloliquefaciens, in particular strain D747 (available as Double NickelTM from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (A1.3) Bacillus pumilus, in particular strain BU F-33 (having NRRU Accession No. 50185); (A1.4) Bacillus subtilis var.
  • Bacillus subtilis var Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (available as Taegro® from Novozymes, US); (A1.5) a Paenibacillus sp. strain having Accession No. NRRU B-50972 or Accession No. NRRU B-67129 and described in International Patent Publication No. WO 2016/154297; and
  • (A2) fungi such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (A2.2) Aureobasidium pullulans blastospores of strain DSM 14941 ; (A2.3) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM14941;
  • (Bl) bacteria for example (Bl . l) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRU Accession No. B21661and described in U.S. Patent No. 6,060,051); (B1.2) Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No.
  • Bacillus pumilus in particular strain GB34 (available as Yield Shield® from Bayer AG, DE);
  • Bacillus amyloliquefaciens in particular strain D747 (available as Double NickelTM from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592);
  • Bacillus subtilis Y 1336 available as BIOBAC ® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos.
  • Bacillus amyloliquefaciens strain MBI 600 (available as SUBTILEX from BASF SE); (B1.8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B 1.9) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO ® or TAEGRO ® ECO (EPA Registration No.
  • Bacillus mycoides, isolate J available as BmJ TGAI or WG from Certis USA
  • Bacillus licheniformis in particular strain SB3086 (available as EcoGuard TM Biofungicide and Green Releaf from Novozymes)
  • B1.12 a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129 and described in International Patent Publication No. WO 2016/154297.
  • the biological control agent is a Bacillus subtilis or Bacillus amyloliquefaciens strain that produces a fengycin or plipastatin-type compound, an iturin-type compound, and/or a surfactin-type compound.
  • Bacillus strains capable of producing lipopeptides include Bacillus subtilis QST713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661and described in U.S. Patent No. 6,060,051), Bacillus amyloliquefaciens strain D747 (available as Double NickelTM from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); Bacillus subtilis MBI600 (available as SUBTILEX ® from Becker Underwood, US EPA Reg. No.
  • Bacillus subtilis Y1336 (available as BIOBAC ® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); Bacillus amyloliquefaciens, in particular strain FZB42 (available as RHIZOVITAL ® from ABiTEP, DE); and Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO ® or TAEGRO ® ECO (EPA Registration No. 70127-5); and
  • (B2) fungi for example: (B2.1) Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660; e.g. Contans ® from Bayer); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y- 30752 (e.g. Shemer®); (B2.3) Microsphaeropsis ochracea (e.g. Microx® from Prophyta); (B2.5) Trichoderma spp., including Trichoderma atroviride, strain SCI described in International Application No.
  • Trichoderma atroviride from Kumiai Chemical Industry
  • Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR);
  • Trichoderma atroviride strain no. V08/002387;
  • B2.40 Trichoderma atroviride, strain NMI no. V08/002388;
  • B2.41 Trichoderma atroviride, strain NMI no. V08/002389;
  • B2.42 Trichoderma atroviride, strain NMI no. V08/002390;
  • Trichoderma atroviride strain LC52 (e.g.
  • Trichoderma atroviride Trichoderma atroviride, strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma atroviride, strain Tl l (IMI352941/ CECT20498); (B2.46) Trichoderma harmatum, (B2.47) Trichoderma harzianum, (B2.48) Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US); (B2.49) Trichoderma harzianum, in particular, strain KD (e.g.
  • Trichoplus from Biological Control Products, SA (acquired by Becker Underwood)); (B2.50) Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert); (B2.51) Trichoderma harzianum, strain TH35 (e.g. Root-Pro by Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g. SoilGard 12G by Certis, US); (B2.53) Trichoderma viride, strain TV 1 (e.g. Trianum-P by Koppert); (B2.54) Ampelomyces quisqualis, in particular strain AQ 10 (e.g.
  • Botector® by bio-ferm, CH (B2.64) Cladosporium cladosporioides, strain H39 (by Stichting Divichting Diviching Diviching Diviching Diviching Diviching Diviching Diviching Diviching Diviching Diviching Diviching Divichoek); (B2.69) Gliocladium catenulatum (Synonym: Clonostachys rosea f catenulate ) strain J1446 (e.g. Prestop ® by AgBio Inc. and also e.g. Primastop® by Kemira Agro Oy); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii) conidia of strain KV01 (e.g.
  • Vertalec® by Koppert/Arysta (B2.71) Penicillium vermiculatum ; (B2.72) Pichia anomala, strain WRL- 076 (NRRL Y-30842); (B2.75) Trichoderma atroviride, strain SKT-l (FERM P- 16510); (B2.76) Trichoderma atroviride, strain SKT-2 (FERM P- 16511); (B2.77) Trichoderma atroviride, strain SKT-3 (FERM P-17021); (B2.78) Trichoderma gamsii (formerly T. viride), strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A.
  • strain WCS850 CBS 276.92; e.g. Dutch Trig by Tree Care Innovations
  • Verticillium chlamydosporium Verticillium chlamydosporium
  • mixtures of Trichoderma asperellum strain ICC 012 and Trichoderma gamsii strain ICC 080 product known as e.g. BIO-TAMTM from Bayer CropScience LP, US).
  • biological control agents which may be combined with the compound and the composition of the invention are: bacteria selected from the group consisting of Bacillus cereus, in particular B. cereus strain CNCM 1-1562 and Bacillus firmus, strain 1-1582 (Accession number CNCM 1-1582), Bacillus subtilis strain OST 30002 (AccessionNo. NRRL B-50421), Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (AccessionNo. ATCC 1276), B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), B. thuringiensis subsp.
  • Bacillus cereus in particular B. cereus strain CNCM 1-1562 and Bacillus firmus
  • strain 1-1582 accesion number CNCM 1-1582
  • Bacillus subtilis strain OST 30002 accesionNo. NRRL B-50421
  • viruses selected from the group consisting of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV), Cydia pomonella (codling moth) granulosis vims (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis vims (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, and Spodoptera littoralis (African cotton leafworm) NPV.
  • Adoxophyes orana sumr fruit tortrix
  • GV granulosis virus
  • Cydia pomonella codling moth
  • granulosis vims GV
  • Helicoverpa armigera cotton bollworm
  • nuclear polyhedrosis vims NPV
  • Spodoptera exigua beet armyworm
  • Spodoptera frugiperda fall armyworm
  • bacteria and fungi which can be added as 'inoculant' to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health.
  • Examples are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suill
  • plant extracts and products formed by microorganisms including proteins and secondary metabolites which can be used as biological control agents such as Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up ( Chenopodium quinoa saponin extract), Pyrethrum/Pyrethrins, Qpassia amara, Quercus, Quillaja, Regalia, "RequiemTM Insecticide", rotenone, pg/n/ ryanodinc, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassica
  • insecticides examples include insecticides, acaricides and nematicides, respectively, which could be mixed with the compound and the composition of the invention, are:
  • Acetylcholinesterase (AChE) inhibitors such as, for example, carbamates, for example alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimcthacarb, XMC and xylylcarb; or organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifo
  • GABA-gated chloride channel blockers such as, for example, cyclodiene-organochlorines, for example chlordane and endosulfan or phenylpyrazoles (fiproles), for example ethiprole and fipronil.
  • Sodium channel modulators such as, for example, pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(lR)-trans-isomer], deltamethrin, empenthrin [(EZ)-(lR)-i
  • Nicotinic acetylcholine receptor (nAChR) competitive modulators such as, for example, neonicotinoids, e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
  • neonicotinoids e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
  • Nicotinic acetylcholine receptor (nAChR) allosteric modulators such as, for example, spinosyns, e.g. spinetoram and spinosad.
  • Glutamate-gated chloride channel (GluCl) allosteric modulators such as, for example, avermectins/milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin.
  • Juvenile hormone mimics such as, for example, juvenile hormone analogues, e.g. hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.
  • Miscellaneous non-specific (multi-site) inhibitors such as, for example, alkyl halides, e.g. methyl bromide and other alkyl halides; or chloropicrine or sulphuryl fluoride or borax or tartar emetic or methyl isocyanate generators, e.g. diazomet and metam.
  • Modulators of Chordotonal Organs such as, for example pymetrozine or flonicamid.
  • Mite growth inhibitors such as, for example clofentezine, hexythiazox and diflovidazin or etoxazole.
  • Microbial disrupters of the insect gut membrane such as, for example Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.l. plant proteins: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl/35Abl .
  • Inhibitors of mitochondrial ATP synthase such as, ATP disrupters such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.
  • ATP disrupters such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.
  • Nicotinic acetylcholine receptor channel blockers such as, for example, bensultap, cartap hydrochloride, thiocylam, and thiosultap-sodium.
  • Inhibitors of chitin biosynthesis type 0, such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
  • Inhibitors of chitin biosynthesis type 1, for example buprofezin.
  • Moulting disrupter in particular for Diptera, i.e. dipterans, such as, for example, cyromazine.
  • Ecdysone receptor agonists such as, for example, chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
  • Octopamine receptor agonists such as, for example, amitraz.
  • Mitochondrial complex III electron transport inhibitors such as, for example, hydramethylnone or acequinocyl or fluacrypyrim.
  • Mitochondrial complex I electron transport inhibitors such as, for example from the group of the METI acaricides, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
  • METI acaricides e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
  • Voltage-dependent sodium channel blockers such as, for example indoxacarb or metaflumizone.
  • Inhibitors of acetyl CoA carboxylase such as, for example, tetronic and tetramic acid derivatives, e.g. spirodiclofen, spiromesifen and spirotetramat.
  • Mitochondrial complex IV electron transport inhibitors such as, for example, phosphines, e.g. aluminium phosphide, calcium phosphide, phosphine and zinc phosphide or cyanides, e.g. calcium cyanide, potassium cyanide and sodium cyanide.
  • Mitochondrial complex II electron transport inhibitors such as, for example, Acto-kctonitrilc derivatives, e.g. cyenopyrafen and cyflumetofen and carboxanilides, such as, for example, pyflubumide.
  • Ryanodine receptor modulators such as, for example, diamides, e.g. chlorantraniliprole, cyantraniliprole and flubendiamide, further active compounds such as, for example, Afldopyropen, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Broflanilide, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclaniliprole, Cycloxaprid, Cyhalodiamide, Dicloromezotiaz, Dicofol, epsilon-Metofluthrin, epsilon- Momfluthrin, Flometoquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluralaner, Fluxametamide, Fufen
  • WO 2010052161 (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-l,8- diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6) , 4-(but-2-yn- l-yloxy)-6-(3,5-dimethylpiperidin-l-yl)-5-fluoropyrimidine (known from W02004/099160) (CAS 792914- 58-0), PF1364 (known from JP2010/018586) (CAS 1204776-60-2), N-[(2E)-l-[(6-chloropyridin-3- yl)methyl]pyridin-2(lH)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012/029672) (CAS 1363400- 41-2), (3£)
  • A-pyrazolc-5-carboxamidc (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); A-[4-chloro-2-[[(l,l-dimethylethyl)amino]carbonyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3- (fluoromcthoxy)- 1 A-Pyrazolc-5-carboxamidc (known from WO 2012/034403 Al) (CAS 1268277-22-0), A-[2-(5-amino- 1 ,3,4-thiadiazol-2-yl)-4-chloiO-6-mcthylphcnyl]-3-bmmo- 1 -(3-chlom-2-pyridinyl)- 1 H- pyrazole-5-carboxamide (known from WO 201 1/085575 Al) (CAS WO
  • safeners which could be mixed with the compound and the composition of the invention are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (- ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-( ⁇ 4-[(methylcarbamoyl)amino]phenyl ⁇ - sulphonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane (CAS 71526- 07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-l,3-oxazolidine (
  • herbicides which could be mixed with the compound and the composition of the invention are:
  • O-ethyl isopropylphosphoramidothioate halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron- methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e.
  • plant growth regulators are:
  • the compounds and compositions of the invention have potent microbicidal activity and/or plant defense modulating potential. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria. They can be particularly useful in crop protection (they control microorganisms that cause plants diseases) or for protecting materials (e.g. industrial materials, timber, storage goods) as described in more details herein below. More specifically, the compounds and compositions of the invention can be used to protect seeds, germinating seeds, emerged seedlings, plants, plant parts, fruits, harvest goods and/or the soil in which the plants grow from unwanted microorganisms.
  • the invention further relates to a method for controlling harmful microorganisms, preferably phytopathogenic harmful fungi, in crop protection and in the protection of materials, wherein at least one compound of formula (I) or a composition comprising such compound is applied to the harmful microorganisms and/or their habitat.
  • harmful microorganisms preferably phytopathogenic harmful fungi
  • at least one compound of formula (I) or a composition comprising such compound is applied to the harmful microorganisms and/or their habitat.
  • the invention further relates to the use of at least one compound of formula (I) or a composition comprising such compound for control of harmful microorganisms, preferably phytopathogenic harmful fungi, in crop protection and in the protection of materials.
  • the invention also relates to the use of at least one compound of formula (I) or a composition comprising such compound for treatment of a transgenic plant or for treatment of seed, preferably seed of a transgenic plant.
  • Control or controlling as used herein encompasses protective, curative and eradicative treatment of unwanted microorganisms.
  • Unwanted microorganisms may be pathogenic bacteria, pathogenic virus, pathogenic oomycetes or pathogenic fungi, more specifically phytopathogenic bacteria, phytopathogenic virus, phytopathogenic oomycetes or phytopathogenic fungi. As detailed herein below, these phytopathogenic microorganims are the causal agents of a broad spectrum of plants diseases.
  • the compound and the composition of the invention can be used as fungicides.
  • fungicide refers to a compound or composition that can be used in crop protection for the control of unwanted fungi, such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and/or for the control of Oomycetes.
  • the compound and the composition of the invention may also be used as antibacterial agent.
  • they may be used in crop protection, for example for the control of unwanted bacteria, such as Pseudomonadaceae, Rhizobiaceae, Xanthomonadaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • the compound and the composition of the invention may also be used as antiviral agent in crop protection.
  • the compound and the composition of the invention may have effects on diseases from plant viruses, such as the tobacco mosaic virus (TMV), tobacco rattle virus, tobacco stunt virus (TStuV), tobacco leaf curl virus (VLCV), tobacco nervilia mosaic virus (TVBMV), tobacco necrotic dwarf virus (TNDV), tobacco streak virus (TSV), potato virus X (PVX), potato viruses Y, S, M, and A, potato acuba mosaic virus (PAMV), potato mop-top virus (PMTV), potato leaf-roll virus (PLRV), alfalfa mosaic virus (AMV), cucumber mosaic vims (CMV), cucumber green mottlemosaic vims (CGMMV), cucumber yellows vims (CuYV), watermelon mosaic vims (WMV), tomato spotted wilt vims (TSWV), tomato ringspot vims (TomRSV), sugarcane mosaic vims (SCMV), rice drawf vims, rice stripe vims, rice black-streaked drawf vims, strawberry mottle vi
  • the present invention also relates to a method for controlling unwanted microorganisms, such as unwanted fungi, oomycetes and bacteria, comprising the step of applying at least one compound of the invention or at least one composition of the invention to the microorganisms and/or their habitat (to the plants, plant parts, seeds, fruits or to the soil in which the plants grow).
  • unwanted microorganisms such as unwanted fungi, oomycetes and bacteria
  • Suitable substrates that may be used for cultivating plants include inorganic based substrates, such as mineral wool, in particular stone wool, perlite, sand or gravel; organic substrates, such as peat, pine bark or sawdust; and petroleum based substrates such as polymeric foams or plastic beads.
  • Effective and plant-compatible amount means an amount that is sufficient to control or destroy the fungi present or liable to appear on the cropland and that does not entail any appreciable symptom of phytotoxicity for said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the crop growth stage, the climatic conditions and the respective compound or composition of the invention used. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
  • the compound and the composition of the invention may be applied to any plants or plant parts.
  • Plants mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the genetically modified plants (GMO or transgenic plants) and the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
  • Genetically modified plants (GMO) are examples of plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the genetically modified plants (GMO or transgenic plants) and the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
  • GMO Genetically modified plants
  • GMO Genetically modified plants
  • the expression“heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome. This gene gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microR A - miRNA - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Plant cultivars are understood to mean plants which have new properties ("traits”) and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
  • Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoots, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
  • the plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
  • Plants which may be treated in accordance with the methods of the invention include the following: cotton, flax, grapevine, fruit, vegetables, such as Rosaceae sp. (for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp. for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries
  • Rosaceae sp. for example pome fruits such as apples and pears, but also
  • Rubiaceae sp. for example coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for example lemons, oranges and grapefruit
  • Solanaceae sp. for example tomatoes
  • Liliaceae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Alliaceae sp. for example leek, onion
  • peas for example peas
  • major crop plants such as Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress), Fabacae sp. (for example bean, peanuts), Papilionaceae sp. (for example soya bean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, swiss chard, beetroot); useful plants and ornamental plants for gardens and wooded areas; and genetically modified varieties of each of these plants.
  • Plants and plant cultivars which may be treated by the above disclosed methods include plants and plant cultivars which are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
  • Plants and plant cultivars which may be treated by the above disclosed methods include those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which may be treated by the above disclosed methods include those plants characterized by enhanced yield characteristics lncreased yield in said plants may be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation.
  • Yield may furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, intemode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants and plant cultivars which may be treated by the above disclosed methods include plants and plant cultivars which are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • plants and plant cultivars which are herbicide-tolerant plants i.e. plants made tolerant to one or more given herbicides.
  • Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • plants and plant cultivars which are insect-resistant transgenic plants i.e. plants made resistant to attack by certain target insects.
  • Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • Plants and plant cultivars which may be treated by the above disclosed methods include plants and plant cultivars which are disease-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance. Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars which are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated by the above disclosed methods include plants and plant cultivars which show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated by the above disclosed methods include plants and plant cultivars, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • plants and plant cultivars which may be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered oil profile characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated by the above disclosed methods include plants and plant cultivars, such as Tobacco plants, with altered post-translational protein modification patterns.
  • Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae ; Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striifdrmis; Uromyces species, for example Uromyces app
  • Pseudomonas species for example Pseudomonas syringae pv. lachrymans
  • Erwinia species for example Erwinia amylovora
  • Liberibacter species for example Liberibacter asiaticus
  • Xyella species for example Xylella fastidiosa
  • Ralstonia species for example Ralstonia solanacearum
  • Dickeya species for example Dickeya solani
  • Clavibacter species for example Clavibacter michiganensis
  • Streptomyces species for example Streptomyces scabies. diseases of soya beans:
  • Alternaria leaf spot (Alternaria spec atrans tenuissima), Anthracnose ( Colletotrichum gloeosporoides dematium var. truncatum), brown spot ( Septoria glycines), cercospora leaf spot and blight ( Cercospora kikuchii), choanephora leaf blight ( Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot ( Dactuliophora glycines), downy mildew ( Peronospora manshurica), drechslera blight ( Drechslera glycini), firogeye leaf spot ( Cercospora sojina), leptosphaerulina leaf spot ( Leptosphaerulina trifolii), phyllostica leaf spot ( Phyllosticta sojaecola), pod and
  • Rhizoctonia solani phytophthora rot (Phytophthora megasperma), brown stem rot ( Phialophora gregata), pythium rot ( Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off ( Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight ( Sclerotinia rolfsii), thielaviopsis root rot ( Thielaviopsis basicola).
  • the compound and the composition of the invention may reduce the mycotoxin content in the harvested material and the foods and feeds prepared therefrom.
  • Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2 -toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec., such as F.
  • verticillioides etc. and also by Aspergillus spec., such as A. flavus, A. parasiticus, A. nomius, A. ochraceus, A. clavatus, A. terreus, A. versicolor, Penicillium spec., such as P. verrucosum, P. viridicatum, P. citrinum, P. expansum, P. claviforme, P. roqueforti, Claviceps spec., such as C. purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec and others.
  • Aspergillus spec. such as A. flavus, A. parasiticus, A. nomius, A. ochraceus, A. clavatus, A. terreus, A. versicolor, Penicillium spec., such as P. verrucosum, P. viridicatum, P. cit
  • the compound and the composition of the invention may also be used in the protection of materials, especially for the protection of industrial materials against attack and destruction by phytopathogenic fungi.
  • the compound and the composition of the invention may be used as antifouling compositions, alone or in combinations with other active ingredients.
  • Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry.
  • industrial materials which are to be protected from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms.
  • Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
  • the compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • the compound and the composition of the invention may also be used against fungal diseases liable to grow on or inside timber.
  • 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 compound and the composition of the invention may be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
  • Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired.
  • Storage goods of vegetable origin for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, may be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting.
  • Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture.
  • Storage goods of animal origin are, for example, hides, leather, furs and hairs.
  • the compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the compound and the composition of the invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi ( Ascomycetes , Basidiomycetes, Deuteromycetes and Zygomycetes ), and against slime organisms and algae.
  • microorganisms of the following genera Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria
  • the compound and the composition of the invention may also be used to protect seeds from unwanted microorganisms, such as phytopathogenic microorganisms, for instance phytopathogenic fungi or phytopathogenic oomycetes.
  • phytopathogenic microorganisms for instance phytopathogenic fungi or phytopathogenic oomycetes.
  • sccd(s) as used herein include dormant seeds, primed seeds, pregerminated seeds and seeds with emerged roots and leaves.
  • the present invention also relates to a method for protecting seeds from unwanted microorganisms which comprises the step of treating the seeds with the compound or the composition of the invention.
  • the treatment of seeds with the compound or the composition of the invention protects the seeds from phytopathogenic microorganisms, but also protects the germinating seeds, the emerging seedlings and the plants after emergence from the treated seeds. Therefore, the present invention also relates to a method for protecting seeds, germinating seeds and emerging seedlings.
  • the seeds treatment may be performed prior to sowing, at the time of sowing or shortly thereafter.
  • the seeds treatment may be performed as follows: the seeds may be placed into a mixer with a desired amount of the compound or the composition of the invention, the seeds and the compound or the composition of the invention are mixed until an homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
  • the invention also relates to seeds coated with the compound or the composition of the invention.
  • the seeds are treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment.
  • seeds can be treated at any time between harvest and shortly after sowing. It is customary to use seeds which have been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seeds which have been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds which, after drying, for example, have been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
  • the amount of the compound or the composition of the invention applied to the seeds is typically such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in case the the compound of the invention would exhibit phytotoxic effects at certain application rates.
  • the intrinsic phenotypes of transgenic plants should also be taken into consideration when determining the amount of the compound of the invention to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound being employed.
  • the compound of the invention can be applied as such, directly to the seeds, i.e. without the use of any other components and without having been diluted. Also the composition of the invention can be applied to the seeds.
  • the compound and the composition of the invention are suitable for protecting seeds of any plant variety.
  • Preferred seeds are that of cereals (such as wheat, barley, rye, millet, triticale, and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, peas, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. More preferred are seeds of wheat, soybean, oilseed rape, maize and rice.
  • the compound and the composition of the invention may be used for treating transgenic seeds, in particular seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect.
  • Seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress may contain at least one heterologous gene which allows the expression of said polypeptide or protein.
  • These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • These heterologous genes preferably originate from Bacillus sp., in which case the gene product is effective against the European com borer and/or the Western com rootworm.
  • the heterologous genes originate from Bacillus thuringiensis.
  • the compound and the composition of the invention may also have very good antimycotic effects. They have a very broad antimycotic activity spectrum, especially against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii.
  • the enumeration of these fungi by no means constitutes a restriction of the mycotic spectrum covered, and is merely of illustrative character.
  • the compound and the composition of the invention may also be used to control important fungal pathogens in fish and Crustacea farming, e.g. saprolegnia diclina in trouts, saprolegnia parasitica in crayfish.
  • the compound and the composition of the invention may therefore be used both in medical and in non medical applications.
  • the compound and the composition of the invention may, at particular concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as bactericides, viricides (including compositions against viroids) or as compositions against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms).
  • the compound and the composition of the invention may intervene in physiological processes of plants and may therefore also be used as plant growth regulators.
  • Plant growth regulators may exert various effects on plants. The effect of the substances depends essentially on the time of application in relation to the developmental stage of the plant, and also on the amounts of active ingredient applied to the plants or their environment and on the type of application. In each case, growth regulators should have a particular desired effect on the crop plants.
  • Growth regulating effects comprise earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kemels/ear, number of ears/m 2 , number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation / earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit/vegetable size, sprouting resistance and reduced lodging.
  • Increased or improved yield is referring to total biomass per hectare, yield per hectare, kemel/fruit weight, seed size and/or hectolitre weight as well as to improved product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, better brewing, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meet quality of silage fed animals, adaptation to cooking and frying; improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage / shelf-life, firmness / softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, colour, etc.; increased desired ingredients such as e.g.
  • protein content protein content, fatty acids, oil content, oil quality, aminoacid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxins, geosmin level, phenolic aromas, lacchase, polyphenol oxidases and peroxidases, nitrate content etc.
  • Plant growth-regulating compounds can be used, for example, to slow down the vegetative growth of the plants.
  • Such growth depression is of economic interest, for example, in the case of grasses, since it is thus possible to reduce the frequency of grass cutting in ornamental gardens, parks and sport facilities, on roadsides, at airports or in fruit crops.
  • Also of significance is the inhibition of the growth of herbaceous and woody plants on roadsides and in the vicinity of pipelines or overhead cables, or quite generally in areas where vigorous plant growth is unwanted.
  • growth regulators for inhibition of the longitudinal growth of cereal. This reduces or completely eliminates the risk of lodging of the plants prior to harvest.
  • growth regulators in the case of cereals can strengthen the culm, which also counteracts lodging.
  • the employment of growth regulators for shortening and strengthening culms allows the deployment of higher fertilizer volumes to increase the yield, without any risk of lodging of the cereal crop.
  • vegetative growth depression allows denser planting, and it is thus possible to achieve higher yields based on the soil surface.
  • Another advantage of the smaller plants obtained in this way is that the crop is easier to cultivate and harvest.
  • Reduction of the vegetative plant growth may also lead to increased or improved yields because the nutrients and assimilates are of more benefit to flower and fruit formation than to the vegetative parts of the plants.
  • growth regulators can also be used to promote vegetative growth. This is of great benefit when harvesting the vegetative plant parts.
  • promoting vegetative growth may also promote generative growth in that more assimilates are formed, resulting in more or larger fruits.
  • beneficial effects on growth or yield can be achieved through improved nutrient use efficiency, especially nitrogen (N)-use efficiency, phosphorous (P)-use efficiency, water use efficiency, improved transpiration, respiration and/or CO 2 assimilation rate, better nodulation, improved Ca-metabolism etc.
  • nitrogen (N)-use efficiency especially nitrogen (N)-use efficiency, phosphorous (P)-use efficiency, water use efficiency, improved transpiration, respiration and/or CO 2 assimilation rate, better nodulation, improved Ca-metabolism etc.
  • growth regulators can be used to alter the composition of the plants, which in turn may result in an improvement in quality of the harvested products. Under the influence of growth regulators, parthenocarpic fruits may be formed. In addition, it is possible to influence the sex of the flowers. It is also possible to produce sterile pollen, which is of great importance in the breeding and production of hybrid seed.
  • growth regulators can control the branching of the plants.
  • by breaking apical dominance it is possible to promote the development of side shoots, which may be highly desirable particularly in the cultivation of ornamental plants, also in combination with an inhibition of growth.
  • side shoots which may be highly desirable particularly in the cultivation of ornamental plants, also in combination with an inhibition of growth.
  • the amount of leaves on the plants can be controlled such that defoliation of the plants is achieved at a desired time.
  • defoliation plays a major role in the mechanical harvesting of cotton, but is also of interest for facilitating harvesting in other crops, for example in viticulture.
  • Defoliation of the plants can also be undertaken to lower the transpiration of the plants before they are transplanted.
  • growth regulators can modulate plant senescence, which may result in prolonged green leaf area duration, a longer grain filling phase, improved yield quality, etc.
  • Growth regulators can likewise be used to regulate fruit dehiscence. On the one hand, it is possible to prevent premature fruit dehiscence. On the other hand, it is also possible to promote fruit dehiscence or even flower abortion to achieve a desired mass (“thinning”). In addition it is possible to use growth regulators at the time of harvest to reduce the forces required to detach the fruits, in order to allow mechanical harvesting or to facilitate manual harvesting.
  • Growth regulators can also be used to achieve faster or else delayed ripening of the harvested material before or after harvest. This is particularly advantageous as it allows optimal adjustment to the requirements of the market. Moreover, growth regulators in some cases can improve the fruit colour. In addition, growth regulators can also be used to synchronize maturation within a certain period of time. This establishes the prerequisites for complete mechanical or manual harvesting in a single operation, for example in the case of tobacco, tomatoes or coffee.
  • growth regulators By using growth regulators, it is additionally possible to influence the resting of seed or buds of the plants, such that plants such as pineapple or ornamental plants in nurseries, for example, germinate, sprout or flower at a time when they are normally not inclined to do so. In areas where there is a risk of frost, it may be desirable to delay budding or germination of seeds with the aid of growth regulators, in order to avoid damage resulting from late frosts.
  • growth regulators can induce resistance of the plants to frost, drought or high salinity of the soil. This allows the cultivation of plants in regions which are normally unsuitable for this purpose.
  • the compound and the composition of the invention may also exhibit a potent strengthening effect in plants. Accordingly, they may be used for mobilizing the defences of the plant against attack by undesirable microorganisms.
  • Plant-strengthening (resistance-inducing) substances in the present context are substances capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesirable microorganisms, develop a high degree of resistance to these microorganisms.
  • plant physiology effects comprise the following:
  • Abiotic stress tolerance comprising tolerance to high or low temperatures, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides etc.
  • Biotic stress tolerance comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria.
  • biotic stress tolerance preferably comprises increased fungal resistance and increased resistance against nematodes and bacteria
  • Increased plant vigor comprising plant health / plant quality and seed vigor, reduced stand failure, improved appearance, increased recovery after periods of stress, improved pigmentation (e.g. chlorophyll content, stay-green effects, etc.) and improved photosynthetic efficiency.
  • the compounds of the invention can be applied as such, or for example in the form of as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with the compound of the invention, synthetic substances impregnated with the compound of the invention, fertilizers or microencapsulations in polymeric substances.
  • Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the compound of the invention by the ultra-low volume method, via a drip irrigation system or drench application, to apply it in- furrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of the invention by means of a wound seal, paint or other wound dressing.
  • the effective and plant-compatible amount of the compound of the invention which is applied to the plants, plant parts, fruits, seeds or soil will depend on various factors, such as the compound/composition employed, the subject of the treatment (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (curative and protective), the type of microorganisms, the development stage of the microorganisms, the sensitivity of the microorganisms, the crop growth stage and the environmental conditions.
  • the application rates can vary within a relatively wide range, depending on the kind of application.
  • the application rate may range from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used).
  • the application rate may range from 0.1 to 200 g per 100 kg of seeds, preferably from 1 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, even more preferably from 2.5 to 12.5 g per 100 kg of seeds.
  • the application rate may range from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
  • the active compounds according to the invention also exhibit a potent strengthening effect in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by undesirable microorganisms.
  • Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesirable microorganisms, develop a high degree of resistance to these microorganisms.
  • plant physiology effects comprise the following:
  • Abiotic stress tolerance comprising temperature tolerance, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides (safener) etc.
  • Biotic stress tolerance comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria.
  • biotic stress tolerance preferably comprises increased fungal resistance and increased resistance against nematodes
  • Increased plant vigor comprising plant health / plant quality and seed vigor, reduced stand failure, improved appearance, increased recovery, improved greening effect and improved photosynthetic efficiency.
  • growth regulators comprising earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kemels/ear, number of ears/m 2 , number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation / earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit/vegetable size, sprouting resistance and reduced lodging.
  • Increased yield referring to total biomass per hectare, yield per hectare, kerne 1/fru it weight, seed size and/or hectolitre weight as well as to increased product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, better brewing, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meet quality of silage fed animals, adaption to cooking and frying; further comprising improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage / shelf-life, firmness / softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, colour, etc.; further comprising increased desired ingredients
  • protein content protein content, fatty acids, oil content, oil quality, aminoacid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; and further comprising decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxines, geosmin level, phenolic aromas, lacchase, polyphenol oxidases and peroxidases, nitrate content etc.
  • decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxines, geosmin level, phenolic aromas, lacchase, polyphenol oxidases and peroxidases, nitrate content etc.
  • Delayed senescence comprising improvement of plant physiology which is manifested, for example, in a longer grain filling phase, leading to higher yield, a longer duration of green leaf colouration of the plant and thus comprising colour (greening), water content, dryness etc..
  • the specific inventive application of the active compound combination makes it possible to prolong the green leaf area duration, which delays the maturation (senescence) of the plant.
  • the main advantage to the farmer is a longer grain filling phase leading to higher yield.
  • sedimentation value is a measure for protein quality and describes according to Zeleny (Zeleny value) the degree of sedimentation of flour suspended in a lactic acid solution during a standard time interval. This is taken as a measure of the baking quality. Swelling of the gluten fraction of flour in lactic acid solution affects the rate of sedimentation of a flour suspension. Both a higher gluten content and a better gluten quality give rise to slower sedimentation and higher Zeleny test values.
  • the sedimentation value of flour depends on the wheat protein composition and is mostly correlated to the protein content, the wheat hardness, and the volume of pan and hearth loaves. A stronger correlation between loaf volume and Zeleny sedimentation volume compared to SDS sedimentation volume could be due to the protein content influencing both the volume and Zeleny value ( Czech J Food Sci. Vol. 27, No. 3: 91-96, 2000).
  • the“falling number” as mentioned herein is a measure for the baking quality of cereals, especially of wheat.
  • the falling number test indicates that sprout damage may have occurred. It means that changes to the physical properties of the starch portion of the wheat kernel has already happened.
  • the falling number instrument analyzes viscosity by measuring the resistance of a flour and water paste to a falling plunger. The time (in seconds) for this to happen is known as the falling number.
  • the falling number results are recorded as an index of enzyme activity in a wheat or flour sample and results are expressed in time as seconds.
  • a high falling number for example, above 300 seconds
  • a low falling number indicates substantial enzyme activity and sprout-damaged wheat or flour.
  • the term“more developed root system” /“improved root growth” refers to longer root system, deeper root growth, faster root growth, higher root dry/fresh weight, higher root volume, larger root surface area, bigger root diameter, higher root stability, more root branching, higher number of root hairs, and/or more root tips and can be measured by analyzing the root architecture with suitable methodologies and Image analysis programmes (e.g. WinRhizo).
  • the term“crop water use efficiency” refers technically to the mass of agriculture produce per unit water consumed and economically to the value of product(s) produced per unit water volume consumed and can e.g. be measured in terms of yield per ha, biomass of the plants, thousand-kernel mass, and the number of ears per m 2 .
  • nitrogen-use efficiency refers technically to the mass of agriculture produce per unit nitrogen consumed and economically to the value of product(s) produced per unit nitrogen consumed, reflecting uptake and utilization efficiency.
  • Fv/Fm is a parameter widely used to indicate the maximum quantum efficiency of photosystem II (PSII). This parameter is widely considered to be a selective indication of plant photosynthetic performance with healthy samples typically achieving a maximum Fv/Fm value of approx. 0.85. Values lower than this will be observed if a sample has been exposed to some type of biotic or abiotic stress factor which has reduced the capacity for photochemical quenching of energy within PSII.
  • Fv/Fm is presented as a ratio of variable fluorescence (Fv) over the maximum fluorescence value (Fm).
  • the Performance Index is essentially an indicator of sample vitality. (See e.g. Advanced Techniques in Soil Microbiology, 2007, 11, 319-341 ; Applied Soil Ecology, 2000, 15, 169-182.)
  • the improvement in greening / improved colour and improved photosynthetic efficiency as well as the delay of senescence can also be assessed by measurement of the net photosynthetic rate (Pn), measurement of the chlorophyll content, e.g. by the pigment extraction method of Ziegler and Ehle, measurement of the photochemical efficiency (Fv/Fm ratio), determination of shoot growth and final root and/or canopy biomass, determination of tiller density as well as of root mortality.
  • Pn net photosynthetic rate
  • Fv/Fm ratio photochemical efficiency
  • plant physiology effects which are selected from the group comprising: enhanced root growth / more developed root system, improved greening, improved water use efficiency (correlating to reduced water consumption), improved nutrient use efficiency, comprising especially improved nitrogen (N)-use efficiency, delayed senescence and enhanced yield.
  • the novel use of the fungicidal compositions of the present invention relates to a combined use of a) preventively and/or curatively controlling pathogenic fungi and/or nematodes, with or without resistance management, and b) at least one of enhanced root growth, improved greening, improved water use efficiency, delayed senescence and enhanced yield. From group b) enhancement of root system, water use efficiency and N-use efficiency is particularly preferred.
  • the mixture was reacted approximately 30 minutes at -78 °C and then approximately 16h at rt following the mixing of the two solutions.
  • the crude product was purified by automated flash chromatography (Combiflash, using a 40 g silica gel cartridge, gradient elution ethyl acetate in heptane 0% 10% 20%) and the product-containing fractions were collected and evaporated, then the residue was further purified by preparative HPLC to provide the title compound (29 mg, 88% LCMS purity, 1% yield based on theory).
  • ketone (II) (1 equivalent) in methanol (approximately 0.3M with respect to ketone (II)) was added 2,4,6-triisopropylbenzenesulfonohydrazide (1 equivalent) and the resulting mixture was stirred at a temperature between 25 °C - 70 °C for a period of 2h - 72h, monitoring reaction progress by LCMS. After the reaction was judged to be complete, the reaction solvent was evaporated and the product was purified either by recrystallization from an appropriate solvent and/or column chromatography to afford the desired product.
  • N'-(2,3-dihydro-lH-inden-l-ylidene)-2,4,6-triisopropylbenzenesulfonohydrazide (VI-01) was prepared according to general procedure 1B from indan-l-one (2.20 g, 16.6 mmol) and 2,4,6- triisopropylbenzenesulfonohydrazide (4.97 g, 16.6 mmol) in methanol (50 mL) at 50 °C for 3h. After which, the reaction was concentrated to approximately 10% of the original volume and placed in the freezer at - 20 °C to induce further solid formation.
  • the solid material was collected by filtration and washed with small portions of cold mcthyl-te/7-butylcthcr. After drying, the solid material was found to contain an impurity, so the entirety of the obtained solid was recombined with the mother liquor and washings and the solvent was evaporated on the rotary evaporator. The residue was purified by flash column chromatography on silica gel (gradient elution, ethyl acetate in n-heptane) and the product-containing fractions were combined. The solvent from the combined fractions was evaporated to approximately 10% of the original volume, during which solid material formed. The solid was collected by filtration and washed with small portions of n- heptane to afford, after drying under vacuum, the title compound (2.18 g, 32% yield based on theory)
  • VT-a The corresponding hydrazone (VT-a) (1 equivalent) was dissolved in THF (approximately 0.4 - 0.5 M with respect to hydrazone (VI-a)) under an argon atmosphere and cooled to -78 °C.
  • n-butyllithium in the following abbreviated n-BuLi
  • n-BuLi 2.2 equivalents, 2.5M in hexanes
  • the resulting mixture was slowly added to a solution of the corresponding ketone (IV) (1 equivalent) in dichloromethane (approximately 0.1 - 0.3M with respect to ketone (IV)) at -78 °C under an argon atmosphere.
  • the reaction was stirred for approximately 30 minutes at -78 °C, or in some cases optionally warmed to rt and stirred for a period of 0.5h - 16h, and was then quenched either at -78 °C or at rt with water and stirred until the mixture reached rt.
  • the mixture was diluted with water and dichloromethane and the organic phase was separated.
  • h LogP value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • c LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1% phosphoric acid and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
  • Lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
  • 1H-NMR data of selected examples are written in form of lH-NMR-peak lists. To each signal peak are listed the d-value in ppm and the signal intensity in round brackets. Between the d-value - signal intensity pairs are semicolons as delimiters.
  • the peak list of an example has therefore the form: di (intensityi); d2 (intensity2); . ; d; (intensity;); . ; d h (intensity n )
  • Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
  • For calibrating chemical shift for 1H spectra we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
  • the 1H-NMR peak lists are similar to classical 1H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
  • the peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
  • Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via“side-products-fingerprints”.
  • An expert who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1H-NMR interpretation.
  • Example A in vivo preventive test on Alternaria brassicae (leaf spot on radish or cabbage!
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • Young plants of radish or cabbage were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Alternaria brassicae spores. The contaminated radish or cabbage plants were incubated for 6 days at 20°C and at 100% relative humidity.
  • Example B in vivo preventive test on Botrvtis cinerea (grey mould!
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of gherkin were treated by spraying the active ingredient prepared as described above.
  • Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores.
  • the contaminated gherkin plants were incubated for 4 to 5 days at l7°C and at 90% relative humidity. The test was evaluated 4 to 5 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Example C in vivo preventive test on Puccinia recondita (brown rust on wheat!
  • Emulsifier lpl of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of wheat were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores.
  • the contaminated wheat plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 10 days at 20°C and at 70-80% relative humidity.
  • the test was evaluated 1 1 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Example D in vivo preventive test on Pyrenophora teres (net blotch on
  • Emulsifier Im ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of barley were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores. The contaminated barley plants were incubated for 48 hours at 20°C and at 100% relative humidity and then for 12 days at 20°C and at 70-80% relative humidity.
  • Example E in vivo preventive test on Septoria tritici (leaf spot on wheat!
  • Emulsifier lpl of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of wheat were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Septoria tritici spores.
  • the contaminated wheat plants were incubated for 72 hours at l7°C and at 100% relative humidity and then for 15 days at 20°C and at 90% relative humidity.
  • Example F in vivo preventive test on Sphaerotheca fulmnea fpowderv mildew on cucurbits!
  • Emulsifier Im ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of gherkin were treated by spraying the active ingredient prepared as described above.
  • Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores.
  • the contaminated gherkin plants were incubated for 8 days at 20°C and at 70-80% relative humidity.
  • the test was evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Example G in vivo preventive test on Uromvces amendiculatus (bean rust)
  • Emulsifier lpl of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of bean were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores.
  • the contaminated bean plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 10 days at 20°C and at 70-80% relative humidity.
  • the test was evaluated 1 1 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Example H in vivo preventive test on Colletotrichum lindemuthianum (leaf spot on bean)
  • Emulsifier 1 m ⁇ of Tween ® 80 per mg of active ingredient
  • the active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of bean were treated by spraying the active ingredient prepared as described above.
  • Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Colletotrichum lindemuthianum spores.
  • the contaminated bean plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 6 days at 20°C and at 90% relative humidity.

