WO2023222589A1 - Herbicidal compounds - Google Patents

Herbicidal compounds Download PDF

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Publication number
WO2023222589A1
WO2023222589A1 PCT/EP2023/062944 EP2023062944W WO2023222589A1 WO 2023222589 A1 WO2023222589 A1 WO 2023222589A1 EP 2023062944 W EP2023062944 W EP 2023062944W WO 2023222589 A1 WO2023222589 A1 WO 2023222589A1
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Prior art keywords
hydrogen
c4alkyl
formula
compound
c4alkoxy
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PCT/EP2023/062944
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French (fr)
Inventor
William Guy Whittingham
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Syngenta Crop Protection Ag
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Publication of WO2023222589A1 publication Critical patent/WO2023222589A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered

Definitions

  • the present invention relates to herbicidally active compounds, as well as to processes and intermediates used for the preparation of such derivatives.
  • the invention further extends to herbicidal compositions comprising such derivatives, as well as to the use of such compounds and compositions for controlling undesirable plant growth: in particular the use for controlling weeds, in crops of useful plants.
  • the present invention is based on the finding that compounds of formula (I) as defined herein, exhibit surprisingly good herbicidal activity.
  • X 1 is C-R 1 , nitrogen, or N + -O _ ;
  • X 2 is C-R 17 or nitrogen
  • X 3 is C-R 18 or nitrogen
  • X 4 is C-R 19 or nitrogen; with the proviso that a maximum of two of X 1 , X 2 , X 3 and X 4 are nitrogen, and X 3 and X 4 are not both nitrogen;
  • Y is C-H or nitrogen
  • B is O, S, or NR 5 ;
  • D is -[C(R e )(R 7 )] n - ; m is an integer from 0 to 2; n is an integer from 1 to 4;
  • R 1 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci
  • R 1 and R 2 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R 16 ; or
  • R 2 and R 19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R 16 ;
  • R 3 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, or Ci-C4alkylsulfonyl;
  • R 4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, or Ci-C4alkylsulfonyl;
  • R 5 is hydrogen, hydroxy, Ci-Cealkyl, or Ci-C4alkoxy
  • R 6 and R 7 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, hydroxy, Ci-C4alkoxy, Ci-C4alkoxycarbonyl, or CH2OR 12 ; provided that R 6 and R 7 are not both hydroxy on the same carbon atom; or two R 6 and R 7 groups, on the same or different carbon atoms, together form a Ci-Csalkylene chain, which contain 0, 1 or 2 oxygen atoms, substituted by 1 to 3 groups represented by R 15 ; or two R 6 and R 7 groups, on the same carbon atom, together form a C2-C3alkene;
  • R 8 is OR 9 , SR 9 , or NR 10 R 11 ;
  • R 9 is hydrogen, Ci-Cwalkyl, Ci-Cwhaloalkyl, Cs-Cealkenyl, Cs-Cehaloalkenyl, Cs-Cealkynyl, C1- C4alkoxyCi-C6alkyl, Ci-C4haloalkoxyCi-C6alkyl, Ce-CwarylCi-Csalkyl, Ce-CwarylCi-Csalkyl substituted by 1 to 4 groups represented by R 13 , heteroarylCi-Csalkyl, or heteroarylCi-Csalkyl substituted by 1 to 3 groups represented by R 13 ;
  • R 10 is hydrogen, Ci-Cealkyl, SO2R 14 ;
  • R 11 is hydrogen or Ci-Cealkyl; or R 10 and R 11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring;
  • R 12 is hydrogen, Ci-C4alkyl, or Ci-C4alkylcarbonyl
  • R 13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl;
  • R 14 is Ci-C4alkyl, Ci-C4haloalkyl, or Ci-C4alkyl(Ci-C4alkyl)amino;
  • R 15 is hydrogen, halogen, Ci-C4alkyl, or Ci-C4haloalkyl
  • R 16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl;
  • R 17 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci
  • R 18 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 19 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 20 and R 21 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ci-C4alkoxy, or - CH2OR 12 ; or two R 20 and R 21 groups together with the carbon atom to which they are attached form a C2-Csalkylene chain, wherein said C2-Csalkylene chain comprises 0, 1 or 2 oxygen atoms, and wherein said C2- Csalkylene chain is substituted by 1 to 3 groups represented by R 15 ; or two R 20 and R 21 groups together with the carbon atom to which they are attached form a C2-C3alkene; and with the proviso that R 1 , R 2 , R 17 , R 18 and R 19 are not all hydrogen.
  • an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically- acceptable diluent or carrier.
  • Such an agricultural composition may further comprise at least one additional active ingredient.
  • a method of controlling or preventing undesirable plant growth wherein a herbicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • Ci-Cealkyl substituted by 1 , 2 or 3 halogens may include, but not be limited to, -CH2CI, -CHCI2, -CCh, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups.
  • Ci-Cealkoxy substituted by 1 , 2 or 3 halogens may include, but not limited to, CH2CIO-, CHCI2O-, CCI3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • amino means an -NH2 group.
  • hydroxy means an -OH group.
  • nitro means an -NO2 group.
  • Ci-Cioalkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to ten carbon atoms, and which is attached to the rest of the molecule by a single bond. Ci-Cealkyl, Ci-C4alkyl, Ci-Csalkyl, and Ci-C2alkyl are to be construed accordingly.
  • Ci-Cwalkyl examples include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1 -methylethyl (iso-propyl), n-butyl, and 1 -dimethylethyl (t- butyl).
  • Ci-C4alkoxy refers to a radical of the formula -OR a where R a is a C1- C4alkyl radical as generally defined above. Ci-Csalkoxy is to be construed accordingly. Examples of C1- 4alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and f-butoxy.
  • Ci-Ciohaloalkyl refers to a Ci-Cwalkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Ci-Cehaloalkyl and Ci- C4haloalkyl is to be construed accordingly.
  • Examples of Ci-Cwhaloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2 ,2,2-trifluoroethyl.
  • C2-C6alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or ( ⁇ -configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • Cs-Cealkenyl, C2-C4alkenyl and C2-C3alkenyl are to be construed accordingly.
  • Examples of C2-C6alkenyl include, but are not limited to, prop-1 -enyl, allyl (prop-2-enyl) and but-1-enyl.
  • C2-C6haloalkenyl refers to a C2-Cealkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Cs-Cehaloalkenyl, C2- C4haloalkenyl and C2-C3haloalkenyl are to be construed accordingly.
  • Examples of C2-Cehaloalkenyl include, but are not limited to chloroethylene, fluoroethylene, 1 ,1 -difluoroethylene, 1 ,1-dichloroethylene and 1 ,1 ,2-trichloroethylene.
  • C2-C6alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C2-C4alkynyl and Cs-Cealkynyl are to be construed accordingly.
  • Examples of C2-Cealkynyl include, but are not limited to, prop-1 -ynyl, propargyl (prop-2-ynyl) and but-1-ynyl.
  • Ci-Cehaloalkoxy refers to a Ci-Cealkoxy group as defined above substituted by one or more of the same or different halogen atoms. Ci-C4haloalkoxy is to be construed accordingly. Examples of Ci-Cehaloalkoxy include, but are not limited to, fluoromethoxy, difluoro methoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.
