WO2023030935A1 - Method for controlling ppo-i resistant weeds - Google Patents

Method for controlling ppo-i resistant weeds Download PDF

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Publication number
WO2023030935A1
WO2023030935A1 PCT/EP2022/073272 EP2022073272W WO2023030935A1 WO 2023030935 A1 WO2023030935 A1 WO 2023030935A1 EP 2022073272 W EP2022073272 W EP 2022073272W WO 2023030935 A1 WO2023030935 A1 WO 2023030935A1
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WIPO (PCT)
Prior art keywords
weeds
ppo
alkyl
formula
resistant
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PCT/EP2022/073272
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French (fr)
Inventor
Andreas Landes
Aimone PORRI
Lucie MEYER
Douglas FINDLEY
Ricardo Hugo PAVON ROMERO
Liliana Parra Rapado
Tobias SEISER
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Basf Se
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Publication of WO2023030935A1 publication Critical patent/WO2023030935A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the invention relates to a method for controlling PPO-i resistant weeds, wherein at least one compound of formula (I) is applied to at least one PPO-i resistant weed, parts of it or its propagation material.
  • PPO-i and PPO-i‘s” respectively stand for “PPO inhibitor(s)”, “PPO inhibitor herbicide(s)”, “PPO-inhibiting herbicide(s)”, and refer to herbicides that inhibit the enzyme protoporphyrinogen IX oxidase of a plant.
  • PPO-i resistant weed(s) stands for “PPO(s) resistant weed(s)”, “PPO inhibitor(s) resistant weed(s)”, “PPO inhibitor(s) herbicide(s) resistant weed(s)”, “PPO-inhibiting herbicide(s) resistant weed(s)”, and refers to a plant that, in relation to a treatment with an appropriate or over-appropriate rate of PPO-i application, has inherited, developed or acquired an ability
  • Herbicide resistant weeds present a serious problem for efficient weed control because such resistant weeds are increasingly widespread and thus weed control by the application of herbicides is no longer effective.
  • PPO-i resistant weeds are a huge problem to farmers.
  • crop protection it is desirable to increase the specificity and reliability of the action of active compounds.
  • crop protection product it is desirable for the crop protection product to control the harmful plants (weeds) effectively and, at the same time, to be tolerated by the useful plants (crops) in question.
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I) wherein the substituents have the following meanings: R 1 NH 2 , C 1 -C 6 -alkyl; R 2 C 1 -C 6 -haloalkyl; R 3 hydrogen or C 1 -C 6 -alkyl; R 4 H or halogen; R 5 halogen, CN, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkylthio, (C 1 - C 3 -alkyl)amino, di(C 1 -C 3 -alkyl
  • the invention relates to a method for controlling PPO-i resistant weeds, which comprises applying compounds of formula (I) to plants, their habitat or on seed according to the present invention.
  • the invention particularly relates to a method for controlling PPO-i resistant weeds in crops which comprises applying compounds of formula (I) according to the method of the present invention to crops, where said PPO herbicide resistant weeds occur or might occur.
  • the present invention also provides a method for controlling PPO-i resistant weeds, wherein agrochemical compositions comprising at least one compounds of formula (I) and auxiliaries customary for formulating crop protection agents are applied to the PPO-i resistant weed, parts of it or its propagation material.
  • the invention furthermore relates to the use of compounds of formula (I) or the agrochemical compositions comprising them for controlling PPO-i resistant weeds.
  • Effective weed control is defined as at least 70% weed suppression or eradication from the crop, or as at least 70% weed plant phytotoxicty, as determined 1-3 weeks after treatment.
  • PPO-i resistant weeds are weeds, which are not controlled by the application of PPO-i’s except the compound of formula (I), whereas the respective sensitive biotype is controlled at that use rate.
  • not controlled means that in a visual rating the weed control (herbicidal effect) is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment; and “controlled” means that in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s except the compound of formula (I).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from fomesafen and lactofen.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, fomesafen and lactofen.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i except the compound of formula (I).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from fomesafen and lactofen.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, fomesafen and lactofen.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s except the compound of formula (I), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e.
  • the weed control in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i except the compound of formula (I), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to azafenidin; i.e. a method for controlling the growth of azafenidin resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to flumioxazin; i.e. a method for controlling the growth of flumioxazin resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to fomesafen; i.e. a method for controlling the growth of fomesafen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to lactofen; i.e. a method for controlling the growth of lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to oxyfluorfen; i.e. a method for controlling the growth of oxyfluorfen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to sulfentrazone; i.e. a method for controlling the growth of sulfentrazone resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin; i.e. a method for controlling the growth of azafenidin resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from fomesafen and lactofen; i.e. a method for controlling the growth of fomesafen and/or lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin, and fomesafen; i.e. a method for controlling the growth of azafenidin, and/or fomesafen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the
  • PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin and lactofen; i.e. a method for controlling the growth of azafenidin and/or lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin, fomesafen and lactofen; i.e.
  • a method for controlling the growth of azafenidin, fomesafen and/or lactofen resistant weeds which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone; i.e.
  • a method for controlling the growth of flumioxazin, fomesafen, lactofen, oxyfluorfen and/or sulfentrazone resistant weeds which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone; i.e.
  • a method for controlling the growth of azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and/or sulfentrazone resistant weeds which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone; i.e.
  • a method for controlling the growth of acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and/or sulfentrazone resistant weeds which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone; i.e.
  • a method for controlling the growth of acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and/or sulfentrazone resistant weeds which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i’s selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i’s selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i’s selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i’s selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • weed control 600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 250 g/ha, of PPO-i’s selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i except the compound of formula (I) at least one PPO-i except the compound of formula (I)
  • the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone
  • PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is ⁇ 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
  • PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone
  • PPO-i resistant weeds are those classified as being “PPO-i resistant” and thus listed according to Anonymous: List of herbicide resistant weeds by herbicide mode of action - weeds resistant to PPO-inhibitors (URL: http://www.weedscience.org/summarv/MOA.aspx).
  • the PPO-i resistant weeds are selected from the group consisting of Acalypha ssp., Amaranthus ssp., Ambrosia ssp., Avena ssp., Conyza ssp., Descurainia ssp., Eleusine spp., Euphorbia ssp., Lolium ssp. and Senecio ssp.; especially preferred Amaranthus ssp. and Ambrosia ssp.; more preferred Amaranthus ssp..
  • the PPO-i resistant weeds are selected from the group consisting of Asian copperleaf (Acalypha australis), smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus), common ragweed (Ambrosia artemisiifolia or Ambrosia eliator), wild oat (Avena fatua), fleabane (Conyza ambigua or Conyza sumatrensis), marestail (Conyza Canadensis), flixweed (Descurainia Hospital), goosegrass (Eleusine indica), wild poinsettia (Euphorbia heterophylla), rigid ryegrass (lolium rigidum) and eastern groundsel (Senecio vernalis); especially preferred smooth
  • the compounds of formula (I) control PPO-i resistant weeds, which contain non-target site resistance (metabolic resistance) and/or PPO-target site resistance, for example, of the following target site mutations within the PPO1 and /or PPO2 enzyme:
  • PPO-i resistant weeds in particular the biotypes of Amaranthus palmeri and Amaranthus tuberculatus, are resistant due to a codon deletion on the nuclear-encoded gene PPX2L that codes for the PPO enzyme which is dual-targeted to the mitochondria and the chloroplasts. This results in a loss of the glycine amino acid in position 210 (see e.g. B. G. Young et al, Characterization of PPO-lnhibitor-Resistant Waterhemp (Amaranthus tuberculatus) Response to Soil-Applied PPO-i’s, Weed Science 2015, 63, 511-521). It is estimated that this mutation accounts for more than 50% of the resistance cases in amaranthus
  • R98L sometimes also referred to as “R128L”
  • R128G mutation (sometimes also referred to as R98G, Arg128Gly mutation) currently mainly found in Amaranthus palmeri and Amaranthus tuberculatus
  • R128M mutation (sometimes also referred to as Arg128Met mutation) currently mainly found in Amaranthus palmeri and Amaranthus tuberculatus
  • R128L mutation (sometimes also referred to as Arg128Leu mutation), so far only found in Ambrosia
  • G399A mutation (sometimes also referred to as Gly399Ala mutation), so far only found in Amaranthus palmeri
  • Double mutant K127N, 1130V (sometimes also referred to as Lys127Asn, Ile130Val double mutation), found in Amaranthus tuberculatus • A212T mutation (sometimes also referred to Ala212Thr mutation), so far only found in Eleusine indica
  • PPO-i resistant weeds are weeds, which contain a AG210, R98L, R128G, R128M, G339A, K127N-I130V, A212T, Arg128His, Arg128Lle or Arg128Lys mutation in the Protox enzyme conferring resistance to PPO-i’s
  • PPO-i resistant weeds are weeds whose Protox enzyme is resistant to the application of PPO-i’s due to a mutation that is expressed as a AG210 or R98L change of said Protox enzyme or equivalents to the PPX2L or PPX2 respectively, in particular that is expressed as a AG210 or R98L change of said Protox enzyme.
  • the invention relates to a method for controlling PPO-i resistant weeds, wherein at least one compound of formula (I) as defined herein is applied to at least one PPO-i resistant weed, parts of it or its propagation material.
  • the compounds of formula (I) as described herein have one or more centres of chirality and, as a consequence, are present as enantiomers or diastereomers, it is possible to use both, the pure enantiomers and diastereomers and their mixtures, according to the invention.
  • the compounds of formula (I) as described herein have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. Suitable are, in general, the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the activity of the active compounds.
  • Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl)ammonium, heptylammonium, dodecylammonium, tetrade
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensulfate, methylsulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • the compounds of formula (I) as described herein might carry a carboxyl group.
  • those compounds of formula (I) according to the invention which carry a carboxyl group, i.e. provided the compounds of formula (I) have a carboxyl group
  • such compounds can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative, for example as amides, such as mono- and di-C 1 -C 6 - alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, C 1 -C 10 -alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters and also as thioesters, for example as C 1 -C 10 -alkylthio esters.
  • Preferred mono- and di-C 1 -C 6 -alkylamides are the methyl and the dimethylamides.
  • Preferred arylamides are, for example, the anilides and the 2- chloroanilides.
  • Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl or isooctyl (2- ethylhexyl) esters.
  • C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl esters are the straight-chain or branched C 1 -C 4 -alkoxy ethyl esters, for example the 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester.
  • An example of a straight-chain or branched C 1 -C 10 -alkylthio ester is the ethylthio ester.
  • the organic moieties mentioned in the definition of the variables R 1 to R 6 and R a to R e are - like the term halogen - collective terms for individual enumerations of the individual group members.
  • the term halogen denotes in each case fluorine, chlorine, bromine or iodine. All hydrocarbon chains can be straight-chain or branched, the prefix C n -C m denoting in each case the possible number of carbon atoms in the group.
  • Examples of such meanings are: - C 1 -C 3 -alkyl and also the C 1 -C 3 -alkyl moieties of di(C 1 -C 3 -alkyl)amino, C 1 -C 3 -alkoxy-C 1 -C 3 - alkyl: for example CH 3 , C 2 H 5 , n-propyl and CH(CH 3 ) 2 ; - C 1 -C 4 -alkyl: for example CH 3 , C 2 H 5 , n-propyl, CH(CH 3 ) 2 , n-butyl, CH(CH 3 )–C 2 H 5 , CH 2 – CH(CH 3 ) 2 and C(CH 3 ) 3 ; - C 1 -C 6 -alkyl and also the C 1 -C 6 -alkyl moieties of C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkyoxy-C 1 -C 6
  • - C 1 -C 3 -haloalkoxy a C 1 -C 3 -alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 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, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2-brom
  • R 2 is C 1 -C 4 -haloalkyl; particularly preferred is C 1 -C 3 -haloalkyl; more preferred is C 1 -C 2 -haloalkyl; especially preferred is CF 3 .
  • R 3 is H or C 1 -C 4 -alkyl; particularly preferred is H or CH 3 ; more preferred is H; also more preferred is CH 3 .
  • R 4 is H, F or Cl; particularly preferred is H or F; especially preferred is F.