Abstract

The present invention relates to novel compounds of formula (I), wherein R1, R2 and R3 are defined as in the claims and specification, and R4 represents a bicyclic moiety of formula (Q), wherein the dotted line A represents a single or double bond, and X1, X2, X3, X4 and X5 are defined as in the claims and specification. It further relates to processes for preparing said compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.

Description

FUNGICIDAL 5-SUBSTITUTED IMIDAZ0L-1-YL CARBINOL DERIVATIVES
The present invention relates to novel 5-substituted imidazol-l-yl carbinol derivatives, to processes and intermediates for preparing these compounds, to compositions comprising those, and to the use thereof as biologically active compounds and compositions, especially for control of harmful microorganisms in crop protection and in the protection of materials.
It is known from WO 2016/156290 Al that certain l-(5-substituted imidazol- 1 -yl)propan-2-ol derivatives and salts thereof show good fungicidal efficacy against a broad spectrum of phytopathogenic fungi and, therefore, are valuable compounds for use in crop protection. Further fungicides comprising a 5-substituted imidazol-l-yl moiety are known from W02018/060073 Al, W02018/060074 Al, W02018/060075 Al, WO2018/060088 Al, WO2018/060090 Al, W02018/060091 Al and WO2018/060093 Al.
However, since the ecological and economic demands made on modem active ingredients, for example fungicides, are increasing constantly, for example with respect to efficacy, activity spectrum, toxicity, selectivity, application rate, formation of residues and favourable manufacture, and there can also be problems, for example, with resistances, there is a constant need to develop novel fungicidal compositions which have advantages over the known compositions at least in some areas.
Hence, object of the invention is to serve this need by providing novel compounds useful for control of harmful microorganisms in crop protection and in the protection of materials, in particular compounds showing fungicidal efficacy.
Surprisingly, it has been found that particular 5-substituted imidazol- 1 -yl carbinol derivatives differing from known compounds by comprising a benzofused at least partially saturated carbocycle or heterocycle are valuable fungicides.
Accordingly, the present invention provides novel triazole derivatives of formula (I)
Figure imgf000002_0001
wherein R1 represents hydrogen, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Cs-Cs-cycloalkyl or C6-Ci4-aryl,
R2 represents hydrogen, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Cs-Cs-cycloalkyl or C6-Ci4-aryl, wherein the aliphatic moieties, excluding cycloalkyl moieties, of R1 and R2 may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, C3-Cs-cycloalkyl, C6-Ci4-aryl, Ci-C4-alkoxy and C1-C4- haloalkoxy, wherein the C3-Cs-cycloalkyl and C6-Ci4-aryl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently from each other from halogen, CN, nitro, Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, and wherein the cycloalkyl and/or C6-Ci4-aryl moieties of R1 and R2 may carry 1, 2, 3, 4, 5 or up to the maximum number of groups Rb which independently of one another are selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy;
R3 represents halogen, hydroxyl, cyano, isocyano, nitro, amino, sulfanyl, pentafluoro^6-sulfanyl, carboxaldehyde, hydroxycarbonyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs-alkyloxy, Ci-C -haloalkyloxy, tri(Ci-Cs-alkyl)silyl, tri(Ci-C8-alkyl)silyl-Ci-C8-alkyl, C3-C7-cycloalkyl, C3-C7- halocycloalkyl, C3-C7-cycloalkenyl, C3-C7-halocycloalkenyl, C3-C7-cycloalkyl-Ci-C8-alkyl, C3-C7- halocycloalkyl-Ci-C8-alkyl, C3-C7-cycloalkyl-C3-C7-cycloalkyl, Ci-C8-alkyl-C3-C7-cycloalkyl, Ci- C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-C8-alkyl)silyl-C3-C7-cycloalkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8-haloalkynyloxy, Ci-Cs- alkylamino, Ci-CVhaloalkylamino, Ci-Cs-cyanoalkoxy, C3-C7-cycloalkyl-Ci-C8-alkoxy, C3-C7- cycloalkoxy, Ci-Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs- haloalkylcarbonyl, Ce-Cw-arylcarbonyl, Ce-Cw-aryl-Ci-Ce-alkylcarbonyl, C3-C7-cycloalkylcarbonyl, C3-C7-halocycloalkylcarbonyl, carbamoyl, A'-Ci -Cx-alky lcarbamoyl, V, V-di-(Ci-Cx-alkyl)carbamoyl, /V- Ci -Cx-alkyloxycarbamoyl, /V- ( C 1 -CN-alkyl )- /V- ( Ci - Cs - a 1 k 0 x y ) a m i n 0 c a rb 0 n y 1 , aminothiocarbonyl, Ci-Ce-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, C3-C7-cycloalkoxycarbonyl, Ci-Cs-alkoxy-Ci-Cs- alkylcarbonyl, Ci-Cs-haloalkoxy-Ci-Cs-alkylcarbonyl, C3-C7-cycloalkoxy-Ci-C8-alkylcarbonyl, N- C3-C7-cycloalkylaminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, C3-C7- cycloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, /V-C 1 -Ch alky lam inocarbonyloxy, /V, /V- d i - ( Ci - Cs - a 1 ky 1 ) a m i n 0 c arb 0 n y 10 x y , Ci-Cs-alkyloxycarbonyloxy, Ci- C8-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs-haloalkylsulfonyl, Ci-Cs- alkylsulfonyloxy, Ci-Cs-haloalkylsulfonyloxy, Ci-Cs-alkylaminosulfamoyl, di-Ci-Cs- alkylaminosulfamoyl, (Ci-C8-alkoxyimino)-Ci-C8-atkyl, (C3-C7-cycloalkoxyimino)-Ci-C8-alkyl, hydroxyimino-Ci-C8-alkyl, (Ci-C8-alkoxyimino)-C3-C7-cycloalkyl, hydroxyimino-C3-C7-cycloalkyl, (Ci-C8-alkylimino)-oxy, (Ci-C8-alkylimino)-oxy-Ci-C8-alkyl, (C3-C7-cycloalkylimino)-oxy-Ci-C8- alkyl, (Ci-C8-alkylimino)-oxy-C3-C7-cycloatkyl, (Ci-C8-alkenyloxyimino)-Ci-C8-atkyl, (Ci-Cs- alkynyloxyimino)-Ci-C8-alkyl, (benzyloxyimino)-Ci-C8-atkyl, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs- alkyl-Ci-C8-thioalkyl, Ci-Cs-alkoxy-Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-haloalkoxy-Ci-Cs-alkyl, benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, benzyloxy, phenyloxy, benzylsulfanyl, benzylamino, phenylsulfanyl, or phenylamino, wherein the benzyl, phenyl, 5- membered heteroaryl, 6-membered heteroaryl, benzyloxy or phenyloxy is non-substituted or substituted by one or more group(s) selected from halogen, hydroxyl, cyano, isocyano, amino, sulfanyl, pentafluoro^6-sulfanyl, carboxaldehyde, hydroxycarbonyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs-alkyloxy, Ci-Cs-haloalkyloxy, tri(Ci-Cs-alkyl)silyl, tri(Ci-Cs-alkyl)silyl-Ci- Cs-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C3-C7-cycloalkenyl, C3-C7-halocycloalkenyl, C3- C7-cycloalkyl-Ci-C8-alkyl, C3-C7-halocycloalkyl-Ci-C8-alkyl, C3-C7-cycloalkyl-C3-C7-cycloalkyl, Ci-C8-alkyl-C3-C7-cycloalkyl, Ci-C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-C8-alkyl)silyl-C3-C7- cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8- alkynyloxy, C2-C8-haloalkynyloxy, Ci-Cs-alkylamino, Ci-Cx-haloalkylamino, Ci-Cs-cyanoalkoxy, C3-C7-cycloalkyl-Ci-C8-alkoxy, C3-C7-cycloalkoxy, Ci-Cs-alkylsulfanyl, C 1 -Cx- hal oal ky 1 su 1 fany 1 , Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, C6-Ci4-arylcarbonyl, C6-Ci4-aryl-Ci-C8- alkylcarbonyl, C3-C7-cycloalkylcarbonyl, C3-C7-halocycloalkylcarbonyl, /V- C 1 - C x - a 1 k y 1 c a rb a m oy 1 , A'-,/V-di-(Ci-C8-alkyl)carbamoyl, A'-Ci -Cx-alky loxycarbamoyl, A^Ci -Cx-alky lfrVfrCi -Cx- alkoxy)aminocarbonyl, aminothiocarbonyl, Ci-Cx-alkoxycarbonyl, Ci-Cx-haloalkoxycarbonyl, C3- C7-cycloalkoxycarbonyl, Ci -Cx-alkoxy-Ci -Cx-alky lcarbonyl, Ci-Cx-haloalkoxy-Ci-Cx-alkylcarbonyl, C3-C7-cycloalkoxy-Ci-C8-alkylcarbonyl, A'-CA^-CA-cycloalkylaminocarbonyl, Ci-Cs- alkylcarbonyloxy, Ci -Cx-haloalkylcarbonyloxy, C3-C7-cycloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci -Cx-haloalkylcarbonylamino, A-- C 1 - C x - a 1 ky 1 a m i n 0 c a rb 0 n y 10 x y , Ai-,A,--di-(Ci- C8-alkyl)aminocarbonyloxy, Ci -Cx-alky loxycarbonyloxy, Ci-Cx-alkylsulfmyl, Ci-Cs- haloalkylsulfinyl, Ci-Cx-alkylsulfonyl, Ci-Cx-haloalkylsulfonyl, Ci -Cx-alky lsulfonyloxy, Ci-Cs- haloalkylsulfonyloxy, Ci -Cx-alky laminosulfamoyl, di-Ci -Cx-alkylaminosulfamoyl, (Ci-Cs- alkoxyimino)-Ci-C8-alkyl, (C3-C7-cycloalkoxyimino)-Ci-C8-alkyl, hydroxy imino-Ci -Cx-alkyl, (Ci- C8-alkoxyimino)-C3-C7-cycloalkyl, hydroxyimino-C3-C7-cycloalkyl, (Ci-C8-alkylimino)-oxy, (Ci- C8-alkylimino)-oxy-Ci-C8-alkyl, (C3-C7-cycloalkylimino)-oxy-Ci-C8-alkyl, (Ci-C8-alkylimino)-oxy- C3-C7-cycloalkyl, (Ci-C8-alkenyloxyimino)-Ci-C8-alkyl, (Ci-C8-alkynyloxyimino)-Ci-C8-alkyl, (benzyloxyimino)-Ci-C8-alkyl, Ci -Cx-alkoxy-Ci -Cx-alkyl, Ci-Cs-alkylthio-Ci-Cs-alkyl, Ci-Cs- alkoxy-Ci-C8-alkoxy-Ci-C8-alkyl, Ci-Cs-haloalkoxy-Ci-Cs-alkyl, benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, benzyloxy, phenyloxy, benzylsulfanyl, benzylamino, phenylsulfanyl, or phenylamino; and
R4 represents a bicyclic moiety of formula (Q)
Figure imgf000004_0001
(Q), wherein the dotted line A represents a single or double bond;
X1, X2, X3, and X4 independently from each other represent hydrogen, halogen, nitro, cyano, sulfanyl, pentafluoroA6-sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C3-C7-cycloalkyl, C3-C7-halocycloalkyl having 1 to 5 halogen atoms, Ci-Cs-haloalkyl-C3-C7- cycloalkyl, C3-C7-cycloalkenyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C6-Ci2-bicycloalkyl, C3-C7- cycloalkyl-C2-C8-alkenyl, C3-C7-cycloalkyl-C2-Cs-alkynyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy having 1 to 5 halogen atoms, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci-Cs- alkylsulfenyl, C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, C3-C7-cycloalkoxy, Ci-Cs-alkylsulfinyl, Ci-C8-alkylsulfonyl, tri(Ci-C8-alkyl)-silyloxy, tri(Ci-C8-alkyl)-silyl, tri(Ci-C8-alkyl)-silyl-C2- Cs-alkynyl, tri(Ci-C8-alkyl)-silyl-C2-C8-alkynyloxy, C6-Ci4-aryl, C6-Ci4-aryloxy, Ce-Cu- arylsulfenyl, 5- or 6-membered heteroaryl, 5- or 6-membered heteroaryloxy, wherein the C6-Ci4-aryl, C6-Ci4-aryloxy, C6-Ci4-arylsulfenyl, 5- or 6-membered heteroaryl, 5- or 6-membered heteroaryloxy is non-substituted or substituted by one or more group(s) independently from each other selected from halogen, cyanosulfanyl, pentafluoroA6-sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoatkyl, Ci-Cs-alkyloxy, Ci-Cs-haloalkyloxy, tri(Ci- C8-alkyl)silyl, tri(Ci-C8-alkyl)silyl-Ci-C8-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C3- C7-cycloalkenyl, C3-C7-halocycloalkenyl, C3-C7-cycloatkyl-Ci-C8-alkyl, C3-C7- halocycloalkyl-Ci-C8-alkyl, C3-C7-cycloalkyl-C3-C7-cycloalkyl, Ci-C8-alkyl-C3-C7- cycloalkyl, Ci-C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-C8-alkyl)silyl-C3-C7-cycloalkyl, C2-C8- alkenyl, C2-Cs-alkynyl, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8- haloalkynyloxy, Ci-Ck-cyanoalkoxy, C3-C7-cycloalkyl-Ci-C8-alkoxy, C3-C7-cycloalkoxy, Ci- Cs-alkylsulfanyl, C 1 -Ck- Hal oal ky lsu 1 fany 1 , Ci-Cs-alkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs- alkylsulfonyl, Ci-Cs-haloalkylsulfonyl, Ci-Cs-alkylsulfonyloxy, Ci-Cs-haloalkylsulfonyloxy, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-alkylthio-Ci-Cs-alkyl, Ci-Cs-alkoxy-Ci-Cs-alkoxy-Ci-Cs- alkyl, Ci-Cs-haloalkoxy-Ci-Cs-atkyl, benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, 6-membered heteroaryloxy, benzyloxy, phenyloxy, benzylsulfanyl, and phenylsulfanyl, wherein the benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, 6-membered heteroaryloxy, benzyloxy, phenyloxy, benzylsulfanyl and phenylsulfanyl is non-substituted or substituted independently from each other by one or more group(s) selected from halogen, CN, nitro, Ci-Cs-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and pentafluoro-l6- sulfanyl; and X5 represents Ci-C3-alkanediyl, -Y-CH2- or -Y-(CH2)2-, wherein Y represents O, S or NY1, wherein Y1 represents hydrogen or Ci-Cs-alkyl; and its salts or N-oxides.
An arrow, as in formula (Q), depicts the bonding position of the shown moiety to the remainder of the molecule.
The salts or N-oxides of the compounds of formula (I) also have fungicidal properties.
Formula (I) provides a general definition of the compounds according to the invention. Preferred radical definitions for the formulae shown above and below are given below. These definitions apply to the end products of formula (I) and likewise to all educts and intermediates.
R1 preferably represents hydrogen, Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl or phenyl, wherein the aliphatic moieties, excluding the cycloalkyl moieties, of R1 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, C3-C6-cycloalkyl, phenyl, Ci-C4-alkoxy and C1-C4- haloalkoxy, wherein C3-C6-cycloalkyl and phenyl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently from each other from halogen, CN, nitro, Ci-C4-atkyl, Ci-C4-alkoxy, C1-C4- haloalkyl, Ci-C4-haloalkoxy, and wherein the cycloalkyl and phenyl moieties of R1 may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups Rb which independently of one another are selected from halogen, CN, nitro, Ci-C4-atkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
R1 more preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, allyl, CH2CºC-CH3, CH2CºCH, cyclopropyl or phenyl, wherein the aliphatic groups, excluding the cycloalkyl moieties, of R1 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from fluorine, chlorine, bromine, iodine, CN or nitro, and wherein the cyclopropyl and phenyl group of R1 may be substituted by 1, 2, 3, 4 or 5 substituents Rb selected independently of one another from fluorine, chlorine, bromine, iodine, CN and nitro.
R1 more preferably represents methyl, /c/7- butyl, cyclopropyl or phenyl, wherein the aliphatic groups, excluding the cycloalkyl moieties, of R1 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from fluorine, chlorine and bromine, and wherein the cyclopropyl and phenyl group of R1 may be substituted by 1 , 2 or 3 substituents Rb selected independently of one another from fluorine, chlorine and bromine.
R1 more preferably represents cyclopropyl or phenyl, wherein the cyclopropyl and phenyl group may be substituted by 1, 2 or 3, preferably 1 or 2 substituents Rb selected independently of one another from fluorine, chlorine and bromine.
R1 more preferably represents cyclopropyl, 1 -fluorocyclopropyl, 1 -chlorocyclopropyl, 1- bromocyclopropyl, phenyl, 2-fluorophenyl, 3 -fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-difluorophenyl,
2.4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl,
2.5-dichlorophenyl, 2,6-dichlorophenyl, 2,3-dibromophenyl, 2,4-dibromophenyl, 2,5- dibromophenyl, 2,6-dibromophenyl, 2-bromo-3-chlorophenyl, 2-bromo-4-chlorophenyl, 2-bromo-5- chlorophenyl, 2-bromo-6-chlorophenyl, 3-bromo-2-chlorophenyl, 3-bromo-4-chlorophenyl, 3- bromo-5-chlorophenyl, 3-bromo-6-chlorophenyl, 4-bromo-2-chlorophenyl, 4-bromo-3- chlorophenyl, 2-bromo-3-fluorophenyl, 2-bromo-4-fluorophenyl, 2-bromo-5-fluorophenyl, 2-bromo- 6-fluorophenyl, 3-bromo-2-fluorophenyl, 3-bromo-4-fluorofluorophenyl, 3-bromo-5-fluorophenyl, 3-bromo-6-fluorophenyl, 4-bromo-2-fluorophenyl, 4-bromo-3 -fluorophenyl, 2-chloro-3- fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5-fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro- 2-fluorophenyl, 3 -chloro-4-fluoro fluorophenyl, 3-chloro-5-fluorophenyl, 3-chloro-6-fluorophenyl, 4- chloro-2-fluorophenyl or 4-chloro-3-fluorophenyl.
R1 more preferably represents 1 -fluorocyclopropyl, 1 -chlorocyclopropyl, 2,3-difluorophenyl, 2,4- difluorophenyl, 2,5-difluorophenyl or 2,6-difluorophenyl.
R1 more preferably represents 1 -chlorocyclopropyl, or 2,4-difluorophenyl.
R1 represents in one particular preferred embodiment 1 -chlorocyclopropyl.
R1 represents in a further particular preferred embodiment 2,4-difluorophenyl.
R1 most preferably represents 1 -chlorocyclopropyl.
R2 preferably represents hydrogen, Ci-C4-alkyl, allyl or propargyl, wherein the aliphatic moieties of R2 may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, wherein the phenyl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently of one another from halogen, CN, nitro, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy. R2 more preferably represents hydrogen, methyl, ethyl, isopropyl or allyl, wherein the aliphatic groups R2 may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, wherein the phenyl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently of one another from halogen, CN, nitro, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy.
R2 more preferably represents hydrogen or methyl, ethyl, isopropyl or allyl.
R2 more preferably represents hydrogen or methyl.
R2 most preferably represents hydrogen.
R3 preferably represents halogen, hydroxyl, cyano, isocyano, nitro, carboxaldehyde, hydroxycarbonyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs-alkyloxy, Ci-Cs-haloalkyloxy, C3-C7- cycloalkyl, C3-C7-halocycloalkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C2-Cs-alkenyloxy, C2-C8- haloalkenyloxy, C3-C8-alkynyloxy, C3-C8-halooalkynyloxy, Ci-Cs-alkylsulfanyl, Ci-Cs- haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, C6-Ci4-arylcarbonyl, C6-Ci4-aryl- Ci-C6-alkylcarbonyl, C3-C7-cycloalkylcarbonyl, C3-C7-halocycloalkylcarbonyl, aminothiocarbonyl, carbamoyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, C3-C7-cycloalkoxycarbonyl, Ci-Cs- alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, C3-C7-cycloalkylcarbonyloxy, benzyl, phenyl, 5- membered heteroaryl, 6-membered heteroaryl, benzyloxy, or phenyloxy, wherein the benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, benzyloxy and phenyloxy is optionally substituted by one or more group(s) selected from halogen, hydroxyl, cyano, isocyano, amino, sulfanyl, pentafluoro^6-sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkyloxy, Ci-Cs-haloalkyloxy, tri(Ci- C8-alkyl)silyl, C3-C7-cycloalkyl, C2-Cs-alkenyl, and C2-Cs-alkynyl.
R3 more preferably represents halogen, cyano, nitro, carboxaldehyde, hydroxycarbonyl, Ci-C4-alkyl, Ci- C4-haloalkyl, Ci-C4-cyanoalkyl, Ci-C4-alkyloxy, Ci-C4-haloalkyloxy, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-atkylsulfanyl, Ci-C4-haloalkylsulfanyl, C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, aminothiocarbonyl, carbamoyl, Ci-C4-alkoxycarbonyl or Ci- C4-halogenoalkoxycarbonyl.
R3 more preferably represents fluorine, chlorine, bromine, iodine, cyano, nitro, aminothiocarbonyl, Ci- C4-haloalkyl or carbamoyl.
R3 more preferably represents fluorine, chlorine, bromine, iodine, cyano, aminothiocarbonyl or C1-C4- haloalkyl. R3 more preferably represents fluorine, chlorine, bromine, iodine, cyano, aminothiocarbonyl, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, l-chloroethyl, 1- bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or l,l,l-trifluoroprop-2-yl.
R3 more preferably represents fluorine, cyano or CF3.
R3 more preferably represents cyano or CF3.
R3 most preferably represents cyano. R4 is a benzo fused at least partially saturated carbocycle or heterocycle which is represented by formula (Q)
Figure imgf000009_0001
wherein the dotted line A represents a single or double bond and the arrow depicts the bonding position of the shown moiety to the remainder of the molecule.
X5 preferably represents -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -Y-CH2- or -Y-(CH2)2-, wherein Y represents O, S or NY1, wherein Y1 represents hydrogen or methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or fer/-butyl.
X5 more preferably represents -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -O-CH2-, -0-(O¾)2-, -S-CH2- or -S- (CH2)2-.
X5 more preferably represents -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -O-CH2- or -S-CH2-. X5 particularly preferred represents -CH2-, -CH2-CH2-, -CH2-CH2-CH2- or -O-CH2-. ln other words, R4 particularly preferred represents a bicyclic moiety of formulae (Ql) to (Q8)
Figure imgf000010_0001
wherein the arrow depicts the bonding position of the shown moiety to the remainder of the molecule, and X1, X2, X3, and X4 are defined as in formula (Q). X1, X2, X3 and X4 preferably represent independently from each other hydrogen, halogen, nitro, cyano, sulfanyl, pentafluoro^6-sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C3-C8- cycloalkyl, Cs-Cs-halocycloalkyl having 1 to 5 halogen atoms, Ci-Cs-haloalkyl-C3-C7-cycloalkyl, C3- C7-cycloalkenyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C6-Ci2-bicycloalkyl, C3-Cs-cycloalkyl-C2-C8-alkenyl, C3-C8-cycloalkyl-C2-C8-alkynyl, Ci-Cx-alkoxy, Ci-Cx-haloalkoxy having 1 to 5 halogen atoms, Ci- C8-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, Ci -Cx-alky lsulfcnyl, C2-C8-alkenyloxy, C3-C8- alkynyloxy, C3-C6-cycloalkoxy, Ci-Cx-alkylsulfmyl, Ci-Cs-alkylsulfonyl, tri(Ci-C8-alkyl)-silyloxy, tri(Ci-C8-alkyl)-silyl, tri(Ci-C8-alkyl)-silyl-C2-C8-alkynyl, tri(Ci-C8-alkyl)-silyl-C2-C8-alkynyloxy, C6-Ci4-aryl, C6-Ci4-aryloxy, C6-Ci4-arylsulfenyl, 5- or 6-membered heteroaryl, or 5- or 6-membered heteroaryloxy, wherein the C6-Ci4-aryl, C6-Ci4-aryloxy, C6-Ci4-arylsulfenyl, 5- or 6-membered heteroaryl, and 5- or 6-membered heteroaryloxy is non-substituted or substituted by one or more group(s) selected from halogen, cyanosulfanyl, pentafluoro^6-sulfanyl, Ci -Cx-alkyl, Ci-Cx-haloalkyl, Ci-Cx-cyanoalkyl, Ci- C8-alkyloxy, Ci-Cs-haloalkyloxy, tri(Ci-C8-alkyl)silyl, tri(Ci-C8-alkyl)silyl-Ci-C8-alkyl, C3-C7- cycloalkyl, C3-C7-halocycloalkyl, C3-C7-cycloalkenyl, C3-C7-halocycloalkenyl, C4-C10- cycloalkylalkyl, C4-Cio-halocycloalkylalkyl, C6-Ci2-cycloalkylcycloalkyl, Ci-C8-alkyl-C3-C7- cycloalkyl, Ci-C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-C8-alkyl)silyl-C3-C7-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C3-C8-alkynyloxy, C3-C8-haloalkynyloxy, Ci-C8-cyanoalkoxy, C4-C8-cycloalkylalkoxy, C3-C6-cycloalkoxy, Ci -Cx-alky lsulfanyl, Ci-Cs- haloalkylsulfanyl, Ci-Cs-atkylsulfinyl, Ci-Cs-haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs- haloalkylsulfonyl, Ci-Cs-alkylsulfonyloxy, Ci-Cs-haloalkylsulfonyloxy, Ci-Cs-alkoxyalkyl, Ci-Cs- alkylthioalkyl, Ci-Cs-alkoxyalkoxyalkyl, Ci-Cs-haloalkoxyalkyl, benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, 6-membered heteroaryloxy, benzyloxy, phenyloxy, benzylsulfanyl, and phenylsulfanyl.
X1, X2, X3 and X4 more preferably represent independently from each other hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C2-Cs-alkenyl, C2-Cs-alkynyl, C3-C8- cycloalkyl-C2-C8-alkenyl, C3-C8-cycloalkyl-C2-C8-alkynyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy having 1 to 5 halogen atoms, Ce-C aryl, or C6-Ci4-aryloxy, wherein the C6-Ci4-aryl and C6-Ci4-aryloxy is non-substituted or substituted by one or more group(s) selected from halogen, Ci-Cs-atkyl, Ci-Cs- haloalkyl, Ci-Cs-alkyloxy, and Ci-Cs-haloalkyloxy.
X1, X2, X3 and X4 more preferably represent independently from each other hydrogen, fluorine, chlorine, bromine, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4- alkynyl, C3-C6-cycloalkyl-C2-C4-alkenyl, C3-C6-cycloatkyl-C2-C4-atkynyl, Ci-C4-alkoxy, C1-C4- haloalkoxy having 1 to 5 halogen atoms, phenyl, or phenyloxy, wherein the phenyl and phenyloxy is non-substituted or substituted by one or more group(s) selected from fluorine, chlorine, bromine, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkyloxy, and Ci-C4-haloalkyloxy.
X1, X2, X3 and X4 more preferably represent independently from each other hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, CF3, vinyl, cyclopropyl-C2-C4-alkynyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert- butoxy, OCF3, phenyl, or phenyloxy, wherein the phenyl and phenyloxy is non-substituted or substituted by one or more group(s) selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, fer/-butyl, and CF3.
X1, X2, X3 and X4 more preferably represent independently from each other hydrogen, fluorine, chlorine, bromine, cyano, methyl, CF3, vinyl, cyclopropyl-ethynyl, methoxy, OCF3, phenyl, or phenyloxy, wherein the phenyl and phenyloxy is non-substituted or substituted by one or more group(s) selected from fluorine, and chlorine.
X1, X2, X3 and X4 more preferably represent independently from each other hydrogen, fluorine, chlorine, methyl or methoxy.
X1 most preferably represents hydrogen.
X2 most preferably represents hydrogen, fluorine or methyl.
X3 most preferably represents hydrogen or methoxy.
X4 most preferably represents hydrogen, fluorine, chlorine, methyl or methoxy.
In one particular preferred embodiment X1, X2, X3 and X4 all represent hydrogen.
In another particular preferred embodiment X1 represents hydrogen, X2 represents hydrogen or methyl and X3 and/or X4 represent fluorine or chlorine.
The radical definitions and explanations given above in general terms or stated within preferred ranges can, however, also be combined with one another as desired, i.e. including between the particular ranges and preferred ranges. They apply both to the end products and correspondingly to precursors and intermediates. In addition, individual definitions may not apply.
Preference is given to those compounds of formula (I) in which each of the radicals have the abovementioned preferred definitions.
Particular preference is given to those compounds of formula (I) in which each of the radicals have the abovementioned more and/or most preferred definitions.
In preferred embodiments of the present invention
R1 represents 1 -fluorocyclopropyl, l-chlorocyclopropyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5- difluorophenyl or 2,6-difluorophenyl;
R2 represents hydrogen; R3 represents fluorine, cyano or CF3, preferably cyano; and
R4 represents a bicyclic moiety of formulae (Ql) to (Q8)
Figure imgf000013_0001
wherein the arrow depicts the bonding position of the shown moiety to the remainder of the molecule, and X1, X2, X3 and X4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci- C4-alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X1 represents hydrogen, X2 represents hydrogen, fluorine or methyl, X3 represents hydrogen or methoxy and X4 represents hydrogen, fluorine, chlorine, methyl or methoxy. In more preferred embodiments of the present invention
R1 represents 1 -chlorocyclopropyl or 2,4-difluorophenyl;
R2 represents hydrogen;
R3 represents cyano; and
R4 represents a bicyclic moiety of formulae (Ql) to (Q8)
Figure imgf000014_0001
Figure imgf000015_0001
wherein the arrow depicts the bonding position of the shown moiety to the remainder of the molecule, and
X1, X2, X3 and X4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci- C4-alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X1 represents hydrogen, X2 represents hydrogen, fluorine or methyl, X3 represents hydrogen or methoxy and X4 represents hydrogen, fluorine, chlorine, methyl or methoxy.
In most preferred embodiments of the present invention
R1 represents 1 -chlorocyclopropyl; R2 represents hydrogen;
R3 represents cyano; and R4 represents a bicyclic moiety of formulae (Ql) to (Q8)
Figure imgf000016_0001
wherein the arrow depicts the bonding position of the shown moiety to the remainder of the molecule, and X1, X2, X3 and X4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci-
C4-alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X1 represents hydrogen, X2 represents hydrogen, fluorine or methyl, X3 represents hydrogen or methoxy and X4 represents hydrogen, fluorine, chlorine, methyl or methoxy. In the definitions of the symbols given in the above formulae, collective terms were used which are generally representative of the following substituents:
Halogen: fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Halogen- substitution is generally indicated by the prefix halo, halogen or halogeno.
Alkyl: saturated, straight-chain or branched hydrocarbyl radical having 1 to 8, preferably 1 to 6, and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C6-alkyl such as methyl, ethyl, propyl (n-propyl), 1 -methylethyl (iso-propyl), butyl (n-butyl), l-methylpropyl (sec-butyl), 2-methylpropyl (iso butyl), l,l-dimethylethyl (tert-butyl), pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, l-ethylpropyl, l,l-dimethylpropyl, l,2-dimethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3 -methylpentyl, 4-methylpentyl, l,l-dimethylbutyl, l,2-dimethylbutyl, l,3-dimethylbutyl,
2.2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, l,l,2-trimethylpropyl,
1.2.2-trimethylpropyl, 1 -ethyl- l-methylpropyl and 1 -ethyl-2-methylpropyl. Particularly, said group is a Ci- C4-alkyl group, e.g. a methyl, ethyl, propyl, 1 -methylethyl (isopropyl), butyl, l-methylpropyl (sec-butyl), 2- methylpropyl (iso-butyl) or l, l-dimethylethyl (tert-butyl) group. This definition also applies to alkyl as part of a composite substituent, for example cycloalkylalkyl, hydroxyalkyl etc., unless defined elsewhere like, for example, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, haloalkyl or haloalkylsulfanyl.
Alkenyl: unsaturated, straight-chain or branched hydrocarbyl radicals having 2 to 8, preferably 2 to 6, and more preferably 2 to 4 carbon atoms and one double bond in any position, for example (but not limited to) C2-C6-alkenyl such as vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, isopropenyl, homoallyl, (E)-but-2- enyl, (Z)-but-2-enyl, (E)-but- 1 -enyl, (Z)-but-l-enyl, 2-methylprop-2-enyl, 1 -methylprop-2-enyl, 2- methylprop- 1 -enyl, (E)-l-methylprop-l-enyl, (Z)-l-methylprop-l-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)- pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-l-enyl, (Z)-pent-l-enyl, 3- methylbut-3-enyl, 2- methylbut-3-enyl, l-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2- enyl, (E)- 1 -methylbut-2-enyl, (Z)-l- methylbut-2-enyl, (E)-3-methylbut-l-enyl, (Z)-3-methylbut-l-enyl, (E)-2- methylbut-l-enyl, (Z)-2-methylbut-l-enyl, (E)-l-methylbut-l-enyl, (Z)-l- methylbut-l-enyl, 1,1- dimethylprop-2-enyl, l-ethylprop-l-enyl, 1 -propylvinyl, 1- isopropylvinyl, (E)-3,3-dimethylprop-l-enyl, (Z)-3,3-dimethylprop-l-enyl, hex-5-enyl, (E)-hex-4- enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-l-enyl, (Z)-hex-l-enyl, 4-methylpent-4-enyl, 3-methylpent-4-enyl, 2-methylpent-4-enyl, 1- methylpent-4-enyl, 4-methylpent-3-enyl, (E)-3-methylpent-3-enyl, (Z)-3- methylpent-3-enyl, (E)-2-methylpent-3-enyl, (Z)-2-methylpent-3-enyl, (E)-l- methylpent-3-enyl, (Z)-l - methylpent-3-enyl, (E)-4-methylpent-2-enyl, (Z)-4- methylpent-2-enyl, (E)-3-methylpent-2-enyl, (Z)-3- methylpent-2-enyl, (E)-2- methylpent-2-enyl, (Z)-2-methylpent-2-enyl, (E)-l -methylpent-2-enyl, (Z)-l- methylpent-2-enyl, (E)-4-methylpent- 1 -enyl, (Z)-4-methylpent-l-enyl, (E)-3- methylpent-l-enyl, (Z)-3- methylpent-l -enyl, (E)-2-methylpent- 1 -enyl, (Z)-2- methylpent-l-enyl, (E)-l -methylpent-l-enyl, (Z)-l- methylpent-l-enyl, 3-ethylbut- 3-enyl, 2-ethylbut-3-enyl, l-ethylbut-3-enyl, (E)-3-ethylbut-2-enyl, (Z)-3- ethylbut-2-enyl, (E)-2-ethylbut-2-enyl, (Z)-2-ethylbut-2-enyl, (E)- 1 -ethylbut-2-enyl, (Z)- 1 -ethylbut-2-enyl, (E)-3-ethylbut-l-enyl, (Z)-3-ethylbut-l-enyl, 2-ethylbut-l-enyl, (E)-l-ethylbut-l-enyl, (Z)-l-ethylbut-l- enyl, 2-propylprop-2-enyl, 1 -propylprop-2- enyl, 2-isopropylprop-2-enyl, 1 -isopropylprop-2-enyl, (E)-2- propylprop- 1 -enyl, (Z)- 2-propylprop-l-enyl, (E)-l-propylprop-l-enyl, (Z)-l-propylprop-l-enyl, (E)-2- isopropylprop-l-enyl, (Z)-2-isopropylprop- 1 -enyl, (E)-l-isopropylprop-l-enyl, (Z)-l- isopropylprop- 1 - enyl, 1 -(1 , 1 -dimethylethyl)ethenyl, buta- 1 ,3-dienyl, penta- 1 ,4-dienyl, hexa- 1 ,5-dienyl or methylhexadienyl. Particularly, said group is vinyl or allyl. This definition also applies to alkenyl as part of a composite substituent, for example haloalkenyl etc., unless defined elsewhere.