  • Ci-C4haloalkoxyCi-C6alkyl refers to a radical of the formula Rb-O-R a - where Rb is a Ci-C4haloalkyl radical as generally defined above, and R a is a Ci-Csalkylene radical as generally defined above.
  • Ci-C4alkoxyCi-C6alkyl refers to a radical of the formula Rb-O-R a - where Rb is a Ci-C4alkyl radical as generally defined above, and R a is a Ci-Csalkylene radical as generally defined above.
  • Ci-C4alkoxyCi-C4alkoxy refers to a radical of the formula Rb-O-R a -O- where Rb is a Ci-C4alkyl radical as generally defined above, and R a is a Ci-C4alkylene radical as generally defined above.
  • Ci-Cealkylcarbonyl refers to a radical of the formula -C(O)R a where R a is a Ci-Cealkyl radical as generally defined above.
  • Examples of Ci-Cealkylcarbonyl include, but are not limited to, acetyl.
  • Ci-Cealkoxycarbonyl refers to a radical of the formula -C(O)OR a where R a is a Ci-Cealkyl radical as generally defined above.
  • Ci-C4alkylamino refers to a radical of the formula R a NH- wherein R a is a Ci-C4alkyl radical as generally defined above.
  • di(Ci-C4alkyl)amino refers to a radical of the formula -N(R a )(Rb), wherein R a and Rb are each individually a Ci-C4alkyl radical as generally defined above.
  • the term “di(Ci- C3alkyl)amino” is to be construed accordingly.
  • Ci-C4alkylcarbonylamino refers to a radical of the formula -C(O)NHR a , wherein R a is a Ci-C4alkyl radical as generally defined above.
  • Ci-C4alkylcarbonyl(Ci-C4alkyl)amino refers to a radical of the formula -NH(R a )C(O)Rb, wherein R a and Rb each independently Ci-C4alkyl radicals as generally defined above.
  • Ci-C4alkoxycarbonylamino refers to a radical of the formula - NHC(O)OR a , wherein R a is a Ci-C4alkyl radical as generally defined above.
  • aminocarbonyl refers to a radical of the formula -C(O)NH2.
  • aminocarbonylamino refers to a radical of the formula -NHC(O)H2.
  • aminothiocarbonyl refers to a radical of the formula -C(S)NH2.
  • Ci-C4alkylaminocarbonylamino refers to a radical of the formula - NHC(O)NHR a , wherein R a is a Ci-C4alkyl radical as generally defined above.
  • Ci-C4alkylsulfonylamino refers to a radical of the formula -NHS(O)2R a where R a is a Ci-C4alkyl radical as generally defined above.
  • Ci-C4haloalkylsulfonylamino refers to a radical of the formula refers to a radical of the formula -NHS(O)2R a where R a is a Ci-C4haloalkyl radical as generally defined above.
  • Ci-C4alkylthio refers to a radical of the formula -SR a , where R a is a Ci- C4alkyl radical as generally defined above.
  • R a is a Ci- C4alkyl radical as generally defined above.
  • Ci-Csalkylsulfanyl and “Ci-C2alkylsulfanyl”, are to be construed accordingly.
  • Examples of Ci-C4alkylsulfanyl include, but are not limited to methylsulfanyl.
  • Ci-C4haloalkylthio refers to a radical of the formula refers to a radical of the formula -SR a , where R a is a Ci-C4haloalkyl radical as generally defined above.
  • Ci-C4alkylsulfinyl refers to a radical of the formula -S(O)R a , where R a is a Ci-C4alkyl radical as generally defined above.
  • Examples of Ci-C4alkylsulfinyl include, but are not limited to methylsulfinyl.
  • Ci-C4alkylsulfonyl refers to a radical of the formula refers to a radical of the formula -S(O)2R a , where R a is a Ci-C4alkyl radical as generally defined above.
  • Examples of Ci- C4alkylsolfanyl include, but are not limited to methylsulfonyl.
  • Ci-C4alkylsulfonyloxy refers to a radical of the formula -OS(O)2R a where R a is a Ci-C4alkyl radical as generally defined above.
  • Ci-C4haloalkylsulfonyloxy refers to a radical of the formula -OS(O)2R a where R a is a Ci-C4haloalkyl radical as generally defined above.
  • Ci-C4haloalkylsulfinyl refers to a radical of the formula -S(O)R a , where R a is a Ci-C4haloalkyl radical as generally defined above.
  • Ci-C4haloalkylsulfonyl refers to a radical of the formula -S(O)2R a , where R a is a Ci-C4haloalkyl radical as generally defined above.
  • Cs-Cecycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4cycloalkyl is to be construed accordingly. Examples of Cs-Cecycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Ce-Cwaryl refers to a 6- to 10-membered aromatic ring system consisting solely of carbon and hydrogen atoms which may be mono-, bi- or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, or indenyl.
  • Ce-CioarylCi-Csalkyl refers to an aryl moiety as generally defined above, which is attached to the rest of the molecule by a Ci-Csalkylene linker as defined above.
  • heteroaryl refers to a 5- or 6- membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heteroaryl include, furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
  • heteroarylCi-Csalkyl refers to a heteroaryl moiety as generally defined above, which is attached to the rest of the molecule by a Ci- Csalkylene linker as defined above.
  • heterocyclyl refers to a stable 4- to 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heterocyclyl examples include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or 6-lactamyl.
  • asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I).
  • formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and ketoenol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of formula (I).
  • where there are di-substituted alkenes these may be present in E or Z form or as mixtures of both in any proportion.
  • the present invention includes all these possible isomeric forms and mixtures thereof for a compound of formula (I).
  • the compounds of formula (I) will typically be provided in the form of an agronomically acceptable salt, a zwitterion or an agronomically acceptable salt of a zwitterion.
  • This invention covers all such agronomically acceptable salts, zwitterions and mixtures thereof in all proportions.
  • Suitable agronomically acceptable salts of the present invention can be with cations that include but are not limited to, metals, conjugate acids of amines and organic cations.
  • suitable metals include aluminium, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron and zinc.
  • Suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, he
  • Suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.
  • X 1 is C-R 1 , nitrogen, or N + -O; preferably C-R 1 or N + -O _ , and more preferably C-R 1 .
  • X 2 is C-R 17 or nitrogen, preferably nitrogen.
  • X 3 is C-R 18 or nitrogen, preferably C-R 18 .
  • X 4 is C-R 19 or nitrogen, preferably C-R 19 .
  • a maximum of one of X 2 , X 3 , and X 4 is nitrogen, more preferably with the proviso that one of X 2 , X 3 , and X 4 is nitrogen.
  • Y is C-H or nitrogen.
  • Y is C-H.
  • B is O, S, or NR 5 .
  • B is O, NH or NCH3, more B is preferably O or NH.
  • m is an integer from 0 to 2.
  • m is 0 or 2, more preferably m is 0.
  • n is an integer from 1 to 4.
  • n is an integer from 1 to 2, more preferably n is 2.