  • R 5 is halogen, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkylthio or C 1 -C 3 - alkoxycarbonyl; preferably is C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy or C 1 -C 3 -alkylthio; particularly preferred is C 1 -C 3 -alkoxy or C 1 -C 3 -alkylthio; especially preferred is C 1 -C 3 -alkoxy; more preferred is OCH 3 .
  • R 6 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -haloalkenyl, C 3 -C 6 -haloalkynyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkoxy- C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl; preferably is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -hal
  • R 6 is hydrogen or C 1 -C 6 -alkyl.
  • n is 1 or 2; particularly preferred is 2; also particularly preferred is 1.
  • Q is O, also preferably is S.
  • W is O, also preferably is S.
  • X is O, also preferably is S.
  • Y is O, also preferably is S.
  • Z is phenyl or pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred is phenyl or pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH 3 or OCH 3 ; especially preferred is phenyl or pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH 3 ; more preferred is phenyl or pyridyl, each of which is unsubstituted.
  • Z is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH 3 or OCH 3 ; especially preferred is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH 3 ; more preferred is phenyl or 2-pyridyl, each of which is unsubstituted.
  • Z is phenyl, which is optionally substituted by 1 substituent selected from the group consisting of halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred is phenyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH 3 or OCH 3 ; especially preferred is phenyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH 3 ; also especially preferred is unsubstituted phenyl.
  • Z is pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred is pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH 3 or OCH 3 ; especially preferred is pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH 3 ; also especially preferred is unsubstituted pyridyl.
  • Z is 2-pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred is 2-pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH 3 or OCH 3 ; especially preferred is 2-pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH 3 ; also especially preferred is unsubstituted 2-pyridyl.
  • Z is selected from the group consisting of Z 1 to Z 13 Z -13 wherein * denotes the point of attachment of Z to X; ** denotes the point of attachment of Z to Q; and R a , R b , R c , R d and R e independently of one another are H, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy; preferably H, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred H, F, Cl, Br, CH 3 or OCH 3 ; especially preferred H, F, Cl or CH 3 ; more preferred H.
  • Z is selected from the group consisting of Z 1 , Z 2 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 and Z 11 as defined above; particularly preferred is selected from the group consisting of Z 1 , Z 4 , Z 5 , Z 6 and Z 7 as defined above; more particularly preferred is selected from the group consisting of Z 1 , Z 4 , Z 5 , Z 6 and Z 7 as defined above; especially preferred is selected from the group consisting of Z 1 and Z 7 as defined above; more preferred is selected from Z 1 as defined above; also more preferred is selected from Z 7 as defined above.
  • Z is selected from the group consisting of Z 1 , Z 2 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 and Z 11 as defined above, wherein R a , R b , R c , R d and R e independently of one another are H, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy; preferably H, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; particularly preferred H, F, Cl, Br, CH 3 or OCH 3 ; especially preferred H, F, Cl or CH 3 ; more preferred H; particularly preferred is selected from the group consisting of Z 1 , Z 4 , Z 5 , Z 6 and Z 7 , as defined above, wherein R a ,
  • R 1 is CH 3 ;
  • R 2 is C 1 -C 3 -haloalkyl;
  • R 3 is hydrogen or CH 3 ;
  • R 4 is H or halogen;
  • R 5 is C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkylthio;
  • R 6 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 3 -C 6 - haloalkenyl, C 3 -C 6 -haloalkynyl, C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 - alkoxy-C 1 -C 6 -alkoxy-C 1 -C 6
  • R 1 is CH 3 ;
  • R 2 is C 1 -C 3 -haloalkyl;
  • R 3 is hydrogen;
  • R 4 is F;
  • R 5 is C 1 -C 3 -alkoxy;
  • R 6 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 1 -C 6 - cyanoalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, n is 1;
  • Q, W, X and Y are O;
  • Z is phenyl, optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH 3 , OCH 3 ;
  • Particular preference is given to compounds of formula (I.
  • the compounds of formula (I. I) preferably the compounds of formulae (1.1.1) to (1.1.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-9, wherein R a , R c and R e are H:
  • the compounds of formula (l.q) preferably the compounds of formulae (l.q.1) to (l.q.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only that R 5 is SCH3:
  • Especially preferred compounds are methyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; methyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; methyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]
  • the compound of formula (I) is the compound (I. a.19):
  • the method according to the present invention comprises the application of compound (I. a.19) to PPO-i resistant weeds.
  • the compound of formula (I) is the compound (I. a.20):
  • the method according to the present invention comprises the application of compound (I. a.20) to PPO-i resistant weeds.
  • the compound of formula (I) is the compound (I. a.21):
  • the method according to the present invention comprises the application of compound (I. a.21) to PPO-i resistant weeds.
  • the method according to the present invention comprises the application of at least one of the compounds selected from (I. a.19), (I. a.20) and (I. a.21) to PPO-i resistant weeds [i.e. the compound of formula (I) is selected from at least one of the compounds of formulae (I. a.19), (I. a.20) and (I. a.21)].
  • the compounds of formula (I) can be prepared by reaction of compounds of formula (II) with alkylating agents of formula (III) in the presence of a base in analogy to known processes (e.g.
  • L 1 is a leaving group such as halogen.
  • alkylating agents of formula (III) are commercially available or can be prepared by known methods (e.g. WO 11/137088).
  • Compounds of formula (II) can be prepared by deprotection of the respective compounds of formula (VI):
  • “PG” is a protecting group selected from the group consisting of C 1 -C 6 -alkyl or (tri-C 1 -C 6 -alkyl)silyl-C 1 -C 4 -alkyl.
  • the compounds of formula (II) can be prepared by treating the compounds of formula (VI), wherein “PG” is methyl, with boron tribromide in a solvent such as dichloromethane at temperatures ranging from 0 °C to 150 °C.
  • Compounds of formula (VI), wherein R 1 is H can be prepared by reaction of amines of formula (VII) with oxazinones of formula (VI), wherein R 1 is H
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the amines of formula (VII) with the oxazinones of formula (VIII) in an organic solvent. Suitable in principle are all solvents which are capable of dissolving the amines of formula (VII) and the oxazinones of formula (VIII) at least partly, and preferably fully under reaction conditions.
  • Suitable solvents are halogenated hydrocarbons such as dichloromethane, 1,2- dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroace
  • acids inorganic acids like hydrochloric acid, hydrobromic acid or sulfuric acid
  • organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid
  • acids inorganic acids like hydrochloric acid, hydrobromic acid or sulfuric acid
  • organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid
  • the acids are generally employed in equimolar amounts, in excess or, if appropriate, be used as solvent, however they can also be employed in catalytic amounts.
  • Those compounds of formula (VI), wherein R 1 is NH2, Ci-Ce-alkyl or Cs-Ce-alkynyl can be prepared by amination or alkylation of those compounds of formula (VI), wherein R 1 is H. Such amination or alkylation can be conducted in analogy to known processes (e.g. WO 05/054208; WO 06/125746).
  • Ci-Ce-alkylhalides and alkinylhalides can be used as alkylation reagents.
  • Suitable amination reagents are known from literature (e.g. US 6333296 or DE 10005284)
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the amines of formula (VII) with the oxazinones of formula (VIII) in an organic solvent. Suitable in principle are all solvents which are capable of dissolving the amines of formula (VII) and the oxazinones of formula (VIII) at least partly, and preferably fully under reaction conditions.
  • Suitable solvents are halogenated hydrocarbons such as dichloromethane, 1 ,2- dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF); nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert.-butanol, organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid,
  • acids inorganic acids like hydrochloric acid, hydrobromic acid or sulfuric acid
  • organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid
  • acids inorganic acids like hydrochloric acid, hydrobromic acid or sulfuric acid
  • organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid
  • the acids are generally employed in equimolar amounts, in excess or, if appropriate, be used as solvent, however they can also be employed in catalytic amounts.
  • the compound of formula (IX) can be prepared by reduction followed by a Sandmeyer reaction from a compound of formula (X).
  • Reduction of the nitro group on a compound of formula (X) can be carried out by catalytic hydrogenation in hydrogen gas at a pressure of 70 to 700 kPa, preferably 270 to 350 kPa, in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20% of metal to carrier, suspended in a solvent such as ethanol at ambient temperature.
  • a metal catalyst such as palladium supported on an inert carrier such as activated carbon
  • Bromination of the resulting amine is facilitated by diazotization with an alkyl nitrite (e.g. isoamyl nitrite) followed by treatment with a copper (I) bromide and/or copper (II) bromide in a solvent such as acetonitrile at a temperature ranging from 0 °C to the reflux temperature of the solvent to give the corresponding compound of formula (IX).
  • an alkyl nitrite e.g. isoamyl nitrite
  • a solvent such as acetonitrile
  • the compounds of formula (X) required for the preparation of compounds of formula (IX) can be prepared by reaction of compounds of formula (XI) with compounds of formula (XII) in the presence of a base:
  • L 3 is a leaving group such as halogen.
  • the reaction is carried out in an organic solvent.
  • Suitable solvents are halogenated hydrocarbons such as dichloromethane, 1 ,2- dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N '-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
  • halogenated hydrocarbons
  • suitable bases include metal-containing bases and nitrogen-containing bases.
  • suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and
  • the bases are generally employed in equimolar amounts or in excess; however they can also be employed as solvent, or, if appropriate, in catalytic amounts.
  • the reaction can be carried out by adding bis(1 , 1 -dimethylethyl) dicarbonate (CAS 24424-99-5) to compounds of formula (XIII) in an organic solvent.
  • a base can be advantages.
  • suitable solvents are halogenated hydrocarbons such as dichloromethane, 1,2- dichloroethane, chloroform.
  • suitable bases are nitrogen-containing bases such as 4-(dimethylamino)pyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN).
  • DMAP 4-(dimethylamino)pyridine
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • DBN 1 ,5-diazabicyclo[4.3.0]non-5-ene
  • the method according to the invention can be employed in a further number of crop plants for eliminating the PPO-i resistant weeds.
  • all the crop plants (cultivated plants) mentioned herein are understood to comprise all species, subspecies, variants and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
  • corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn.
  • all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).
  • soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856).
  • the indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (Maturity Group, (MG) 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins.
  • all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
  • Preferred crops are Arachis hypogaea, Beta vulgaris spec, altissima, Brassica napus var. napus, Brassica oleracea, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cynodon dactylon, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hordeum vulgare, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Medicago sativa, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris, Pistacia vera, Pisum s
  • Especially preferred crops are crops of cereals, corn, soybeans, rice, oilseed rape, cotton, peas, lentils, peanuts or permanent crops.
  • PPO-i resistant weed species are Asian copperleaf (Acalypha australis), smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus), common ragweed (Ambrosia artemisiifolia or Ambrosia eliator), wild oat (Avena fatua), fleabane (Conyza ambigua or Conyza sumatrensis), marestail (Conyza Canadensis), flixweed (Descurainia Hospital), goosegrass (Eleusine indica), wild poinsettia (Euphorbia heterophylla), rigid ryegrass (lolium rigidum) and eastern groundsel (Senecio vernalis).
  • Asian copperleaf Acalypha australis
  • the PPO-i resistant weeds to be controlled are selected from the group consisting of smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus) and common ragweed (Ambrosia artemisiifolia or Ambrosia eliator); preferably are selected from smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus) and tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus); particularly preferably are selected from the group consisting of preferred Palmer amaranth (Amaranthus Palmeri) and tall/common waterhemp
  • the PPO-i resistant weed to be controlled is smooth pigweed.
  • the PPO-i resistant weed to be controlled is Palmer amaranth. In another particularly preferred embodiment of the invention, the PPO-i resistant weed to be controlled is redroot pigweed.
  • the PPO-i resistant weed to be controlled is tall/common waterhemp.
  • the PPO-i resistant weed to be controlled is common ragweed.
  • the compounds of formula (I), or herbicidal compositions comprising the compounds of formula (I), can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading, watering or treatment of the seed or mixing with the seed.
  • the use forms depend on the intended purpose; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
  • a formulation comprises a pesticidally effective amount of a compound of formula (I).
  • effective amount denotes an amount of the compound of formula (I), which is sufficient for controlling undesired vegetation, especially for controlling undesired vegetation in crops (i.e. cultivated plants) and which does not result in a substantial damage to the treated crop plants.