Alkynyl: straight-chain or branched hydrocarbyl groups having 2 to 8, preferably 2 to 6, and more preferably 2 to 4 carbon atoms and one triple bond in any position, for example (but not limited to) Ck-CVralkynyl, such as ethynyl, prop-l-ynyl, prop-2 -ynyl, but-l-ynyl, but-2-ynyl, but-3-ynyl, 1 -methylprop-2-ynyl, pent-l-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, 2-methylbut-3-ynyl, 1 -methylbut-3-ynyl, l-methylbut-2-ynyl, 3- methylbut-l-ynyl, 1 -ethylprop-2-ynyl, hex-l-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 3- methylpent-4-ynyl, 2-methylpent-4-ynyl, 1 -methylpent-4-ynyl, 2-methylpent-3-ynyl, l-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1 -methylpent-2-ynyl, 4-methylpent-l-ynyl, 3-methylpent-l-ynyl, 2-ethylbut-3-ynyl, l-ethylbut-3-ynyl, 1 -ethylbut-2-ynyl, 1 -propylprop-2-ynyl, 1 -isopropylprop-2-ynyl, 2,2-dimethylbut-3- ynyl, l,l-dimethylbut-3-ynyl, l,l-dimethylbut-2-ynyl, or 3,3-dimethylbut-l-ynyl group. Particularly, said alkynyl group is ethynyl, prop-l-ynyl, or prop-2-ynyl. This definition also applies to alkynyl as part of a composite substituent, for example haloalkynyl etc., unless defined elsewhere.
Alkoxy: saturated, straight-chain or branched alkoxy radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C6-alkoxy such as methoxy, ethoxy, propoxy, 1 -methylethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1- methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1- dimethylpropoxy, 1,2-dimethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4- methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2- trimethylpropoxy, 1 -ethyl- 1 -methylpropoxy and l-ethyl-2-methylpropoxy. This definition also applies to alkoxy as part of a composite substituent, for example haloalkoxy, alkynylalkoxy, etc., unless defined elsewhere.
Alkoxycarbonyl: an alkoxy group which has 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms (as specified above) and is bonded to the skeleton via a carbonyl group (-C(=0)-). This definition also applies to alkoxycarbonyl as part of a composite substituent, for example cycloalkylalkoxycarbonyl etc., unless defined elsewhere.
Alkylsulfanyl: saturated, straight-chain or branched alkylsulfanyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C6-alkylsulfanyl such as methylsulfanyl, ethylsulfanyl, propylsulfanyl, 1-methylethylsulfanyl, butylsulfanyl, 1-methylpropyl- sulfanyl, 2-methylpropylsulfanyl, l,l-dimethylethylsulfanyl, pentylsulfanyl, l-methylbutylsulfanyl, 2- methylbutylsulfanyl, 3-methylbutylsulfanyl, 2,2-dimethylpropylsulfanyl, 1 -ethylpropylsulfanyl, 1,1- dimethylpropylsulfanyl, 1 ,2-dimethylpropylsulfanyl, hexylsulfanyl, 1 -methylpentylsulfanyl, 2- methylpentylsulfanyl, 3 -methylpentylsulfanyl, 4-methylpentylsulfanyl, l, l-dimethylbutylsulfanyl, 1,2- dimethylbutylsulfanyl, 1 ,3-dimethylbutylsulfanyl, 2,2-dimethylbutylsulfanyl, 2,3-dimethylbutylsulfanyl,
3.3-dimethylbutylsulfanyl, l-ethylbutylsulfanyl, 2-ethylbutylsulfanyl, l, l,2-trimethylpropylsulfanyl, 1,2,2- trimethylpropylsulfanyl, 1 -ethyl- l-methylpropylsulfanyl and 1 -ethyl-2-methylpropylsulfanyl. This definition also applies to alkylsulfanyl as part of a composite substituent, for example haloalkylsulfanyl etc., unless defined elsewhere.
Alkylsulfinyl: saturated, straight-chain or branched alkylsulfinyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C6-alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1 -methylethylsulfinyl, butylsulfinyl, l-methylpropylsulfinyl, 2-methylpropylsulfinyl, l,l-dimethylethylsulfinyl, pentylsulfinyl, 1 -methylbutylsulfinyl, 2- methylbutylsulfinyl, 3 -methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1 -ethylpropylsulfinyl, 1,1- dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, hexylsulfinyl, 1 -methylpentylsulfinyl, 2-methylpentyl- sulfinyl, 3 -methylpentylsulfinyl, 4-methylpentylsulfinyl, l,l-dimethylbutylsulfinyl, 1 ,2-dimethyl- butylsulfinyl, l,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3- dimethylbutylsulfinyl, 1 -ethylbutylsulfinyl, 2-ethylbutylsulfinyl, l,l,2-trimethylpropylsulfinyl, 1,2,2- trimethylpropylsulfinyl, 1 -ethyl- 1 -methylpropylsulfinyl and 1 -ethyl-2-methylpropylsulfinyl. This definition also applies to alkylsulfinyl as part of a composite substituent, for example haloalkylsulfinyl etc., unless defined elsewhere.
Alkylsulfonyl: saturated, straight-chain or branched alkylsulfonyl radicals having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, for example (but not limited to) Ci-C6-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropyl- sulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1 -methylbutylsulfonyl, 2- methylbutylsulfonyl, 3 -methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1 -ethylpropylsulfonyl, 1,1- dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methyl- pentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2- dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl,
3.3-dimethylbutylsulfonyl, 1 -ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2- trimethylpropylsulfonyl, 1 -ethyl- 1 -methylpropylsulfonyl and l-ethyl-2-methylpropylsulfonyl. This definition also applies to alkylsulfonyl as part of a composite substituent, for example alkylsulfonylalkyl etc., unless defined elsewhere.
Monoalkylamino represents an amino radical having one alkyl residue with 1 to 4 carbon atoms attached to the nitrogen atom. Non-limiting examples include methylamino, ethylamino, n-propylamino, isopropyl- amino, n-butylamino and tert-butylamino. Dialkylamino represents an amino radical having two independently selected alkyl residues with 1 to 4 carbon atoms each attached to the nitrogen atom. Non-limiting examples include /V, /V- d i m c t h y 1 a m i n o , /V,/V- diethyl ami no, /V, /V- d i i s o p ro py 1 a m i n o , /V- c t h y 1 - /V- m c t h y 1 a m i n o , /V- m c t h y 1 - /V- n - p r o py 1 a m i n o , /V-iso- p ro p y 1 - /V- n - p ro p y 1 a m i n o and /V- 1 c rt - b u t y 1 - /V- m c t h y 1 a m i n o .
Cycloalkyl: monocyclic, saturated hydrocarbyl groups having 3 to 10, preferably 3 to 8 and more preferably
3 to 6 carbon ring members, for example (but not limited to) cyclopropyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as part of a composite substituent, for example cycloalkylalkyl etc., unless defined elsewhere.
Cycloalkenyl: monocyclic, partially unsaturated hydrocarbyl groups having 3 to 10, preferably 3 to 8 and more preferably 3 to 6 carbon ring members, for example (but not limited to) cyclopropenyl, cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as part of a composite substituent, for example cycloalkenylalkyl etc., unless defined elsewhere.
Cycloalkoxy: monocyclic, saturated cycloalkyloxy radicals having 3 to 10, preferably 3 to 8 and more preferably 3 to 6 carbon ring members, for example (but not limited to) cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as part of a composite substituent, for example cycloalkoxyalkyl etc., unless defined elsewhere.
Haloalkyl: straight-chain or branched alkyl groups having 1 to 8, preferably 1 to 6 and more preferably 1 to
4 carbon atoms (as specified above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as specified above, for example (but not limited to) Ci-C3-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and l, l , l-trifluoroprop-2-yl. This definition also applies to haloalkyl as part of a composite substituent, for example haloalkylaminoalkyl etc., unless defined elsewhere.
Haloalkenyl and haloalkynyl are defined analogously to haloalkyl except that, instead of alkyl groups, alkenyl and alkynyl groups are present as part of the substituent.
Haloalkoxy: straight-chain or branched alkoxy groups having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms (as specified above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as specified above, for example (but not limited to) Ci-C3-haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoro- ethoxy and l,l,l-trifluoroprop-2-oxy. This definition also applies to haloalkoxy as part of a composite substituent, for example haloalkoxyalkyl etc., unless defined elsewhere.
Haloalkylsulfanyl: straight-chain or branched alkylsulfanyl groups having 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms (as specified above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as specified above, for example (but not limited to) Ci-C3-haloalkylsulfanyl such as chloromethylsulfanyl, bromomethylsulfanyl, dichloromethylsulfanyl, trichloromethylsulfanyl, fluoromethylsulfanyl, difluoromethylsulfanyl, trifluoromethylsulfanyl, chlorofluoromethylsulfanyl, dichlorofluoromethylsulfanyl, chlorodifluoromethylsulfanyl, 1 -chloroethylsulfanyl, 1 -bromoethylsulfanyl, l-fluoroethylsulfanyl, 2-fluoroethylsulfanyl, 2,2-difluoroethylsulfanyl, 2,2,2-trifluoroethylsulfanyl, 2- chloro-2-fluoroethylsulfanyl, 2-chloro-2,2-difluoroethylsulfanyl, 2,2-dichloro-2-fluoroethylsulfanyl, 2,2,2- trichloroethylsulfanyl, pentafluoroethylsulfanyl and l,l,l-trifluoroprop-2-ylsulfanyl. This definition also applies to haloalkylsulfanyl as part of a composite substituent, for example haloalkylsulfanylalkyl etc., unless defined elsewhere.
Aryl: mono-, bi- or tricyclic aromatic or partially aromatic group having 6 to 14 carbon atoms, for example (but not limited to) phenyl, naphthyl, tetrahydronapthyl, indenyl and indanyl. The binding to the superordinate general structure can be carried out via any possible ring member of the aryl residue. Aryl is preferably selected from phenyl, 1 -naphthyl and 2-naphthyl. Phenyl is particularly preferred.
Heteroaryl: 5 or 6-membered cyclic aromatic group containing at least 1, if appropriate also 2, 3, 4 or 5 heteroatoms, wherein the heteroatoms are each selected independently of one another from the group S, N and O, and which group can also be part of a bi- or tricyclic system having up to 14 ring members, wherein the ring system can be formed with one or two further cycloalkyl, cycloalkenyl, heterocyclyl, aryl and/or heteroaryl residues and wherein benzofused 5 or 6-membered heteroaryl groups are preferred. The binding to the superordinate general structure can be carried out via any possible ring member of the heteroaryl residue. Examples of 5-membered heteroaryl groups which are attached to the skeleton via one of the carbon ring members are fur-2-yl, fur-3-yl, thien-2-yl, thien-3-yl, pyrrol-2-yl, pyrrol-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, imidazol-2-yl, imidazole-4-yl, l,2,4-oxadiazol-3-yl, l,2,4-oxadiazol-5-yl, l,2,4-thiadiazol-3-yl, l,2,4-thiadiazol-5-yl, l,2,4-triazol-3-yl, l,3,4-oxadiazol-2-yl, l,3,4-thiadiazol-2-yl and l,3,4-triazol-2-yl. Examples of 5- membered heteroaryl groups which are attached to the skeleton via a nitrogen ring member are pyrrol- 1-yl, pyrazol-l-yl, 1,2,4-triazol-l-yl, imidazol-l-yl, 1,2,3-triazol-l-yl and 1,3,4-triazol-l-yl. Examples of 6- membered heteroaryl groups are pyridine-2-yl, pyridine-3 -yl, pyridine-4-yl, pyridazin-3-yl, pyridazin-4- yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazine-2-yl, l,3,5-triazin-2-yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl. Examples of benzofused 5-membered heteroaryl groups are indol-l-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-l-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-l-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1 -benzofuran-2-yl, l-benzofuran-3-yl, l-benzofuran-4-yl, l-benzofuran-5-yl, 1- benzofuran-6-yl, l-benzofuran-7-yl, l-benzothiophen-2-yl, l-benzothiophen-3-yl, 1 -benzothiophen-4-yl, 1- benzothiophen-5-yl, 1 -benzothiophen-6-yl, l-benzothiophen-7-yl, l,3-benzothiazol-2-yl, l,3-benzothiazol-
4-yl, l,3-benzothiazol-5-yl, l,3-benzothiazol-6-yl, l,3-benzothiazol-7-yl, l,3-benzoxazol-2-yl, 1,3- benzoxazol-4-yl, l,3-benzoxazol-5-yl, l,3-benzoxazol-6-yl and l,3-benzoxazol-7-yl. Examples of benzofused 6-membered heteroaryl groups are quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-l-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-
5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl. Further examples of 5- or 6-membered heteroaryls which are part of a bicyclic ring system are l,2,3,4-tetrahydroquinolin-l-yl, 1 ,2,3,4- tetrahydroquinolin-2-yl, l,2,3,4-tetrahydroquinolin-7-yl, 1 ,2,3,4-tetrahydroquinolin-8-yl, 1 ,2,3,4- tetrahydroisoquinolin-l-yl, l,2,3,4-tetrahydroisoquinolin-2-yl, l,2,3,4-tetrahydroisoquinolin-5-yl, 1 ,2,3,4- tetrahydroisoquinolin-6-yl and l,2,3,4-tetrahydroisoquinolin-7-yl. This definition also applies to heteroaryl as part of a composite substituent, for example heteroarylalkyl etc., unless defined elsewhere.
Heterocyclyl: three- to seven-membered, saturated or partially unsaturated heterocyclic group containing at least one, if appropriate up to four heteroatoms and/or heterogroups independently selected from the group consisting of N, O, S, S(=0), S(=0)2 and di-(Ci-C4)alkylsilyl, which group can be benzofused. The binding to the superordinate general structure can be carried out via a ring carbon atom or, if possible, via a ring nitrogen atom of the heterocyclic group. Saturated heterocyclic groups in this sense are for example (but not limited to) oxiranyl, aziridinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin- 5-yl, oxazolidin-2-yl, oxazolidin-4-yl, oxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-4-yl, thiazolidin-5-yl, imidazolidin-2-yl, imidazolidin-4-yl, l,2,4-oxadiazolidin-3-yl, l,2,4-oxadiazolidin-5-yl, 1,3,4- oxadiazolidin-2-yl, l,2,4-thiadiazolidin-3-yl, l,2,4-thiadiazolidin-5-yl, l,3,4-thiadiazolidin-2-yl, 1,2,4- triazolidin-3-yl, l,3,4-triazolidin-2-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, l,3-dioxan-5-yl, tetrahydropyran-2-yl, tetrahydropyran-4-yl, tetrahydrothien-2-yl, hexahydropyridazin-3-yl, hexa- hydropyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-2-yl, l,3,5-hexahydrotriazin-2-yl and l,2,4-hexahydrotriazin-3-yl. Partially unsaturated heterocyclic groups in this sense are for example (but not limited to) 2,3 -dihydro fur-2-yl, 2,3 -dihydro fur- 3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4- dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4- yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4- isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3- isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-l-yl, 2,3-dihydropyrazol-2-yl, 2,3- dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-l-yl, 3,4- dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-l-yl, 4,5- dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3- dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4- dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4- dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl. Examples of benzofused heterocyclic groups are indolin-l- yl, indolin-2-yl, indolin-3-yl, isoindolin-l-yl, isoindolin-2-yl, 2,3-dihydrobenzofuran-2-yl and 2,3- dihydrobenzofuran-3-yl. This definition also applies to heterocyclyl as part of a composite substituent, for example heterocyclylalkyl etc., unless defined elsewhere.
Oxo represents a doubly bonded oxygen atom.
Thiooxo represents a doubly bonded sulfur atom.
Optionally substituted groups may be mono- or polysubstituted, where the substituents in the case of polysubstitutions may be identical or different.
Not included are combinations which are against natural laws and which the person skilled in the art would therefore exclude based on his/her expert knowledge. Ring structures having three or more adjacent oxygen atoms, for example, are excluded.
Isomers
Depending on the nature of the substituents, the compounds of the invention may be present in the form of different stereoisomers. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixture of these isomers. Where a compound can be present in two or more tautomer forms in equilibrium, reference to the compound by means of one tautomeric description is to be considered to include all tautomer forms.
Illustration of the processes and intermediates
The present invention is furthermore related to processes for preparing compounds of formula (I). The present invention furthermore relates to intermediates such as compounds of formula (VI) and the preparation thereof.
The compounds (I) can be obtained by various routes in analogy to prior art processes known (see e.g. J. Agric. Food Chem. (2009) 57, 4854-4860; EP-A 0 275 955; DE-A 40 03 180; EP-A 0 1 13 640; EP-A 0 126 430; WO-A 2013/007767; WO 2016/156290 Al ; and references cited in those documents) and by synthesis routes shown schematically below and in the experimental part of this application. Unless indicated otherwise, the radicals X1, X2, X3, X4, X5, R1, R2, R3 and R4 and the bond A have the meanings given above for the compounds of formula (I). These definitions apply not only to the end products of the formula (I) but likewise to all intermediates. If individual compounds (I) cannot be obtained by those routes, they can be prepared by derivatization of other compounds (I).
Only for better understanding of the following schemes the alcohols of formula (I) (R2 = H), wherein the dotted line A represents a double bond, have been denominated as alcohols (I-Ha) and the alcohols of formula (I) (R2 = H), wherein the dotted line A represents a single bond, as alcohols (I-Hb), although such alcohols (I-Ha) and (I-Hb) are encompassed by general formula (I) as defined above. To additionally assist understanding of the following schemes, compounds of formula (I), wherein the dotted line A represents a double bond, have been denominated as compounds of formula (la), and compounds of formula (I), wherein the dotted line A represents a single bond, have been denominated as compounds of formula (lb), although such compounds of formula (la) and (lb) are encompassed by the general formula (I) as defined above.
Process A (Scheme 1):
Figure imgf000024_0001
Figure imgf000025_0001
The ketones (II), which are either commercially available or prepared using methods known to a person skilled in the art, can be converted to vinyl halides (III) using methods described in the literature (see: ./. Org. Chern. 2007, 72, 2216-2219; Org. Lett. 2015, 17, 18-21), including classical methods such as the reaction with PBr3 or POCI3 in a suitable inert solvent, including but not limited to: dichloromethane, 1,2- dichloroethane or toluene (Scheme 1 ). The vinyl halides (III) can be reacted either with metals (e.g. lithium, magnesium or zinc, in an appropriate form such as metallic powder or turnings) or with alkylmetal reagents (such as e.g. solutions of methyllithium, n-butyllithium, phenyllithium, s-butyllithium, ter/.-butyllithium or isopropylmagnesium halide, with or without added salts such as lithium chloride) and subsequently reacted with ketones (IV), optionally in the presence of added salts such as lithium chloride preferably under anhydrous conditions to obtain compounds of the general formula (I-Ha). Depending on the carbonyl substrate, it can be advantageous to perform an intermediate transmetalation step with e.g. trialkoxyzirconium(IV) or trialkoxytitanium(IV) chloride [see e.g. Weidmann, Seebach, Angew. Chem. Int. Ed. 1983, 22(1), 31-45], cerium(III) trichloride [see e.g. Imamoto el al., J. Am. Chem. Soc. 1989, 1 11 (12), pp 4392-4398], lanthanum(III) trichloride [see e.g. Krasovskiy et al, Angew. Chem. Int. Ed. 2006, 45(3), 497-500], magnesium(II) dichloride [see e.g. Metzger et al, Angew. Chem. Int. Ed. 2010, 49(27), 4665- 4668], zinc(II) dichloride [see e.g. Hatano et al., J. Org. Chem. 2010, 75(15), 5008-5016], or manganese(II) dichloride [see e.g. Quinio et al, Synlett 2015, 26(04), 514-518]
As the solvent, all common solvents inert under the reaction conditions, such as for example ethers (such as e.g. diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran), dichloromethane, or mixtures thereof can be used and the reaction can be effected in mixtures of two or more of these solvents.
The reaction is preferably performed at temperatures between -78 °C and refluxing temperature of the solvent, more preferably between -78 °C and 25 °C.
By derivatization of an alcohol (I-Ha) with an alkylating agent R2a-LG' compounds of the general formula (la) can be obtained. LG1 is a replaceable group as listed in scheme 1 above, particularly preferred Br, I and methylsulfonyloxy. These derivatizations are optionally performed in the presence of a base such as NaH and in the presence of an organic solvent such as tetrahydrofuran.
Process B (Scheme 2):
Figure imgf000026_0001
Hydrazones of the general structure (VI) can be prepared by reacting ketones (II) and hydrazines (V) in an inert reaction solvent, preferably alcohols such as methanol, ethanol or isopropanol, or hydrocarbon solvents such as benzene or toluene, in analogy to various known methods, optionally in the presence of a dehydrating agent and/or acid, including but not limited to: activated molecular sieves, anhydrous inorganic salts such as magnesium sulphate or sodium sulphate, titanium(IV) oxides, such as titanium tetraethoxide or titanium tetraisopropoxide, toluenesulphonic acid, phosphoric acid or thionyl chloride. A reaction apparatus able to sequester water may also be used, such as a Dean Stark trap or a Soxhlet apparatus. The hydrazones (VI) can be reacted with an appropriate base, such as an alkyllithium (see: Org. Lett. 2013, 15, 3894-3897, including methyllithium, n-butyllithium, s-butyllithium, fer/.-butyllithium, phenyllithium, lithium amides such as lithium diisopropyl amide, lithium tetramethylpiperidine, alkylmagnesium reagents (see: Org. Lett. 2012, 14, 2250-2253) including Grignard reagents such as isopropylmagnesium halides, using methods known to a person skilled in the art as the Shapiro Reaction, with or without added salts such as lithium chloride) and subsequently reacted with ketones (IV), optionally in the presence of added salts such as lithium chloride, preferably under anhydrous conditions to obtain compounds of the general formula (I-Ha). Depending on the carbonyl substrate, it can be advantageous to perform an intermediate transmetalation step using methods described for process step (III) (I-Ha) shown in scheme 1 above. As the solvent, all common solvents inert under the reaction conditions, such as for example ethers (such as e.g. diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran), dichloromethane, or mixtures thereof can be used and the reaction can be effected in mixtures of two or more of these solvents.
The reaction is preferably performed at temperatures between -78 °C and refluxing temperature of the solvent, more preferably between -78 °C and 25 °C. By derivatization of alcohol (I-Ha) with an alkylating agent R2a-LG' compounds of the general formula (la) can be obtained as described above for process A (scheme 1).
Process C (Scheme 3):
Figure imgf000027_0001
Vinyl alcohols (I-Ha) may be converted to alcohols (I-Hb) using methods known to a person skilled in the art for carbon-carbon double bond reduction, such as hydrogenation using a metal catalyst, including palladium, platinum, rhodium, iridium, cobalt metals or salts thereof, optionally under pressure of hydrogen, or using a transfer hydrogenation reagent, such as cyclohexadiene, an alkyl silane such as triethylsilane or polymethylhydrosiloxane or similar, or by reaction with diimidc (sec: .!. Org. Chem. 2009, 74, 3186-3188; Org. Lett. 2010, 12, 5418-5421) or by hydroboration and subsequent deboronation.
As the solvent, all common solvents inert under the reaction conditions, such as for example ethers (such as e.g. diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran), ethyl acetate, or mixtures thereof can be used and the reaction can be effected in mixtures of two or more of these solvents.
The reaction is preferably performed at temperatures between 0 °C and refluxing temperature of the solvent, more preferably between 25 °C and 100 °C.
By derivatization of alcohol (I-Hb) with an alkylating agent R2a-LG' compounds of the general formula (lb) can be obtained in analogy to the procedure described above for process A (scheme 1).
General
The processes A to C according to the invention are optionally performed using one or more reaction auxiliaries.
Useful reaction auxiliaries are, as appropriate, inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogencarbonates, hydrides, hydroxides or alkoxides, for example sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or calcium hydrogencarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; and also basic organic nitrogen compounds, for example trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethylpyridine, 5-ethyl-2-methylpyridine, 4-dimethylaminopyridine, N-methylpiperidine, l,4-diazabicyclo[2.2.2]-octane (DABCO), 1,5- diazabicyclo[4.3.0]-non-5-ene (DBN) or l,8-diazabicyclo[5.4.0]-undec-7-ene (DBU). Useful reaction auxiliaries are, as appropriate, inorganic or organic acids. These preferably include inorganic acids, for example hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulphuric acid, phosphoric acid and nitric acid, and acidic salts such as NaHSCri and KHSO4, or organic acids, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono- or diunsaturated C6-C20 fatty acids, alkylsulphuric monoesters, alkylsulphonic acids (sulphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulphonic acids or aryldisulphonic acids (aromatic radicals, such as phenyl and naphthyl, which bear one or two sulphonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which bear one or two phosphonic acid radicals), where the alkyl and aryl radicals may bear further substituents, for example p- toluenesulphonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.
The processes A to C are optionally performed using one or more diluents. Useful diluents are virtually all inert organic solvents. Unless otherwise indicated for the above described processes, these preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether, dibutyl ether and methyl tert-butyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, for example acetonitrile and propionitrile, amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylenesulphone and hexamethylphosphoramide and DMPU.
In the processes outlined above, the reaction temperatures can be varied within a relatively wide range. In general, the temperatures employed are between -78°C and 250°C, preferably temperatures between -78°C and 150°C.
The reaction time varies as a function of the scale of the reaction and of the reaction temperature, but is generally between a few minutes and 48 hours.
The processes are generally performed under standard pressure. However, it is also possible to work under elevated or reduced pressure.
For performance of the processes, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the components used in each case in a relatively large excess. After a reaction has ended, the compounds are optionally separated from the reaction mixture by one of the customary separation techniques. If necessary, the compounds are purified by recrystallization or chromatography.
If appropriate, in the processes A to C also salts and/or N-oxides of the starting compounds can be used.
Particular suitable intermediates are compounds of formula (VI)
Figure imgf000030_0001
wherein
X1, X2, X3, X4 and X5 are defined as in formula (I) and
R5 represents Ci-Cs-alkyl, C6-Ci4-aryl or 5- or 6-membered heteroaryl, wherein the Ci-Cs-alkyl may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra as defined in formula (I), and the C6-Ci4-aryl and 5- or 6-membered heteroaryl groups may carry 1, 2, 3, 4, 5 or up to the maximum number of groups Rb as defined in formula (I).
The preferred, more preferred and most preferred definitions of X1, X2, X3, X4 and X5given with regard to formula (I) apply mutatis mutandis.
R5 preferably represents Ci-C4-alkyl or C6-Ci4-aryl, wherein the Ci-C4-alkyl group may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, C3-C6-cycloalkyl, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and wherein the C6-Ci4-aryl moiety may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups Rb which independently of one another are selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
R5 more preferably represents Ci-C4-alkyl or phenyl, wherein the Ci-C4-alkyl group may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, C3-C6-cycloalkyl, phenyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, and wherein the phenyl moiety may carry 1 , 2, 3, 4, 5 or up to the maximum number of identical or different groups Rb which independently of one another are selected from halogen, CN, nitro, Ci- C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