  • R 1 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 1 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, most preferably R 1 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl. In one set of embodiments, R 1 is halogen, preferably chlorine.
  • R 2 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 2 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, most preferably hydrogen, fluorine, chlorine, methyl or trifluoromethyl. More preferably still, R 2 is hydrogen; or
  • R 2 and R 19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R 16 .
  • R 2 and R 19 together with the carbon atoms to which they are attached form a 5-membered saturated ring, optionally containing one or two oxygen atoms, and which may be substituted with 1 or 2 groups represented by R 16 .
  • R 3 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, or Ci-C4alkylsulfonyl.
  • R 3 is hydrogen, chlorine or fluorine, more preferably hydrogen or fluorine. Even more preferably, R 3 is fluorine.
  • R 4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, or Ci-C4alkylsulfonyl.
  • R 4 is hydrogen, chlorine, bromine, cyano or aminothiocarbonyl, more preferably chlorine, bromine or cyano, more preferably still, chlorine or bromine. Even more preferably, R 4 is chlorine.
  • R 5 is hydrogen, hydroxy, Ci-Cealkyl, or Ci-C4alkoxy. Preferably, R 5 is hydrogen.
  • R 6 and R 7 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, hydroxy, Ci-C4alkoxy, Ci-C4alkoxycarbonyl, or -CH2OR 12 ; provided that R 6 and R 7 are not both hydroxy on the same carbon atom, or two R 6 and R 7 groups, on the same or different carbon atoms, together form a Ci-Csalkylene chain, which contain 0, 1 or 2 oxygen atoms, substituted by 1 to 3 groups represented by R 15 ; or two R 6 and R 7 groups, on the same carbon atom, together form a C2-C3alkene.
  • R 6 and R 7 are each independently hydrogen, halogen, Ci-C4alkyl or Ci-C4alkoxycarbonyl, more preferably hydrogen, halogen or Ci-C2alkyl, more preferably still hydrogen, chlorine or methyl. Even more preferably still, R 6 and R 7 are each independently hydrogen or methyl. In a particularly preferred embodiment, R 6 and R 7 are both hydrogen.
  • R 8 is OR 9 , SR 9 , or NR 10 R 11 .
  • R 8 is OR 9 .
  • R 9 is hydrogen, Ci-Cioalkyl, Ci-Ciohaloalkyl, Cs-Cealkenyl, Cs-Cehaloalkenyl, Cs-Cealkynyl, Ci- C4alkoxyCi-C6alkyl, Ci-C4haloalkoxyCi-C6alkyl, Ce-CwarylCi-Csalkyl, Ce-CwarylCi-Csalkyl substituted by 1 to 4 groups represented by R 13 , heteroarylCi-Csalkyl, or heteroarylCi-Csalkyl substituted by 1 to 3 groups represented by R 13 .
  • R 9 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C2alkoxyCi- C2alkyl, phenylCi-C2alkyl or phenylCi-C2alkyl substituted by 1-2 groups R 13 , more preferably hydrogen, Ci-C4alkyl, Ci-C2alkoxyCi-C2alkyl or phenylCi-C2alkyl, more preferably still hydrogen, Ci-C4alkyl or phenylCi-C2alkyl. Even more preferably, R 9 is Ci-C4alkyl. Even more preferably still, R 9 is methyl.
  • R 10 is hydrogen, Ci-Cealkyl, SO2R 14 .
  • R 10 is hydrogen or SO2R 14 , more preferably SO2R 14 .
  • R 11 is hydrogen or Ci-Cealkyl. Preferably R 11 is hydrogen.
  • R 10 and R 11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring.
  • R 12 is hydrogen, Ci-C4alkyl, or Ci-C4alkylcarbonyl.
  • R 12 is hydrogen, Ci-C2alkyl or C1- C2alkylcarbonyl, more preferably hydrogen or methyl.
  • R 13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl.
  • R 13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano or C1- C4alkylsulfonyl.
  • R 14 is Ci-C4alkyl, Ci-C4haloalkyl, or Ci-C4alkyl(Ci-C4alkyl)amino.
  • R 14 is Ci-C4alkyl or C1- C4alkyl(Ci-C4alkyl)amino, more preferably methyl or isopropyl(methyl)amino.
  • R 15 is hydrogen, halogen, Ci-C4alkyl, or Ci-C4haloalkyl.
  • R 15 is hydrogen, halogen or C1- C2alkyl, more preferably hydrogen or methyl, more preferably still, hydrogen.
  • R 16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl.
  • R 16 is halogen, more preferably fluorine.
  • R 17 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 17 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, most preferably hydrogen, fluorine, chlorine, methyl or tri fluoromethyl.
  • R 18 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 18 hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, more preferably still, hydrogen, fluorine, chlorine, methyl or trifluoromethyl. Even more preferably, R 18 is hydrogen.
  • R 19 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino
  • R 19 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, more preferably still hydrogen, fluorine, chlorine, methyl, difluoromethyl, trifluoromethyl or 1 ,1 -difluoroethyl. Even more preferably, R 19 is chlorine.
  • R 20 and R 21 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ci-C4alkoxy, or - CH2OR 12 .
  • R 20 and R 21 are each independently hydrogen, Ci-C4alkyl or Ci-C2alkoxy, more preferably hydrogen or Ci-C2alkyl, more preferably still hydrogen or methyl.
  • X 1 , X 2 , X 3 , and X 4 are nitrogen
  • X 2 or X 3 is nitrogen
  • one of X 1 , X 2 , X 3 , and X 4 is nitrogen
  • X 2 is nitrogen
  • a preferred subset of compounds is one in which:
  • X 1 is C-R 1 ;
  • X 2 is nitrogen
  • X 3 is C-R 18 ;
  • X 4 is C-R 19 ;
  • Y is C-H
  • R 1 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl
  • R 2 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl
  • R 3 is hydrogen, chlorine or fluorine
  • R 4 is chlorine, bromine or cyano
  • R 6 and R 7 are each independently hydrogen, halogen or Ci-C2alkyl
  • R 8 is OR 9 ;
  • R 9 is hydrogen, Ci-C4alkyl, Ci-C2alkoxyCi-C2alkyl or phenylCi-C2alkyl;
  • R 18 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl
  • R 19 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl.
  • R 20 and R 21 are each independently hydrogen or Ci-C2alkyl. Another preferred subset of compounds is one in which:
  • X 1 is C-R 1 ;
  • X 2 is C-R 17 ;
  • X 3 is nitrogen
  • X 4 is C-R 19 ;
  • Y is C-H
  • R 1 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl
  • R 2 and R 19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which contains one or two heteroatoms selected nitrogen, oxygen and sulfur and which is substituted with 1 to 4 groups represented by R 16 ;
  • R 3 is hydrogen, chlorine or fluorine
  • R 4 is chlorine, bromine or cyano
  • R 6 and R 7 are independently hydrogen, halogen or Ci-C2alkyl
  • R 8 is OR 9 ;
  • R 9 is hydrogen, Ci-C4alkyl, Ci-C2alkoxyCi-C2alkyl or phenylCi-C2alkyl;
  • R 16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano or Ci-C4alkylsulfonyl;
  • R 17 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl.