  • Such an amount can vary in a broad range and is dependent on various factors, such as the undesired vegetation to be controlled, the treated crop plants or material, the climatic conditions and the specific compound of formula (I) used.
  • formulations e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g.
  • WP WP
  • SP WS
  • DP DS
  • pressings e.g. BR, TB, DT
  • granules e.g. WG, SG, GR, FG, GG, MG
  • insecticidal articles e.g. LN
  • gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • the formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkylated
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound of formula (I) on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • a compound of formula (I) in an agitated ball mill, 20-60 wt% of a compound of formula (I) according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type formulation up to 40 wt% binder (e.g. polyvinylalcohol) is added.
  • WG, SG Water-dispersible granules and water-soluble granules
  • a compound of formula (I) according to the invention are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound of formula (I) according to the invention are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound of formula (I) according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1-5 wt% thickener e.g. carboxymethylcellulose
  • a compound of formula (I) according to the invention 5-20 wt% of a compound of formula (I) according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g.
  • a compound of formula (I) according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
  • solid carrier e.g. finely divided kaolin
  • Granules (GR, FG) 0.5-30 wt% of a compound of formula (I) according to the invention is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • organic solvent e.g. aromatic hydrocarbon
  • the formulation types i) to xi) may optionally comprise further auxiliaries, such as 0,1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1-1 wt% colorants.
  • auxiliaries such as 0,1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1-1 wt% colorants.
  • Application can be done before, during and/or after, preferably during and/or after, the emergence of the PPO-i resistant weeds.
  • the inventive method i.e. the compounds of formula (I), or the formulations comprising them, are applied to the plants mainly by spraying the leaves.
  • the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 50 to 1000 l/ha (for example from 100 to 200 l/ha).
  • the compounds of formula (I), or the formulations comprising them may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.
  • the inventive method i.e. the compounds of formula (I), or the formulations comprising them, can be applied pre-, post-emergence or pre-plant, or together with the seed of a crop plant. It is also possible to apply the method, i.e. the compounds of formula (I), or the formulations comprising them, by applying seed, pretreated with the compounds of formula (I), or the formulations comprising them, of a crop plant.
  • application techniques may be used in which the combinations are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesired vegetation growing underneath, or the bare soil surface (post-directed, lay-by).
  • the inventive method i.e. the compounds of formula (I), or the formulations comprising them, can be applied by treating seed.
  • the treatment of seeds comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of formula (I), or the formulations prepared therefrom.
  • the combinations can be applied diluted or undiluted.
  • seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms.
  • seed describes corns and seeds.
  • the seed used can be seed of the crop plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
  • the amount of active substance applied i.e.of the compounds of formula (I), without formulation auxiliaries, are from 0.001 to 2 kg per ha, preferably from 0.002 to 1 kg per ha, more preferably from 0.005 to 0.5 kg per ha and in particular from 0.01 to 0.25 kg per ha.
  • the application rate of the compounds of formula (I), is from 0.001 to 3 kg/ha, preferably from 0.002 to 2 kg/ha and in particular from 0.005 to 1 kg/ha of active substance (a.s.).
  • the rates of application of the compounds of formula (I) according to the present invention are from 0.1 g/ha to 3000 g/ha, preferably 5 g/ha to 500 g/ha, depending on the control target, the season, the target plants and the growth stage.
  • the application rates of the compounds of formula (I) are in the range from 0.1 g/ha to 5000 g/ha and preferably in the range from 1 g/ha to 2500 g/ha or from 2 g/ha to 2000 g/ha.
  • the application rate of the compounds of formula (I) is 0.1 to 1000 g/ha, preferably 1 to 750 g/ha, more preferably 5 to 500 g/ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • the amounts of active substances applied i.e. of compounds of formula (I) are generally in amounts of from 0.001 to 10 kg per 100 kg of seed.
  • Example 1 - step 2 tert-butyl N-[2-fluoro-5-(2-methoxyphenoxy)-4-nitro-phenyl]carbamate
  • a solution of tert-butyl N-(2,5-difluoro-4-nitro-phenyl)carbamate (250 g, 911 mmol) and K 2 CO 3 (377 g, 2733 mmol) in acetonitrile (2.5 L) was added 2-methoxyphenol (136 g, 1094 mmol) at 15 °C. Then the mixture was stirred at 80 °C for 18 h. The mixture was filtered and the filtrate was concentrated.
  • Example 1 – step 3 tert-butyl N-[4-amino-2-fluoro-5-(2-methoxyphenoxy)phenyl]carbamate
  • tert-butyl N-[2-fluoro-5-(2-methoxyphenoxy)-4-nitro-phenyl]carbamate 210 g, 555 mmol
  • Pd/C 21 g
  • H 2 50 Psi
  • Example 1 - step 4 tert-butyl N-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]carbamate
  • isoamyl nitrite 10.5 g, 90 mmol
  • the mixture was warmed to 60 °C.
  • tert-butyl N-[4-amino-2- fluoro-5-(2-methoxyphenoxy)phenyl]-carbamate 31g, 60mmol was added in portions at 60 °C and stirred for 1 h at 60 °C.
  • Example 1 - step 5 4-bromo-2-fluoro-5-(2-methoxyphenoxy)aniline
  • tert-butyl N-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]carbamate (3 g, 7.3 mmol) was added 4N HCl in ethylacetate (30 mL) in portions at 0 °C and stirred for 16 h at 20 °C.
  • the mixture was poured into H 2 O, extracted with ethylacetate, and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated to give 4-bromo-2-fluoro-5-(2- methoxyphenoxy)aniline (2.3 g, crude) as a brown solid.
  • Example 1 – step 6 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-6-(trifluoromethyl)-1H- pyrimidine-2,4-dione
  • 4-bromo-2-fluoro-5-(2-methoxyphenoxy)aniline 1.8 g, 5.8 mol
  • 2-(dimethylamino)-4-(trifluoromethyl)-1,3-oxazin-6-one CAS 141860-79-9, 1.8 g, 8.7 mmol
  • Example 1 - step 7 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-1-methyl-6-(trifluoro- methyl)-pyrimidine-2,4-dione
  • acetonitrile 40 mL
  • K 2 CO 3 4.7 g, 34.2 mmol
  • methyliodide 2.5 g, 17.3 mmol
  • Example 1 step 8 3-[4-bromo-2-fluoro-5-(2-hydroxyphenoxy)phenyl]-1-methyl-6-(trifluoro- methyl)-pyrimidine-2,4-dione
  • BBr 3 3.5 g, 13.9 mmol
  • Example 1 – step 9 methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)- pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate
  • 3-[4-bromo-2-fluoro-5-(2-hydroxyphenoxy)phenyl]-1-methyl-6-(trifluoromethyl)- pyrimidine-2,4-dione (1 g, 2.1 mmol) in DMF (10 mL) was added Cs 2 CO 3 (2.1 g, 6.3 mmol), methyl 2-bromo-2-methoxyacetate (CAS 5193-96-4, 772 mg, 4.2 mol) at 10 °C.
  • test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
  • the test plants were kept at 10 – 25°C or 20 – 35°C, respectively.
  • the test period extended over 2 to 4 weeks. During this time, the test plants were tended, and their response to the individual treatments was evaluated.

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Abstract

A method for controlling PPO-i resistant weeds, wherein compounds of formula (I), wherein the variables are defined as given in the description and claims; wherein the PPO-i resistant weeds are weeds being resistant to PPO-i's except the compounds of formula (I), are applied to the PPO-i resistant weed, parts of it or its propagation material.

Description

Method for controlling PPO-i resistant weeds
Description
The invention relates to a method for controlling PPO-i resistant weeds, wherein at least one compound of formula (I) is applied to at least one PPO-i resistant weed, parts of it or its propagation material.
As used herein, the terms “PPO-i”and “PPO-i‘s” respectively stand for “PPO inhibitor(s)”, “PPO inhibitor herbicide(s)”, “PPO-inhibiting herbicide(s)”, and refer to herbicides that inhibit the enzyme protoporphyrinogen IX oxidase of a plant.
As used herein, the term “PPO-i resistant weed(s)” stands for “PPO(s) resistant weed(s)”, “PPO inhibitor(s) resistant weed(s)”, “PPO inhibitor(s) herbicide(s) resistant weed(s)”, “PPO-inhibiting herbicide(s) resistant weed(s)”, and refers to a plant that, in relation to a treatment with an appropriate or over-appropriate rate of PPO-i application, has inherited, developed or acquired an ability
(1) to survive that treatment, if it is one that is lethal to (i.e. eradicates) the wild type weed; or
(2) to exhibit significant vegetative growth or thrive after that treatment, if it is one that suppresses growth of the wild-type weed.
Herbicide resistant weeds present a serious problem for efficient weed control because such resistant weeds are increasingly widespread and thus weed control by the application of herbicides is no longer effective. In particular PPO-i resistant weeds are a huge problem to farmers.
Thus, there is a need for an effective and efficient method for the control of herbicide resistant weeds, in particular PPO-i resistant weeds.
In crop protection, it is desirable to increase the specificity and reliability of the action of active compounds. In particular, it is desirable for the crop protection product to control the harmful plants (weeds) effectively and, at the same time, to be tolerated by the useful plants (crops) in question.
Thus, there is a need for a novel method to effectively control herbicide resistant weeds, in particular PPO-i resistant weeds, which at the same time is tolerated by the useful plants (crops) in question.
Surprisingly it has been found that compounds of formula (I) provide an efficient control against PPO-i resistant weeds.
The compounds of formula (I) and a general procedure for their production are known from WO 2021/175689.
However, an acceptable efficacy of compounds of formula (I) against PPO-i resistant weeds is unknown. Accordingly, the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I)
Figure imgf000003_0001
wherein the substituents have the following meanings: R1 NH2, C1-C6-alkyl; R2 C1-C6-haloalkyl; R3 hydrogen or C1-C6-alkyl; R4 H or halogen; R5 halogen, CN, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, (C1- C3-alkyl)amino, di(C1-C3-alkyl)amino, C1-C3-alkoxy-C1-C3-alkyl, C1-C3- alkoxycarbonyl; R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-haloalkyl, C3-C6- haloalkenyl, C3-C6-haloalkynyl, C1-C6-cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6- alkoxy-C1-C6-alkoxy-C1-C6-alkyl, di(C1-C6-alkoxy)C1-C6-alkyl, C1-C6-haloalkoxy-C1- C6-alkyl, C3-C6-alkenyloxy-C1-C6-alkyl, C3-C6-haloalkenyloxy-C1-C6-alkyl, C3-C6- alkenyloxy-C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl, C1-C6-alkylsulfinyl- C1-C6-alkyl, C1-C6-alkylsulfonyl-C1-C6-alkyl, C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6- alkoxycarbonyl-C1-C6-alkyl, C1-C6-haloalkoxycarbonyl-C1-C6-alkyl, C3-C6- alkenyloxycarbonyl-C1-C6-alkyl, C3-C6-alkynyloxycarbonyl-C1-C6-alkyl; n 1 to 3; Q, W, X, and Y independently of one another O or S; Z phenyl or pyridyl, each of which is optionally substituted by 1 to 4 substituents selected from the group consisting of halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy; including their agriculturally acceptable salts, amides, esters or thioesters, provided the compounds of formula (I) have a carboxyl group; wherein the PPO-i resistant weeds are weeds that are resistant to at least one PPO-i except the compounds of formula (I). The invention relates to a method for controlling PPO-i resistant weeds, which comprises applying compounds of formula (I) to plants, their habitat or on seed according to the present invention. The invention particularly relates to a method for controlling PPO-i resistant weeds in crops which comprises applying compounds of formula (I) according to the method of the present invention to crops, where said PPO herbicide resistant weeds occur or might occur.
The present invention also provides a method for controlling PPO-i resistant weeds, wherein agrochemical compositions comprising at least one compounds of formula (I) and auxiliaries customary for formulating crop protection agents are applied to the PPO-i resistant weed, parts of it or its propagation material.
The invention furthermore relates to the use of compounds of formula (I) or the agrochemical compositions comprising them for controlling PPO-i resistant weeds.
Further embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be illustrated below of the subject matter of the invention can be applied not only in the respective given combination but also in other combinations without leaving the scope of the invention.