R5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups Rb which independently of one another are selected from halogen, CN, nitro, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy.
R5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups Rb which independently of one another are selected from fluorine, chlorine, bromine, iodine, CN, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
R5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2 or 3 identical or different groups Rb which independently of one another are selected from fluorine, chlorine, bromine, iodine, CN, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
R5 more preferably represents phenyl, wherein the phenyl moiety may carry 1, 2 or 3 identical or different groups Rb which independently of one another are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
R5 more preferably represents phenyl, substituted by 1 , 2 or 3, preferably 3, identical or different groups Rb which independently of one another are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl.
R5 more preferably represents phenyl, substituted by 1 , 2 or 3, preferably 3, identical or different groups Rb which independently of one another are selected from methyl, ethyl, n-propyl and isopropyl.
R5 most preferably represents 2,4,6-triisopropylphenyl.
Preference is given to those compounds of formula (VI) in which each of the radicals have the abovementioned preferred definitions.
Particular preference is given to those compounds of formula (VI) in which each of the radicals have the abovementioned more and/or most preferred definitions. In other words preference and particular preference is given to those compounds of formula (VI), wherein
X5 represents -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -O-CH2-, -0-(CH2)2-, -S-CH2- or -S-(CH2)2-, preferably -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -O-CH2- or -S-CH2-, more preferably -CH2-, -CH2-CH2-, -CH2-CH2-CH2- or -O-CH2-,
X1, X2, X3 and X4 represent independently from each other hydrogen, fluorine, chlorine, bromine, C1-C4- alkyl or Ci-C4-alkoxy, preferably hydrogen, fluorine, chlorine, methyl or methoxy, more preferably X1 represents hydrogen, X2 represents hydrogen, fluorine or methyl, X3 represents hydrogen or methoxy and X4 represents hydrogen, fluorine, chlorine, methyl or methoxy, and
R5 represents phenyl, substituted by 1, 2 or 3, preferably 3, identical or different groups Rb which independently of one another are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. -butyl, preferably represents phenyl, substituted by 1, 2 or 3, preferably 3, identical or different groups Rb which independently of one another are selected from methyl, ethyl, n-propyl and isopropyl, more preferably represents 2,4,6-triisopropylphenyl.
Salts
Depending on the nature of the substituents, the compounds of the invention and intermediates thereof may be present in the form of the free compound and/or an agriculturally acceptable salt thereof. The term“agriculturally acceptable salt” refers to a salt of a compound of the invention with acids or bases which are agriculturally acceptable.
Depending on the nature of the substituents defined above, the compounds of formula (I) and intermediates thereof may have acidic or basic properties and can form salts, if appropriate also inner salts, or adducts with inorganic or organic acids or with bases or with metal ions. If the compounds carry amino, alkylamino or other groups which induce basic properties, these compounds can be reacted with acids to give salts, or they are directly obtained as salts in the synthesis. If the compound carries hydroxyl, carboxyl or other groups which induce acidic properties, these compounds can be reacted with bases to give salts. Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines having (Ci-C4)-alkyl groups, mono-, di- and trialkanolamines of (Ci-C4)-alkanols, choline and also chlorocholine.
The salts obtainable in this manner also have fungicidal properties.
Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulphuric acid, phosphoric acid and nitric acid, and acidic salts, such as NaHS04 and KHSO4. Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, maleic acid, fumaric acid, tartaric acid, sorbic acid oxalic acid, alkylsulphonic acids (sulphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulphonic acids or aryldisulphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulphonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphonic acid radicals), where the alkyl and aryl radicals may carry further substituents, for example p- toluenesulphonic acid, 1,5-naphthalenedisulphonic acid, salicylic acid, p-aminosalicylic acid, 2- phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.
Suitable metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminium, tin and lead, and also of the first to eighth transition group, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to the metal ions of the elements of the fourth period. Here, the metals can be present in various valencies that they can assume.
The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary methods for forming salts, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and be isolated in a known manner, for example by filtration, and, if required, be purified by washing with an inert organic solvent.
Suitable anions of the salts are those which are preferably derived from the following acids: hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulphuric acid.
The metal salt complexes of compounds of the formula (1) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (1). Metal salt complexes can be isolated in a known manner, for example by filtration, and, if required, be purified by recrystallization.
Salts of the intermediates can also be prepared according to the processes mentioned above for the salts of compounds of formula (1).
N-oxides of compounds of the formula (1) or intermediates thereof can be obtained in a simple manner by customary processes, for example by N-oxidation with hydrogen peroxide (H2O2), peracids, for example peroxy sulfuric acid or peroxy carboxylic acids, such as meta-chloroperoxybenzoic acid or peroxymonosulfuric acid (Caro's acid).
Crystalline Form The compound of the invention may exist in multiple crystalline and/or amorphous forms. Crystalline forms include unsolvated crystalline forms, solvates and hydrates.
Compositions /Formulations
The present invention further relates to compositions for controlling harmful microorganisms, preferably for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I) and at least one carrier and/or surfactant. The compositions may be applied to the microorganisms and/or in their habitat.
A carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert. The carrier generally improves the application of the compounds, for instance, to plants, plants parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates. Examples of typically useful solid carriers for preparing granules include, but are not limited to crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof. Examples of suitable solvents include polar and nonpolar organic chemical liquids, for example from the classes of aromatic and nonaromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyols (which may optionally also be substituted, etherified and/or esterified, such as butanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide). The carrier may also be a liquefied gaseous extender, i.e. liquid which is gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide. The amount of carrier typically ranges from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99% by weight of the composition.
The surfactant can be an ionic (cationic or anionic) or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s) and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols and derivatives of compounds containing sulfates, sulfonates, phosphates (for example, alkylsulfonates, alkyl sulfates, arylsulfonates) and protein hydrolysates, lignosulfite waste liquors and methylcellulose. A surfactant is typically used when the compound of the invention and/or the carrier is insoluble in water and the application is made with water. Then, the amount of surfactants typically ranges from 5 to 40% by weight of the composition.
The composition may comprise at least one other suitable auxiliary.
Further examples of suitable auxiliaries include water repellents, siccatives, binders (adhesive, tackifier, fixing agent, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone and tylose), thickeners, stabilizers (e.g. cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability), dyes or pigments (such as inorganic pigments, e.g. iron oxide, titanium oxide and Prussian Blue ; organic dyes, e.g. alizarin, azo and metal phthalocyanine dyes), antifoams (e.g. silicone antifoams and magnesium stearate), preservatives (e.g. dichlorophene and benzyl alcohol hemiformal), secondary thickeners (cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica), stickers, gibberellins and processing auxiliaries, mineral and vegetable oils, perfumes, waxes, nutrients (including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrants, sequestering agents and complex formers.
The choice of the auxiliaries is related to the intended mode of application of the compound of the invention and/or on the physical properties. Furthermore, the auxiliaries may be chosen to impart particular properties (technical, physical and/or biological properties) to the compositions or use forms prepared therefrom. The choice of auxiliaries may allow customizing the compositions to specific needs.
The composition of the invention may be in any customary form, such as solutions (e.g aqueous solutions), emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural or synthetic products impregnated with the compound of the invention, fertilizers and also microencapsulations in polymeric substances. The compound of the invention may be present in a suspended, emulsified or dissolved form.
The composition of the invention may be provided to the end user as ready-for-use formulation, i.e. the compositions may be directly applied to the plants or seeds by a suitable device, such as a spraying or dusting device. Alternatively, the compositions may be provided to the end user in the form of concentrates which have to be diluted, preferably with water, prior to use.
The composition of the invention can be prepared in conventional manners, for example by mixing the compound of the invention with one or more suitable auxiliaries, such as disclosed herein above. The composition according to the invention contains generally from 0.01 to 99% by weight, preferably from 0.05 to 98% by weight, more preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80% by weight of the compound of the invention. It is possible that a composition comprises two or more compounds of the invention. In such case the outlined ranges refer to the total amount of compounds of the present invention.
Mixtures /Combinations
The compound and the composition of the invention can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or semiochemicals. This may allow to broaden the activity spectrum or to prevent development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th Edition.
Examples of especially preferred fungicides which could be mixed with the compound and the composition of the invention are:
1) Inhibitors of the ergosterol biosynthesis, for example (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.01 1) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) Pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) triticonazole, (1.026) (lR,2S,5S)-5- (4-chlorobenzyl)-2-(chloromethyl)-2-methyl- 1 -( 1 H- 1 ,2,4-triazol- 1 -ylmethyl)cyclopentanol, ( 1.027)
( 1 S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl- 1 -(1 H- 1 ,2,4-triazol- 1 -ylmethyl)cyclopentanol,
( 1.028) (2R)-2-( 1 -chlorocyclopropyl)-4- [( 1 R)-2,2-dichlorocyclopropyl] - 1 -( 1 H- 1 ,2,4-triazol- 1 -yl)butan-2- ol, ( 1.029) (2R)-2-( 1 -chlorocyclopropyl)-4-[( 1 S)-2,2-dichlorocyclopropyl]- 1 -(1 H- 1 ,2,4-triazol- 1 -yl)butan- 2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-l-(lH-l,2,4-triazol-l-yl)propan-2- ol, (1.031) (2S)-2-( 1 -chlorocyclopropyl)-4-[( 1 R)-2,2-dichlorocyclopropyl]- 1 -(1 H- 1 ,2,4-triazol- 1 -yl)butan-
2-ol, (1.032) (2S)-2-(l -chlorocyclopropyl)-4- [( 1 S)-2,2-dichlorocyclopropyl]- 1 -( 1 H- 1 ,2,4-triazol- 1 - yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]- 1 -(1 H- 1 ,2,4-triazol- 1 - yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-l,2-oxazol-4-yl](pyridin-
3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)- 1 ,2-oxazol-4-yl](pyridin-3- yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-l,2-oxazol-4-yl](pyridin-3- yl)methanol, (1.037) 1 -({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl- 1 ,3-dioxolan-2- yl} methyl)- 1 H- 1 ,2,4-triazole, ( 1.038) 1 -( {(2S,4S)-2- [2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl- 1,3- dioxolan-2-yl}methyl)-lH- 1,2, 4-triazole, (1.039) l- {[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl] mcthyl j - 1H- 1 ,2,4-triazol-5-yl thiocyanate, ( 1.040) 1 - { [rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluoro- phenyl)oxiran-2-yl]methyl} - 1 H- 1 ,2,4-triazol-5-yl thiocyanate, (1.041) l- { [rel(2R,3 S)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)oxiran-2-yl]methyl} - 1 H- 1 ,2,4-triazol-5-yl thiocyanate, ( 1.042) 2-[(2R,4R,5R)- 1 -
(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H- l,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4- yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-l-(2,4- dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.047) 2- [(2S,4R,5S)-l -(2, 4-dichlorophenyl)-5-hydroxy-2, 6, 6-trimethylheptan-4-yl]-2,4-dihydro-3H- 1,2, 4-triazole-
3-thione, ( 1.048) 2-[(2S,4S,5R)- 1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4- dihydro-3H-l,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.050) 2-[l-(2,4-dichlorophenyl)-5- hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4- dichlorophenoxy)phenyl]- 1 -(1 H- 1 ,2,4-triazol- 1 -yl)propan-2-ol, ( 1.052) 2- [2-chloro-4-(4- chlorophenoxy)phenyl] - 1 -( 1 H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, ( 1.053) 2- [4-(4-chlorophenoxy)-2-
(trifluoromethyl)phenyl]- 1 -(1H-1 ,2,4-triazol- 1 -yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-
(trifluoromethyl)phenyl]-l-(lH-l,2,4-triazol-l-yl)pentan-2-ol, (1.055) Mefentrifluconazole, (1.056) 2- { [3 - (2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-l,2,4-triazole-3-thione, (1.057) 2- {[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H- l,2,4-triazole-3-thione, (1.058) 2- {[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl] mcthyl j -2,4-dihydro-3H- 1 ,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl- l-(lH-l,2,4-triazol-l-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-l- {[3-(2-chlorophenyl)-2-(2,4- difluorophenyl)oxiran-2-yl]methyl} - 1 H- 1 ,2,4-triazole, (1.061) 5-(allylsulfanyl)- 1 - { [rel(2R,3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl} - 1 H- 1 ,2,4-triazole, ( 1.062) 5-(allylsulfanyl)- 1 - { [rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl} - 1 H- 1 ,2,4-triazole, ( 1.063) N'- (2,5-dimethyl-4- {[3-(l,l,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N- methylimidoformamide, (1.064) N'-(2,5-dimethyl-4- {[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N- ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4- {[3-(2, 2,3,3- tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-
4- {[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidofonnamide, (1.067) N'-(2,5- dimethyl-4- {3-[(l,l,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068) N'-(2,5-dimethyl-4- {3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimido- formamide, (1.069) N'-(2,5-dimethyl-4- {3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl- N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4- {3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N- ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N- methylimidoformamide, (1.072) N'-(4- {[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N- ethyl-N-methylimidoformamide, (1.073) N'-(4- {3-[(difluoromethyl)sulfanyl]phenoxy} -2,5- dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5-bromo-6-(2,3-dihydro- lH-inden-2- yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'- {4-[(4,5-dichloro-l,3-thiazol- 2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076) N'- {5-bromo-6-[(lR)-l-(3,5- difluorophenyl)ethoxy]-2-methylpyridin-3-yl} -N-ethyl-N-methylimidoformamide, (1.077) N'- {5-bromo-6- [(lS)-l-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'- {5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidofonnamide, (1.079) N'- {5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl} -N-ethyl-N- methylimidoformamide, (1.080) N'- {5-bromo-6-[l-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N- ethyl-N-methylimidoformamide, (1.081) Ipfentrifluconazole.
2) Inhibitors of the respiratory chain at complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer lR,4S,9S), (2.011) isopyrazam (anti- epimeric enantiomer lS,4R,9R), (2.012) isopyrazam (anti-epimeric racemate lRS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate lRS,4SR,9RS and anti-epimeric racemate lRS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer lR,4S,9R), (2.015) isopyrazam (syn-epimeric enantiomer lS,4R,9S), (2.016) isopyrazam (syn-epimeric racemate lRS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) Pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N- (1,1 , 3 -trimethyl-2, 3-dihydro- lH-inden-4-yl)- 1 H-pyrazole-4-carboxamide, (2.023) 1 ,3-dimethyl-N-[(3R)- 1,1 , 3 -trimethyl-2, 3-dihydro- lH-inden-4-yl]- lH-pyrazole-4-carboxamide, (2.024) 1 ,3-dimethyl-N-[(3S)- 1,1 , 3 -trimethyl-2, 3-dihydro- lH-inden-4-yl]- lH-pyrazole-4-carboxamide, (2.025) 1 -methyl-3-
(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-lH-pyrazole-4-carboxamide, (2.026) 2-fluoro-6- (trifluoromethyl)-N-( 1 , 1 ,3-trimethyl-2, 3-dihydro- 1 H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)- 1 - methyl-N-( 1 , 1 , 3 -trimethyl-2, 3-dihydro- lH-inden-4-yl)- 1 H-pyrazole-4-carboxamide, (2.028) 3-
(difluoromethyl)- 1 -methyl-N- [(3R)- 1 , 1 ,3 -trimethyl-2,3 -dihydro- 1 H-inden-4-yl] - 1 H-pyrazole-4- carboxamide, (2.029) 3 -(difluoromethyl)- 1 -methyl-N- [(3 S)- 1, 1 ,3 -trimethyl-2,3 -dihydro- 1 H-inden-4-yl]- lH-pyrazole-4-carboxamide, (2.030) Fluindapyr, (2.031) 3-(difhroromethyl)-N-[(3R)-7-fluoro-l,l,3- trimethyl-2,3-dihydro-lH-inden-4-yl]-l-methyl-lH-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)- N-[(3 S)-7-fluoro- 1 , 1 ,3-trimethyl-2,3-dihydro- 1 H-inden-4-yl] - 1 -methyl- 1 H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4- {[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4- amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l -methyl- 1H- pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5- fluoro- 1 -methyl- lH-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3- (difluoromethyl)-5-fluoro-l -methyl- lH-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N- cyclopropyl-3-(difluoromethyl)-5-fluoro-l -methyl- lH-pyrazole-4-carboxamide, (2.038) N-(5-chloro-2- isopropylbenzyl)-N-cyclopropyl-3 -(difluoromethyl)-5-fluoro- 1 -methyl- 1 H-pyrazole-4-carboxamide, (2.039) N-[(lR,4S)-9-(dichloromethylene)- 1,2,3, 4-tetrahydro-l, 4-methanonaphthalen-5-yl]-3-
(difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide, (2.040) N- [( 1 S,4R)-9-(dichloromethylene)-
1,2,3,4-tetrahydro- 1 ,4-methanonaphthalen-5-yl]-3 -(difluoromethyl)- 1 -methyl- lH-pyrazole-4-carboxamide, (2.041 ) N- [ 1 -(2,4-dichlorophenyl)- 1 -methoxypropan-2-yl]-3 -(difluoromethyl)- 1 -methyl- 1 H-pyrazole-4- carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro- 1 -methyl- lH-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclo- propyl-3-(difluoromethyl)-5-fluoro-l -methyl- lH-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2- (trifluoromethyl)benzyl] -N-cyclopropyl-3 -(difluoromethyl)-5-fluoro- 1 -methyl- 1 H-pyrazole-4- carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-N-[5-methyl-2-
(trifluoromethyl)benzyl]-lH-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro- N-(2-fluoro-6-isopropylbenzyl)- 1 -methyl- lH-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3- (difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)- 1 -methyl- 1 H-pyrazole-4- carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)- 1 -methyl- 1 H- pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2- isopropylbenzyl)- 1 -methyl- lH-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2- ethyl-4,5-dimethylbenzyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3- (difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.053) N- cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-l-methyl-lH-pyrazole-4- carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-l- methyl- lH-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3- (difluoromethyl)-5-fluoro- 1 -methyl- 1 H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2- cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (2.057) pyrapropoyne.
3) Inhibitors of the respiratory chain at complex III, for example (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2- {2-[({[(lE)-l-(3- {[(E)-l-fluoro-2- phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide,
(3.022) (2E,3Z)-5 - { [ 1 -(4-chlorophenyl)- 1 H-pyrazol-3-yl] oxy} -2-(methoxyimino)-N,3 -dimethylpent-3 - enamide, (3.023) (2R)-2- {2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide,
(3.024) (2S)-2- {2-[(2,5-dimethylphenoxy)methyl]phenyl} -2-methoxy-N-methylacetamide, (3.025)
(3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6- methyl-4, 9-dioxo-l,5-dioxonan-7-yl 2-methylpropanoate, (3.026) mandestrobin, (3.027) N-(3 -ethyl-3, 5,5- trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5- {[l-(4-chloro-2- fluorophenyl)-lH-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl {5- [3-(2,4-dimethylphenyl)-lH-pyrazol-l-yl]-2-methylbenzyl}carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid. 4) Inhibitors of the mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb,
(4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate- methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3- chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.01 1) 3-chloro-5-(6- chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N- (2,6-difluorophenyl)- 1 ,3-dimethyl- 1 H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo- 6-fluorophenyl)-l, 3-dimethyl- lH-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2- bromophenyl)-l, 3-dimethyl- lH-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6- fluorophenyl)- 1 ,3-dimethyl- 1 H-pyrazo 1-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)- 1 ,3 -dimethyl- 1 H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)- 1 ,3 -dimethyl- lH-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)- 1 ,3-dimethyl- 1H- pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-l, 3-dimethyl- 1H- pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-l,3-dimethyl-lH-pyrazol-5- amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-l, 3-dimethyl- lH-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4- (2-chloro-4-fluorophenyl)- 1 ,3-dimethyl- 1 H-pyrazo 1-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4- fluorophenyl)-l, 3-dimethyl- 1 H-pyrazo 1-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4- fluorophenyl)- 1 ,3-dimethyl- 1 H-pyrazo 1-5-amine.
5) Compounds capable to have a multisite action, for example (5.001) bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+) sulfate, (5.010) dithianon, (5.01 1) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][l,4]dithiino[2,3- c] [ 1 ,2]thiazole-3-carbonitrile.
6) Compounds capable to induce a host defence, for example (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil.
7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-l-yl)quinoline.
8) Inhibitors of the ATP production, for example (8.001) silthiofam.
9) Inhibitors of the cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one, (9.009) (2Z)-3- (4-tert-butylphenyl)-3 -(2-chloropyridin-4-yl)- 1 -(morpholin-4-yl)prop-2-en- 1 -one. 10) Inhibitors of the lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
11) Inhibitors of the melanin biosynthesis, for example (1 1.001) tricyclazole, (1 1.002) 2,2,2-trifluoroethyl {3-methyl- l-[(4-methylbenzoyl)amino]butan-2-yl} carbamate.
12) Inhibitors of the nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
13) Inhibitors of the signal transduction, for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
14) Compounds capable to act as an uncoupler, for example (14.001) fluazinam, (14.002) meptyldinocap.
15) Further compounds, for example (15.001) Abscisic acid, (15.002) benthiazole, (15.003) bethoxazin,
(15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufiraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.01 1) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and salts, (15.025) phosphorous acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone), (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) l-(4- {4-[(5R)-5- (2, 6-difluorophenyl)-4, 5-dihydro- 1 ,2-oxazol-3-yl] - 1 ,3 -thiazol-2-yl}piperidin- 1 -yl)-2- [5 -methyl-3 - (trifluoromethyl)- 1 H-pyrazol- 1 -yl] ethanone, ( 15.032) 1 -(4- {4- [(5 S)-5-(2,6-difluorophenyl)-4,5-dihydro- l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yljethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipymetitrone, (15.035) 2-[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]- 1-[4-(4- {5-[2-(prop-2-yn- 1 -yloxy)phenyl]-4,5-dihydro- l,2-oxazol-3- yl} - 1 ,3-thiazol-2-yl)piperidin- 1 -yljethanone, (15.036) 2-[3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]- 1-[4-(4- {5-[2-chloro-6-(prop-2-yn- 1 -yloxy)phenyl]-4, 5-dihydro- 1 ,2-oxazol-3-yl} - 1 ,3-thiazol-2-yl)piperidin- 1 - yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4- {5-[2-fluoro-6-(prop-2-yn-l- yloxy)phenyl]-4, 5-dihydro- 1 ,2-oxazol-3-yl}- 1 ,3-thiazol-2-yl)piperidin- 1-yl] ethanone, (15.038) 2-[6-(3- fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2- {(5R)-3-[2-(l - { [3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4, 5-dihydro- 1 ,2-oxazol-5- yl} -3 -chlorophenyl methanesulfonate, ( 15.040) 2- {(5 S)-3 - [2-( 1 - { [3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 - yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4, 5-dihydro- l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, ( 15.041 ) Ipflufenoquin, ( 15.042) 2- {2-fluoro-6- [(8-fluoro-2-methylquinolin-3 -yl)oxy]phenyl} propan-2-ol, (15.043) 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]- 4, 5-dihydro-l,2-oxazol-5-yl} -3 -chlorophenyl methanesulfonate, (15.044) 2- {3-[2-(l- {[3,5- bis(difluoromethyl)- lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4, 5-dihydro- l,2-oxazol-5- yl [ phenyl methanesulfonate, (15.045) 2-phenylphenol and salts, (15.046) 3-(4, 4, 5-trifluoro-3, 3-dimethyl- 3,4-dihydroisoquinolin-l-yl)quinoline, (15.047) quinofumelin, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-ammo-5-fluoropyrimidin-2(lH)-one), (15.049) 4-oxo-4-[(2- phenylethyl)amino]butanoic acid, (15.050) 5-amino- 1, 3, 4-thiadiazole-2 -thiol, (15.051) 5-chloro-N'-phenyl- N'-(prop-2-yn-l-yl)thiophene-2-sulfonohydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4- amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5- (quinolin-3-yl)-2,3-dihydro- 1 ,4-benzoxazepine, (15.055) but-3-yn- 1 -yl {6-[( { [(Z)-( 1 -methyl- lH-tetrazol-5- yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) ethyl (2Z)-3-amino-2-cyano-3- phenylacrylate, (15.057) phenazine-1 -carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2: 1), (15.061) tert-butyl {6-[({[(l-methyl-lH-tetrazol-5- yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-l- [(4-methylphenyl)sulfonyl]-3 ,4-dihydropyrimidin-2( 1 H)-one, ( 15.063) aminopyrifen.
All named mixing partners of the classes (1) to (15) as described here above can be present in the form of the free compound and/or, if their functional groups enable this, an agriculturally acceptable salt thereof.
The compound and the composition of the invention may also be combined with one or more biological control agents.
Examples of biological control agents which may be combined with the compound and the composition of the invention are:
(A) Antibacterial agents selected from the group of:
(A1 ) bacteria, such as (A1 A) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRU Accession No. B2166 land described in U.S. Patent No. 6,060,051); (A1.2) Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (A1.3) Bacillus pumilus, in particular strain BU F-33 (having NRRU Accession No. 50185); (A1.4) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available as Taegro® from Novozymes, US); (A1.5) a Paenibacillus sp. strain having Accession No. NRRU B-50972 or Accession No. NRRU B-67129 and described in International Patent Publication No. WO 2016/154297; and
(A2) fungi, such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (A2.2) Aureobasidium pullulans blastospores of strain DSM 14941 ; (A2.3) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM14941;
(B) Fungicides selected from the group of:
(Bl) bacteria, for example (Bl . l) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRU Accession No. B21661and described in U.S. Patent No. 6,060,051); (B1.2) Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No. 6,245,551); (B 1.3) Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE); (B1.4) Bacillus pumilus, in particular strain BU F-33 (having NRRL Accession No. 50185); (B1.5) Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); (B1.6) Bacillus subtilis Y 1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); (B1.7) Bacillus amyloliquefaciens strain MBI 600 (available as SUBTILEX from BASF SE); (B1.8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B 1.9) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127- 5); (B 1.10) Bacillus mycoides, isolate J (available as BmJ TGAI or WG from Certis USA); (B 1.11 ) Bacillus licheniformis, in particular strain SB3086 (available as EcoGuard TM Biofungicide and Green Releaf from Novozymes); (B1.12) a Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129 and described in International Patent Publication No. WO 2016/154297.