  • R 20 and R 21 are each independently hydrogen or Ci-C2alkyl.
  • a more preferred subset of compounds is one in which:
  • X 1 is C-R 1 ;
  • X 2 is nitrogen
  • X 3 is C-R 18 ;
  • X 4 is C-R 19 ;
  • Y is C-H
  • R 1 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl
  • R 2 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl
  • R 3 is hydrogen or fluorine
  • R 4 is chlorine or bromine
  • R 6 and R 7 are each independently hydrogen, chlorine or methyl
  • R 8 is OR 9 ;
  • R 9 is hydrogen, Ci-C4alkyl or phenylCi-C2alkyl
  • R 18 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl
  • R 19 is hydrogen, fluorine, chlorine, methyl, difluoromethyl, trifluoromethyl or 1 ,1 -difluoroethyl.
  • R 20 and R 21 are each independently hydrogen or methyl. Another more preferred subset of compounds is one in which:
  • X 1 is C-R 1 ;
  • X 2 is C-R 17 ;
  • X 3 is nitrogen
  • X 4 is C-R 19 ;
  • Y is C-H
  • R 1 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl
  • R 2 and R 19 together with the carbon atoms to which they are attached form a saturated 5-membered ring, which contains one or two oxygen atoms and which is substituted with 1 to 3 groups represented by R 16 ;
  • R 3 is hydrogen or fluorine
  • R 4 is chlorine or bromine
  • R 6 and R 7 are each independently hydrogen, chlorine or methyl
  • R 8 is OR 9 ;
  • R 9 is hydrogen, Ci-C4alkyl or phenylCi-C2alkyl
  • R 16 is halogen
  • R 17 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl
  • R 20 and R 21 are each independently hydrogen or methyl.
  • a further more more preferred subset of compounds is one in which:
  • X 1 is C-R 1 ;
  • X 2 is nitrogen
  • X 3 is C-R 18 ;
  • X 4 is C-R 19 ;
  • Y is C-H
  • R 1 is halogen
  • R 2 is hydrogen
  • R 3 is halogen
  • R 4 is halogen
  • R 6 and R 7 are both hydrogen
  • R 8 is OR 9 ;
  • R 9 is Ci-C 3 alkyl
  • R 18 is hydrogen
  • R 19 is halogen; and R 20 and R 21 are each independently hydrogen or methyl.
  • a particularly preferred subset of compounds is one in which:
  • X 1 is C-R 1 ;
  • X 2 is nitrogen
  • X 3 is C-R 18 ;
  • X 4 is C-R 19 ;
  • Y is C-H
  • R 1 is chlorine
  • R 2 is hydrogen
  • R 3 is fluorine
  • R 4 is chlorine
  • R 6 and R 7 are both hydrogen
  • R 8 is OR 9 ;
  • R 9 is methyl
  • R 18 is hydrogen
  • R 19 is chlorine
  • R 20 and R 21 are each independently hydrogen or methyl.
  • Table 1 below discloses 1140 specific compounds of formula (I), designated compounds 1-1 to 1-1140 respectively, wherein R 3 is hydrogen, R 4 is chlorine, R 20 is hydrogen, R 21 is hydrogen, m is 0, Y is C-H and B is oxygen.
  • ‘W erein X 4 is C-R 19 , and R 2 and R 19 together with the carbon atoms to which they are attached form a saturated 5-membered ring comprising two oxygen atoms, and which is substituted with 2 groups represented by R 16 , wherein both R 16 groups are fluoro.
  • the starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods.
  • the starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.
  • a mixture of a compound of formula (A) and a compound of formula (B), wherein Hal represents a halogen atom, for example a chlorine, bromine or iodine atom may be treated with a metal catalyst, such as palladium acetate, optionally in the presence of a suitable ligand, such as a phosphine ligand, for example S-Phos, or a preformed complex of a metal and a ligand, such as dppf palladium dichloride, and a base, such as potassium acetate, in a suitable solvent such as dioxane.
  • a metal catalyst such as palladium acetate
  • a suitable ligand such as a phosphine ligand, for example S-Phos
  • a base such as potassium acetate
  • a compound of formula (C) may be treated with a metal halide, such as potassium iodide, and a nitrosylating reagent, such as sodium nitrite and toluene sulphonic acid, in a suitable solvent, such as a mixture of water and acetontrile.
  • a metal halide such as potassium iodide
  • a nitrosylating reagent such as sodium nitrite and toluene sulphonic acid
  • Anilines of formula (C) may be prepared from nitro compounds of formula (D) as shown in reaction scheme 3.
  • a compound of formula (D) can be treated with a reducing agent, such as iron and ammonium chloride, in a suitable solvent, such as a mixture of water and ethanol.
  • a reducing agent such as iron and ammonium chloride
  • Nitro compounds of formula (D) in which m is 0 may be prepared from thiols of formula (E) and compounds of formula (F), in which LG represents a leaving group, for example a halogen atom, such as a chlorine atom, as shown in reaction scheme 4.
  • LG represents a leaving group, for example a halogen atom, such as a chlorine atom, as shown in reaction scheme 4.
  • a nitro compound of formula (E) may be treated with a compound of formula (F) in the presence of a base, such as triethylamine, in a suitable solvent such as acetonitrile.
  • a base such as triethylamine
  • Nitro compounds of formula (E) are available or may be prepared by methods well known in the literature.
  • an acid of formula (H) may be treated with an activating agent such as oxalyl chloride in a suitable solvent, such as dichloromethane and dimethylformamide, and the resulting intermediate then treated with an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane.
  • an activating agent such as oxalyl chloride in a suitable solvent, such as dichloromethane and dimethylformamide
  • an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane.
  • Alcohols and amines of formula (G) and acids of formula (H) are available or may be prepared by methods well known in the literature.
  • a thiol of formula (J) may be treated with a compound of formula (F) in the presence of a base, such as triethylamine, in a suitable solvent such as acetonitrile.
  • a base such as triethylamine
  • Thiols of formula (J) may be prepared from sulphonyl chlorides of formula (K) as shown in reaction scheme 7.
  • a sulphonyl chloride of formula (K) may be treated with a reducing agent, such as tin dichloride, in a suitable solvent, such as a mixture of water and acetic acid.
  • a reducing agent such as tin dichloride
  • Sulphonyl chlorides of formula (K) can be prepared from compounds of formula (L) as shown in reaction scheme 8.
  • a compound of formula (L) may be treated with a sulphonylating agent, such as chlorosulphonic acid.
  • a mixture of a compound of formula (A) and a compound of formula (M), wherein Hal represents a halogen atom, for example a chlorine, bromine or iodine atom, may be treated with a metal catalyst, such as palladium acetate, optionally in the presence of a suitable ligand, such as a phosphine ligand, for example S-Phos, or a preformed complex of a metal and a ligand, such as dppf palladium dichloride, and a base, such as potassium acetate, in a suitable solvent such as dioxane.
  • a metal catalyst such as palladium acetate
  • a suitable ligand such as a phosphine ligand, for example S-Phos
  • a base such as potassium acetate
  • a compound of formula (N) may be treated with a metal halide, such as potassium iodide, and a nitrosylating reagent, such as sodium nitrite and toluene sulphonic acid, in a suitable solvent, such as a mixture of water and acetontrile.