As used herein, the terms "controlling" and "combating" are synonyms.
As used herein, the terms "undesirable vegetation", "harmful plants" and “weeds” are synonyms.
Effective weed control is defined as at least 70% weed suppression or eradication from the crop, or as at least 70% weed plant phytotoxicty, as determined 1-3 weeks after treatment.
Thus, PPO-i resistant weeds are weeds, which are not controlled by the application of PPO-i’s except the compound of formula (I), whereas the respective sensitive biotype is controlled at that use rate.
Here, “not controlled” means that in a visual rating the weed control (herbicidal effect) is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment; and “controlled” means that in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment.
Preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s except the compound of formula (I).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from fomesafen and lactofen.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, fomesafen and lactofen.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
Preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i except the compound of formula (I).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from fomesafen and lactofen.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, fomesafen and lactofen.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone.
Preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s except the compound of formula (I), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment). Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of PPO-i’s selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i except the compound of formula (I), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application of at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment).
According to a specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to azafenidin; i.e. a method for controlling the growth of azafenidin resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to a specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to flumioxazin; i.e. a method for controlling the growth of flumioxazin resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to fomesafen; i.e. a method for controlling the growth of fomesafen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to lactofen; i.e. a method for controlling the growth of lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to oxyfluorfen; i.e. a method for controlling the growth of oxyfluorfen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to sulfentrazone; i.e. a method for controlling the growth of sulfentrazone resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin; i.e. a method for controlling the growth of azafenidin resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from fomesafen and lactofen; i.e. a method for controlling the growth of fomesafen and/or lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin, and fomesafen; i.e. a method for controlling the growth of azafenidin, and/or fomesafen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the
PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin and lactofen; i.e. a method for controlling the growth of azafenidin and/or lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin, fomesafen and lactofen; i.e. a method for controlling the growth of azafenidin, fomesafen and/or lactofen resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone; i.e. a method for controlling the growth of flumioxazin, fomesafen, lactofen, oxyfluorfen and/or sulfentrazone resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone; i.e. a method for controlling the growth of azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and/or sulfentrazone resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone; i.e. a method for controlling the growth of acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and/or sulfentrazone resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
According to another specific embodiment the present invention provides a method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I), wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone; i.e. a method for controlling the growth of acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and/or sulfentrazone resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I).
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 200 g/ha, of PPO-i’s except the compound of formula (I), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 250 g/ha or lower, especially preferred 50 to 250 g/ha, of PPO-i’s selected from azafenidin, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
400 g/ha or lower, particularly preferred 200 g/ha or lower, especially preferred 50 to 200 g/ha, of PPO-i’s selected from fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 250 g/ha or lower, especially preferred 50 to 250 g/ha, more preferred 50 to 200 g/ha, of PPO-i’s selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 50 to 300 g/ha, more preferred 70 to2500 g/ha, of PPO-i’s selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate. Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 50 to 300 g/ha, more preferred 70 to 250 g/ha, of PPO-i’s selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 250 g/ha, of PPO-i’s selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 250 g/ha, of PPO-i’s selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 200 g/ha, of at least one PPO-i except the compound of formula (I), whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate. Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 250 g/ha or lower, especially preferred 50 to 250 g/ha, of at least one PPO-i selected from azafenidin, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
400 g/ha or lower, particularly preferred 200 g/ha or lower, especially preferred 50 to 200 g/ha, of at least one PPO-i selected from fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 250 g/ha or lower, especially preferred 50 to 250 g/ha, more preferred 50 to 200 g/ha, of at least one PPO-i selected from azafenidin, fomesafen and lactofen, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 50 to 300 g/ha, more preferred 70 to 250 g/ha, of at least one PPO-i selected from flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
500 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 50 to 300 g/ha, more preferred 70 to 250 g/ha, of at least one PPO-i selected from azafenidin, flumioxazin, fomesafen, lactofen, oxyfluorfen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 250 g/ha, of at least one PPO-i selected from acifluorfen, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably, PPO-i resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is < 70 % of weed suppression or eradication as determined 1-3 weeks after treatment) by the application rate of
600 g/ha or lower, particularly preferred 300 g/ha or lower, especially preferred 10 to 250 g/ha, of at least one PPO-i selected from acifluorfen, azafenidin, carfentrazone, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorfen, pyraflufen and sulfentrazone, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is > 90 % of weed suppression or eradication as determined 1-3 weeks after treatment) at that use rate.
Also preferably PPO-i resistant weeds are those classified as being “PPO-i resistant” and thus listed according to Anonymous: List of herbicide resistant weeds by herbicide mode of action - weeds resistant to PPO-inhibitors (URL: http://www.weedscience.org/summarv/MOA.aspx).
Particularly preferred the PPO-i resistant weeds are selected from the group consisting of Acalypha ssp., Amaranthus ssp., Ambrosia ssp., Avena ssp., Conyza ssp., Descurainia ssp., Eleusine spp., Euphorbia ssp., Lolium ssp. and Senecio ssp.; especially preferred Amaranthus ssp. and Ambrosia ssp.; more preferred Amaranthus ssp..
Also particularly preferred the PPO-i resistant weeds are selected from the group consisting of Asian copperleaf (Acalypha australis), smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus), common ragweed (Ambrosia artemisiifolia or Ambrosia eliator), wild oat (Avena fatua), fleabane (Conyza ambigua or Conyza sumatrensis), marestail (Conyza Canadensis), flixweed (Descurainia Sophia), goosegrass (Eleusine indica), wild poinsettia (Euphorbia heterophylla), rigid ryegrass (lolium rigidum) and eastern groundsel (Senecio vernalis); especially preferred smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus) and common ragweed (Ambrosia artemisiifolia or Ambrosia eliator); more preferred smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus) and tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus); most preferred Palmer amaranth (Amaranthus Palmeri) and tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus.
In contrast to market products the compounds of formula (I) control PPO-i resistant weeds, which contain non-target site resistance (metabolic resistance) and/or PPO-target site resistance, for example, of the following target site mutations within the PPO1 and /or PPO2 enzyme:
Most PPO-i resistant weeds, in particular the biotypes of Amaranthus palmeri and Amaranthus tuberculatus, are resistant due to a codon deletion on the nuclear-encoded gene PPX2L that codes for the PPO enzyme which is dual-targeted to the mitochondria and the chloroplasts. This results in a loss of the glycine amino acid in position 210 (see e.g. B. G. Young et al, Characterization of PPO-lnhibitor-Resistant Waterhemp (Amaranthus tuberculatus) Response to Soil-Applied PPO-i’s, Weed Science 2015, 63, 511-521). It is estimated that this mutation accounts for more than 50% of the resistance cases in amaranthus
A second type of mutation, in particular in a resistant biotype of Ambrosia artemisiifolia, was identified as a mutation that expressed a R98L (sometimes also referred to as “R128L”) change of the PPX2 enzyme (S. L. Rousonelos, R. M. Lee, M. S. Moreira, M. J. VanGessel, P. J. Tranel, Characterization of a Common Ragweed (Ambrosia artemisiifolia) Population Resistant to ALS- and PPO-i’s, Weed Science 60, 2012, 335-344.).
Following additional types of mutations have been identified:
• R128G mutation (sometimes also referred to as R98G, Arg128Gly mutation) currently mainly found in Amaranthus palmeri and Amaranthus tuberculatus
• R128M mutation (sometimes also referred to as Arg128Met mutation) currently mainly found in Amaranthus palmeri and Amaranthus tuberculatus,
• R128L mutation (sometimes also referred to as Arg128Leu mutation), so far only found in Ambrosia
• G399A mutation (sometimes also referred to as Gly399Ala mutation), so far only found in Amaranthus palmeri
• Double mutant K127N, 1130V (sometimes also referred to as Lys127Asn, Ile130Val double mutation), found in Amaranthus tuberculatus • A212T mutation (sometimes also referred to Ala212Thr mutation), so far only found in Eleusine indica
• Arg128His mutation
• Arg128lle mutation
• Arg128Lys mutation
Accordingly, preferably PPO-i resistant weeds are weeds, which contain a AG210, R98L, R128G, R128M, G339A, K127N-I130V, A212T, Arg128His, Arg128Lle or Arg128Lys mutation in the Protox enzyme conferring resistance to PPO-i’s
Accordingly, also preferably PPO-i resistant weeds are weeds whose Protox enzyme is resistant to the application of PPO-i’s due to a mutation that is expressed as a AG210 or R98L change of said Protox enzyme or equivalents to the PPX2L or PPX2 respectively, in particular that is expressed as a AG210 or R98L change of said Protox enzyme.
The invention relates to a method for controlling PPO-i resistant weeds, wherein at least one compound of formula (I) as defined herein is applied to at least one PPO-i resistant weed, parts of it or its propagation material.
If the compounds of formula (I) as described herein are capable of forming geometrical isomers, for example E/Z isomers, it is possible to use both, the pure isomers and mixtures thereof, according to the invention.
If the compounds of formula (I) as described herein have one or more centres of chirality and, as a consequence, are present as enantiomers or diastereomers, it is possible to use both, the pure enantiomers and diastereomers and their mixtures, according to the invention.
Within the substituents of the compounds of formula (I), instead of hydrogen also the corresponding isotope deuterium can be used.
If the compounds of formula (I) as described herein have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. Suitable are, in general, the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the activity of the active compounds.
Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl)ammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium (olamine salt), 2-(2- hydroxyeth-1-oxy)eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (diolamine salt), tris(2-hydroxyethyl)ammonium (trolamine salt), tris(2- hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N- trimethylethanolammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium, and finally the salts of polybasic amines such as N,N-bis- (3-aminopropyl)methylamine and diethylenetriamine. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensulfate, methylsulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. The compounds of formula (I) as described herein might carry a carboxyl group. Compounds of formula (I) as described herein having a carboxyl group, i.e. those compounds of formula (I) according to the invention, which carry a carboxyl group, i.e. provided the compounds of formula (I) have a carboxyl group, such compounds can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative, for example as amides, such as mono- and di-C1-C6- alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, C1-C10-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters and also as thioesters, for example as C1-C10-alkylthio esters. Preferred mono- and di-C1-C6-alkylamides are the methyl and the dimethylamides. Preferred arylamides are, for example, the anilides and the 2- chloroanilides. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl or isooctyl (2- ethylhexyl) esters. Preferred C1-C4-alkoxy-C1-C4-alkyl esters are the straight-chain or branched C1-C4-alkoxy ethyl esters, for example the 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester. An example of a straight-chain or branched C1-C10-alkylthio ester is the ethylthio ester. The organic moieties mentioned in the definition of the variables R1 to R6 and Ra to Re , are - like the term halogen - collective terms for individual enumerations of the individual group members. The term halogen denotes in each case fluorine, chlorine, bromine or iodine. All hydrocarbon chains can be straight-chain or branched, the prefix Cn-Cm denoting in each case the possible number of carbon atoms in the group. Examples of such meanings are: - C1-C3-alkyl and also the C1-C3-alkyl moieties of di(C1-C3-alkyl)amino, C1-C3-alkoxy-C1-C3- alkyl: for example CH3, C2H5, n-propyl and CH(CH3)2; - C1-C4-alkyl: for example CH3, C2H5, n-propyl, CH(CH3)2, n-butyl, CH(CH3)–C2H5, CH2– CH(CH3)2 and C(CH3)3; - C1-C6-alkyl and also the C1-C6-alkyl moieties of C1-C6-cyanoalkyl, C1-C6-alkyoxy-C1-C6- alkyl, C1-C6-alkoxy-C1-C6-alkoxy-C1-C6-alkyl, di(C1-C6-alkoxy)C1-C6-alkyl, C1-C6-haloalkoxy-C1- C6-alkyl, C3-C6-alkenyloxy-C1-C6-alkyl, C3-C6-haloalkenyloxy-C1-C6-alkyl, C3-C6-alkenyloxy-C1- C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl, C1-C6-alkylsulfinyl-C1-C6-alkyl, C1-C6- alkylsulfonyl-C1-C6-alkyl, C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl, C1- C6-haloalkoxycarbonyl-C1-C6-alkyl, C3-C6-alkenyloxycarbonyl-C1-C6-alkyl, C3-C6- alkynyloxycarbonyl-C1-C6-alkyl: C1-C4-alkyl as mentioned above, and also, for example, n- pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably methyl, ethyl, n– propyl, 1–methylethyl, n–butyl, 1,1–dimethylethyl, n–pentyl or n–hexyl; - C1-C3-haloalkyl: C1-C3-alkyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2- chloroethyl, 2-bromoethyl, 2-iodoethyl, 1,1-difluoroethyl, 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, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2- chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3- trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl; - C1-C4-haloalkyl: C1-C4-alkyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2- chloroethyl, 2-bromoethyl, 2-iodoethyl, 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, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2- chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3- trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4- fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 1,1,2,2,-tetrafluoroethyl and 1- trifluoromethyl-1,2,2,2-tetrafluoroethyl; - C1-C6-haloalkyl: C1-C4-haloalkyl as mentioned above, and also, for example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl; - C3-C6-alkenyl and also the C3-C6-alkenyl moieties of C3-C6-alkenyloxy-C1-C6-alkyl, C3- C6-alkenyloxy-C1-C6-alkoxy-C1-C6-alkyl, C3-C6-alkenyloxycarbonyl-C1-C6-alkyl: for example 1- propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2- methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2- butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3- methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1- ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1- methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl- 2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1- dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3- dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3- dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3- dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2- ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1- ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl; - C3-C6-haloalkenyl and also the C3-C6-haloalkenyl moieties of C3-C6-haloalkenyloxy-C1- C6-alkyl: a C3-C6-alkenyl radical as mentioned above which is partially or fully substituted by 210558 fluorine, chlorine, bromine and/or iodine, for example 2-chloroprop-2-en-1-yl, 3-chloroprop-2-en- 1-yl, 2,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-en-1-yl, 2,3,3-trichloro-2-en-1-yl, 2,3- dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2,3-dibromoprop-2-en-1- yl, 3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromo-2-en-1-yl or 2,3-dibromobut-2-en-1-yl; - C3-C6-alkynyl and also the C3-C6-alkynyl moieties of C3-C6-alkynyloxycarbonyl-C1-C6- alkyl: for example 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl- 3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1- pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3- butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2- ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl; - C3-C6-haloalkynyl: a C3-C6-alkynyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 1,1-difluoroprop-2-yn-1-yl, 3-chloroprop-2-yn-1-yl, 3-bromoprop-2-yn-1-yl, 3-iodoprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4- chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl; - C1-C3-alkoxy and also the C1-C3-alkoxy moieties of C1-C3-alkoxy-C1-C3-alkyl, C1-C3- alkoxycarbonyl: for example methoxy, ethoxy, propoxy; - C1-C4-alkoxy: for example methoxy, ethoxy, propoxy, 1-methylethoxy butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy; - C1-C6-alkoxy and also the C1-C6-alkoxy moieties of C1-C6-alkyoxy-C1-C6-alkyl, C1-C6- alkoxy-C1-C6-alkoxy-C1-C6-alkyl, di(C1-C6-alkoxy)C1-C6-alkyl, C3-C6-alkenyloxy-C1-C6-alkoxy-C1- C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl: C1-C4-alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 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 1- ethyl-2-methylpropoxy. - C1-C3-haloalkoxy: a C1-C3-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 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, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3- dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromo- methyl)-2-bromoethoxy; - C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 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, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3- dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromo- methyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy; - C1-C6-haloalkoxy and also the C1-C6-haloalkoxy moieties of C1-C6-haloalkoxy-C1-C6- alkyl, C1-C6-haloalkoxycarbonyl-C1-C6-alkyl: a C1-C4-haloalkoxy as mentioned above, and also, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and dodecafluorohexoxy; - C1-C3-alkylthio: for example methylthio, ethylthio, propylthio, 1-methylethylthio; - C1-C4-alkylthio: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio; - C1-C6-alkylthio and also the C1-C6-alkylthio moieties of C1-C6-alkylthio-C1-C6-alkyl: C1-C4- alkylthio as mentioned above, and also, for example, pentylthio, 1-methylbutylthio, 2-methyl- butylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-di- methylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methyl- pentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2- ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1- ethyl-2-methylpropylthio; - C1-C6-alkylsulfinyl (C1-C6-alkyl-S(=O)-) and also the C1-C6-alkylsulfinyl moieties of C1-C6- alkylsulfinyl-C1-C6-alkyl: for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-me- thylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-di- methylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3- methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3- methylpentylsulfinyl, 4-methylpentyl-sulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutyl-sulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutyl- sulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2- trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl; - C1-C6-alkylsulfonyl (C1-C6-alkyl-S(O)2-) and also the C1-C6-alkylsulfonyl moieties of C1- C6-alkylsulfonyl-C1-C6-alkyl: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1- methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methyl-propylsulfonyl, 1,1- dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2,2- dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2- methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethyl- butylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethyl- propylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2- methylpropylsulfonyl; - (C1-C3-alkyl)amino: for example methylamino, ethylamino, propylamino, 1-methylethyl- amino. The preferred embodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another. According to a preferred embodiment of the invention preference is also given to a method for controlling PPO-i resistant weeds, wherein the variables within the compounds of formula (I) to be applied have, either independently or in combination with one another, the following meanings: Preferred are the compounds of formula (I) wherein R1 is NH2 or C1-C6-alkyl; particularly preferred is CH3; also particularly preferred is NH2. Also preferred are the compounds of formula (I) wherein R2 is C1-C4-haloalkyl; particularly preferred is C1-C3-haloalkyl; more preferred is C1-C2-haloalkyl; especially preferred is CF3. Also preferred are the compounds of formula (I) wherein R3 is H or C1-C4-alkyl; particularly preferred is H or CH3; more preferred is H; also more preferred is CH3. Also preferred are the compounds of formula (I) wherein R4 is H, F or Cl; particularly preferred is H or F; especially preferred is F. Also preferred are the compounds of formula (I) wherein R5 is halogen, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio or C1-C3- alkoxycarbonyl; preferably is C1-C3-alkoxy, C1-C3-haloalkoxy or C1-C3-alkylthio; particularly preferred is C1-C3-alkoxy or C1-C3-alkylthio; especially preferred is C1-C3-alkoxy; more preferred is OCH3. Also preferred are the compounds of formula (I) wherein R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-haloalkyl, C3-C6-haloalkenyl, C3-C6-haloalkynyl, C1-C6-cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy- C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl; preferably is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-haloalkyl, C1-C6- cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl; particularly preferred is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6- cyanoalkyl or C1-C6-alkoxy-C1-C6-alkyl; especially preferred is hydrogen, C1-C6-alkyl, or C3-C6-alkenyl; more preferred is hydrogen, CH3, C2H5 or CH2CH=CH2; most preferred is hydrogen, CH3 or C2H5. Also preferred are the compounds of formula (I) wherein R6 is hydrogen or C1-C6-alkyl. Also preferred are the compounds of formula (I) wherein n is 1 or 2; particularly preferred is 2; also particularly preferred is 1. Also preferred are the compounds of formula (I) wherein Q is O, also preferably is S. Also preferred are the compounds of formula (I) wherein W is O, also preferably is S. Also preferred are the compounds of formula (I) wherein X is O, also preferably is S. Also preferred are the compounds of formula (I) wherein Y is O, also preferably is S. Also preferred are the compounds of formula (I) wherein Z is phenyl or pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred is phenyl or pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3 or OCH3; especially preferred is phenyl or pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH3; more preferred is phenyl or pyridyl, each of which is unsubstituted. Also preferred are the compounds of formula (I) wherein Z is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3 or OCH3; especially preferred is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH3; more preferred is phenyl or 2-pyridyl, each of which is unsubstituted. Also preferred are the compounds of formula (I) wherein Z is phenyl, which is optionally substituted by 1 substituent selected from the group consisting of halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred is phenyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3 or OCH3; especially preferred is phenyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH3; also especially preferred is unsubstituted phenyl. Also preferred are the compounds of formula (I) wherein Z is pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred is pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3 or OCH3; especially preferred is pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH3; also especially preferred is unsubstituted pyridyl. Also preferred are the compounds of formula (I) wherein Z is 2-pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred is 2-pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3 or OCH3; especially preferred is 2-pyridyl, which is optionally substituted by 1 substituent selected from the group consisting of F, Cl or CH3; also especially preferred is unsubstituted 2-pyridyl. Also preferred are the compounds of formula (I) wherein Z is selected from the group consisting of Z1 to Z13
Figure imgf000025_0001
Z-13 wherein * denotes the point of attachment of Z to X; ** denotes the point of attachment of Z to Q; and Ra, Rb, Rc, Rd and Re independently of one another are H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; preferably H, halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred H, F, Cl, Br, CH3 or OCH3; especially preferred H, F, Cl or CH3; more preferred H. Also preferred are the compounds of formula (I) wherein Z is selected from the group consisting of Z1, Z2, Z4, Z5, Z6, Z7, Z8, Z9, Z10 and Z11 as defined above; particularly preferred is selected from the group consisting of Z1, Z4, Z5, Z6 and Z7 as defined above; more particularly preferred is selected from the group consisting of Z1, Z4, Z5, Z6 and Z7 as defined above; especially preferred is selected from the group consisting of Z1 and Z7 as defined above; more preferred is selected from Z1 as defined above; also more preferred is selected from Z7 as defined above. Also preferred are the compounds of formula (I) wherein Z is selected from the group consisting of Z1, Z2, Z4, Z5, Z6, Z7, Z8, Z9, Z10 and Z11 as defined above, wherein Ra, Rb, Rc, Rd and Re independently of one another are H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; preferably H, halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred H, F, Cl, Br, CH3 or OCH3; especially preferred H, F, Cl or CH3; more preferred H; particularly preferred is selected from the group consisting of Z1, Z4, Z5, Z6 and Z7, as defined above, wherein Ra, Rb, Rc, Rd and Re independently of one another are H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; preferably H, halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred H, F, Cl, Br, CH3 or OCH3; especially preferred H, F, Cl or CH3; more preferred H; especially preferred is selected from the group consisting of Z1 and Z7 as defined above, wherein Ra, Rb, Rc, Rd and Re independently of one another are H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; preferably H, halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred H, F, Cl, Br, CH3 or OCH3; especially preferred H, F, Cl or CH3; more preferred H; more preferred is Z1 as defined above, wherein Ra, Rb, Rc, Rd and Re independently of one another are H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; preferably H, halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred H, F, Cl, Br, CH3 or OCH3; especially preferred H, F, Cl or CH3; more preferred H; also more preferred is Z7 as defined above, wherein Ra, Rb, Rc, Rd and Re independently of one another are H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; preferably H, halogen, C1-C6-alkyl or C1-C6-alkoxy; particularly preferred H, F, Cl, Br, CH3 or OCH3; especially preferred H, F, Cl or CH3; more preferred H. Also preferred are the compounds of formula (I) wherein R1 is CH3; R2 is C1-C3-haloalkyl; R3 is hydrogen or CH3; R4 is H or halogen; R5 is C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio; R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-haloalkyl, C3-C6- haloalkenyl, C3-C6-haloalkynyl, C1-C6-cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6- alkoxy-C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl, n is 1; Q, W and Y are O; X is O or S; Z is phenyl or 2-pyridyl, each of which is optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3, OCH3. Also preferred are the compounds of formula (I) wherein R1 is CH3; R2 is C1-C3-haloalkyl; R3 is hydrogen; R4 is F; R5 is C1-C3-alkoxy; R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-haloalkyl, C1-C6- cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl, n is 1; Q, W, X and Y are O; Z is phenyl, optionally substituted by 1 substituent selected from the group consisting of F, Cl, Br, CH3, OCH3; Particular preference is given to compounds of formula (I.a) (corresponds to formula (I) wherein R1 is CH3, R2 is CF3, R3 is H, n is 1, Q, W, X and Y are O, and Z is Z-1 as defined, wherein Ra, Rb, Rc and Rd are H:
Figure imgf000028_0001
wherein the variables R4, R5, and R6 have the meanings, in particular the preferred meanings, as defined above; special preference is given to the compounds of formulae (I .a.1 ) to (I. a.36) of Table A, where the definitions of the variables R4, R5, and R6 are of particular importance for the compounds according to the invention not only in combination with one another but in each case also on their own: Table A
Figure imgf000028_0002
Figure imgf000029_0004
Also preferred are the compounds of formula (l.b), preferably the compounds of formulae (l.b.1) to (l.b.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Q is S:
Figure imgf000029_0001
Also preferred are the compounds of formula (l.c), preferably the compounds of formulae (l.c.1) to (l.c.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-2, wherein Ra, Rb, Rc and Re are H:
Figure imgf000029_0002
Also preferred are the compounds of formula (l.d), preferably the compounds of formulae (l.d.1) to (l.d.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-3, wherein Ra, Rb, Rd and Re are H:
Figure imgf000029_0003
Also preferred are the compounds of formula (l.e), preferably the compounds of formulae (l.e.1) to (l.e.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.56) only in that Z is Z-4, wherein Rb, Rc and Rd are H:
Figure imgf000030_0001
Also preferred are the compounds of formula (l.f), preferably the compounds of formulae (l.f.1) to (l.f.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-5, wherein Ra, Rc and Rd are H:
Figure imgf000030_0002
Also preferred are the compounds of formula (l.g), preferably the compounds of formulae (l.g.1) to (l.g.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-6, wherein Ra, Rb and Rd are H:
Figure imgf000030_0003
Also preferred are the compounds of formula (l.h), preferably the compounds of formulae (l.h.1) to (l.h.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-7, wherein Ra, Rb and Rc are H:
Figure imgf000030_0004
Also preferred are the compounds of formula (l.i), preferably the compounds of formulae (l.i.1) to (l.i.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-7, wherein Ra, Rb and Rc are H, and Q is S:
Figure imgf000031_0001
Also preferred are the compounds of formula (l.k), preferably the compounds of formulae (l.k.1) to (l.k.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-8, wherein Rb, Rc and Re are H:
Figure imgf000031_0002
Also preferred are the compounds of formula (I. I), preferably the compounds of formulae (1.1.1) to (1.1.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-9, wherein Ra, Rc and Re are H:
Figure imgf000031_0003
Also preferred are the compounds of formula (l.m), preferably the compounds of formulae (l.m.1) to (l.m.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-10, wherein Ra, Rb and Re are H:
Figure imgf000031_0004
Also preferred are the compounds of formula (l.n), preferably the compounds of formulae (l.n.1) to (l.n.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-11 , wherein Ra, Rb and Rc are H:
Figure imgf000032_0001
Also preferred are the compounds of formula (l.o), preferably the compounds of formulae (1.0.1) to (I. o.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-12, wherein Rb, Rd and Re are H:
Figure imgf000032_0002
Also preferred are the compounds of formula (l.p), preferably the compounds of formulae (l.p.1) to (l.p.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that Z is Z-13, wherein Ra, Rd and Re are H:
Figure imgf000032_0003
Also preferred are the compounds of formula (l.q) preferably the compounds of formulae (l.q.1) to (l.q.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only that R5 is SCH3:
Figure imgf000032_0004
Also preferred are the compounds of formula (l.r), preferably the compounds of formulae (l.r.1) to (l.r.36), which differ from the corresponding compounds of formulae (l.a.1) to (I. a.36) only in that R3 is CH3:
Figure imgf000033_0001
Also preferred are the compounds of formulae (I. a), (l.h), (l.q), and (l.r); particularly preferred the compounds of formulae (I. a); also particularly preferred the compounds of formulae (l.h).