In some embodiments, the biological control agent is a Bacillus subtilis or Bacillus amyloliquefaciens strain that produces a fengycin or plipastatin-type compound, an iturin-type compound, and/or a surfactin-type compound. For background, see the following review article: Ongena, M., et ah,“ Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol,” Trends in Microbiology, Vol 16, No. 3, March 2008, pp. 115-125. Bacillus strains capable of producing lipopeptides include Bacillus subtilis QST713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661and described in U.S. Patent No. 6,060,051), Bacillus amyloliquefaciens strain D747 (available as Double Nickel™ from Certis, US, having accession number FERM BP-8234 and disclosed in US Patent No. 7,094,592); Bacillus subtilis MBI600 (available as SUBTILEX® from Becker Underwood, US EPA Reg. No. 71840-8); Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277); Bacillus amyloliquefaciens, in particular strain FZB42 (available as RHIZOVITAL® from ABiTEP, DE); and Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5); and
(B2) fungi, for example: (B2.1) Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660; e.g. Contans ® from Bayer); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y- 30752 (e.g. Shemer®); (B2.3) Microsphaeropsis ochracea (e.g. Microx® from Prophyta); (B2.5) Trichoderma spp., including Trichoderma atroviride, strain SCI described in International Application No. PCT/IT2008/000196); (B2.6) Trichoderma harzianum rifai strain KRL-AG2 (also known as strain T-22, /ATCC 208479, e.g. PLANTSHIELD T-22G, Rootshield®, and TurfShield from BioWorks, US); (B2.14) Gliocladium roseum, strain 321U from W.F. Stoneman Company LLC; (B2.35) Talaromyces flavus, strain Vl l7b; (B2.36) Trichoderma asperellum, strain ICC 012 from Isagro; (B2.37) Trichoderma asperellum, strain SKT-l (e.g. ECO-HOPE® from Kumiai Chemical Industry); (B2.38) Trichoderma atroviride, strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR); (B2.39) Trichoderma atroviride, strain no. V08/002387; (B2.40) Trichoderma atroviride, strain NMI no. V08/002388; (B2.41) Trichoderma atroviride, strain NMI no. V08/002389; (B2.42) Trichoderma atroviride, strain NMI no. V08/002390; (B2.43) Trichoderma atroviride, strain LC52 (e.g. Tenet by Agrimm Technologies Limited); (B2.44) Trichoderma atroviride, strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma atroviride, strain Tl l (IMI352941/ CECT20498); (B2.46) Trichoderma harmatum, (B2.47) Trichoderma harzianum, (B2.48) Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US); (B2.49) Trichoderma harzianum, in particular, strain KD (e.g. Trichoplus from Biological Control Products, SA (acquired by Becker Underwood)); (B2.50) Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert); (B2.51) Trichoderma harzianum, strain TH35 (e.g. Root-Pro by Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g. SoilGard 12G by Certis, US); (B2.53) Trichoderma viride, strain TV 1 (e.g. Trianum-P by Koppert); (B2.54) Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia); (B2.56) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (B2.57) Aureobasidium pullulans, in particular blastospores of strain DSM 14941 ; (B2.58 ) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH); (B2.64) Cladosporium cladosporioides, strain H39 (by Stichting Dienst Landbouwkundig Onderzoek); (B2.69) Gliocladium catenulatum (Synonym: Clonostachys rosea f catenulate ) strain J1446 (e.g. Prestop ® by AgBio Inc. and also e.g. Primastop® by Kemira Agro Oy); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii) conidia of strain KV01 (e.g. Vertalec® by Koppert/Arysta); (B2.71) Penicillium vermiculatum ; (B2.72) Pichia anomala, strain WRL- 076 (NRRL Y-30842); (B2.75) Trichoderma atroviride, strain SKT-l (FERM P- 16510); (B2.76) Trichoderma atroviride, strain SKT-2 (FERM P- 16511); (B2.77) Trichoderma atroviride, strain SKT-3 (FERM P-17021); (B2.78) Trichoderma gamsii (formerly T. viride), strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.); (B2.79) Trichoderma harzianum, strain DB 103 (e.g., T-Gro 7456 by Dagutat Biolab); (B2.80) Trichoderma polysporum, strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden); (B2.81) Trichoderma stromaticum (e.g. Tricovab by Ceplac, Brazil); (B2.83) Ulocladium oudemansii, in particular strain HRU3 (e.g. Botry-Zen® by Botry- Zen Ltd, NZ); (B2.84) Verticillium albo-atrum (formerly V. dahliae), strain WCS850 (CBS 276.92; e.g. Dutch Trig by Tree Care Innovations); (B2.86) Verticillium chlamydosporium ; (B2.87) mixtures of Trichoderma asperellum strain ICC 012 and Trichoderma gamsii strain ICC 080 (product known as e.g. BIO-TAM™ from Bayer CropScience LP, US).
Further examples of biological control agents which may be combined with the compound and the composition of the invention are: bacteria selected from the group consisting of Bacillus cereus, in particular B. cereus strain CNCM 1-1562 and Bacillus firmus, strain 1-1582 (Accession number CNCM 1-1582), Bacillus subtilis strain OST 30002 (AccessionNo. NRRL B-50421), Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (AccessionNo. ATCC 1276), B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), B. thuringiensis subsp. kurstaki strain HD-l, B. thuringiensis subsp. tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode)-PR3 (Accession Number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRL B-50550), and Streptomyces galbus strain AQ 6047 (Acession Number NRRL 30232); fungi and yeasts selected from the group consisting of Beauveria bassiana, in particular strain ATCC 74040, Lecanicillium spp., in particular strain HRO LEC 12, Metarhizium anisopliae, in particular strain F52 (DSM3884 or ATCC 90448), Paecilomyces fumosoroseus (how: Isaria fumosorosea), in particular strain IFPC 200613, or strain Apopka 97 (Accesion No. ATCC 20874), and Paecilomyces lilacinus, in particular P. lilacinus strain 251 (AGAL 89/030550); viruses selected from the group consisting of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV), Cydia pomonella (codling moth) granulosis vims (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis vims (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, and Spodoptera littoralis (African cotton leafworm) NPV. bacteria and fungi which can be added as 'inoculant' to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health. Examples are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., and Streptomyces spp. plant extracts and products formed by microorganisms including proteins and secondary metabolites which can be used as biological control agents, such as Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up ( Chenopodium quinoa saponin extract), Pyrethrum/Pyrethrins, Qpassia amara, Quercus, Quillaja, Regalia, "Requiem™ Insecticide", rotenone, pg/n/ ryanodinc, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extract, in particular oilseed rape powder or mustard powder.
Examples of insecticides, acaricides and nematicides, respectively, which could be mixed with the compound and the composition of the invention, are:
(1) Acetylcholinesterase (AChE) inhibitors, such as, for example, carbamates, for example alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimcthacarb, XMC and xylylcarb; or organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S- methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl 0-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.
(2) GABA-gated chloride channel blockers, such as, for example, cyclodiene-organochlorines, for example chlordane and endosulfan or phenylpyrazoles (fiproles), for example ethiprole and fipronil.
(3) Sodium channel modulators, such as, for example, pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(lR)-trans-isomer], deltamethrin, empenthrin [(EZ)-(lR)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(lR)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)- isomer)], tralomethrin and transfluthrin or DDT or methoxychlor.
(4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, such as, for example, neonicotinoids, e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
(5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as, for example, spinosyns, e.g. spinetoram and spinosad.
(6) Glutamate-gated chloride channel (GluCl) allosteric modulators, such as, for example, avermectins/milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin.
(7) Juvenile hormone mimics, such as, for example, juvenile hormone analogues, e.g. hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen. (8) Miscellaneous non-specific (multi-site) inhibitors, such as, for example, alkyl halides, e.g. methyl bromide and other alkyl halides; or chloropicrine or sulphuryl fluoride or borax or tartar emetic or methyl isocyanate generators, e.g. diazomet and metam.
(9) Modulators of Chordotonal Organs, such as, for example pymetrozine or flonicamid. (10) Mite growth inhibitors, such as, for example clofentezine, hexythiazox and diflovidazin or etoxazole.
(11) Microbial disrupters of the insect gut membrane, such as, for example Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.l. plant proteins: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl/35Abl . (12) Inhibitors of mitochondrial ATP synthase, such as, ATP disrupters such as, for example, diafenthiuron or organotin compounds, for example azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon.
(13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient, such as, for example, chlorfenapyr, DNOC and sulfluramid.
(14) Nicotinic acetylcholine receptor channel blockers, such as, for example, bensultap, cartap hydrochloride, thiocylam, and thiosultap-sodium.
(15) Inhibitors of chitin biosynthesis, type 0, such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
(16) Inhibitors of chitin biosynthesis, type 1, for example buprofezin. (17) Moulting disrupter (in particular for Diptera, i.e. dipterans), such as, for example, cyromazine.
(18) Ecdysone receptor agonists, such as, for example, chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
(19) Octopamine receptor agonists, such as, for example, amitraz.
(20) Mitochondrial complex III electron transport inhibitors, such as, for example, hydramethylnone or acequinocyl or fluacrypyrim.
(21) Mitochondrial complex I electron transport inhibitors, such as, for example from the group of the METI acaricides, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
(22) Voltage-dependent sodium channel blockers, such as, for example indoxacarb or metaflumizone. (23) Inhibitors of acetyl CoA carboxylase, such as, for example, tetronic and tetramic acid derivatives, e.g. spirodiclofen, spiromesifen and spirotetramat.
(24) Mitochondrial complex IV electron transport inhibitors, such as, for example, phosphines, e.g. aluminium phosphide, calcium phosphide, phosphine and zinc phosphide or cyanides, e.g. calcium cyanide, potassium cyanide and sodium cyanide.
(25) Mitochondrial complex II electron transport inhibitors, such as, for example, Acto-kctonitrilc derivatives, e.g. cyenopyrafen and cyflumetofen and carboxanilides, such as, for example, pyflubumide.
(28) Ryanodine receptor modulators, such as, for example, diamides, e.g. chlorantraniliprole, cyantraniliprole and flubendiamide, further active compounds such as, for example, Afldopyropen, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Broflanilide, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclaniliprole, Cycloxaprid, Cyhalodiamide, Dicloromezotiaz, Dicofol, epsilon-Metofluthrin, epsilon- Momfluthrin, Flometoquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluralaner, Fluxametamide, Fufenozide, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, kappa-Bifenthrin, kappa-Tefluthrin, Lotilaner, Meperfluthrin, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Spirobudiclofen, Tetramethylfluthrin, Tetraniliprole, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thiofluoximate, Triflumezopyrim and iodomethane; furthermore preparations based on Bacillus firmus (1-1582, BioNeem, Votivo), and also the following compounds: l- {2-fluoro-4-methyl-5- [(2,2,2-trifluoroethyl)sulphinyl]phenyl} -3-(trifluoromethyl)- 1H- 1 ,2,4-triazole-5-amine (known from W02006/043635) (CAS 885026-50-6), {l'-[(2E)-3-(4-chlorophenyl)prop-2-en-l-yl]-5-fluorospiro[indol- 3,4'-piperidin]-l(2H)-yl}(2-chloropyridin-4-yl)methanone (known from W02003/106457) (CAS 637360- 23-7), 2-chloro-N-[2-{ l-[(2E)-3-(4-chlorophenyl)prop-2-en-l-yl]piperidin-4-yl}-4-
(trifluoromethyl)phenyl]isonicotinamide (known from W02006/003494) (CAS 872999-66-1), 3-(4-chloro- 2,6-dimethylphenyl)-4-hydroxy-8-methoxy- 1 ,8-diazaspiro[4.5]dec-3-en-2-one (known from
WO 2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-l,8- diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6) , 4-(but-2-yn- l-yloxy)-6-(3,5-dimethylpiperidin-l-yl)-5-fluoropyrimidine (known from W02004/099160) (CAS 792914- 58-0), PF1364 (known from JP2010/018586) (CAS 1204776-60-2), N-[(2E)-l-[(6-chloropyridin-3- yl)methyl]pyridin-2(lH)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012/029672) (CAS 1363400- 41-2), (3£)-3-[l-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-l,l,l-trifluoro-propan-2-one (known from WO2013/144213) (CAS 1461743-15-6), , V-[3-(benzylcarbamoyl)-4-chlorophenyl]-l-methyl-3-
(pentafluoroethyl)-4-(trifluoromethyl)-liF-pyrazole-5-carboxamide (known from W02010/051926) (CAS 1226889-14-0), 5-bromo-4-chloro-V-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2- pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5- dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-V-(cA-l-oxido-3-thietanyl)- benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-A-(/ra«,y-l- oxido-3-thietanyl)-benzamide and 4-[(5 S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3- isoxazolyl]-2-mcthyl-A-(c/.v- 1 -oxido-3-thictanyl)bcnzamidc (known from WO 2013/050317 Al) (CAS 1332628-83-7), A-[3-chloro-l-(3-pyridinyl)-lA-pyrazol-4-yl]-A-ethyl-3-[(3,3,3-trifluoropropyl)sulfmyl]- propanamide, (+)-A-[3-chloro-l-(3-pyridinyl)-lA-pyrazol-4-yl]-A-ethyl-3-[(3,3,3-trifluoropropyl)sulfmyl] -propanamide and (-)-A-[3-chloro- l -(3-pyridinyl)- l //-pyrazol-4-yl]-A-cthyl-3-[(3,3,3-trifluoropropyl) sulfmyl]-propanamide (known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 Al) (CAS 1477923-37-7), 5-[[(2£)-3-chloro-2-propen-l-yl]amino]-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]- 4-[(trifluoromethyl)sulfmyl]-lA-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS 1105672- 77-2), 3 -bromo-A- [4-chloro-2-methyl-6- [(methylamino)thioxomethyl]phenyl] - 1 -(3 -chloro-2-pyridinyl)-
1 A-pyrazolc-5-carboxamidc, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); A-[4-chloro-2-[[(l,l-dimethylethyl)amino]carbonyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3- (fluoromcthoxy)- 1 A-Pyrazolc-5-carboxamidc (known from WO 2012/034403 Al) (CAS 1268277-22-0), A-[2-(5-amino- 1 ,3,4-thiadiazol-2-yl)-4-chloiO-6-mcthylphcnyl]-3-bmmo- 1 -(3-chlom-2-pyridinyl)- 1 H- pyrazole-5-carboxamide (known from WO 201 1/085575 Al) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4- [(3,3-dichloro-2-propen- 1 -yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1 108184-52-6); (2 E)- and 2(Z)-2-[2-(4-cyanophcnyl)- 1 -[3-(trifluoromcthyl) phenyl] ethylidene] - A- [4-(difluoromethoxy)phenyl] -hydrazinecarboxamide (known from
CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichlorocthcnyl)-2,2-dimcthyl-4-( l A-bcnzimidazol-2-yl) phenyl-cyclopropanecarboxylic acid ester (known from CN 103524422 A) (CAS 1542271-46-4); (4a5)-7- chloro-2,5-dihydro-2- [[(methoxycarbonyl) [4- [(trifluoromethyl)thio]phenyl] amino]carbonyl]-indeno [ 1 ,2-e] [ 1 ,3,4]oxadiazinc-4a(3//)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69- 2); 6-deoxy-3 -Oethyl-2,4-di-0-methyl-, 1 - [A- [4- [ 1 - [4-( 1 , 1 ,2,2,2-pentafluoroethoxy)phenyl] - 1 H- 1 ,2,4- triazol-3-yl]phenyl]carbamate]-a-L-mannopyranose (known from US 2014/0275503 Al) (CAS 1181213- 14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza- bicyclo[3.2. l ] octane (CAS 1253850-56-4), (8-an//)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy) -3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2. l ] octane (CAS 933798-27-7), (8-si«)-8-(2- cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3 -(6-trifluoromethyl-pyridazin-3 -yl)-3 -aza-bicyclo [3.2.1 ] octane (known from WO 2007040280 Al, WO 2007040282 Al) (CAS 934001-66-8), N-[3-chloro-l-(3- pyridinyl)-lH-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]-propanamide (known from WO 2015/058021 Al, WO 2015/058028 Al) (CAS 1477919-27-9) and N-[4-(aminothioxomethyl)-2-methyl-6- [(methylamino)carbonyl]phenyl]-3-bromo- 1 -(3-chloro-2-pyridinyl)- 1 A-pyrazolc-5-carboxamidc (known from CN 103265527 A) (CAS 1452877-50-7), 5-(l,3-dioxan-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy] -pyrimidine (known from WO 2013/115391 Al) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-4- hydroxy-8-methoxy-l-methyl-l,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010/066780 Al, WO 2011/151 146 Al) (CAS 1229023-34-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-l -methyl- 1,8- diazaspiro[4.5]decane-2,4-dione (known from WO 2014/187846 Al) (CAS 1638765-58-8), 3-(4-chloro-2, 6-dimethylphenyl)-8-methoxy- 1 -methyl-2-oxo- l,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010/066780 Al, WO 201 1151 146 Al) (CAS 1229023-00-0), N-[l-[(6-chloro-3- pyridinyl)mcthyl]-2( l //)-pyridinylidcnc]-2,2,2-trifluoro-acctamidc (known from DE 3639877 Al, WO 2012029672 Al) (CAS 1363400-41-2), [N(£)]-N-[ l -[(6-chloro-3-pyridinyl)mcthyl]-2( l H)-pyridinylidcnc] -2,2,2-trifluoro-acetamide, (known from WO 2016005276 Al) (CAS 1689566-03-7), [N(Z)]-N-[l-[(6- chloro-3-pyridinyl)methyl]-2(lH)-pyridinylidene]-2,2,2-frifluoro-acetamide, (CAS 1702305-40-5), 3 -endo- 3-[2-propoxy-4-(trifluoromethyl)phenoxy]-9-[[5-(trifluoromethyl)-2-pyridinyl]oxy]-9- azabicyclo[3.3. l]nonane (known from WO 201 1/105506 Al, WO 2016/133011 Al) (CAS 1332838-17-1).
Examples of safeners which could be mixed with the compound and the composition of the invention are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (- ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}- sulphonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-l-oxa-4-azaspiro[4.5]decane (CAS 71526- 07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-l,3-oxazolidine (CAS 52836-31-4).
Examples of herbicides which could be mixed with the compound and the composition of the invention are:
Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, amehyn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammoniumsulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate, and -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, - diolamin, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, triisopropanolammonium, and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, -isooctyl, - potassium, and -sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl- pyrazolate (DTP), dicamba, dichlobenil, 2-(2, 4-dichlorobenzyl)-4, 4-dimethyl- l,2-oxazolidin-3 -one, 2-(2,5- dichlorobenzyl)-4, 4-dimethyl- l,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-9600, F-5231, i.e. N-{2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5- dihydro-lH-tetrazol-l-yl]phenyl}ethanesulfonamide, F-7967, i. e. 3-[7-chloro-5-fluoro-2-(trifluoromethyl)- 1 H-benzimidazol-4-yl] - 1 -methyl-6-(trifluoromethyl)pyrimidine-2,4( 1 H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluoroglycofen, fluoroglycofen- ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium, and -trimesium, H-9201, i.e. 0-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphoramidothioate, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron- methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e. 1 -(dimethoxyphosphoryl) ethyl-(2,4- dichlorophenoxy)acetate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin- ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, -potassium and -sodium, ipfencarbazone, iso- proturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, i.e. 3-({[5-(difluoromethyl)-l-methyl-3- (trifluoromethyl)- 1 H-pyrazol-4-yl]methyl} sulfonyl)-5,5-dimethyl-4, 5-dihydro- 1 ,2-oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2- ethylhexyl, -isopropylammonium, -potassium, and -sodium, MCPB, MCPB-methyl, -ethy,l and -sodium, mecoprop, mecoprop-sodium, and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2- ethylhexyl, and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e. N-(3-chloro-4-isopropylphenyl)-2-methylpentan amide, NGGC-01 1, napropamide, NC-310, i.e. [5-(benzyloxy)-l-methyl-lH-pyrazol-4-yl](2,4-dichlorophenyl)- methanone, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop- P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e. 1- ethoxy-3 -methyl- l-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. l-[7-fluoro-3-oxo-4-(prop-2-yn-l-yl)-3,4-dihydro-2H-l,4-benzoxazin-6-yl]-3-propyl-2-thioxo- imidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron- methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflu- sulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vemolate, XDE-848, ZJ-0862, i.e. 3,4-dichloro- N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl} aniline, and the following compounds:
Figure imgf000052_0001
Examples for plant growth regulators are:
Acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, Brassinolid, catechine, chlormequat chloride, cloprop, cyclanilide, 3 -(cycloprop- l-enyl) propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, -disodium, and - mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic hydrazide, mepiquat chloride, l-methylcyclopropene, methyl jasmonate, 2-(l-naphthyl)acetamide, l-naphthylacetic acid, 2- naphthyloxyacetic acid, nitrophenolate-mixture, paclobutrazol, N-(2-phenylethyl)-beta-alanine, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.
Methods and uses
The compounds and compositions of the invention have potent microbicidal activity and/or plant defense modulating potential. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria. They can be particularly useful in crop protection (they control microorganisms that cause plants diseases) or for protecting materials (e.g. industrial materials, timber, storage goods) as described in more details herein below. More specifically, the compounds and compositions of the invention can be used to protect seeds, germinating seeds, emerged seedlings, plants, plant parts, fruits, harvest goods and/or the soil in which the plants grow from unwanted microorganisms.
Hence, the invention further relates to a method for controlling harmful microorganisms, preferably phytopathogenic harmful fungi, in crop protection and in the protection of materials, wherein at least one compound of formula (I) or a composition comprising such compound is applied to the harmful microorganisms and/or their habitat.
The invention further relates to the use of at least one compound of formula (I) or a composition comprising such compound for control of harmful microorganisms, preferably phytopathogenic harmful fungi, in crop protection and in the protection of materials.
The invention also relates to the use of at least one compound of formula (I) or a composition comprising such compound for treatment of a transgenic plant or for treatment of seed, preferably seed of a transgenic plant.
Control or controlling as used herein encompasses protective, curative and eradicative treatment of unwanted microorganisms. Unwanted microorganisms may be pathogenic bacteria, pathogenic virus, pathogenic oomycetes or pathogenic fungi, more specifically phytopathogenic bacteria, phytopathogenic virus, phytopathogenic oomycetes or phytopathogenic fungi. As detailed herein below, these phytopathogenic microorganims are the causal agents of a broad spectrum of plants diseases.
More specifically, the compound and the composition of the invention can be used as fungicides. For the purpose of the specification, the term“fungicide” refers to a compound or composition that can be used in crop protection for the control of unwanted fungi, such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and/or for the control of Oomycetes.
The compound and the composition of the invention may also be used as antibacterial agent. In particular, they may be used in crop protection, for example for the control of unwanted bacteria, such as Pseudomonadaceae, Rhizobiaceae, Xanthomonadaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae. The compound and the composition of the invention may also be used as antiviral agent in crop protection. For example the compound and the composition of the invention may have effects on diseases from plant viruses, such as the tobacco mosaic virus (TMV), tobacco rattle virus, tobacco stunt virus (TStuV), tobacco leaf curl virus (VLCV), tobacco nervilia mosaic virus (TVBMV), tobacco necrotic dwarf virus (TNDV), tobacco streak virus (TSV), potato virus X (PVX), potato viruses Y, S, M, and A, potato acuba mosaic virus (PAMV), potato mop-top virus (PMTV), potato leaf-roll virus (PLRV), alfalfa mosaic virus (AMV), cucumber mosaic vims (CMV), cucumber green mottlemosaic vims (CGMMV), cucumber yellows vims (CuYV), watermelon mosaic vims (WMV), tomato spotted wilt vims (TSWV), tomato ringspot vims (TomRSV), sugarcane mosaic vims (SCMV), rice drawf vims, rice stripe vims, rice black-streaked drawf vims, strawberry mottle vims (SMoV), strawberry vein banding vims (SVBV), strawberry mild yellow edge vims (SMYEV), strawberry crinkle vims (SCrV), broad beanwilt vims (BBWV), and melon necrotic spot vims (MNSV).
The present invention also relates to a method for controlling unwanted microorganisms, such as unwanted fungi, oomycetes and bacteria, comprising the step of applying at least one compound of the invention or at least one composition of the invention to the microorganisms and/or their habitat (to the plants, plant parts, seeds, fruits or to the soil in which the plants grow).
Typically, when the compound and the composition of the invention are used in curative or protective methods for controlling phytopathogenic fungi and/or phytopathogenic oomycetes, an effective and plant- compatible amount thereof is applied to the plants, plant parts, fruits, seeds or to the soil or substrates in which the plants grow. Suitable substrates that may be used for cultivating plants include inorganic based substrates, such as mineral wool, in particular stone wool, perlite, sand or gravel; organic substrates, such as peat, pine bark or sawdust; and petroleum based substrates such as polymeric foams or plastic beads. Effective and plant-compatible amount means an amount that is sufficient to control or destroy the fungi present or liable to appear on the cropland and that does not entail any appreciable symptom of phytotoxicity for said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the crop growth stage, the climatic conditions and the respective compound or composition of the invention used. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
Plants and plant parts
The compound and the composition of the invention may be applied to any plants or plant parts.
Plants mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the genetically modified plants (GMO or transgenic plants) and the plant cultivars which are protectable and non-protectable by plant breeders’ rights. Genetically modified plants (GMO)
Genetically modified plants (GMO or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The expression“heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome. This gene gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microR A - miRNA - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoots, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
Plants which may be treated in accordance with the methods of the invention include the following: cotton, flax, grapevine, fruit, vegetables, such as Rosaceae sp. (for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons, oranges and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumber), Alliaceae sp. (for example leek, onion), Papilionaceae sp. (for example peas); major crop plants, such as Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress), Fabacae sp. (for example bean, peanuts), Papilionaceae sp. (for example soya bean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, swiss chard, beetroot); useful plants and ornamental plants for gardens and wooded areas; and genetically modified varieties of each of these plants.
Plants and plant cultivars which may be treated by the above disclosed methods include plants and plant cultivars which are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
Plants and plant cultivars which may be treated by the above disclosed methods include those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which may be treated by the above disclosed methods include those plants characterized by enhanced yield characteristics lncreased yield in said plants may be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield may furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, intemode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
Plants and plant cultivars which may be treated by the above disclosed methods include plants and plant cultivars which are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars which are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars which are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars which are disease-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance. Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars which are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars which show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated by the above disclosed methods include plants and plant cultivars, such as Tobacco plants, with altered post-translational protein modification patterns.