  • a metal halide such as potassium iodide
  • a nitrosylating reagent such as sodium nitrite and toluene sulphonic acid
  • Compounds of formula (I) may also be prepared from acids of formula (P) and alcohols or amines of formula (G) as shown in reaction scheme 11 .
  • an acid of formula (P) may be treated with an activating agent such as oxalyl chloride in a suitable solvent, such as dichloromethane and dimethylformamide, and the resulting intermediate then treated with an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane.
  • an activating agent such as oxalyl chloride in a suitable solvent, such as dichloromethane and dimethylformamide
  • an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane.
  • Acids of formula (P) may be prepared from esters of formula (Q), in which R represents an alkyl or similar group, as shown in reaction scheme 12.
  • a compound of formula (Q) may be treated with hydrochloric acid in a suitable solvent, such as dioxane.
  • Esters of formula (Q) in which m is 0 may be prepared from thiols of formula (J) and esters of formula (R), in which LG represents a leaving group, for example a halogen atom, such as a chlorine atom, and R represents an alkyl or similar group, as shown in reaction scheme 13.
  • LG represents a leaving group, for example a halogen atom, such as a chlorine atom, and R represents an alkyl or similar group, as shown in reaction scheme 13.
  • a thiol of formula (J) may be treated with a compound of formula (R) in the presence of a base, such as triethylamine, in a suitable solvent such as acetonitrile.
  • a base such as triethylamine
  • a suitable solvent such as acetonitrile.
  • Esters of formula (R) are available or may be prepared by methods well known in the literature.
  • a compound of formula (l-A) may be treated with an oxidising agent, for example oxone or metachloroperbenzoic acid, in a suitable solvent, such as acetonitrile or dichloromethane.
  • an oxidising agent for example oxone or metachloroperbenzoic acid
  • a suitable solvent such as acetonitrile or dichloromethane.
  • a compound of formula (l-D) may be treated with hydrochloric acid in a suitable solvent, such as dioxane.
  • a compound of formual (l-C) may be treated with a halogenating reagent, such as oxalyl chloride, in a suitable solvent, such as dichloromethane, to form an acyl halide which may be treated with a reagent HNR 10 R 11 in the presence of a base, such as triethylamine, in a suitable solvent, such as dichloromethane.
  • a halogenating reagent such as oxalyl chloride
  • a suitable solvent such as dichloromethane
  • the compounds according to the invention can be used as herbicidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • soluble liquids soluble liquids, water-soluble concentrates or water soluble granules are preferred.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, /V,/V-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol di
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • composition of the present may further comprise at least one additional pesticide.
  • additional pesticide is a herbicide and/or herbicide safener.
  • compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures.
  • specific examples of such mixtures include (wherein “I” represents a compound of formula (I)):- 1 + acetochlor; I + acifluorfen (including acifluorfen-sodium); I + aclonifen; I + alachlor; I + alloxydim; I + ametryn; I + amicarbazone; I + amidosulfuron; I + aminocyclopyrachlor ; I + aminopyralid; I + amitrole; I + asulam; I + atrazine; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bilanafos; I + bifenox; I + bispyribac-sodium; I + bixlozone; I + bromacil; I + bromoxynil; I + butachlor; I
  • the mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.
  • the compound of formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
  • the mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1.
  • the mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the mixing partner).
  • Compounds of formula (I) of the present invention may also be combined with herbicide safeners.
  • Preferred combinations include:- I + benoxacor, I + cloquintocet (including cloquintocet-mexyl); I + cyprosulfamide; I + dichlormid; I + fenchlorazole (including fenchlorazole-ethyl); I + fenclorim; I + fluxofenim; l+ furilazole I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including mefenpyr-diethyl); I + metcamifen; I + N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino] benzenesulfonamide and I + oxabetrinil.
  • the safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14 th Edition (BCPC), 2006.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
  • the mixing ratio of compound of formula (I) to safener is from 100:1 to 1 :10, especially from 20:1 to 1 :1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the safener).
  • the compounds of formula (I) of this invention are useful as herbicides.
  • the present invention therefore further comprises a method for controlling unwanted plants comprising applying to the said plants or a locus comprising them, an effective amount of a compound of the invention or a herbicidal composition containing said compound.
  • Controlling means killing, reducing or retarding growth or preventing or reducing germination.
  • the plants to be controlled are unwanted plants (weeds).
  • Locus means the area in which the plants are growing or will grow.
  • the rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha. A preferred range is 10-200g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • Useful plants in which the composition according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.
  • Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
  • the compounds of the present invention can be used in methods of controlling undesired vegetation in crop plants which are tolerant to protoporphyrinogen oxidase (PPO) inhibitors.
  • PPO protoporphyrinogen oxidase
  • Such plants can be obtained, for example, by transforming crop plants with nucleic acids which encode a suitable protoporphyrinogen oxidase, which may contain a mutation in order to make it more resistant to the PPO inhibitor.
  • nucleic acids and crop plants are disclosed in WO95/34659, WO97/32011 , W02007/024739, WO2012/080975, WO2013/189984, WO2015/022636,
  • WO2015/022640 WO2015/092706, WO2016/099153, WO2017/023778, WO2017/039969, WO2017/217793, WO2017/217794, WO2018/114759, WO2019/117578, WO2019/117579 and WO2019/118726.
  • the present invention also provides a method for controlling undesired vegetation at a plant cultivation site, the method comprising the steps of: a) providing, at said site, a plant that comprises at least one nucleic acid comprising a nucleotide sequence encoding a protoporphyrinogen oxidase (PPO) polypeptide which is resistant or tolerant to a "PPO inhibiting herbicide”; b) applying to said site an effective amount of said herbicide, wherein the PPO inhibiting herbicide is a compound of formula (I) as herein defined.
  • PPO protoporphyrinogen oxidase
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes.
  • Compounds of formula (I) and compositions of the invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species.
  • monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor.
  • dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium.
  • Unwanted plants are to be understood as also including those weeds that have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD- inhibitors) by evolution, by conventional methods of breeding or by genetic engineering. Examples include Amaranthus palmeri that has evolved resistance to glyphosate and/or acetolactate synthase (ALS) inhibiting herbicides.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD- inhibitors
  • Examples include Amaranthus palmeri that has evolved resistance to glyphosate and/or acetolactate synthase (ALS) inhibiting herbicides.
  • the compounds of the present invention can be used in methods of controlling unwanted plants or weeds which are resistant to protoporphyrinogen oxidase (PPO) inhibitors.
  • PPO protoporphyrinogen oxidase
  • Amaranthus palmeri and Amaranthus tuberculatus populations have evolved as PPO-resistant weeds e.g. due to amino acid substitutions in PPX2L such as those occurring at amino acids R128 (also referred to as R98) and G399, or a codon (glycine) deletion in PPX2L at codon 210 (A210), the codon numbering being based on NCBI reference DQ3861 14.