Also preferred are the compounds of formulae (l.a.1) to (1.a.36), (l.h.1) to (l.h.36), (l.q.1) to (l.q.36) and (l.r.1) to (l.r.36); particularly preferred the compounds of formula (l.a.1) to (1.a.36).
Also preferred are the compounds of formulae (I. a.19), (I. a.20), (I. a.21), (I. a.25), (I. a.26), (l.a.27), (l.a.31), (l.h.20), (l.q.20), and (l.r.20); particularly preferred the compounds of formulae (I. a.19), (I. a.20), (I. a.21), (I. a.25), (I. a.26), (l.a.27) and (l.a.31); also particularly preferred the compounds of formulae (I. a.20), (l.h.20), (l.q.20) and (l.r.20).
Especially preferred compounds are methyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; methyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; methyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetic acid;
(2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetic acid;
(2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetic acid; ethyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; ethyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; ethyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; allyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; allyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; allyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; prop-2-ynyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; prop-2-ynyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; prop-2-ynyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; cyanomethyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; cyanomethyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; cyanomethyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate;
2-methoxyethyl rac-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate;
2-methoxyethyl (2S)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate;
2-methoxyethyl (2R)-2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate; methyl rac-2-[2-[2-bromo-5-[3,5-dimethyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-4-fluoro- phenoxy]phenoxy]-2-methoxy-acetate; methyl (2S)-2-[2-[2-bromo-5-[3,5-dimethyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-4-fluoro- phenoxy]phenoxy]-2-methoxy-acetate; methyl (2R)-2-[2-[2-bromo-5-[3,5-dimethyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-4-fluoro- phenoxy]phenoxy]-2-methoxy-acetate; methyl rac-2-[[3-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]-2-pyridyl]oxy]-2-methoxy-acetate; methyl (2S)-2-[[3-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]-2-pyridyl]oxy]-2-methoxy-acetate; methyl (2R)-2-[[3-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]-2-pyridyl]oxy]-2-methoxy-acetate.
In a particularly preferred embodiment, the compound of formula (I) is the compound (I. a.19):
Figure imgf000034_0001
Accordingly, in a preferred embodiment of the present invention the method according to the present invention comprises the application of compound (I. a.19) to PPO-i resistant weeds.
In another particularly preferred embodiment, the compound of formula (I) is the compound (I. a.20):
Figure imgf000035_0001
Accordingly, in a preferred embodiment of the present invention the method according to the present invention comprises the application of compound (I. a.20) to PPO-i resistant weeds.
In another particularly preferred embodiment, the compound of formula (I) is the compound (I. a.21):
Figure imgf000035_0002
Accordingly, in a preferred embodiment of the present invention the method according to the present invention comprises the application of compound (I. a.21) to PPO-i resistant weeds.
In another preferred embodiment of the present invention the method according to the present invention comprises the application of at least one of the compounds selected from (I. a.19), (I. a.20) and (I. a.21) to PPO-i resistant weeds [i.e. the compound of formula (I) is selected from at least one of the compounds of formulae (I. a.19), (I. a.20) and (I. a.21)].
The compounds of formula (I) can be prepared by reaction of compounds of formula (II) with alkylating agents of formula (III) in the presence of a base in analogy to known processes (e.g.
WO 11/137088):
Figure imgf000035_0003
Within the alkylating agents of formula (III), L1 is a leaving group such as halogen.
The alkylating agents of formula (III) are commercially available or can be prepared by known methods (e.g. WO 11/137088).
Compounds of formula (II) can be prepared by deprotection of the respective compounds of formula (VI):
Figure imgf000036_0001
Within the compounds of formula (VI) “PG” is a protecting group selected from the group consisting of C1-C6-alkyl or (tri-C1-C6-alkyl)silyl-C1-C4-alkyl. For example, the compounds of formula (II) can be prepared by treating the compounds of formula (VI), wherein “PG” is methyl, with boron tribromide in a solvent such as dichloromethane at temperatures ranging from 0 °C to 150 °C. Compounds of formula (VI), wherein R1 is H, can be prepared by reaction of amines of formula (VII) with oxazinones of formula
Figure imgf000036_0002
Figure imgf000036_0003
(VI), wherein R1 is H The reaction may in principle be carried out in substance. However, preference is given to reacting the amines of formula (VII) with the oxazinones of formula (VIII) in an organic solvent. Suitable in principle are all solvents which are capable of dissolving the amines of formula (VII) and the oxazinones of formula (VIII) at least partly, and preferably fully under reaction conditions. Examples of suitable solvents are halogenated hydrocarbons such as dichloromethane, 1,2- dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N- dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
It is also possible to use mixtures of the solvents mentioned.
As acids inorganic acids like hydrochloric acid, hydrobromic acid or sulfuric acid, as well as organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid, can be used.
The acids are generally employed in equimolar amounts, in excess or, if appropriate, be used as solvent, however they can also be employed in catalytic amounts.
Those compounds of formula (VI), wherein R1 is NH2, Ci-Ce-alkyl or Cs-Ce-alkynyl, can be prepared by amination or alkylation of those compounds of formula (VI), wherein R1 is H. Such amination or alkylation can be conducted in analogy to known processes (e.g. WO 05/054208; WO 06/125746).
As alkylation reagents commercially available Ci-Ce-alkylhalides and alkinylhalides can be used.
Suitable amination reagents are known from literature (e.g. US 6333296 or DE 10005284)
The compounds of formula (VIII) required for the preparation of compounds of formula (VI) are commercially available or can be prepared by known methods.
The amines of formula (VII) required for the preparation of compounds of formula (VI) can be prepared from the corresponding compound of formula (IX):
Figure imgf000037_0001
Within the compound of formula (IX) the group “PG” is a protecting group as defined above for the compounds of formula (VI).
The reaction may in principle be carried out in substance. However, preference is given to reacting the amines of formula (VII) with the oxazinones of formula (VIII) in an organic solvent. Suitable in principle are all solvents which are capable of dissolving the amines of formula (VII) and the oxazinones of formula (VIII) at least partly, and preferably fully under reaction conditions.
Examples of suitable solvents are halogenated hydrocarbons such as dichloromethane, 1 ,2- dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF); nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert.-butanol, organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N '-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
As acids inorganic acids like hydrochloric acid, hydrobromic acid or sulfuric acid, as well as organic acids like formic acid, acetic acid, propionic acid, oxalic acid, methylbenzenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid, trifluoroacetic acid, can be used.
The acids are generally employed in equimolar amounts, in excess or, if appropriate, be used as solvent, however they can also be employed in catalytic amounts.
The compounds of formula (IX) required for the preparation of compounds of formula (VII) can be prepared from the corresponding nitro compounds of formula (X):
Figure imgf000038_0001
The compound of formula (IX) can be prepared by reduction followed by a Sandmeyer reaction from a compound of formula (X).
Reduction of the nitro group on a compound of formula (X) can be carried out by catalytic hydrogenation in hydrogen gas at a pressure of 70 to 700 kPa, preferably 270 to 350 kPa, in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20% of metal to carrier, suspended in a solvent such as ethanol at ambient temperature.
Bromination of the resulting amine is facilitated by diazotization with an alkyl nitrite ( e.g. isoamyl nitrite) followed by treatment with a copper (I) bromide and/or copper (II) bromide in a solvent such as acetonitrile at a temperature ranging from 0 °C to the reflux temperature of the solvent to give the corresponding compound of formula (IX).
The compounds of formula (X) required for the preparation of compounds of formula (IX) can be prepared by reaction of compounds of formula (XI) with compounds of formula (XII) in the presence of a base:
Figure imgf000038_0002
Within the compounds of formula (XI) L3 is a leaving group such as halogen.
The reaction is carried out in an organic solvent.
Examples of suitable solvents are halogenated hydrocarbons such as dichloromethane, 1 ,2- dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N '-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
It is also possible to use mixtures of the solvents mentioned.
Examples of suitable bases include metal-containing bases and nitrogen-containing bases. Examples of suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; metal organic compounds, preferably alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alkoxides such as potassium tert-butoxide, potassium tertpentoxide; and furthermore organic bases, such as tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidinge, lutidine, N-methylmorpholine and 4-dimethylaminopyridine and also bicyclic amines.
The bases are generally employed in equimolar amounts or in excess; however they can also be employed as solvent, or, if appropriate, in catalytic amounts.
The compounds of formula (XII) required for the preparation of compounds of formula (X) are commercially available or can be prepared by known methods.
The compounds of formula (XI) required for the preparation of compounds of formula (X) can be prepared from compounds of formula (XIII):
Figure imgf000039_0001
The reaction can be carried out by adding bis(1 , 1 -dimethylethyl) dicarbonate (CAS 24424-99-5) to compounds of formula (XIII) in an organic solvent. The addition of a base can be advantages. Examples of suitable solvents are halogenated hydrocarbons such as dichloromethane, 1,2- dichloroethane, chloroform.