Pathogens
Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae ; Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striifdrmis; Uromyces species, for example Uromyces appendiculatus; diseases caused by pathogens from the group of the Oomycetes, for example Albugo species, for example Albugo Candida, Bremia species, for example Bremia lactucae; Peronospora species, for example Peronospora pisi or P. brassicae; Phytophthora species, for example Phytophthora infestans; Plasmopara species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum; leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola; Cladiosporium species, for example Cladiosporium cucumerinum; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium ) or Cochliobolus miyabeanus; Colletotrichum species, for example Colletotrichum lindemuthanium; Corynespora species, for example Corynespora cassiicola; Cycloconium species, for example Cycloconium oleaginum; Diaporthe species, for example Diaporthe citri; Elsinoe species, for example Elsinoe fawcettii; Gloeosporium species, for example Gloeosporium laeticolor; Glomerella species, for example Glomerella cingulata; Guignardia species, for example Guignardia bidwelli; Leptosphaeria species, for example Leptosphaeria maculans; Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale; Mycosphaerella species, for example Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis; Phaeosphaeria species, for example Phaeosphaeria nodorum; Pyrenophora species, for example Pyrenophora teres or Pyrenophora tritici repentis; Ramularia species, for example Ramularia collo-cygni or Ramularia areola, Rhynchosporium species, for example Rhynchosporium secalis; Septoria species, for example Septoria apii or Septoria lycopersici; Stagonospora species, for example Stagonospora nodorum, Typhula species, for example Typhula incarnata; Venturia species, for example Venturia inaequalis; root and stem diseases caused, for example, by Corticium species, for example Corticium graminearum, Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis, Plasmodiophora species, for example Plasmodiophora brassicae; Rhizoctonia species, for example Rhizoctonia solani; Sarocladium species, for example Sarocladium oryzae; Sclerotium species, for example Sclerotium oryzae; Tapesia species, for example Tapesia acuformis; Thielaviopsis species, for example Thielaviopsis basicola; ear and panicle diseases (including com cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium cladosporioides; Claviceps species, for example Claviceps purpurea; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Monographella species, for example Monographella nivalis; Stagnospora species, for example Stagnospora nodorum; diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana ; Tilletia species, for example Tilletia caries or Tilletia controversa; Urocystis species, for example Urocystis occulta, Ustilago species, for example Ustilago nuda; fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus ; Botrytis species, for example Botrytis cinerea, Monilinia species, for example Monilinia laxa; Penicillium species, for example Penicillium expansum or Penicillium purpurogenum; Rhizopus species, for example Rhizopus stolonifer; Sclerotinia species, for example Sclerotinia sclerotiorum; Verticilium species, for example Verticilium alboatrum; seed- and soil-borne rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species, for example Alternaria brassicicola; Aphanomyces species, for example Aphanomyces euteiches; Ascochyta species, for example Ascochyta lends, Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium herbarum; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosporium); Colletotrichum species, for example Colletotrichum coccodes; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Macrophomina species, for example Macrophomina phaseolina; Microdochium species, for example Microdochium nivale; Monographella species, for example Monographella nivalis; Penicillium species, for example Penicillium expansum; Phoma species, for example Phoma lingam; Phomopsis species, for example Phomopsis sojae; Phytophthora species, for example Phytophthora cactorum; Pyrenophora species, for example Pyrenophora graminea; Pyricularia species, for example Pyricularia oryzae; Pythium species, for example Pythium ultimum; Rhizoctonia species, for example Rhizoctonia solani; Rhizopus species, for example Rhizopus oryzae; Sclerotium species, for example Sclerotium rolfsii; Septoria species, for example Septoria nodorum; Typhula species, for example Typhula incarnata; Verticillium species, for example Verticillium dahliae; cancers, galls and witches’ broom caused, for example, by Nectria species, for example Nectria galligena; wilt diseases caused, for example, by Verticillium species, for example Verticillium longisporum; Fusarium species, for example Fusarium oxysporum; deformations of leaves, flowers and fruits caused, for example, by Exobasidium species, for example Exobasidium vexans; Taphrina species, for example Taphrina deformans; degenerative diseases in woody plants, caused, for example, by Esca species, for example Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea; Ganoderma species, for example Ganoderma boninense; diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solani; Helminthosporium species, for example Helminthosporium solani; diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; Erwinia species, for example Erwinia amylovora; Liberibacter species, for example Liberibacter asiaticus; Xyella species, for example Xylella fastidiosa; Ralstonia species, for example Ralstonia solanacearum; Dickeya species, for example Dickeya solani; Clavibacter species, for example Clavibacter michiganensis; Streptomyces species, for example Streptomyces scabies. diseases of soya beans:
Fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec atrans tenuissima), Anthracnose ( Colletotrichum gloeosporoides dematium var. truncatum), brown spot ( Septoria glycines), cercospora leaf spot and blight ( Cercospora kikuchii), choanephora leaf blight ( Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot ( Dactuliophora glycines), downy mildew ( Peronospora manshurica), drechslera blight ( Drechslera glycini), firogeye leaf spot ( Cercospora sojina), leptosphaerulina leaf spot ( Leptosphaerulina trifolii), phyllostica leaf spot ( Phyllosticta sojaecola), pod and stem blight ( Phomopsis sojae), powdery mildew ( Microsphaera diffusa), pyrenochaeta leaf spot ( Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight ( Rhizoctonia solani), rust ( Phakopsora pachyrhizi, Phakopsora meibomiae), scab ( Sphaceloma glycines), stemphylium leaf blight ( Stemphylium botryosum), sudden death syndrome ( Fusarium virguliforme), target spot ( Corynespora cassiicola).
Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot ( Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot ( Mycoleptodiscus terrestris), neocosmospora ( Neocosmospora vasinfecta), pod and stem blight ( Diaporthe phaseolorum), stem canker ( Diaporthe phaseolorum var. caulivora), phytophthora rot ( Phytophthora megasperma), brown stem rot ( Phialophora gregata), pythium rot ( Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off ( Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight ( Sclerotinia rolfsii), thielaviopsis root rot ( Thielaviopsis basicola).
Mycotoxins
In addition, the compound and the composition of the invention may reduce the mycotoxin content in the harvested material and the foods and feeds prepared therefrom. Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2 -toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec., such as F. acuminatum, F. asiaticum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum ( Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides etc., and also by Aspergillus spec., such as A. flavus, A. parasiticus, A. nomius, A. ochraceus, A. clavatus, A. terreus, A. versicolor, Penicillium spec., such as P. verrucosum, P. viridicatum, P. citrinum, P. expansum, P. claviforme, P. roqueforti, Claviceps spec., such as C. purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec and others.
Material Protection
The compound and the composition of the invention may also be used in the protection of materials, especially for the protection of industrial materials against attack and destruction by phytopathogenic fungi.
In addition, the compound and the composition of the invention may be used as antifouling compositions, alone or in combinations with other active ingredients.
Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry. For example, industrial materials which are to be protected from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms. Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
The compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
In the case of treatment of wood the compound and the composition of the invention may also be used against fungal diseases liable to grow on or inside timber.
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. In addition, the compound and the composition of the invention may be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
The compound and the composition of the invention may also be employed for protecting storage goods. Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired. Storage goods of vegetable origin, for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, may be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting. Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture. Storage goods of animal origin are, for example, hides, leather, furs and hairs. The compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. The compound and the composition of the invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi ( Ascomycetes , Basidiomycetes, Deuteromycetes and Zygomycetes ), and against slime organisms and algae. Examples include microorganisms of the following genera: Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Cladosporium spp., Paecilomyces spp. Mucor spp., Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus, Candida spp. and Saccharomyces spp., such as Saccharomyces cerevisae.
Seed Treatment
The compound and the composition of the invention may also be used to protect seeds from unwanted microorganisms, such as phytopathogenic microorganisms, for instance phytopathogenic fungi or phytopathogenic oomycetes. The term sccd(s) as used herein include dormant seeds, primed seeds, pregerminated seeds and seeds with emerged roots and leaves.
Thus, the present invention also relates to a method for protecting seeds from unwanted microorganisms which comprises the step of treating the seeds with the compound or the composition of the invention.
The treatment of seeds with the compound or the composition of the invention protects the seeds from phytopathogenic microorganisms, but also protects the germinating seeds, the emerging seedlings and the plants after emergence from the treated seeds. Therefore, the present invention also relates to a method for protecting seeds, germinating seeds and emerging seedlings.
The seeds treatment may be performed prior to sowing, at the time of sowing or shortly thereafter.
When the seeds treatment is performed prior to sowing (e.g. so-called on-seed applications), the seeds treatment may be performed as follows: the seeds may be placed into a mixer with a desired amount of the compound or the composition of the invention, the seeds and the compound or the composition of the invention are mixed until an homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
The invention also relates to seeds coated with the compound or the composition of the invention.
Preferably, the seeds are treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, seeds can be treated at any time between harvest and shortly after sowing. It is customary to use seeds which have been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seeds which have been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds which, after drying, for example, have been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
The amount of the compound or the composition of the invention applied to the seeds is typically such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in case the the compound of the invention would exhibit phytotoxic effects at certain application rates. The intrinsic phenotypes of transgenic plants should also be taken into consideration when determining the amount of the compound of the invention to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound being employed.
The compound of the invention can be applied as such, directly to the seeds, i.e. without the use of any other components and without having been diluted. Also the composition of the invention can be applied to the seeds.
The compound and the composition of the invention are suitable for protecting seeds of any plant variety. Preferred seeds are that of cereals (such as wheat, barley, rye, millet, triticale, and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, peas, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. More preferred are seeds of wheat, soybean, oilseed rape, maize and rice.
The compound and the composition of the invention may be used for treating transgenic seeds, in particular seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect. Seeds of plants capable of expressing a polypeptide or protein which acts against pests, herbicidal damage or abiotic stress may contain at least one heterologous gene which allows the expression of said polypeptide or protein. These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. These heterologous genes preferably originate from Bacillus sp., in which case the gene product is effective against the European com borer and/or the Western com rootworm. Particularly preferably, the heterologous genes originate from Bacillus thuringiensis.
Antimycotic Effects
The compound and the composition of the invention may also have very good antimycotic effects. They have a very broad antimycotic activity spectrum, especially against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The enumeration of these fungi by no means constitutes a restriction of the mycotic spectrum covered, and is merely of illustrative character.
The compound and the composition of the invention may also be used to control important fungal pathogens in fish and Crustacea farming, e.g. saprolegnia diclina in trouts, saprolegnia parasitica in crayfish.
The compound and the composition of the invention may therefore be used both in medical and in non medical applications.
Plant Growth Regulation
The compound and the composition of the invention may, at particular concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as bactericides, viricides (including compositions against viroids) or as compositions against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms).
The compound and the composition of the invention may intervene in physiological processes of plants and may therefore also be used as plant growth regulators. Plant growth regulators may exert various effects on plants. The effect of the substances depends essentially on the time of application in relation to the developmental stage of the plant, and also on the amounts of active ingredient applied to the plants or their environment and on the type of application. In each case, growth regulators should have a particular desired effect on the crop plants.
Growth regulating effects, comprise earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kemels/ear, number of ears/m2, number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation / earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit/vegetable size, sprouting resistance and reduced lodging. Increased or improved yield is referring to total biomass per hectare, yield per hectare, kemel/fruit weight, seed size and/or hectolitre weight as well as to improved product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, better brewing, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meet quality of silage fed animals, adaptation to cooking and frying; improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage / shelf-life, firmness / softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, colour, etc.; increased desired ingredients such as e.g. protein content, fatty acids, oil content, oil quality, aminoacid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxins, geosmin level, phenolic aromas, lacchase, polyphenol oxidases and peroxidases, nitrate content etc.
Plant growth-regulating compounds can be used, for example, to slow down the vegetative growth of the plants. Such growth depression is of economic interest, for example, in the case of grasses, since it is thus possible to reduce the frequency of grass cutting in ornamental gardens, parks and sport facilities, on roadsides, at airports or in fruit crops. Also of significance is the inhibition of the growth of herbaceous and woody plants on roadsides and in the vicinity of pipelines or overhead cables, or quite generally in areas where vigorous plant growth is unwanted.
Also important is the use of growth regulators for inhibition of the longitudinal growth of cereal. This reduces or completely eliminates the risk of lodging of the plants prior to harvest. In addition, growth regulators in the case of cereals can strengthen the culm, which also counteracts lodging. The employment of growth regulators for shortening and strengthening culms allows the deployment of higher fertilizer volumes to increase the yield, without any risk of lodging of the cereal crop.
In many crop plants, vegetative growth depression allows denser planting, and it is thus possible to achieve higher yields based on the soil surface. Another advantage of the smaller plants obtained in this way is that the crop is easier to cultivate and harvest.
Reduction of the vegetative plant growth may also lead to increased or improved yields because the nutrients and assimilates are of more benefit to flower and fruit formation than to the vegetative parts of the plants. Alternatively, growth regulators can also be used to promote vegetative growth. This is of great benefit when harvesting the vegetative plant parts. However, promoting vegetative growth may also promote generative growth in that more assimilates are formed, resulting in more or larger fruits.
Furthermore, beneficial effects on growth or yield can be achieved through improved nutrient use efficiency, especially nitrogen (N)-use efficiency, phosphorous (P)-use efficiency, water use efficiency, improved transpiration, respiration and/or CO2 assimilation rate, better nodulation, improved Ca-metabolism etc.
Likewise, growth regulators can be used to alter the composition of the plants, which in turn may result in an improvement in quality of the harvested products. Under the influence of growth regulators, parthenocarpic fruits may be formed. In addition, it is possible to influence the sex of the flowers. It is also possible to produce sterile pollen, which is of great importance in the breeding and production of hybrid seed.
Use of growth regulators can control the branching of the plants. On the one hand, by breaking apical dominance, it is possible to promote the development of side shoots, which may be highly desirable particularly in the cultivation of ornamental plants, also in combination with an inhibition of growth. On the other hand, however, it is also possible to inhibit the growth of the side shoots. This effect is of particular interest, for example, in the cultivation of tobacco or in the cultivation of tomatoes.
Under the influence of growth regulators, the amount of leaves on the plants can be controlled such that defoliation of the plants is achieved at a desired time. Such defoliation plays a major role in the mechanical harvesting of cotton, but is also of interest for facilitating harvesting in other crops, for example in viticulture. Defoliation of the plants can also be undertaken to lower the transpiration of the plants before they are transplanted.
Furthermore, growth regulators can modulate plant senescence, which may result in prolonged green leaf area duration, a longer grain filling phase, improved yield quality, etc.
Growth regulators can likewise be used to regulate fruit dehiscence. On the one hand, it is possible to prevent premature fruit dehiscence. On the other hand, it is also possible to promote fruit dehiscence or even flower abortion to achieve a desired mass (“thinning”). In addition it is possible to use growth regulators at the time of harvest to reduce the forces required to detach the fruits, in order to allow mechanical harvesting or to facilitate manual harvesting.
Growth regulators can also be used to achieve faster or else delayed ripening of the harvested material before or after harvest. This is particularly advantageous as it allows optimal adjustment to the requirements of the market. Moreover, growth regulators in some cases can improve the fruit colour. In addition, growth regulators can also be used to synchronize maturation within a certain period of time. This establishes the prerequisites for complete mechanical or manual harvesting in a single operation, for example in the case of tobacco, tomatoes or coffee.
By using growth regulators, it is additionally possible to influence the resting of seed or buds of the plants, such that plants such as pineapple or ornamental plants in nurseries, for example, germinate, sprout or flower at a time when they are normally not inclined to do so. In areas where there is a risk of frost, it may be desirable to delay budding or germination of seeds with the aid of growth regulators, in order to avoid damage resulting from late frosts.
Finally, growth regulators can induce resistance of the plants to frost, drought or high salinity of the soil. This allows the cultivation of plants in regions which are normally unsuitable for this purpose.
Plant Defense Modulators
The compound and the composition of the invention may also exhibit a potent strengthening effect in plants. Accordingly, they may be used for mobilizing the defences of the plant against attack by undesirable microorganisms.
Plant-strengthening (resistance-inducing) substances in the present context are substances capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesirable microorganisms, develop a high degree of resistance to these microorganisms.
Further, in context with the present invention plant physiology effects comprise the following:
Abiotic stress tolerance, comprising tolerance to high or low temperatures, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides etc.
Biotic stress tolerance, comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria. In context with the present invention, biotic stress tolerance preferably comprises increased fungal resistance and increased resistance against nematodes and bacteria
Increased plant vigor, comprising plant health / plant quality and seed vigor, reduced stand failure, improved appearance, increased recovery after periods of stress, improved pigmentation (e.g. chlorophyll content, stay-green effects, etc.) and improved photosynthetic efficiency.
Application
The compounds of the invention can be applied as such, or for example in the form of as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with the compound of the invention, synthetic substances impregnated with the compound of the invention, fertilizers or microencapsulations in polymeric substances.
Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the compound of the invention by the ultra-low volume method, via a drip irrigation system or drench application, to apply it in- furrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of the invention by means of a wound seal, paint or other wound dressing.
The effective and plant-compatible amount of the compound of the invention which is applied to the plants, plant parts, fruits, seeds or soil will depend on various factors, such as the compound/composition employed, the subject of the treatment (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (curative and protective), the type of microorganisms, the development stage of the microorganisms, the sensitivity of the microorganisms, the crop growth stage and the environmental conditions.
When the compound of the invention is used as a fungicide, the application rates can vary within a relatively wide range, depending on the kind of application. For the treatment of plant parts, such as leaves, the application rate may range from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used). For the treatment of seeds, the application rate may range from 0.1 to 200 g per 100 kg of seeds, preferably from 1 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, even more preferably from 2.5 to 12.5 g per 100 kg of seeds. For the treatment of soil, the application rate may range from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
These application rates are merely examples and are not intended to limit the scope of the present invention. Resistance Induction / Plant Health and other effects
The active compounds according to the invention also exhibit a potent strengthening effect in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by undesirable microorganisms.
Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesirable microorganisms, develop a high degree of resistance to these microorganisms.
The active compounds according to the invention are also suitable for increasing the yield of crops. In addition, they show reduced toxicity and are well tolerated by plants. Further, in context with the present invention plant physiology effects comprise the following:
Abiotic stress tolerance, comprising temperature tolerance, drought tolerance and recovery after drought stress, water use efficiency (correlating to reduced water consumption), flood tolerance, ozone stress and UV tolerance, tolerance towards chemicals like heavy metals, salts, pesticides (safener) etc..
Biotic stress tolerance, comprising increased fungal resistance and increased resistance against nematodes, viruses and bacteria. In context with the present invention, biotic stress tolerance preferably comprises increased fungal resistance and increased resistance against nematodes
Increased plant vigor, comprising plant health / plant quality and seed vigor, reduced stand failure, improved appearance, increased recovery, improved greening effect and improved photosynthetic efficiency.
Effects on plant hormones and/or functional enzymes.
Effects on growth regulators (promoters), comprising earlier germination, better emergence, more developed root system and/or improved root growth, increased ability of tillering, more productive tillers, earlier flowering, increased plant height and/or biomass, shorting of stems, improvements in shoot growth, number of kemels/ear, number of ears/m2, number of stolons and/or number of flowers, enhanced harvest index, bigger leaves, less dead basal leaves, improved phyllotaxy, earlier maturation / earlier fruit finish, homogenous riping, increased duration of grain filling, better fruit finish, bigger fruit/vegetable size, sprouting resistance and reduced lodging.
Increased yield, referring to total biomass per hectare, yield per hectare, kerne 1/fru it weight, seed size and/or hectolitre weight as well as to increased product quality, comprising: improved processability relating to size distribution (kernel, fruit, etc.), homogenous riping, grain moisture, better milling, better vinification, better brewing, increased juice yield, harvestability, digestibility, sedimentation value, falling number, pod stability, storage stability, improved fiber length/strength/uniformity, increase of milk and/or meet quality of silage fed animals, adaption to cooking and frying; further comprising improved marketability relating to improved fruit/grain quality, size distribution (kernel, fruit, etc.), increased storage / shelf-life, firmness / softness, taste (aroma, texture, etc.), grade (size, shape, number of berries, etc.), number of berries/fruits per bunch, crispness, freshness, coverage with wax, frequency of physiological disorders, colour, etc.; further comprising increased desired ingredients such as e.g. protein content, fatty acids, oil content, oil quality, aminoacid composition, sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols, starch content, nutritional quality, gluten content/index, energy content, taste, etc.; and further comprising decreased undesired ingredients such as e.g. less mycotoxines, less aflatoxines, geosmin level, phenolic aromas, lacchase, polyphenol oxidases and peroxidases, nitrate content etc.
Sustainable agriculture, comprising nutrient use efficiency, especially nitrogen (N)-usc efficiency, phosphours (P)-use efficiency, water use efficiency, improved transpiration, respiration and/or CO2 assimilation rate, better nodulation, improved Ca-metabolism etc..
Delayed senescence, comprising improvement of plant physiology which is manifested, for example, in a longer grain filling phase, leading to higher yield, a longer duration of green leaf colouration of the plant and thus comprising colour (greening), water content, dryness etc.. Accordingly, in the context of the present invention, it has been found that the specific inventive application of the active compound combination makes it possible to prolong the green leaf area duration, which delays the maturation (senescence) of the plant. The main advantage to the farmer is a longer grain filling phase leading to higher yield. There is also an advantage to the farmer on the basis of greater flexibility in the harvesting time.