  • the compounds of the present invention can be used in methods of controlling Amaranthus palmeri and/or Amaranthus tuberculatus with mutations or deletions at the previously mentioned codons or equivalents, and it would be obvious to try the compounds to control unwanted plants or weeds with other mutations conferring tolerance or resistance to PPO inhibitors that may arise.
  • the compounds of formula (I) are also useful for pre-harvest desiccation in crops, for example, but not limited to, potatoes, soybean, sunflowers and cotton.
  • Pre-harvest desiccation is used to desiccate crop foliage without significant damage to the crop itself to aid harvesting.
  • Compounds/compositions of the invention are particularly useful in non-selective burn-down applications, and as such may also be used to control volunteer or escape crop plants.
  • Step 1 Synthesis of 3,5-dichloro-2-(4-chloro-2-fluoro-phenyl)pyridine
  • Step 3 Synthesis of 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenethiol
  • Triphenylphosphine (4.0 g, 15 mmol) was added portionwise to a stirred solution of 2-chloro-5-(3,5- dichloro-2-pyridyl)-4-fluoro-benzenesulfonyl chloride (1 .8 g, 4.3 mmol) in tetra hydrofuran (22 ml) at room temperature.
  • Water 3.6 ml
  • Water (40 ml) and ethyl acetate (90 ml) were added and the phases separated.
  • Step 4 Synthesis of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro- phenyl]sulfanylpropanoate (Compound 8-374)
  • Triethylamine (1.3 ml, 9.1 mmol) and methyl 3-hydroxy propanoate (0.48 ml, 5.0 mmol) were added dropwise to a stirred solution of 2-bromopropanoyl bromide (0.49 ml, 4,5 mmol) in acetonitrile (15 ml) at 0 °C.
  • the resulting mixture was stirred at 0 °C for 1 hour, then ambient temperature for 2 hours.
  • Water (20 ml) and ethyl acetate (60 ml) were added, the phases separated and the aqueous phase extracted with ethyl acetate (60 ml).
  • Step 1 Synthesis of methyl 3-(2-bromopropanoylamino)propanoate
  • Triethylamine (2.6 ml, 9.1 mmol) and 2-bromopropanoyl bromide (0.97 ml, 9.1 mmol) were added to a stirred mixture of (3-methoxy-3-oxo-propyl)ammonium chloride (1.42 g, 10 mmol) in acetonitrile (30 ml) at 0 °C. The resulting mixture was stirred at 0 °C for 1 hour, then ambient temperature for 2 hours. Water (20 ml) and ethyl acetate (60 ml) were added, the phases separated and the aqueous phase extracted with ethyl acetate (60 ml).
  • Step 2 Synthesis of methyl 3-[2-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro- phenyl]sulfanylpropanoylamino]propanoate (Compound 26-374)
  • Methyl 3-(2-bromopropanoylamino)propanoate (130 mg, 0.53 mmol) was added to a stirred mixture of 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenethiol (prepared as described in Example 1 , Step 3; 200 mg, 0.49 mmol), caesium carbonate (160 mg, 0.50 mmol) and acetonitrile (4 ml) and the resulting mixture stirred at ambient temperature for 1 hour.
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with waterto give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
  • Kaolin 94 % mineral filler 96 % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruder granules
  • Active ingredient 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Active ingredient 8 % polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • AMAPA Amaranthus palmeri
  • LPE Lolium perenne
  • EPHHL Euphorbia heterophylla
  • IPHE Ipomoea hederacea
  • SETFA Setaria faberi
  • Echinochloa crus-galli Echinochloa crus-galli
  • IF50 11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether
  • IF50 11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether

Abstract

Compounds of the formula (I), (I), wherein the substituents are as defined in claim 1, useful as a pesticides, especially as herbicides.

Description

HERBICIDAL COMPOUNDS
The present invention relates to herbicidally active compounds, as well as to processes and intermediates used for the preparation of such derivatives. The invention further extends to herbicidal compositions comprising such derivatives, as well as to the use of such compounds and compositions for controlling undesirable plant growth: in particular the use for controlling weeds, in crops of useful plants.
US2014/048827, W02016/120116 and W02020/239607 describe herbicidal derivatives.
The present invention is based on the finding that compounds of formula (I) as defined herein, exhibit surprisingly good herbicidal activity. Thus, according to the present invention there is provided a compound of formula (I) or an agronomically acceptable salt thereof:
Figure imgf000002_0001
wherein
X1 is C-R1, nitrogen, or N+-O_;
X2 is C-R17 or nitrogen;
X3 is C-R18 or nitrogen;
X4 is C-R19 or nitrogen; with the proviso that a maximum of two of X1, X2, X3 and X4 are nitrogen, and X3 and X4 are not both nitrogen;
Y is C-H or nitrogen;
B is O, S, or NR5;
D is -[C(Re)(R7)]n- ; m is an integer from 0 to 2; n is an integer from 1 to 4;
R1 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci- C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11; R2 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-C6alkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, CO2R9, or CONR10R11; or
R1 and R2 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R16; or
R2 and R19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R16;
R3 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, or Ci-C4alkylsulfonyl;
R4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, or Ci-C4alkylsulfonyl;
R5 is hydrogen, hydroxy, Ci-Cealkyl, or Ci-C4alkoxy;
R6 and R7 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, hydroxy, Ci-C4alkoxy, Ci-C4alkoxycarbonyl, or CH2OR12; provided that R6 and R7 are not both hydroxy on the same carbon atom; or two R6 and R7 groups, on the same or different carbon atoms, together form a Ci-Csalkylene chain, which contain 0, 1 or 2 oxygen atoms, substituted by 1 to 3 groups represented by R15; or two R6 and R7 groups, on the same carbon atom, together form a C2-C3alkene;
R8 is OR9, SR9, or NR10R11;
R9 is hydrogen, Ci-Cwalkyl, Ci-Cwhaloalkyl, Cs-Cealkenyl, Cs-Cehaloalkenyl, Cs-Cealkynyl, C1- C4alkoxyCi-C6alkyl, Ci-C4haloalkoxyCi-C6alkyl, Ce-CwarylCi-Csalkyl, Ce-CwarylCi-Csalkyl substituted by 1 to 4 groups represented by R13, heteroarylCi-Csalkyl, or heteroarylCi-Csalkyl substituted by 1 to 3 groups represented by R13;
R10 is hydrogen, Ci-Cealkyl, SO2R14;
R11 is hydrogen or Ci-Cealkyl; or R10 and R11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring;
R12 is hydrogen, Ci-C4alkyl, or Ci-C4alkylcarbonyl;
R13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl;
R14 is Ci-C4alkyl, Ci-C4haloalkyl, or Ci-C4alkyl(Ci-C4alkyl)amino;
R15 is hydrogen, halogen, Ci-C4alkyl, or Ci-C4haloalkyl;
R16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl;
R17 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R18 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R19 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R20 and R21 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ci-C4alkoxy, or - CH2OR12; or two R20 and R21 groups together with the carbon atom to which they are attached form a C2-Csalkylene chain, wherein said C2-Csalkylene chain comprises 0, 1 or 2 oxygen atoms, and wherein said C2- Csalkylene chain is substituted by 1 to 3 groups represented by R15; or two R20 and R21 groups together with the carbon atom to which they are attached form a C2-C3alkene; and with the proviso that R1, R2, R17, R18 and R19 are not all hydrogen.