Examples of suitable bases are nitrogen-containing bases such as 4-(dimethylamino)pyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN).
The compounds of formula (XIII) required for the preparation of compounds of formula (XI) are commercially available or can be prepared by known methods.
The method according to the invention can be employed in a further number of crop plants for eliminating the PPO-i resistant weeds.
According to the invention all the crop plants (cultivated plants) mentioned herein are understood to comprise all species, subspecies, variants and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
For example, corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).
Further, most soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856). The indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (Maturity Group, (MG) 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec, altissima, Beta vulgaris spec, rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. Silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Preferred crops are Arachis hypogaea, Beta vulgaris spec, altissima, Brassica napus var. napus, Brassica oleracea, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cynodon dactylon, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hordeum vulgare, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Medicago sativa, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris, Pistacia vera, Pisum sativum, Prunus dulcis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Triticale, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Especially preferred crops are crops of cereals, corn, soybeans, rice, oilseed rape, cotton, peas, lentils, peanuts or permanent crops.
Examples of PPO-i resistant weed species are Asian copperleaf (Acalypha australis), smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus), common ragweed (Ambrosia artemisiifolia or Ambrosia eliator), wild oat (Avena fatua), fleabane (Conyza ambigua or Conyza sumatrensis), marestail (Conyza Canadensis), flixweed (Descurainia Sophia), goosegrass (Eleusine indica), wild poinsettia (Euphorbia heterophylla), rigid ryegrass (lolium rigidum) and eastern groundsel (Senecio vernalis).
Preferred is the method according to the invention, wherein the PPO-i resistant weeds to be controlled are selected from the group consisting of smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus) and common ragweed (Ambrosia artemisiifolia or Ambrosia eliator); preferably are selected from smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus) and tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus); particularly preferably are selected from the group consisting of preferred Palmer amaranth (Amaranthus Palmeri) and tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus).
In another particularly preferred embodiment of the invention, the PPO-i resistant weed to be controlled is smooth pigweed.
In another particularly preferred embodiment of the invention, the PPO-i resistant weed to be controlled is Palmer amaranth. In another particularly preferred embodiment of the invention, the PPO-i resistant weed to be controlled is redroot pigweed.
In another particularly preferred embodiment of the invention, the PPO-i resistant weed to be controlled is tall/common waterhemp.
In another particularly preferred embodiment of the invention, the PPO-i resistant weed to be controlled is common ragweed.
The agrochemical compositions which can be used for the method according to the invention comprise an herbicidal effective amount of at least one compound of formula (I) and auxiliaries which are customary for the formulation of crop protection agents.
The compounds of formula (I), or herbicidal compositions comprising the compounds of formula (I), can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading, watering or treatment of the seed or mixing with the seed. The use forms depend on the intended purpose; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
A formulation comprises a pesticidally effective amount of a compound of formula (I). The term "effective amount" denotes an amount of the compound of formula (I), which is sufficient for controlling undesired vegetation, especially for controlling undesired vegetation in crops (i.e. cultivated plants) and which does not result in a substantial damage to the treated crop plants. Such an amount can vary in a broad range and is dependent on various factors, such as the undesired vegetation to be controlled, the treated crop plants or material, the climatic conditions and the specific compound of formula (I) used.
The compound of formula (I), their N-oxides, salts amides, esters or thioesters can be converted into customary types of formulations, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further formulation types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound of formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for formulation types and their preparation are: i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound of formula (I) according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water. ii) Dispersible concentrates (DC)
5-25 wt% of a compound of formula (I) according to the invention and 1-10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion. iii) Emulsifiable concentrates (EC)
15-70 wt% of compound of formula (I) according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)
5-40 wt% of compound of formula (I) according to the invention and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% waterinsoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound of formula (I) according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type formulation up to 40 wt% binder (e.g. polyvinylalcohol) is added. vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound of formula (I) according to the invention are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound of formula (I) according to the invention are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance. viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound of formula (I) according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. iv) Microemulsion (ME)
5-20 wt% of a compound of formula (I) according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion. iv) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4’-diisocyanate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt%. The wt% relate to the total CS formulation. ix) Dustable powders (DP, DS)
1-10 wt% of a compound of formula (I) according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%. x) Granules (GR, FG) 0.5-30 wt% of a compound of formula (I) according to the invention is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or the fluidized bed. xi) Ultra-low volume liquids (UL)
1-50 wt% of a compound of formula (I) according to the invention are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
The formulation types i) to xi) may optionally comprise further auxiliaries, such as 0,1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1-1 wt% colorants.
Application can be done before, during and/or after, preferably during and/or after, the emergence of the PPO-i resistant weeds.
The inventive method, i.e. the compounds of formula (I), or the formulations comprising them, are applied to the plants mainly by spraying the leaves. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 50 to 1000 l/ha (for example from 100 to 200 l/ha). The compounds of formula (I), or the formulations comprising them, may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.
Application of the compounds of formula (I), or the formulations comprising them, can be done before, during and/or after, preferably during and/or after, the emergence of the undesired vegetation.
Application of the compounds of formula (I), or the formulations can be carried out before or during sowing.
The inventive method, i.e. the compounds of formula (I), or the formulations comprising them, can be applied pre-, post-emergence or pre-plant, or together with the seed of a crop plant. It is also possible to apply the method, i.e. the compounds of formula (I), or the formulations comprising them, by applying seed, pretreated with the compounds of formula (I), or the formulations comprising them, of a crop plant.
If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the combinations are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesired vegetation growing underneath, or the bare soil surface (post-directed, lay-by).
In a further embodiment, the inventive method, i.e. the compounds of formula (I), or the formulations comprising them, can be applied by treating seed. The treatment of seeds comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of formula (I), or the formulations prepared therefrom. Here, the combinations can be applied diluted or undiluted.
The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the crop plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
When employed according to the method of the invention, the amount of active substance applied, i.e.of the compounds of formula (I), without formulation auxiliaries, are from 0.001 to 2 kg per ha, preferably from 0.002 to 1 kg per ha, more preferably from 0.005 to 0.5 kg per ha and in particular from 0.01 to 0.25 kg per ha.
In another embodiment of the invention, the application rate of the compounds of formula (I), is from 0.001 to 3 kg/ha, preferably from 0.002 to 2 kg/ha and in particular from 0.005 to 1 kg/ha of active substance (a.s.).
In another preferred embodiment of the invention, the rates of application of the compounds of formula (I) according to the present invention (total amount of compounds of formula (I)) are from 0.1 g/ha to 3000 g/ha, preferably 5 g/ha to 500 g/ha, depending on the control target, the season, the target plants and the growth stage.
In another preferred embodiment of the invention, the application rates of the compounds of formula (I) are in the range from 0.1 g/ha to 5000 g/ha and preferably in the range from 1 g/ha to 2500 g/ha or from 2 g/ha to 2000 g/ha.
In another preferred embodiment of the invention, the application rate of the compounds of formula (I) is 0.1 to 1000 g/ha, preferably 1 to 750 g/ha, more preferably 5 to 500 g/ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
In another embodiment of the invention, to treat the seed, the amounts of active substances applied, i.e. of compounds of formula (I), are generally in amounts of from 0.001 to 10 kg per 100 kg of seed.
A Preparation examples
Example 1
Methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate
Figure imgf000047_0001
Example 1 - step1: tert-Butyl N-(2,5-difluoro-4-nitro-phenyl)carbamate
Figure imgf000048_0001
4-Dimethylaminopyridine (12.2 g, 100 mmol) was added to a solution of 2,5-difluoro-4-nitro- aniline (CAS 1542-36-5; 172 g, 1 mol), bis-(1,1-dimethylethyl) dicarbonate (327 g, 1.5 mol) in dichloromethane (2 L) at 25 °C. The mixture was stirred at 25 °C for 18 h. The resulting mixture was concentrated and purified with silica gel column (ethylacetate : petrolether 1:9) to give tert- butyl N-(2,5-difluoro-4-nitro-phenyl)carbamate (250 g, 91.2%) as yellow solid. 1H NMR (CDCl3400MHz): δ ppm = 8.27 (dd, J=13.1, 6.6 Hz, 1 H), 7.91 (dd, J=10.6, 6.6 Hz, 1 H), 7.05 (br s, 1 H), 1.57 (s, 9H). Example 1 - step 2: tert-butyl N-[2-fluoro-5-(2-methoxyphenoxy)-4-nitro-phenyl]carbamate
Figure imgf000048_0002
To a solution of tert-butyl N-(2,5-difluoro-4-nitro-phenyl)carbamate (250 g, 911 mmol) and K2CO3 (377 g, 2733 mmol) in acetonitrile (2.5 L) was added 2-methoxyphenol (136 g, 1094 mmol) at 15 °C. Then the mixture was stirred at 80 °C for 18 h. The mixture was filtered and the filtrate was concentrated. The residue was diluted with ethylacetate, washed with H2O, brine, dried over Na2SO4 and concentrated. The residue was triturated with ethylacetate : petrolether 1:3 (1 L) to give tert-butyl N-[2-fluoro-5-(2-methoxyphenoxy)-4-nitro-phenyl]carbamate (220 g, 64%) as yellow solid. 1H NMR (400 MHz, DMSO-d6) δ ppm = 9.63 (s, 1 H) 8.04 (d, J=10.6 Hz, 1 H), 7.45 (d, J=6.7 Hz, 1 H), 7.19 - 7.29 (m, 2 H), 7.13 (d, J=7.7 Hz, 1 H), 6.98 - 7.03 (m, 1 H), 3.74 (s, 3 H), 1.37 (s, 9 H). Example 1 – step 3: tert-butyl N-[4-amino-2-fluoro-5-(2-methoxyphenoxy)phenyl]carbamate
Figure imgf000048_0003