Therein“sedimentation value” is a measure for protein quality and describes according to Zeleny (Zeleny value) the degree of sedimentation of flour suspended in a lactic acid solution during a standard time interval. This is taken as a measure of the baking quality. Swelling of the gluten fraction of flour in lactic acid solution affects the rate of sedimentation of a flour suspension. Both a higher gluten content and a better gluten quality give rise to slower sedimentation and higher Zeleny test values. The sedimentation value of flour depends on the wheat protein composition and is mostly correlated to the protein content, the wheat hardness, and the volume of pan and hearth loaves. A stronger correlation between loaf volume and Zeleny sedimentation volume compared to SDS sedimentation volume could be due to the protein content influencing both the volume and Zeleny value ( Czech J Food Sci. Vol. 27, No. 3: 91-96, 2000).
Further the“falling number” as mentioned herein is a measure for the baking quality of cereals, especially of wheat. The falling number test indicates that sprout damage may have occurred. It means that changes to the physical properties of the starch portion of the wheat kernel has already happened. Therein, the falling number instrument analyzes viscosity by measuring the resistance of a flour and water paste to a falling plunger. The time (in seconds) for this to happen is known as the falling number. The falling number results are recorded as an index of enzyme activity in a wheat or flour sample and results are expressed in time as seconds. A high falling number (for example, above 300 seconds) indicates minimal enzyme activity and sound quality wheat or flour. A low falling number (for example, below 250 seconds) indicates substantial enzyme activity and sprout-damaged wheat or flour.
The term“more developed root system” /“improved root growth” refers to longer root system, deeper root growth, faster root growth, higher root dry/fresh weight, higher root volume, larger root surface area, bigger root diameter, higher root stability, more root branching, higher number of root hairs, and/or more root tips and can be measured by analyzing the root architecture with suitable methodologies and Image analysis programmes (e.g. WinRhizo). The term“crop water use efficiency” refers technically to the mass of agriculture produce per unit water consumed and economically to the value of product(s) produced per unit water volume consumed and can e.g. be measured in terms of yield per ha, biomass of the plants, thousand-kernel mass, and the number of ears per m2.
The term“nitrogen-use efficiency” refers technically to the mass of agriculture produce per unit nitrogen consumed and economically to the value of product(s) produced per unit nitrogen consumed, reflecting uptake and utilization efficiency.
Improvement in greening / improved colour and improved photosynthetic efficiency as well as the delay of senescence can be measured with well-known techniques such as a HandyPea system (Hansatech). Fv/Fm is a parameter widely used to indicate the maximum quantum efficiency of photosystem II (PSII). This parameter is widely considered to be a selective indication of plant photosynthetic performance with healthy samples typically achieving a maximum Fv/Fm value of approx. 0.85. Values lower than this will be observed if a sample has been exposed to some type of biotic or abiotic stress factor which has reduced the capacity for photochemical quenching of energy within PSII. Fv/Fm is presented as a ratio of variable fluorescence (Fv) over the maximum fluorescence value (Fm). The Performance Index is essentially an indicator of sample vitality. (See e.g. Advanced Techniques in Soil Microbiology, 2007, 11, 319-341 ; Applied Soil Ecology, 2000, 15, 169-182.)
The improvement in greening / improved colour and improved photosynthetic efficiency as well as the delay of senescence can also be assessed by measurement of the net photosynthetic rate (Pn), measurement of the chlorophyll content, e.g. by the pigment extraction method of Ziegler and Ehle, measurement of the photochemical efficiency (Fv/Fm ratio), determination of shoot growth and final root and/or canopy biomass, determination of tiller density as well as of root mortality.
Within the context of the present invention preference is given to improving plant physiology effects which are selected from the group comprising: enhanced root growth / more developed root system, improved greening, improved water use efficiency (correlating to reduced water consumption), improved nutrient use efficiency, comprising especially improved nitrogen (N)-use efficiency, delayed senescence and enhanced yield.
Within the enhancement of yield preference is given as to an improvement in the sedimentation value and the falling number as well as to the improvement of the protein and sugar content - especially with plants selected from the group of cereals (preferably wheat).
Preferably the novel use of the fungicidal compositions of the present invention relates to a combined use of a) preventively and/or curatively controlling pathogenic fungi and/or nematodes, with or without resistance management, and b) at least one of enhanced root growth, improved greening, improved water use efficiency, delayed senescence and enhanced yield. From group b) enhancement of root system, water use efficiency and N-use efficiency is particularly preferred.
Preparation examples
Preparation of compounds of the formula (I) according to process A:
General procedure A
Figure imgf000073_0001
To a solution of the corresponding vinyl bromide (III-Br) (1.0 - 1.1 equivalents) dissolved in diethyl ether (0.2 - 0.4M with respect to vinyl bromide (III-Br)) under an argon atmosphere and cooled to -78 °C was added slowly a solution of t-butyllithium (1.7M in pentane, 2.1 equivalents). The resulting mixture was stirred 15 minutes at this temperature, before being warmed to room temperature (= 2l°C, in the following referred to as rt) and stirred for approximately 30 minutes. This solution was slowly added to a solution of the corresponding ketone (IV) (1 equivalent) dissolved in dichloromethane (0.05-0.2M with respect to ketone (IV)) under an argon atmosphere and cooled to -78 °C. The reaction mixture was stirred for approximately 30 minutes at -78 °C, or in some cases was warmed to rt and stirred for a period of 0.5h - l6h, and was then quenched either at -78 °C or at rt with water and stirred until the mixture reached rt. The mixture was diluted with water and dichloromethane and the organic phase was separated. The remaining aqueous phase was extracted twice with ethyl acetate and the combined organic phases were dried over anhydrous magnesium sulphate, filtered and the solvent was removed under reduced pressure using a rotary evaporator. The residue obtained was purified using preparative HPLC to afford the corresponding desired vinyl alcohol (I-Ha).
Preparation of 1 -G2-( 1 -chlorocvclot>rot>yl)-2-(3.4-dihydronat)hthalen- 1 -yl)-2-hvdroxyethyl1- 1 H-imidazole- 5-carbonitrile (T01)
Figure imgf000073_0002
1 - [2-( 1 -chlorocyclopropyl)-2-(3 ,4-dihydronaphthalen- 1 -yl)-2-hydroxyethyl]- 1 H-imidazole-5-carbonitrile (1-01) was prepared according to general procedure A from 4-bromo-l,2-dihydronaphthalene (1.10 g, 5.24 mmol) in diethyl ether (20 mL), t-butyllithium (5.9 mL, 10.0 mmol, 1.7M solution in pentane) and l-[2-(l- chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.00 g, 4.77 mmol) in dichloromethane (40 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (65 mg, 98% LCMS purity, 4% yield based on theory). MS (ESI): 340.1 1 ([M+H]+)
Preparation of 1 -G2-( l -chloiOcvclooiOoyl )-2-(5.7- limcthyl-3.4-dihvdiOnaohthalcn- l -yl )-2-hvdiOxycthyl1- 1 H-imidazole-5-carbonitrile (1-02 )
Figure imgf000074_0001
1 - [2-( 1 -chlorocyclopropyl)-2-(5,7-dimethyl-3 ,4-dihydronaphthalen- 1 -yl)-2-hydroxyethyl]- 1 H-imidazole- 5-carbonitrile (T02) was prepared according to general procedure A from 4-bromo-6, 8-dimethyl- 1,2- dihydronaphthalene (1.19 g, 5.00 mmol) in diethyl ether (15 mL), t-butyllithium (5.9 mL, 10.0 mmol, 1.7M solution in pentane) and l-[2-(l-chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.00 g, 4.77 mmol) in dichloromethane (40 mL). The mixture was reacted approximately 30 minutes at -78 °C and then approximately 16h at rt following the mixing of the two solutions. The crude product was purified by automated flash chromatography (Combiflash, using a 40 g silica gel cartridge, gradient elution ethyl acetate in heptane 0% 10% 20%) and the product-containing fractions were collected and evaporated, then the residue was further purified by preparative HPLC to provide the title compound (29 mg, 88% LCMS purity, 1% yield based on theory).
MS (ESI): 368.15 ([M+H]+) Preparation of 1 -G2-11 -chlorocvclopropyf)-2-f5-chloro-3.4-dihvdronaphthalen- l-ylV2-hvdroxyethyll- 1H- imidazole-5-carbonitrile (1-03 )
Figure imgf000074_0002
1 - [2-( 1 -chlorocyclopropyl)-2-(5 -chloro-3 ,4-dihydronaphthalen- 1 -yl)-2-hydroxyethyl] - 1 H-imidazole-5- carbonitrile (T03) was prepared according to general procedure A from 4-bromo-8-chloro-l,2- dihydronaphthalene (1.63 g, 6.67 mmol) in diethyl ether (15 mL), t-butyllithium (8.3 mL, 14.0 mmol, 1.7M solution in pentane) and l-[2-(l-chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.40 g, 6.67 mmol) in dichloromethane (30 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (219 mg, 95% LCMS purity, 8% yield based on theory).
MS (ESI): 374.07 ([M+H]+)
Preparation of 1 -G2-G 1 - -2-(5-fluoro-3.4-dihvdronaphthalcn- 1 -ylV2-hvdroxyethyll- 1 H-
Figure imgf000075_0001
imidazole-5-carbonitrile (1-04 )
Figure imgf000075_0002
1 - [2-( 1 -chlorocyclopropyl)-2-(5-fluoro-3 ,4-dihydronaphthalen- 1 -yl)-2-hydroxyethyl]- 1 H-imidazole-5- carbonitrile (1-04) was prepared according to general procedure A from 4-bromo-8-fluoro-l,2- dihydronaphthalene (1.73 g, 7.63 mmol) in diethyl ether (15 mL), t-butyllithium (9.4 mL, 16.0 mmol, 1.7M solution in pentane) and l-[2-(l-chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.60 g, 7.63 mmol) in dichloromethane (30 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (181 mg, 98% LCMS purity, 6% yield based on theory).
MS (ESI): 358.10 ([M+H]+)
Preparation of 1 -G2-G 1 -chlorocvclopropylV2-hvdroxy-2-f5-methoxy-3.4-dihvdronaphthalen- 1 -vDcthyll- 1 H- imidazole-5-carbonitrile (1-05 )
Figure imgf000075_0003
1 - [2-( 1 -chlorocyclopropyl)-2-hydroxy-2-(5 -methoxy-3 ,4-dihydronaphthalen- 1 -yl)ethyl] - 1 H-imidazole-5 - carbonitrile (1-05) was prepared according to general procedure A from 4-bromo-8-methoxy-l,2- dihydronaphthalene (1.14 g, 4.77 mmol) in diethyl ether (10 mL), t-butyllithium (5.9 mL, 10.0 mmol, 1.7M solution in pentane) and l-[2-(l-chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.00 g, 4.77 mmol) in dichloromethane (20 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (31 mg, 95% LCMS purity, 2% yield based on theory).
MS (ESI): 370.12 ([M+H]+) Preparation of 1 -G2-11 -chlorocvclopropyf)-2-hvdroxy-2-f6-methoxy-3.4-dihvdronaphthalen- 1 -vDcthyll- 1 H- imidazole-5-carbonitrile (1-06 )
Figure imgf000076_0001
1 - [2-( 1 -chlorocyclopropyl)-2-hydroxy-2-(6-methoxy-3 ,4-dihydronaphthalen- 1 -yl)ethyl] - 1 H-imidazole-5 - carbonitrile (T06) was prepared according to general procedure A from 4-bromo-7-methoxy-l,2- dihydronaphthalene (1.60 g, 6.67 mmol) in diethyl ether (15 mL), t-butyllithium (5.9 mL, 10.0 mmol, 1.7M solution in pentane) and l-[2-(l-chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.40 g, 4.77 mmol) in dichloromethane (30 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (36 mg, 91% LCMS purity, 1% yield based on theory). MS (ESI): 370.12 ([M+H]+)
Preparation of 1 -G2-(1 -chlorocvclot>rot)yl)-2-(6-fluoro-2H-chromen-4-yl)-2-hvdroxyethyll- 1 H-imidazole-5- carbonitrile (T07)
Figure imgf000076_0002
1 - [2-( 1 -chlorocyclopropyl)-2-(6-fluoro-2H-chromen-4-yl)-2-hydroxyethyl] - 1 H-imidazole-5 -carbonitrile (I- 07) was prepared according to general procedure A from 4-bromo-6-fluoro-2H-chromene (1.08 g, 4.72 mmol) in diethyl ether (10 mL), t-butyllithium (5.8 mL, 9.9 mmol, 1.7M solution in pentane) and l-[2-(l- chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (0.99 g, 4.72 mmol) in dichloromethane (20 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (189 mg, 99% LCMS purity, 11% yield based on theory). MS (ESI): 360.08 ([M+H]+)
Preparation of 1 -G2-G 1 -chlorocvclopropyl)-2-f6.7-dihvdro-5H-benzo|71annulen-9-yl)-2-hvdroxyethyl1- 1H- imida7ole-5-carbonitrile (Ί-08
Figure imgf000077_0001
1 - [2-( 1 -chlorocyclopropyl)-2-(6,7-dihydro-5H-benzo [7]annulen-9-yl)-2-hydroxyethyl]- 1 H-imidazole-5 - carbonitrile (1-08) was prepared according to general procedure A from 9-bromo-6,7-dihydro-5H- benzo[7]annulene (0.73 g, 3.29 mmol) in diethyl ether (7 mL), t-butyllithium (4.1 mL, 6.9 mmol, 1.7M solution in pentane) and l-[2-(l-chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (0.69 g, 3.29 mmol) in dichloromethane (20 mL). The mixture was reacted approximately 30 minutes at -78 °C following the mixing of the two solutions, affording the title compound after preparative HPLC purification (94 mg, 99% LCMS purity, 8% yield based on theory).
MS (ESI): 354.13 ([M+H]+)
Preparation of compounds of the formula according to process B:
Figure imgf000077_0002
General procedure 1B
Figure imgf000077_0003
To a solution of ketone (II) (1 equivalent) in methanol (approximately 0.3M with respect to ketone (II)) was added 2,4,6-triisopropylbenzenesulfonohydrazide (1 equivalent) and the resulting mixture was stirred at a temperature between 25 °C - 70 °C for a period of 2h - 72h, monitoring reaction progress by LCMS. After the reaction was judged to be complete, the reaction solvent was evaporated and the product was purified either by recrystallization from an appropriate solvent and/or column chromatography to afford the desired product.
Preparation of N - 2.3 -dihvdro- 1 H-inden- 1 -ylidene)-2.4.6-triisopropylbenzenesulfonohvdrazide (VI-01 )
Figure imgf000078_0001
N'-(2,3-dihydro-lH-inden-l-ylidene)-2,4,6-triisopropylbenzenesulfonohydrazide (VI-01) was prepared according to general procedure 1B from indan-l-one (2.20 g, 16.6 mmol) and 2,4,6- triisopropylbenzenesulfonohydrazide (4.97 g, 16.6 mmol) in methanol (50 mL) at 50 °C for 3h. After which, the reaction was concentrated to approximately 10% of the original volume and placed in the freezer at - 20 °C to induce further solid formation. The solid material was collected by filtration and washed with small portions of cold mcthyl-te/7-butylcthcr. After drying, the solid material was found to contain an impurity, so the entirety of the obtained solid was recombined with the mother liquor and washings and the solvent was evaporated on the rotary evaporator. The residue was purified by flash column chromatography on silica gel (gradient elution, ethyl acetate in n-heptane) and the product-containing fractions were combined. The solvent from the combined fractions was evaporated to approximately 10% of the original volume, during which solid material formed. The solid was collected by filtration and washed with small portions of n- heptane to afford, after drying under vacuum, the title compound (2.18 g, 32% yield based on theory)
MS (ESI): 413.22 ([M+H]+) Preparation of compounds of the formula (I) according to process B:
General procedure 2B
Figure imgf000078_0002
The corresponding hydrazone (VT-a) (1 equivalent) was dissolved in THF (approximately 0.4 - 0.5 M with respect to hydrazone (VI-a)) under an argon atmosphere and cooled to -78 °C. To this solution was slowly added a solution of n-butyllithium (in the following abbreviated n-BuLi) (2.2 equivalents, 2.5M in hexanes) and the resulting mixture stirred 15 min, then warmed to 0 °C for approximately 30 minutes, until gas evolution ceased, and then warmed to rt for approximately 10 minutes. The resulting mixture was slowly added to a solution of the corresponding ketone (IV) (1 equivalent) in dichloromethane (approximately 0.1 - 0.3M with respect to ketone (IV)) at -78 °C under an argon atmosphere. The reaction was stirred for approximately 30 minutes at -78 °C, or in some cases optionally warmed to rt and stirred for a period of 0.5h - 16h, and was then quenched either at -78 °C or at rt with water and stirred until the mixture reached rt. The mixture was diluted with water and dichloromethane and the organic phase was separated. The remaining aqueous phase was extracted twice with ethyl acetate and the combined organic phases were dried over anhydrous magnesium sulphate, filtered and the solvent was removed under reduced pressure using a rotary evaporator. The residue obtained was purified using preparative HPLC to afford the corresponding desired vinyl alcohol (I-Ha).
Preparation of 1 -G2-G 1 -chlorocvclot)rot)yl)-2-hvdroxy-2-nH-inden-3-yl)ethyll- 1 H-imidazole-5-carbonitrile (L09)
Figure imgf000079_0001
1 - [2-( 1 -chlorocyclopropyl)-2-hydroxy-2-( 1 H-inden-3 -yl)ethyl] - 1 H-imidazole-5-carbonitrile (1-09) was prepared according to general procedure 2B from N'-(2, 3-dihydro- lH-inden-l -ylidene)-2, 4,6- triisopropylbenzenesulfonohydrazide (VI-01) (1.97 g, 4.77 mmol) in THF (10 mL) and l-[2-(l- chlorocyclopropyl)-2-oxoethyl]-lH-imidazole-5-carbonitrile (1.00 g, 4.77 mmol) in dichloromethane (20 mL). The mixture was reacted approximately 90 minutes after warming from -78 °C to rt, following the mixing of the two solutions. The title compound was obtained after purification by preparative HPLC (126 mg, 95% LCMS purity, 8% yield based on theory).
MS (ESI): 326.10 ([M+H]+)
Preparation of compounds of the formula (lb) according to process C:
General procedure C
Figure imgf000079_0002
The corresponding vinyl alcohol (I-Ha) was dissolved in ethyl acetate (approximately 0.01 - 0.05M with respect to alcohol (I-Ha)) and hydrogenated using an H-Cube apparatus (ThalesNano H-Cube Hydrogenation Reactor) using (unless otherwise specified) a 10% Pd/C ThalesNano cartridge (THS-011 11- 12EA) at full ¾ pressure (approximately 6 bar) with a flow rate of 1 mL/min at a temperature from 25 °C - 100 °C. In the event of incomplete conversion to product, multiple re-injections of the reaction volume were carried out until the conversion was complete, as judged by LCMS. After reaction completion, the solvent was evaporated and purified either by flash column chromatography or preparative HPLC to afford the corresponding desired product.
Preparation of 1 - G2-P -chlorocvclopropyl)-2-hvdroxy-2-( 1.2.3.4-tetrahvdronar)hthalen- 1 -vDcthyll- 1 H- imidazole-5-carbonitrile (1- 10 )
Figure imgf000080_0001
1 - [2-( 1 -chlorocyclopropyl)-2-hydroxy-2-( 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yljethyl] - 1 H-imidazole-5- carbonitrile (I- 10) was prepared according to general procedure C from l-[2-(l-chlorocyclopropyl)-2-(3,4- dihydronaphthalen-l-yl)-2-hydroxyethyl]-lH-imidazole-5-carbonitrile (60 mg, 0.17 mmol) in ethyl acetate (6 mL) at full ¾ pressure (approximately 6 bar) with a flow rate of 1 mL/min at 40 °C. After two consecutive injections/reaction cycles, the solvent was evaporated and the residue was purified by automated flash chromatography on silica gel (CombiFlash system, ethyl acetate in n-heptane gradient elution) to afford the title compound as an approximately 5: 1 mixture of diastereomers (56 mg, 97.5% LCMS purity, 90% yield based on theory).
MS (ESI): 342.13 ([M+H]+) (Major Diastereomer), MS (ESI): 342.13 ([M+H]+) (Minor Diastereomer)
Preparation of l-r2-(l-chlorocvclopropyl)-2-(5-fluoro-L2.3.4-tetrahvdronaphthalen-l-yl)-2-hvdroxyethyll- lH-imidazole-5-carbonitrile (1-11)
Figure imgf000080_0002
1 - [2-( 1 -chlorocyclopropyl)-2-(5 -fluoro- 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl)-2-hydroxyethyl]- 1 H-imidazole- 5-carbonitrile (I- 11) was prepared according to general procedure C from l-[2-(l-chlorocyclopropyl)-2-(5- fluoro-3,4-dihydronaphthalen-l-yl)-2-hydroxyethyl]-lH-imidazole-5-carbonitrile (130 mg, 0.36 mmol) in ethyl acetate (10 mL) at full ¾ pressure (approximately 6 bar) with a flow rate of 1 mL/min at 35 °C. After four additional injections/reaction cycles at 50 °C, 60 °C, 70 °C and once again at 70 °C, the solvent was evaporated and the residue was purified by automated flash chromatography on silica gel (CombiFlash system, ethyl acetate in n-heptane gradient elution) to afford the title compound as an approximately 10: 1 mixture of diastereomers (85 mg, 95% LCMS purity, 61% yield based on theory).
MS (ESI): 360.12 ([M+H]+) (Major Diastereomer), MS (ESI): 360.12 ([M+H]+) (Minor Diastereomer) Preparation of 1 - G2-P -chlorocvclopropyl!-2-(6-fluoro-3.4-dihvdro-2H-chromen-4-ylV2-hvdroxyethyl1- 1 H- imidazole-5-carbonitrile (1- 12 )
Figure imgf000081_0001
l-[2-(l-chlorocyclopropyl)-2-(6-fluoro-3,4-dihydro-2H-chromen-4-yl)-2-hydroxyethyl]-lH-imidazole-5- carbonitrile (1-12) was prepared according to general procedure C from l-[2-(l-chlorocyclopropyl)-2-(6- fluoro-2H-chromen-4-yl)-2-hydroxyethyl]-lH-imidazole-5-carbonitrile (131 mg, 0.36 mmol) in ethyl acetate (15 mL) at full Ffl pressure (approximately 6 bar) with a flow rate of 1 mL/min at 35 °C. After two additional injections/reaction cycles each at 70 °C, the solvent was evaporated and the residue (approximately 8: 1 mixture of diastereomers by LCMS) was purified by automated flash chromatography on silica gel (CombiFlash system, ethyl acetate in n-heptane gradient elution) to afford the title compound as the major diastereomer (89 mg, 100% LCMS purity, 68% yield based on theory). The minor diastereomer in this case was isolated as a 1 : 1 mixture with residual unreacted starting material ( 10 mg, 50% LCMS purity, 4% yield based on theory).
MS (ESI): 362.10 ([M+H]+) (Major Diastereomer), MS (ESI): 362.10 ([M+H]+) (Minor Diastereomer)
The following tables illustrate in a non-limiting manner examples of compounds according to the invention. The compounds have been prepared according to the preparation examples given above or in analogy thereto.
Table 1 : Compounds according to formula (I)
Figure imgf000082_0001
Figure imgf000082_0003
Table 2: Compounds according to formula (VI)
Figure imgf000082_0002
Figure imgf000083_0001
LogP values:
Measurement of LogP values was performed according to EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed phase columns with the following methods: |a| LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1% formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
|h LogP value is determined by measurement of LC-UV, in a neutral range, with 0.001 molar ammonium acetate solution in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile). [c] LogP value is determined by measurement of LC-UV, in an acidic range, with 0.1% phosphoric acid and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).
If more than one LogP value is available within the same method, all the values are given and separated by
Calibration was done with straight-chain alkan2-ones (with 3 to 16 carbon atoms) with known LogP values (measurement of LogP values using retention times with linear interpolation between successive alkanones).
Lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
NMR-Peak lists
1H-NMR data of selected examples are written in form of lH-NMR-peak lists. To each signal peak are listed the d-value in ppm and the signal intensity in round brackets. Between the d-value - signal intensity pairs are semicolons as delimiters.
The peak list of an example has therefore the form: di (intensityi); d2 (intensity2); . ; d; (intensity;); . ; dh (intensityn)
Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown. For calibrating chemical shift for 1H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur but not necessarily.
The 1H-NMR peak lists are similar to classical 1H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation.
Additionally they can show like classical 1H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities.
To show compound signals in the delta-range of solvents and/or water the usual peaks of solvents, for example peaks of DMSO in DMSO-D6 and the peak of water are shown in our 1H-NMR peak lists and have usually on average a high intensity .
The peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via“side-products-fingerprints”. An expert, who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values) can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1H-NMR interpretation.
Further details of NMR-data description with peak lists you find in the publication“Citation of NMR Peaklist Data within Patent Applications” of the Research Disclosure Database Number 564025.
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000086_0002
_
Use Examples
Example A: in vivo preventive test on Alternaria brassicae (leaf spot on radish or cabbage!
Solvent: 5% by volume of dimethyl sulfoxide (DMSO)
10% by volume of acetone Emulsifier: Imΐ of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
Young plants of radish or cabbage were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Alternaria brassicae spores. The contaminated radish or cabbage plants were incubated for 6 days at 20°C and at 100% relative humidity.
The test was evaluated 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed. In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: 1-01.
Example B: in vivo preventive test on Botrvtis cinerea (grey mould!
Solvent: 5% by volume of dimethyl sulfoxide (DMSO)
10% by volume of acetone Emulsifier: Imΐ of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of gherkin were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores. The contaminated gherkin plants were incubated for 4 to 5 days at l7°C and at 90% relative humidity. The test was evaluated 4 to 5 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01. Example C: in vivo preventive test on Puccinia recondita (brown rust on wheat!
Solvent: 5% by volume of dimethyl sulfoxide (DMSO)
10% by volume of acetone
Emulsifier: lpl of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of wheat were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores. The contaminated wheat plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 10 days at 20°C and at 70-80% relative humidity.
The test was evaluated 1 1 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01. Example D: in vivo preventive test on Pyrenophora teres (net blotch on
Figure imgf000088_0001
Solvent: 5% by volume of dimethyl sulfoxide (DMSO)
10% by volume of acetone
Emulsifier: Imΐ of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of barley were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores. The contaminated barley plants were incubated for 48 hours at 20°C and at 100% relative humidity and then for 12 days at 20°C and at 70-80% relative humidity.
The test was evaluated 14 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed. ln this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01.
Example E: in vivo preventive test on Septoria tritici (leaf spot on wheat!
Solvent: 5% by volume of dimethyl sulfoxide (DMSO) 10% by volume of acetone
Emulsifier: lpl of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of wheat were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Septoria tritici spores. The contaminated wheat plants were incubated for 72 hours at l7°C and at 100% relative humidity and then for 15 days at 20°C and at 90% relative humidity.
The test was evaluated 19 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01.
Example F : in vivo preventive test on Sphaerotheca fulmnea fpowderv mildew on cucurbits!
Solvent: 5% by volume of dimethyl sulfoxide (DMSO) 10% by volume of acetone
Emulsifier: Imΐ of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration. The young plants of gherkin were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores. The contaminated gherkin plants were incubated for 8 days at 20°C and at 70-80% relative humidity.
The test was evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01. Example G: in vivo preventive test on Uromvces amendiculatus (bean rust)
Solvent: 5% by volume of dimethyl sulfoxide (DMSO)
10% by volume of acetone
Emulsifier: lpl of Tween® 80 per mg of active ingredient
The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of bean were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80.
After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores. The contaminated bean plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 10 days at 20°C and at 70-80% relative humidity.
The test was evaluated 1 1 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
In this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01. Example H: in vivo preventive test on Colletotrichum lindemuthianum (leaf spot on bean)
Solvent: 5% by volume of dimethyl sulfoxide (DMSO)
10% by volume of acetone
Emulsifier: 1 mΐ of Tween® 80 per mg of active ingredient The active ingredients were made soluble and homogenized in a mixture of dimethyl sulfoxide/acetone/ /Tween® 80 and then diluted in water to the desired concentration.
The young plants of bean were treated by spraying the active ingredient prepared as described above. Control plants were treated only with an aqueous solution of acetone/dimethyl sulfoxide/ Tween® 80. After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Colletotrichum lindemuthianum spores. The contaminated bean plants were incubated for 24 hours at 20°C and at 100% relative humidity and then for 6 days at 20°C and at 90% relative humidity.
The test was evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed. ln this test, the following compounds according to the invention showed efficacy of at least 70% at a concentration of 500 ppm of active ingredient: 1-01.