According to a second aspect of the invention, there is provided an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically- acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingredient.
According to a third aspect of the invention, there is provided a method of controlling or preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) as a herbicide.
According to a fifth aspect of the invention, there is provided a process for the preparation of compounds of formula (I).
Where substituents are indicated as being “optionally substituted”, this means that they may or may not carry one or more identical or different substituents, e.g., one, two or three R13 substituents. For example, Ci-Cealkyl substituted by 1 , 2 or 3 halogens, may include, but not be limited to, -CH2CI, -CHCI2, -CCh, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, Ci-Cealkoxy substituted by 1 , 2 or 3 halogens, may include, but not limited to, CH2CIO-, CHCI2O-, CCI3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.
As used herein, the term "halogen" or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
As used herein, “cyano” means a -CN group.
As used herein, “amino” means an -NH2 group.
As used herein, “hydroxy” means an -OH group.
As used herein, “nitro” means an -NO2 group.
As used herein, the term "Ci-Cioalkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to ten carbon atoms, and which is attached to the rest of the molecule by a single bond. Ci-Cealkyl, Ci-C4alkyl, Ci-Csalkyl, and Ci-C2alkyl are to be construed accordingly. Examples of Ci-Cwalkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1 -methylethyl (iso-propyl), n-butyl, and 1 -dimethylethyl (t- butyl).
As used herein, the term "Ci-C4alkoxy" refers to a radical of the formula -ORa where Ra is a C1- C4alkyl radical as generally defined above. Ci-Csalkoxy is to be construed accordingly. Examples of C1- 4alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and f-butoxy.
As used herein, the term "Ci-Ciohaloalkyl" refers to a Ci-Cwalkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Ci-Cehaloalkyl and Ci- C4haloalkyl is to be construed accordingly. Examples of Ci-Cwhaloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2 ,2,2-trifluoroethyl.
As used herein, the term "C2-C6alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (^-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond. Cs-Cealkenyl, C2-C4alkenyl and C2-C3alkenyl are to be construed accordingly. Examples of C2-C6alkenyl include, but are not limited to, prop-1 -enyl, allyl (prop-2-enyl) and but-1-enyl.
As used herein, the term “C2-C6haloalkenyl” refers to a C2-Cealkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Cs-Cehaloalkenyl, C2- C4haloalkenyl and C2-C3haloalkenyl are to be construed accordingly. Examples of C2-Cehaloalkenyl include, but are not limited to chloroethylene, fluoroethylene, 1 ,1 -difluoroethylene, 1 ,1-dichloroethylene and 1 ,1 ,2-trichloroethylene.
As used herein, the term "C2-C6alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond. C2-C4alkynyl and Cs-Cealkynyl are to be construed accordingly. Examples of C2-Cealkynyl include, but are not limited to, prop-1 -ynyl, propargyl (prop-2-ynyl) and but-1-ynyl.
As used herein, the term "Ci-Cehaloalkoxy" refers to a Ci-Cealkoxy group as defined above substituted by one or more of the same or different halogen atoms. Ci-C4haloalkoxy is to be construed accordingly. Examples of Ci-Cehaloalkoxy include, but are not limited to, fluoromethoxy, difluoro methoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.
As used herein, the term "Ci-C4haloalkoxyCi-C6alkyl" refers to a radical of the formula Rb-O-Ra- where Rb is a Ci-C4haloalkyl radical as generally defined above, and Ra is a Ci-Csalkylene radical as generally defined above.
As used herein, the term "Ci-C4alkoxyCi-C6alkyl" refers to a radical of the formula Rb-O-Ra- where Rb is a Ci-C4alkyl radical as generally defined above, and Ra is a Ci-Csalkylene radical as generally defined above.
As used herein, the term "Ci-C4alkoxyCi-C4alkoxy" refers to a radical of the formula Rb-O-Ra-O- where Rb is a Ci-C4alkyl radical as generally defined above, and Ra is a Ci-C4alkylene radical as generally defined above.
As used herein, the term "Ci-Cealkylcarbonyl" refers to a radical of the formula -C(O)Ra where Ra is a Ci-Cealkyl radical as generally defined above. Examples of Ci-Cealkylcarbonyl include, but are not limited to, acetyl.
As used herein, the term "Ci-Cealkoxycarbonyl" refers to a radical of the formula -C(O)ORa where Ra is a Ci-Cealkyl radical as generally defined above.
As used herein, the term "Ci-C4alkylamino” refers to a radical of the formula RaNH- wherein Ra is a Ci-C4alkyl radical as generally defined above.
As used herein, the term "di(Ci-C4alkyl)amino” refers to a radical of the formula -N(Ra)(Rb), wherein Ra and Rb are each individually a Ci-C4alkyl radical as generally defined above. The term “di(Ci- C3alkyl)amino” is to be construed accordingly. As used herein, the term "Ci-C4alkylcarbonylamino” refers to a radical of the formula -C(O)NHRa, wherein Ra is a Ci-C4alkyl radical as generally defined above.
As used herein, the term "Ci-C4alkylcarbonyl(Ci-C4alkyl)amino” refers to a radical of the formula -NH(Ra)C(O)Rb, wherein Ra and Rb each independently Ci-C4alkyl radicals as generally defined above.
As used herein, the term "Ci-C4alkoxycarbonylamino” refers to a radical of the formula - NHC(O)ORa, wherein Ra is a Ci-C4alkyl radical as generally defined above.
As used herein, the term “aminocarbonyl” refers to a radical of the formula -C(O)NH2.
As used herein, the term "aminocarbonylamino” refers to a radical of the formula -NHC(O)H2.
As used herein, the term “aminothiocarbonyl” refers to a radical of the formula -C(S)NH2.
As used herein, the term "Ci-C4alkylaminocarbonylamino” refers to a radical of the formula - NHC(O)NHRa, wherein Ra is a Ci-C4alkyl radical as generally defined above.
As used herein, the term "Ci-C4alkylsulfonylamino” refers to a radical of the formula -NHS(O)2Ra where Ra is a Ci-C4alkyl radical as generally defined above.
As used herein, the term "Ci-C4haloalkylsulfonylamino” refers to a radical of the formula refers to a radical of the formula -NHS(O)2Ra where Ra is a Ci-C4haloalkyl radical as generally defined above.
As used herein, the term "Ci-C4alkylthio” refers to a radical of the formula -SRa, where Ra is a Ci- C4alkyl radical as generally defined above. The terms “Ci-Csalkylsulfanyl” and “Ci-C2alkylsulfanyl”, are to be construed accordingly. Examples of Ci-C4alkylsulfanyl include, but are not limited to methylsulfanyl.
As used herein, the term "Ci-C4haloalkylthio” refers to a radical of the formula refers to a radical of the formula -SRa, where Ra is a Ci-C4haloalkyl radical as generally defined above.