To the solution of tert-butyl N-[2-fluoro-5-(2-methoxyphenoxy)-4-nitro-phenyl]carbamate (210 g, 555 mmol) in ethanol (3.6 L) was added Pd/C (21 g) under N2 and stirred at 25 °C under H2 (50 Psi) for 24 h. The mixture was filtered and concentrated to give tert-butyl N-[4-amino-2-fluoro-5- (2-methoxyphenoxy)phenyl]carbamate (170 g, 80.6%) as a brown solid. 1H NMR (400 MHz, DMSO-d6) δ ppm = 8.34 (br s, 1 H), 7.06 - 7.15 (m, 2 H), 6.86 - 6.93 (m, 1 H), 6.78 - 6.84 (m, 1 H), 6.61 (br s, 1 H), 6.55 (d, J=12.1 Hz, 1 H), 5.02 (s, 2 H), 3.79 (s, 3 H), 1.36 (s, 9 H). Example 1 - step 4: tert-butyl N-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]carbamate
Figure imgf000049_0001
To the mixture of CuBr2 (26.6 g, 120 mmol) in acetonitrile (200 mL) was added isoamyl nitrite (10.5 g, 90 mmol) at 25 °C. Then, the mixture was warmed to 60 °C. tert-butyl N-[4-amino-2- fluoro-5-(2-methoxyphenoxy)phenyl]-carbamate (31g, 60mmol) was added in portions at 60 °C and stirred for 1 h at 60 °C. Then the mixture was diluted with H2O, extracted with ethylacetate twice. The organic layer was washed with brine, dried over Na2SO4 and concentrated. The crude was purified by column (ethylacetate : petrolether 1 : 4) to give tert-butyl N-[4-bromo-2- fluoro-5-(2-methoxyphenoxy)phenyl]carbamate (13 g, 52.5%) as a brown solid. 1H NMR (400 MHz, CDCl3) δ ppm = 7.72 (br s, 1H), 7.33 (d, J=10.2 Hz, 1H), 7.13 - 7.07 (m, 1H), 7.02 - 6.99 (m, 1H), 6.92 - 6.86 (m, 1H), 6.83 - 6.79 (m, 1H), 6.61 (br s, 1H), 3.88 (s, 3H), 1.45 (s, 9H). Example 1 - step 5: 4-bromo-2-fluoro-5-(2-methoxyphenoxy)aniline
Figure imgf000049_0002
To tert-butyl N-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]carbamate (3 g, 7.3 mmol) was added 4N HCl in ethylacetate (30 mL) in portions at 0 °C and stirred for 16 h at 20 °C. The mixture was poured into H2O, extracted with ethylacetate, and the organic layer was washed with brine, dried over Na2SO4 and concentrated to give 4-bromo-2-fluoro-5-(2- methoxyphenoxy)aniline (2.3 g, crude) as a brown solid. 1H NMR (400MHz, CDCl3) δ ppm = 7.23 (d, J=10.2 Hz, 1H), 7.15 - 7.09 (m, 1H), 7.01 (dd, J=1.2, 8.1 Hz, 1H), 6.93 - 6.88 (m, 1H), 6.87 - 6.83 (m, 1H), 6.27 (d, J=8.2 Hz, 1H), 3.87 (s, 3H), 3.69 (br s, 2H). Example 1 – step 6: 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-6-(trifluoromethyl)-1H- pyrimidine-2,4-dione
Figure imgf000049_0003
To a solution of 4-bromo-2-fluoro-5-(2-methoxyphenoxy)aniline (1.8 g, 5.8 mol) in acetic acid (5 mL) was added 2-(dimethylamino)-4-(trifluoromethyl)-1,3-oxazin-6-one (CAS 141860-79-9, 1.8 g, 8.7 mmol) at 20 °C. The mixture was stirred at 75 °C for 16 h. The mixture was poured into water and extracted with ethylacetate. The organic layer was washed with brine, dried over Na2SO4 and concentrated to give 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-6- (trifluoromethyl)-1H-pyrimidine-2,4-dione (3.2 g, crude) as a black solid. Example 1 - step 7: 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-1-methyl-6-(trifluoro- methyl)-pyrimidine-2,4-dione
Figure imgf000050_0001
To a mixture of 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-6-(trifluoromethyl)-1H- pyrimidine-2,4-dione (4.1 g, 8.6 mmol) in acetonitrile (40 mL) was added K2CO3 (4.7 g, 34.2 mmol) and methyliodide (2.5 g, 17.3 mmol) dropwise with stirring at 25 °C. Then, it was stirred for 16 h at 60 °C. The mixture was filtered, and the filtrate was concentrated. The crude was triturated. with ethylacetate : petrolether 1 : 10 (30 mL) to give 3-[4-bromo-2-fluoro-5-(2- methoxyphenoxy)phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione (3.4 g, crude) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ ppm = 7.54 (d, J=8.7 Hz, 1H), 7.20 - 7.14 (m, 1H), 7.05 (dd, J=1.5, 7.9 Hz, 1H), 7.00 (dd, J=1.2, 8.2 Hz, 1H), 6.97 - 6.92 (m, 1H), 6.57 (d, J=6.4 Hz, 1H), 6.30 (s, 1H), 3.81 (s, 3H), 3.51 (s, 3H). Example 1 step 8: 3-[4-bromo-2-fluoro-5-(2-hydroxyphenoxy)phenyl]-1-methyl-6-(trifluoro- methyl)-pyrimidine-2,4-dione
Figure imgf000050_0002
To a solution of 3-[4-bromo-2-fluoro-5-(2-methoxyphenoxy)phenyl]-1-methyl-6-(trifluoro- methyl)pyrimidine-2,4-dione (3.4 g, 6.9 mmol) in CH2Cl2 (50 mL) was added BBr3 (3.5 g, 13.9 mmol) dropwise with stirring at 0 °C. The mixture was stirred at 25 °C for 2 h. The mixture was poured into ice water and extracted with ethylacetate. The organic layer was washed with brine (100 mL), dried over Na2SO4, filtered and concentrated to give 3-[4-bromo-2-fluoro-5-(2- hydroxyphenoxy)phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione (2.3 g, 66% over steps 6, 7 and 8) as a yellow solid. 1H NMR (400 MHz, CDCl3-d) δ ppm = 7.56 (d, J = 8.8 Hz, 1H), 7.08 - 7.01 (m, 2H), 6.90 - 6.81 (m, 3H), 6.31 (s, 1H), 5.66 (br s, 1H), 3.53 - 3.50 (s, 3H). Example 1 – step 9: methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)- pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate
Figure imgf000051_0001
To a solution of 3-[4-bromo-2-fluoro-5-(2-hydroxyphenoxy)phenyl]-1-methyl-6-(trifluoromethyl)- pyrimidine-2,4-dione (1 g, 2.1 mmol) in DMF (10 mL) was added Cs2CO3 (2.1 g, 6.3 mmol), methyl 2-bromo-2-methoxyacetate (CAS 5193-96-4, 772 mg, 4.2 mol) at 10 °C. Then the reaction was stirred at 10 °C for 16 h. The mixture was poured into water and extracted with ethylacetate. The organic layer was washed with brine (30 ml), dried over anhydrous Na2SO4, concentrated. The crude was purified by column (ethylacetate : petrolether 1 : 5) and by prep-HPLC (acetonitrile - H2O) to give methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-pyrimidin-1- yl]phenoxy]phenoxy]-2-methoxy-acetate (0.285 g, 23%) as white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm = 7.94 (d, J=8.8 Hz, 1H), 7.23 (d, J=1.8 Hz, 1H), 7.23 - 7.18 (m, 1H), 7.15 - 7.10 (m, 1H), 7.08 - 7.04 (m, 1H), 6.96 (d, J=6.6 Hz, 1H), 6.50 (d, J=1.8 Hz, 1H), 5.67 (d, J=1.8 Hz, 1H), 3.68 (d, J=1.8 Hz, 3H), 3.35 (s, 3H), 3.29 (d, J=6.6 Hz, 3H). The compounds listed below in tables 1 and 2 can be prepared similarly to the example mentioned above.
Figure imgf000051_0002
Table 1
Figure imgf000051_0003
*[M+NH4]; **[M+Na]
Figure imgf000052_0001
Table 2
Figure imgf000052_0002
B Use examples The herbicidal activity of the compound of formula (I) was demonstrated by the following experiments: The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species. For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the test plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. Depending on the species, the test plants were kept at 10 – 25°C or 20 – 35°C, respectively. The test period extended over 2 to 4 weeks. During this time, the test plants were tended, and their response to the individual treatments was evaluated. Evaluation was carried out using a scale from 0 to 100.100 means no emergence of the test plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85. The plants used in the greenhouse experiment were of the following species and biotype:
Table 3
Figure imgf000053_0001
determined by pyrosequencing analysis
The results shown in the following tables 4 and 5 demonstrate that compound (I. a.20) has very good activity on both sensitive (w.1, w.2 and w.7) and resistant weeds (w.3 to w.6, w.8 to w.14) whereas the known PPO-i azafenidin shows much weaker control of resistant in comparison to sensitive biotypes:
Table 4
Figure imgf000053_0002
Table 5
Figure imgf000053_0003
The results shown in the following tables 6 and 7 demonstrate that compound (I. a.20) has very good activity on both sensitive (w.1, w.2 and w.7) and resistant weeds (w.4, w.5, w.6, w.8 to w.13) whereas the known PPO-i saflufenacil shows much weaker control of resistant in comparison to sensitive biotypes:
Table 6
Figure imgf000054_0001
Table 7
Figure imgf000054_0002

Claims

Claims: 1. A method for controlling the growth of PPO-i resistant weeds, which comprises contacting such weeds, parts of the weeds, propagation material of the weeds or a habitat of the weeds with at least one compound of formula (I)
Figure imgf000055_0001
wherein the substituents have the following meanings: R1 NH2, C1-C6-alkyl; R2 C1-C6-haloalkyl; R3 hydrogen or C1-C6-alkyl; R4 H or halogen; R5 halogen, CN, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, (C1-C3-alkyl)amino, di(C1-C3-alkyl)amino, C1-C3-alkoxy-C1-C3-alkyl, C1-C3- alkoxycarbonyl; R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-haloalkyl, C3-C6- haloalkenyl, C3-C6-haloalkynyl, C1-C6-cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1- C6-alkoxy-C1-C6-alkoxy-C1-C6-alkyl, di(C1-C6-alkoxy)C1-C6-alkyl, C1-C6-halo- alkoxy-C1-C6-alkyl, C3-C6-alkenyloxy-C1-C6-alkyl, C3-C6-haloalkenyloxy-C1-C6- alkyl, C3-C6-alkenyloxy-C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl, C1-C6-alkylsulfinyl-C1-C6-alkyl, C1-C6-alkylsulfonyl-C1-C6-alkyl, C1-C6- alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl, C1-C6- haloalkoxycarbonyl-C1-C6-alkyl, C3-C6-alkenyloxycarbonyl-C1-C6-alkyl, C3-C6- alkynyloxycarbonyl-C1-C6-alkyl; n 1 to 3; Q, W, X, and Y independently of one another O or S; Z phenyl or pyridyl, each of which is optionally substituted by 1 to 4 substituents selected from the group consisting of halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy; including their agriculturally acceptable salts, amides, esters or thioesters, provided the compounds of formula (I) have a carboxyl group; wherein the PPO-i resistant weeds are weeds, that are resistant to at least one PPO-i except the compounds of formula (I).
2. The method according to claim 1, wherein the PPO-i resistant weeds are resistant to at least one PPO-i selected from azafenidin.
3. The method according to claim 1, wherein the PPO-i resistant weeds are resistant to at least one PPO-i selected from fomesafen and lactofen.
4. The method according to any of claims 1 to 3, wherein the PPO-i resistant weeds are not controlled by the application rate of 600 g/ha or lower of at least one PPO-i except the compound of formula (I).
5. The method according to any of claims 1 to 4, wherein the PPO-i resistant weeds are selected from the group consisting of Acalypha ssp., Amaranthus ssp., Ambrosia ssp., Avena ssp., Conyza ssp., Descurainia ssp., Eleusine spp., Euphorbia ssp., Lolium ssp. and Senecio ssp.
6. The method according to any of claims 1 to 4, wherein the PPO-i resistant weeds are selected from the group consisting of Asian copperleaf (Acalypha australis), smooth pigweed (Amaranthus hybridus), Palmer amaranth (Amaranthus Palmeri), redroot pigweed (Amaranthus retroflexus), tall/common waterhemp (Amaranthus tuberculatus, Amaranthus rudis or Amaranthus tamariscinus), common ragweed (Ambrosia artemisiifolia or Ambrosia eliator), wild oat (Avena fatua), fleabane (Conyza ambigua or Conyza sumatrensis), marestail (Conyza Canadensis), flixweed (Descurainia Sophia), goosegrass (Eleusine indica), wild poinsettia (Euphorbia heterophylla), rigid ryegrass (lolium rigidum) and eastern groundsel (Senecio vernalis).
7. The method according to any of claims 1 to 3, wherein the PPO-i resistant weeds are selected from the group consisting of Palmer amaranth and tall/common waterhemp.
8. The method according to any of claims 1 to 7, wherein the PPO-i resistant weeds contain a AG210, R98L, R128G, R128M, G339A, K127N-I130V, A212T, Arg128His, Arg128Lle or Arg128Lys mutation in the Protox enzyme conferring resistance to PPO-i’s.
9. The method according to any of claims 1 to 8, wherein the PPO-i resistant weeds contain a AG210 or R98L mutation in the Protox enzyme conferring resistance to PPO-i’s.
10. The method according to any of claims 1 to 9, wherein the compound of formula (I) is selected from the compounds of formula (I. a):
Figure imgf000056_0001
wherein the variables R4, R5, and R6 are as defined in claim 1.
11 . The method according to any of claims 1 to 9, wherein the compound of formula (I) is the compound of formula (I. a.20):
Figure imgf000057_0001
12. The method according to any of claims 1 to 11, wherein an agrochemical composition comprising at least one compound of formula (I) and auxiliaries customary for formulating crop protection agents is applied.
13. The use of compounds of formula (I) as defined in claims 1 , 10 or 11 for controlling PPO-i resistant weeds.
14. The use of the composition as defined in claim 12 for controlling PPO-i resistant weeds.
15. Method for controlling PPO-i resistant weeds as claimed in any of claims 1 to 11, wherein the compound of formula (I) is applied in a locus where PPO tolerant crops are grown.
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