Claims

Claims
Compound of formula (I)
Figure imgf000092_0001
wherein
R1 represents hydrogen, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C3-Cs-cycloalkyl or Ce-Cu- aryl,
R2 represents hydrogen, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C3-Cs-cycloalkyl or Ce-Cu- aryl, wherein the aliphatic moieties, excluding cycloalkyl moieties, of R1 and R2 may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, C3-Cs-cycloalkyl, Ce-Cu- aryl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, wherein the C3-Cs-cycloalkyl and C6-Ci4-aryl may be substituted by 1, 2, 3, 4 or 5 substituents selected independently from each other from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, and wherein the cycloalkyl and/or C6-Ci4-aryl moieties of R1 and R2 may carry 1, 2, 3, 4, 5 or up to the maximum number of groups Rb which independently of one another are selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and C1-C4- haloalkoxy;
R3 represents halogen, hydroxyl, cyano, isocyano, nitro, amino, sulfanyl, pentafluoroG6-sulfanyl, carboxaldehyde, hydroxycarbonyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs- alkyloxy, Ci-Cs-haloalkyloxy, tri(Ci-Cs-alkyl)silyl, tri(Ci-C8-alkyl)silyl-Ci-Cs-alkyl, C3-C7- cycloalkyl, C3-C7-halocycloalkyl, C3-C7-cycloalkenyl, C3-C7-halocycloalkenyl, C3-C7- cycloalkyl-Ci-C8-alkyl, C3-C7-halocycloalkyl-Ci-C8-alkyl, C3-C7-cycloalkyl-C3-C7- cycloalkyl, Ci-C8-alkyl-C3-C7-cycloalkyl, Ci-C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-Cs- alkyl)silyl-C3-C7-cycloalkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C2-Cs-alkenyloxy, C2-C8- haloalkenyloxy, C2-Cs-alkynyloxy, C2-C8-haloalkynyloxy, Ci-Cs-alkylamino, Ci-Cs- haloalkylamino, Ci-Cs-cyanoalkoxy, C3-C7-cycloalkyl-Ci-C8-alkoxy, C3-C7-cycloalkoxy, Ci- Cs-alkylsulfanyl, Ci-Cs-haloalkylsulfanyl, Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkylcarbonyl, G,- Cwarylcarbonyl, C6-Ci4-aryl-Ci-C6-alkylcarbonyl, C3-C7-cycloalkylcarbonyl, C3-C7- halocycloalkylcarbonyl, carbamoyl, /V- G - C'x - a 1 k y 1 c a rb a m 0 y 1 , /V, /V-di-(C 1 -G-alkyl )carbamoy 1, /V-G -G-alkyloxycarbamoyl, /V-(G -G-alkyl )-/V-(G -G-alkoxy)aminocarbonyl, aminothiocarbonyl, Ci-Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, C3-C7- cycloalkoxycarbonyl, Ci-Cs-alkoxy-Ci-Cs-alkylcarbonyl, Ci-Cs-haloalkoxy- -Cs- alkylcarbonyl, C3-C7-cycloalkoxy-Ci-Cs-alkylcarbonyl, /V- Cs - C- - c y c 10 a 1 k y 1 a m i n oc a rb 0 ny 1 , Ci-Cs-alkylcarbonyloxy, Ci-Cs-haloalkylcarbonyloxy, C3-C7-cycloalkylcarbonyloxy, Ci-Cs- alkylcarbonylamino, Ci-Cs-haloalkylcarbonylamino, /V- Ci - Cs - a 1 k y 1 a m i n oc a rb 0 n y 10 x y , NN- di-(Ci-C8-alkyl)aminocarbonyloxy, Ci-Cs-alkyloxycarbonyloxy, Ci-Cs-alkylsulfmyl, Ci-Cs- haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs-haloalkylsulfbnyl, Ci-Cs-alkylsulfonyloxy, Ci- C8-haloalkylsulfonyloxy, Ci-Cs-alkylaminosulfamoyl, di-Ci -Cs-alkylaminosulfamoyl, (Ci-Cs- alkoxyimino)-Ci-C8-alkyl, (C3-C7-cycloalkoxyimino)-Ci-C8-alkyl, hydroxy imino-Ci -Cs-alkyl, (Ci-C8-alkoxyimino)-C3-C7-cycloalkyl, hydroxyimino-C3-C7-cycloalkyl, (Ci-Cs-alkylimino)- oxy, (Ci-C8-alkylimino)-oxy-Ci-C8-atkyl, (C3-C7-cycloatkylimino)-oxy-Ci-C8-alkyl, (Ci-Cs- alkylimino)-oxy-C3-C7-cycloalkyl, (Ci-C8-alkenyloxyimino)-Ci-C8-atkyl, (Ci-Cs- alkynyloxyimino)-Ci-C8-alkyl, (benzyloxyimino)-Ci-C8-alkyl, Ci -Cs-alkoxy-C'i -Cs-alkyl, Ci- C8-alkyl-Ci-C8-thioalkyl, Ci -Cs-alkoxy-C'i -Cs-alkoxy-C'i -Cs-alkyl, Ci -C's-haloalkoxy-C'i -Cs- alkyl, benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, benzyloxy, phenyloxy, benzylsulfanyl, benzylamino, phenylsulfanyl, or phenylamino, wherein the benzyl, phenyl, 5- membered heteroaryl, 6-membered heteroaryl, benzyloxy or phenyloxy is non-substituted or substituted by one or more group(s) selected from halogen, hydroxyl, cyano, isocyano, amino, sulfanyl, pentafluoro^6-sulfanyl, carboxaldehyde, hydroxycarbonyl, Ci -Cs-alkyl, C' I -C' S- haloalkyl, C'l -C's-cyanoalkyl, C'l-C's-alkyloxy, C'l-C's-haloalkyloxy, tri(Ci-C8-alkyl)silyl, tri(Ci- C8-alkyl)silyl-Ci-C8-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C3-C7-cycloalkenyl, C3- C7-halocycloalkenyl, C3-C7-cycloalkyl-Ci-C8-alkyl, C3-C7-halocycloalkyl-Ci-C8-alkyl, C3-C7- cycloalkyl-C3-C7-cycloalkyl, Ci-C8-alkyl-C3-C7-cycloalkyl, Ci-C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-C8-alkyl)silyl-C3-C7-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C2-C8-alkenyloxy, C2- C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8-haloalkynyloxy, C' l-C's-alkylamino, C' I -C'S- haloalkylamino, C' l-C's-cyanoalkoxy, C3-C7-cycloalkyl-Ci-C8-alkoxy, C3-C7-cycloalkoxy, Ci- Cs-alkylsulfanyl, C 1 -C's- hal oal ky 1 su 1 fany 1 , C'l-C's-alkylcarbonyl, C'l-C's-haloalkylcarbonyl, G,- Ci4-arylcarbonyl, C6-Ci4-aryl-Ci-C8-alkylcarbonyl, C3-C7-cycloalkylcarbonyl, C3-C7- halocycloalkylcarbonyl, /V-C'i -C's-alkylcarbamoyl, /V,/V-di-(C'i-C'8-alkyl)carbamoyl, /V-C'i-C's- alkyloxycarbamoyl, /V- ( C 1 - C's - a 1 ky 1 ) - /V- ( C's - C's - a 1 k 0 x y ) a m i n 0 c a rb 0 n y 1 , aminothiocarbonyl, Ci- Cs-alkoxycarbonyl, Ci-Cs-haloalkoxycarbonyl, C3-C7-cycloalkoxycarbonyl, C'l -C's-alkoxy-C'i- Cs-alkylcarbonyl, Ci -C's-haloalkoxy-C'i -Cs-alkylcarbonyl, C3-C7-cycloalkoxy-Ci-C8- alkylcarbonyl, /V-C'3-C'7-cycloalkylaminocarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs- haloalkylcarbonyloxy, C3-C7-cycloalkylcarbonyloxy, Ci-Cs-alkylcarbonylamino, Ci-Cs- haloalkylcarbonylamino, /V- Ci - C's - a 1 ky 1 a m i n 0 c arb 0 n y 10 x y , /V' /V-di-fC'i-C's- alkyl)aminocarbonyloxy, Ci-Cs-alkyloxycarbonyloxy, Ci-Cs-alkylsulfinyl, Ci-Cs- haloalkylsulfinyl, Ci-Cs-alkylsulfonyl, Ci-Cs-haloalkylsulfonyl, Ci-Cs-alkylsulfonyloxy, Ci- C8-haloalkylsulfonyloxy, Ci-Cs-alkylaminosulfamoyl, di-Ci-Cs-alkylaminosulfamoyl, (Ci-Cs- alkoxyimino)-Ci-C8-alkyl, (C3-C7-cycloalkoxyimino)-Ci-C8-alkyl, hydroxyimino-Ci-Cs-alkyl, (Ci-C8-alkoxyimino)-C3-C7-cycloalkyl, hydroxyimino-C3-C7-cycloalkyl, (Ci-Cs-alkylimino)- oxy, (Ci-C8-alkylimino)-oxy-Ci-C8-alkyl, (C3-C7-cycloalkylimino)-oxy-Ci-Cs-alkyl, (Ci-Cs- alkylimino)-oxy-C3-C7-cycloalkyl, (Ci-C8-alkenyloxyimino)-Ci-C8-alkyl, (Ci-Cs- alkynyloxyimino)-Ci-C8-alkyl, (benzyloxyimino)-Ci-Cs-alkyl, Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci- C8-alkylthio-Ci-C8-alkyl, Ci-Cs-alkoxy-Ci-Cs-alkoxy-Ci-Cs-alkyl, Ci-Cs-haloalkoxy-Ci-Cs- alkyl, benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, benzyloxy, phenyloxy, benzylsulfanyl, benzylamino, phenylsulfanyl, or phenylamino; and
R4 represents a bicyclic moiety of formula (Q)
Figure imgf000094_0001
(Q),
wherein the dotted line A represents a single or double bond;
X1, X2, X3, and X4 independently from each other represent hydrogen, halogen, nitro, cyano, sulfanyl, pentafluoroA6-sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl having 1 to 5 halogen atoms, C3-C7-cycloalkyl, C3-C7-halocycloalkyl having 1 to 5 halogen atoms, Ci-Cs- haloalkyl-C3-C7-cycloalkyl, C3-C7-cycloalkenyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Ce-Cu- bicycloalkyl, C3-C7-cycloalkyl-C2-Cs-alkenyl, C3-C7-cycloalkyl-C2-Cs-alkynyl, Ci-Cs- alkoxy, Ci-Cs-haloalkoxy having 1 to 5 halogen atoms, Ci-Cs-alkoxycarbonyl, Ci-Cs- haloalkoxycarbonyl, Ci-Cs-alkylsulfenyl, C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, C3-C7- cycloalkoxy, Ci-Cs-alkylsulfinyl, Ci-Cs-alkylsulfonyl, tri(Ci-Cs-alkyl)-silyloxy, tri(Ci- C8-atkyl)-silyl, tri(Ci-C8-alkyl)-silyl-C2-C8-alkynyl, tri(Ci-C8-alkyl)-silyl-C2-C8- alkynyloxy, C6-Ci4-aryl, C6-Ci4-aryloxy, C6-Ci4-arylsulfenyl, 5- or 6-membered heteroaryl, 5- or 6-membered heteroaryloxy, wherein the C6-Ci4-aryl, C6-Ci4-aryloxy, C6-Ci4-arylsulfenyl, 5- or 6-membered heteroaryl, 5- or 6-membered heteroaryloxy is non-substituted or substituted by one or more group(s) independently from each other selected from halogen, cyanosulfanyl, pentafluoro^6-sulfanyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-cyanoalkyl, Ci-Cs- alkyloxy, Ci-Cs-haloalkyloxy, tri(Ci-Cs-alkyl)silyl, tri(Ci-Cs-alkyl)silyl-Ci-C8-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C3-C7-cycloalkenyl, C3-C7-halocycloalkenyl, C3-C7-cycloalkyl-Ci-C8-alkyl, C3-C7-halocycloalkyl-Ci-C8-alkyl, C3-C7-cycloalkyl-C3- C7-cycloalkyl, Ci-C8-alkyl-C3-C7-cycloalkyl, Ci-C8-alkoxy-C3-C7-cycloalkyl, tri(Ci-C8- alkyl)silyl-C3-C7-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C2-C8-alkenyloxy, C2-C8- haloalkenyloxy, C2-C8-alkynyloxy, C2-C8-haloalkynyloxy, Ci-Cs-cyanoalkoxy, C3-C7- cycloalkyl-Ci-C8-alkoxy, C3-C7-cycloalkoxy, Ci-Cs-alkylsulfanyl, Ci-Cs- haloalkylsulfanyl, Ci-Ck-alkylsultinyl, Ci-Cs-haloalkylsulfmyl, Ci-Ck-alkylsulfonyl, Ci- C8-haloalkylsulfonyl, Ci-Ck-alkylsulfonyloxy, Ci-Ck-haloalkylsulfonyloxy, Ci-Cs- alkoxy-Ci-C8-alkyl, Ci-Cs-alkylthio-Ci-Cs-alkyl, C 1 -Ck-al koxy-C 1 -Ck-alkoxy-C 1 -CV alkyl, Ci-Cs-haloalkoxy-Ci-Cs-alkyl, benzyl, phenyl, 5-membered heteroaryl, 6- membered heteroaryl, 6-membered heteroaryloxy, benzyloxy, phenyloxy, benzylsulfanyl, and phenylsulfanyl, wherein the benzyl, phenyl, 5-membered heteroaryl, 6-membered heteroaryl, 6- membered heteroaryloxy, benzyloxy, phenyloxy, benzylsulfanyl and phenylsulfanyl is non-substituted or substituted independently from each other by one or more group(s) selected from halogen, CN, nitro, Ci-Cs-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy and pentafluoro-l6-sulfanyl; and
X5 represents Ci-C3-alkanediyl, -Y -CH2- or -Y -(0¾)2-, wherein Y represents O, S or NY1, wherein Y1 represents hydrogen or Ci-Cs-alkyl; and its salts or N-oxides.
2. Compound of formula (I) according to claim 1 , wherein R1 represents cyclopropyl or phenyl, wherein the cyclopropyl and phenyl group may be substituted by 1, 2 or 3, preferably 1 or 2 substituents Rb selected independently of one another from fluorine, chlorine and bromine, and/or
R2 represents hydrogen and its salts or N-oxides. Compound of formula (I) according to claim 1 , wherein
R1 represents l-chlorocyclopropyl, and/or
R2 represents hydrogen and its salts or N-oxides.
4. Compound of formula (I) according to at least one of claims 1 to 3, wherein
R3 represents fluorine, chlorine, bromine, iodine, cyano, nitro, aminothiocarbonyl, C1-C4- haloalkyl or carbamoyl, and its salts or N-oxides. 5. Compound of formula (I) according to at least one of claims 1 to 3, wherein R3 represents cyano, and its salts or N-oxides.
Compound of formula (I) according to at least one of claims 1 to 5, wherein R4 represents a bicyclic moiety of formulae (Ql) to (Q8)
Figure imgf000096_0001
Figure imgf000097_0001
wherein the arrow depicts the bonding position of the shown moiety to the remainder of the molecule, and X1, X2, X3, and X4 are defined as in formula (Q), and its salts or N-oxides. 7. Compound of formula (I) according to at least one of claims 1 to 6, wherein
X1, X2, X3 and X4 represent independently from each other hydrogen, fluorine, chlorine, methyl or methoxy, and its salts or N-oxides.
Compound of formula (I) according to claim 1 , wherein R1 represents 1 -chlorocyclopropyl;
R2 represents hydrogen;
R3 represents cyano; and
R4 represents a bicyclic moiety of formulae (Ql) to (Q8)
Figure imgf000098_0001
wherein the arrow depicts the bonding position of the shown moiety to the remainder of the molecule, and X1, X2, X3 and X4 represent independently from each other hydrogen, fluorine, chlorine, bromine, Ci-C4-alkyl or Ci-C4-alkoxy, and its salts or N- oxides.
9. Composition for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I) according to claim 1, 2, 3, 4, 5, 6, 7 or 8 and at least one carrier and/or surfactant.
10. Method for controlling harmful microorganisms in crop protection and in the protection of materials, characterized in that at least one compound of formula (I) according to claim 1, 2, 3, 4, 5, 6, 7 or 8 and/or a composition according to claim 9 is applied to the harmful microorganisms and/or their habitat.
PCT/EP2019/076410 2018-10-01 2019-09-30 Fungicidal 5-substituted imidazol-1-yl carbinol derivatives WO2020070050A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18197864 2018-10-01
EP18197864.4 2018-10-01

Publications (1)

Publication Number Publication Date
WO2020070050A1 true WO2020070050A1 (en) 2020-04-09

Family

ID=63720529

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/076410 WO2020070050A1 (en) 2018-10-01 2019-09-30 Fungicidal 5-substituted imidazol-1-yl carbinol derivatives

Country Status (1)

Country Link
WO (1) WO2020070050A1 (en)

Citations (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113640A2 (en) 1982-12-14 1984-07-18 Ciba-Geigy Ag 1-Azolyl-2-aryl-3-fluoralkan-2-ols as microbicides
EP0126430A2 (en) 1983-05-19 1984-11-28 Ciba-Geigy Ag Process for the preparation of 1-triazolylethylether-derivatives, and microbicidal compositions containing novel 1-triazolyl-phenoxyphenylethylether-derivatives as active ingredients and their use
DE3639877A1 (en) 1986-11-21 1988-05-26 Bayer Ag HETARYLALKYL SUBSTITUTED 5- AND 6-RINGHETEROCYCLES
EP0275955A1 (en) 1987-01-21 1988-07-27 Ciba-Geigy Ag Microbicidal composition
DE4003180A1 (en) 1990-02-03 1991-08-08 Bayer Ag Halo-allyl-azolyl derivs. - are microbicide(s) for protecting plants and materials from fungal and bacterial attack
US6060051A (en) 1997-05-09 2000-05-09 Agraquest, Inc. Strain of bacillus for controlling plant diseases and corn rootworm
US6245551B1 (en) 1999-03-30 2001-06-12 Agraquest, Inc. Strain of Bacillus pumilus for controlling plant diseases caused by fungi
WO2003106457A1 (en) 2002-06-14 2003-12-24 Syngenta Limited Spiroindolinepiperidine derivatives
WO2004099160A1 (en) 2003-05-12 2004-11-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and pests controlling composition containing the same
WO2006003494A2 (en) 2004-06-28 2006-01-12 Syngenta Participations Ag Piperidine derivatives and their use as insecticides, acaricides, molluscicides or nematicides
WO2006043635A1 (en) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient
US7094592B2 (en) 2001-11-26 2006-08-22 Kumiai Chemical Industry Co., Ltd. Bacillus sp. D747 strain, plant disease controlling agents and insect pest controlling agents using the same and control method using the agents
WO2007040280A1 (en) 2005-10-06 2007-04-12 Nippon Soda Co., Ltd. Cyclic amine compound and pest control agent
CN101337937A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 N-benz-3-substituted amino pyrazoles compounds with insecticidal activity
CN101337940A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity
JP2010018586A (en) 2008-07-14 2010-01-28 Meiji Seika Kaisha Ltd Substance pf1364, its manufacturing method, producing strain and agricultural/horticultural insecticide having the substance as active ingredient
WO2010051926A2 (en) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft New halogen-substituted bonds
WO2010052161A2 (en) 2008-11-06 2010-05-14 Syngenta Participations Ag Herbicidal compositions
CN101715774A (en) 2008-10-09 2010-06-02 浙江化工科技集团有限公司 Preparation and use of compound having insecticidal activity
WO2010066780A1 (en) 2008-12-12 2010-06-17 Syngenta Participations Ag Spiroheterocyclic n-oxypiperidines as pesticides
WO2011085575A1 (en) 2010-01-15 2011-07-21 江苏省农药研究所股份有限公司 Ortho-heterocyclyl formanilide compounds, their synthesis methods and use
WO2011105506A1 (en) 2010-02-25 2011-09-01 日本曹達株式会社 Cyclic amine compound and miticide
WO2011151146A1 (en) 2010-05-31 2011-12-08 Syngenta Participations Ag Method of crop enhancement
WO2012029672A1 (en) 2010-08-31 2012-03-08 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Noxious organism control agent
WO2012034403A1 (en) 2010-09-14 2012-03-22 中化蓝天集团有限公司 Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof
CN102391261A (en) 2011-10-14 2012-03-28 上海交通大学 N-substituted dioxazine compound as well as preparation method and application thereof
WO2013007767A1 (en) 2011-07-13 2013-01-17 Basf Se Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2013050317A1 (en) 2011-10-03 2013-04-11 Syngenta Limited Polymorphs of an isoxazoline derivative
CN103109816A (en) 2013-01-25 2013-05-22 青岛科技大学 Thiobenzamide compounds and application thereof
CN103232431A (en) 2013-01-25 2013-08-07 青岛科技大学 Dihalogenated pyrazole amide compound and its use
WO2013115391A1 (en) 2012-02-01 2013-08-08 日本農薬株式会社 Arylalkyloxy pyrimidine derivative, pesticide for agricultural and horticultural use containing arylalkyloxy pyrimidine derivative as active ingredient, and use of same
CN103265527A (en) 2013-06-07 2013-08-28 江苏省农用激素工程技术研究中心有限公司 Anthranilamide compound as well as preparation method and application thereof
WO2013144213A1 (en) 2012-03-30 2013-10-03 Basf Se N-substituted pyridinylidene compounds and derivatives for combating animal pests
EP2647626A1 (en) 2012-04-03 2013-10-09 Syngenta Participations AG. 1-Aza-spiro[4.5]dec-3-ene and 1,8-diaza-spiro[4.5]dec-3-ene derivatives as pesticides
WO2013162716A2 (en) 2012-04-27 2013-10-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
CN103524422A (en) 2013-10-11 2014-01-22 中国农业科学院植物保护研究所 Benzimidazole derivative, and preparation method and purpose thereof
US20140213448A1 (en) 2012-04-27 2014-07-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US20140275503A1 (en) 2013-03-13 2014-09-18 Dow Agrosciences Llc Process for the preparation of certain triaryl rhamnose carbamates
WO2014187846A1 (en) 2013-05-23 2014-11-27 Syngenta Participations Ag Tank-mix formulations
WO2015058021A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2015058028A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2016005276A1 (en) 2014-07-07 2016-01-14 Bayer Cropscience Aktiengesellschaft Process for preparing fluorinated iminopyridine compounds
WO2016133011A1 (en) 2015-02-17 2016-08-25 日本曹達株式会社 Agrochemical composition
WO2016154297A1 (en) 2015-03-26 2016-09-29 Bayer Cropscience Lp A novel paenibacillus strain, antifungal compounds, and methods for their use
WO2016156290A1 (en) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazole derivatives
WO2018060090A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 5-substituted imidazolylmethyloxirane derivatives as fungicides
WO2018060088A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 5-substituted imidazolylmethyldioxolane derivatives as fungiciides
WO2018060093A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 1,5-substituted imidazole derivatives as fungicides for crop protection.
WO2018060075A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 1 -[2-(1 -chlorocyclopropyl)-2-hydroxy-3-(3-phenyl-1,2-oxazol-5-yl)propyl]-1h-imidazole-5-carbonitrile derivatives and related compounds as fungicides for crop protection
WO2018060073A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazole derivatives
WO2018060091A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazolylmethyl derivatives
WO2018060074A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazolylmethyl derivatives

Patent Citations (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113640A2 (en) 1982-12-14 1984-07-18 Ciba-Geigy Ag 1-Azolyl-2-aryl-3-fluoralkan-2-ols as microbicides
EP0126430A2 (en) 1983-05-19 1984-11-28 Ciba-Geigy Ag Process for the preparation of 1-triazolylethylether-derivatives, and microbicidal compositions containing novel 1-triazolyl-phenoxyphenylethylether-derivatives as active ingredients and their use
DE3639877A1 (en) 1986-11-21 1988-05-26 Bayer Ag HETARYLALKYL SUBSTITUTED 5- AND 6-RINGHETEROCYCLES
EP0275955A1 (en) 1987-01-21 1988-07-27 Ciba-Geigy Ag Microbicidal composition
DE4003180A1 (en) 1990-02-03 1991-08-08 Bayer Ag Halo-allyl-azolyl derivs. - are microbicide(s) for protecting plants and materials from fungal and bacterial attack
US6060051A (en) 1997-05-09 2000-05-09 Agraquest, Inc. Strain of bacillus for controlling plant diseases and corn rootworm
US6245551B1 (en) 1999-03-30 2001-06-12 Agraquest, Inc. Strain of Bacillus pumilus for controlling plant diseases caused by fungi
US7094592B2 (en) 2001-11-26 2006-08-22 Kumiai Chemical Industry Co., Ltd. Bacillus sp. D747 strain, plant disease controlling agents and insect pest controlling agents using the same and control method using the agents
WO2003106457A1 (en) 2002-06-14 2003-12-24 Syngenta Limited Spiroindolinepiperidine derivatives
WO2004099160A1 (en) 2003-05-12 2004-11-18 Sumitomo Chemical Company, Limited Pyrimidine compounds and pests controlling composition containing the same
WO2006003494A2 (en) 2004-06-28 2006-01-12 Syngenta Participations Ag Piperidine derivatives and their use as insecticides, acaricides, molluscicides or nematicides
WO2006043635A1 (en) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient
WO2007040280A1 (en) 2005-10-06 2007-04-12 Nippon Soda Co., Ltd. Cyclic amine compound and pest control agent
WO2007040282A1 (en) 2005-10-06 2007-04-12 Nippon Soda Co., Ltd. Bridged cyclic amine compound and pest control agent
JP2010018586A (en) 2008-07-14 2010-01-28 Meiji Seika Kaisha Ltd Substance pf1364, its manufacturing method, producing strain and agricultural/horticultural insecticide having the substance as active ingredient
CN101337937A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 N-benz-3-substituted amino pyrazoles compounds with insecticidal activity
CN101337940A (en) 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity
CN101715774A (en) 2008-10-09 2010-06-02 浙江化工科技集团有限公司 Preparation and use of compound having insecticidal activity
WO2010051926A2 (en) 2008-11-05 2010-05-14 Bayer Cropscience Aktiengesellschaft New halogen-substituted bonds
WO2010052161A2 (en) 2008-11-06 2010-05-14 Syngenta Participations Ag Herbicidal compositions
WO2010066780A1 (en) 2008-12-12 2010-06-17 Syngenta Participations Ag Spiroheterocyclic n-oxypiperidines as pesticides
WO2011085575A1 (en) 2010-01-15 2011-07-21 江苏省农药研究所股份有限公司 Ortho-heterocyclyl formanilide compounds, their synthesis methods and use
WO2011105506A1 (en) 2010-02-25 2011-09-01 日本曹達株式会社 Cyclic amine compound and miticide
WO2011151146A1 (en) 2010-05-31 2011-12-08 Syngenta Participations Ag Method of crop enhancement
WO2012029672A1 (en) 2010-08-31 2012-03-08 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Noxious organism control agent
WO2012034403A1 (en) 2010-09-14 2012-03-22 中化蓝天集团有限公司 Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof
WO2013007767A1 (en) 2011-07-13 2013-01-17 Basf Se Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2013050317A1 (en) 2011-10-03 2013-04-11 Syngenta Limited Polymorphs of an isoxazoline derivative
CN102391261A (en) 2011-10-14 2012-03-28 上海交通大学 N-substituted dioxazine compound as well as preparation method and application thereof
WO2013115391A1 (en) 2012-02-01 2013-08-08 日本農薬株式会社 Arylalkyloxy pyrimidine derivative, pesticide for agricultural and horticultural use containing arylalkyloxy pyrimidine derivative as active ingredient, and use of same
WO2013144213A1 (en) 2012-03-30 2013-10-03 Basf Se N-substituted pyridinylidene compounds and derivatives for combating animal pests
EP2647626A1 (en) 2012-04-03 2013-10-09 Syngenta Participations AG. 1-Aza-spiro[4.5]dec-3-ene and 1,8-diaza-spiro[4.5]dec-3-ene derivatives as pesticides
US20140213448A1 (en) 2012-04-27 2014-07-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
WO2013162716A2 (en) 2012-04-27 2013-10-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
WO2013162715A2 (en) 2012-04-27 2013-10-31 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
CN103109816A (en) 2013-01-25 2013-05-22 青岛科技大学 Thiobenzamide compounds and application thereof
CN103232431A (en) 2013-01-25 2013-08-07 青岛科技大学 Dihalogenated pyrazole amide compound and its use
US20140275503A1 (en) 2013-03-13 2014-09-18 Dow Agrosciences Llc Process for the preparation of certain triaryl rhamnose carbamates
WO2014187846A1 (en) 2013-05-23 2014-11-27 Syngenta Participations Ag Tank-mix formulations
CN103265527A (en) 2013-06-07 2013-08-28 江苏省农用激素工程技术研究中心有限公司 Anthranilamide compound as well as preparation method and application thereof
CN103524422A (en) 2013-10-11 2014-01-22 中国农业科学院植物保护研究所 Benzimidazole derivative, and preparation method and purpose thereof
WO2015058021A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2015058028A1 (en) 2013-10-17 2015-04-23 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
WO2016005276A1 (en) 2014-07-07 2016-01-14 Bayer Cropscience Aktiengesellschaft Process for preparing fluorinated iminopyridine compounds
WO2016133011A1 (en) 2015-02-17 2016-08-25 日本曹達株式会社 Agrochemical composition
WO2016154297A1 (en) 2015-03-26 2016-09-29 Bayer Cropscience Lp A novel paenibacillus strain, antifungal compounds, and methods for their use
WO2016156290A1 (en) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazole derivatives
WO2018060090A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 5-substituted imidazolylmethyloxirane derivatives as fungicides
WO2018060088A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 5-substituted imidazolylmethyldioxolane derivatives as fungiciides
WO2018060093A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 1,5-substituted imidazole derivatives as fungicides for crop protection.
WO2018060075A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft 1 -[2-(1 -chlorocyclopropyl)-2-hydroxy-3-(3-phenyl-1,2-oxazol-5-yl)propyl]-1h-imidazole-5-carbonitrile derivatives and related compounds as fungicides for crop protection
WO2018060073A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazole derivatives
WO2018060091A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazolylmethyl derivatives
WO2018060074A1 (en) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Novel 5-substituted imidazolylmethyl derivatives

Non-Patent Citations (18)

* Cited by examiner, † Cited by third party
Title
ADVANCED TECHNIQUES IN SOIL MICROBIOLOGY, vol. 77, 2007, pages 319 - 341
APPLIED SOIL ECOLOGY, vol. I5, 2000, pages 169 - 182
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 1332838-17-1
CZECH J. FOOD SCI., vol. 21, no. 3, 2000, pages 91 - 96
HATANO ET AL., J. ORG. CHEM., vol. 75, no. 15, 2010, pages 5008 - 5016
IMAMOTO ET AL., J. AM. CHEM. SOC., vol. 111, no. 12, 1989, pages 4392 - 4398
J. AGRIC. FOOD CHEM., vol. 57, 2009, pages 4854 - 4860
J. ORG. CHEM., vol. 72, 2007, pages 2216 - 2219
J. ORG. CHEM., vol. 74, 2009, pages 3186 - 3188
KRASOVSKIY ET AL., ANGEW. CHEM. INT. ED., vol. 45, no. 3, 2006, pages 497 - 500
METZGER ET AL., ANGEW. CHEM. INT. ED., vol. 49, no. 27, 2010, pages 4665 - 4668
ONGENA, M. ET AL.: "Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol", TRENDS IN MICROBIOLOGY, vol. 16, no. 3, March 2008 (2008-03-01), pages 115 - 125, XP022509718, doi:10.1016/j.tim.2007.12.009
ORG. LETT., vol. 12, 2010, pages 5418 - 5421
ORG. LETT., vol. 14, 2012, pages 2250 - 2253
ORG. LETT., vol. 15, 2013, pages 3894 - 3897
ORG. LETT., vol. 17, 2015, pages 18 - 21
QUINIO ET AL., SYNLETT, vol. 26, no. 04, 2015, pages 514 - 518
WEIDMANNSEEBACH, ANGEW. CHEM. INT. ED., vol. 22, no. 1, 1983, pages 31 - 45

Similar Documents

Publication Publication Date Title
US20220144815A1 (en) 1,3,4-oxadiazoles and their derivatives as new antifungal agents
US20210009541A1 (en) Fungicidal oxadiazoles
WO2019197371A1 (en) Oxadiazoline derivatives
JP2023525349A (en) Triazine and pyrimidine (thio)amide compounds as fungicidal compounds
EP3708565A1 (en) Pyrimidinyloxyphenylamidines and the use thereof as fungicides
US11213031B2 (en) Tetrazolylpropyl derivatives and their use as fungicides
WO2020182929A1 (en) Substituted ureas and derivatives as new antifungal agents
WO2021255070A1 (en) Active compound combinations
US20230278994A1 (en) Heterocyclyl pyrimidines and triazines as novel fungicides
WO2021255170A1 (en) 1,3,4-oxadiazole pyrimidines as fungicides
WO2021239766A1 (en) Active compound combinations
WO2021255089A1 (en) 1,3,4-oxadiazole pyrimidines and 1,3,4-oxadiazole pyridines as fungicides
WO2019162228A1 (en) 1-(5-substituted imidazol-1-yl)but-3-en derivatives and their use as fungicides
US20200275656A1 (en) Trisubstitutedsilylmethylphenoxyquinolines and analogues
US20200231607A1 (en) Trisubstitutedsilylheteroaryloxyquinolines and analogues
US20200079801A1 (en) Trisubstitutedsilylbenzylbenzimidazoles and analogues
WO2020070050A1 (en) Fungicidal 5-substituted imidazol-1-yl carbinol derivatives
WO2020020816A1 (en) Novel triazole derivatives
WO2020020813A1 (en) Fungicidal active compound combinations
EP3915971A1 (en) Phenyl-s(o)n-phenylamidines and the use thereof as fungicides
WO2022058327A1 (en) Substituted ureas and derivatives as new antifungal agents
EP3986874A1 (en) Benzylphenyl hydroxyisoxazolines and analogues as new antifungal agents
WO2020254490A1 (en) Phenoxyphenyl hydroxyisoxazolines and analogues as new antifungal agents
WO2021255169A1 (en) 1,3,4-oxadiazole pyrimidines as fungicides
EP3986892A1 (en) Hydroxyisoxazolines and use thereof as fungicides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19784004

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19784004

Country of ref document: EP

Kind code of ref document: A1