As used herein, the term "Ci-C4alkylsulfinyl” refers to a radical of the formula -S(O)Ra, where Ra is a Ci-C4alkyl radical as generally defined above. The terms “Ci-Csalkylsulfinyl” and “Ci-C2alkylsulfinyl”, are to be construed accordingly. Examples of Ci-C4alkylsulfinyl include, but are not limited to methylsulfinyl.
As used herein, the term "Ci-C4alkylsulfonyl” refers to a radical of the formula refers to a radical of the formula -S(O)2Ra, where Ra is a Ci-C4alkyl radical as generally defined above. The terms “Ci- Csalkylsulfonyl” and “Ci-C2alkylsulfonyl”, are to be construed accordingly. Examples of Ci- C4alkylsolfanyl include, but are not limited to methylsulfonyl.
As used herein, the term "Ci-C4alkylsulfonyloxy” refers to a radical of the formula -OS(O)2Ra where Ra is a Ci-C4alkyl radical as generally defined above.
As used herein, the term "Ci-C4haloalkylsulfonyloxy” refers to a radical of the formula -OS(O)2Ra where Ra is a Ci-C4haloalkyl radical as generally defined above.
As used herein, the term "Ci-C4haloalkylsulfinyl” refers to a radical of the formula -S(O)Ra, where Ra is a Ci-C4haloalkyl radical as generally defined above.
As used herein, the term "Ci-C4haloalkylsulfonyl” refers to a radical of the formula -S(O)2Ra, where Ra is a Ci-C4haloalkyl radical as generally defined above.
As used herein, the term "Cs-Cecycloalkyl" refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4cycloalkyl is to be construed accordingly. Examples of Cs-Cecycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. As used herein, the term "Ce-Cwaryl” refers to a 6- to 10-membered aromatic ring system consisting solely of carbon and hydrogen atoms which may be mono-, bi- or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, or indenyl.
As used herein, the term " Ce-CioarylCi-Csalkyl” refers to an aryl moiety as generally defined above, which is attached to the rest of the molecule by a Ci-Csalkylene linker as defined above.
As used herein, except where explicitly stated otherwise, the term "heteroaryl" refers to a 5- or 6- membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heteroaryl include, furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
As used herein, except where explicitly stated otherwise, the term " heteroarylCi-Csalkyl " refers to a heteroaryl moiety as generally defined above, which is attached to the rest of the molecule by a Ci- Csalkylene linker as defined above.
As used herein, except where explicitly stated otherwise, the term "heterocyclyl" or "heterocyclic" refers to a stable 4- to 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or 6-lactamyl.
The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I). Likewise, formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and ketoenol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of formula (I). Similarly, where there are di-substituted alkenes, these may be present in E or Z form or as mixtures of both in any proportion. The present invention includes all these possible isomeric forms and mixtures thereof for a compound of formula (I).
The compounds of formula (I) will typically be provided in the form of an agronomically acceptable salt, a zwitterion or an agronomically acceptable salt of a zwitterion. This invention covers all such agronomically acceptable salts, zwitterions and mixtures thereof in all proportions.
Suitable agronomically acceptable salts of the present invention can be with cations that include but are not limited to, metals, conjugate acids of amines and organic cations. Examples of suitable metals include aluminium, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron and zinc. Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N- methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2- amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.
The following list provides definitions, including preferred definitions, for substituents X1, X2, X3, X4, Y, B, D, m, n, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20 and R21 with reference to the compounds of formula (I) according to the invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.
X1 is C-R1, nitrogen, or N+-O; preferably C-R1 or N+-O_, and more preferably C-R1.
X2 is C-R17 or nitrogen, preferably nitrogen.
X3 is C-R18 or nitrogen, preferably C-R18.
X4 is C-R19 or nitrogen, preferably C-R19.
Preferably with the proviso that a maximum of one of X2, X3, and X4 is nitrogen, more preferably with the proviso that one of X2, X3, and X4 is nitrogen.
Y is C-H or nitrogen. Preferably Y is C-H.
B is O, S, or NR5. Preferably B is O, NH or NCH3, more B is preferably O or NH. m is an integer from 0 to 2. Preferably m is 0 or 2, more preferably m is 0. n is an integer from 1 to 4. Preferably n is an integer from 1 to 2, more preferably n is 2.
R1 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci- C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11. Preferably R1 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, most preferably R1 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl. In one set of embodiments, R1 is halogen, preferably chlorine.
R2 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, CO2R9, or CONR10R11. Preferably R2 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, most preferably hydrogen, fluorine, chlorine, methyl or trifluoromethyl. More preferably still, R2 is hydrogen; or
R2 and R19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R16. Preferably, R2 and R19 together with the carbon atoms to which they are attached form a 5-membered saturated ring, optionally containing one or two oxygen atoms, and which may be substituted with 1 or 2 groups represented by R16.
R3 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, or Ci-C4alkylsulfonyl. Preferably R3 is hydrogen, chlorine or fluorine, more preferably hydrogen or fluorine. Even more preferably, R3 is fluorine.
R4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, or Ci-C4alkylsulfonyl. Preferably R4 is hydrogen, chlorine, bromine, cyano or aminothiocarbonyl, more preferably chlorine, bromine or cyano, more preferably still, chlorine or bromine. Even more preferably, R4 is chlorine.
R5 is hydrogen, hydroxy, Ci-Cealkyl, or Ci-C4alkoxy. Preferably, R5 is hydrogen.
R6 and R7 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, hydroxy, Ci-C4alkoxy, Ci-C4alkoxycarbonyl, or -CH2OR12; provided that R6 and R7 are not both hydroxy on the same carbon atom, or two R6 and R7 groups, on the same or different carbon atoms, together form a Ci-Csalkylene chain, which contain 0, 1 or 2 oxygen atoms, substituted by 1 to 3 groups represented by R15; or two R6 and R7 groups, on the same carbon atom, together form a C2-C3alkene. Preferably R6 and R7 are each independently hydrogen, halogen, Ci-C4alkyl or Ci-C4alkoxycarbonyl, more preferably hydrogen, halogen or Ci-C2alkyl, more preferably still hydrogen, chlorine or methyl. Even more preferably still, R6 and R7 are each independently hydrogen or methyl. In a particularly preferred embodiment, R6 and R7 are both hydrogen. R8 is OR9, SR9, or NR10R11. Preferably R8 is OR9.
R9 is hydrogen, Ci-Cioalkyl, Ci-Ciohaloalkyl, Cs-Cealkenyl, Cs-Cehaloalkenyl, Cs-Cealkynyl, Ci- C4alkoxyCi-C6alkyl, Ci-C4haloalkoxyCi-C6alkyl, Ce-CwarylCi-Csalkyl, Ce-CwarylCi-Csalkyl substituted by 1 to 4 groups represented by R13, heteroarylCi-Csalkyl, or heteroarylCi-Csalkyl substituted by 1 to 3 groups represented by R13. Preferably R9 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C2alkoxyCi- C2alkyl, phenylCi-C2alkyl or phenylCi-C2alkyl substituted by 1-2 groups R13, more preferably hydrogen, Ci-C4alkyl, Ci-C2alkoxyCi-C2alkyl or phenylCi-C2alkyl, more preferably still hydrogen, Ci-C4alkyl or phenylCi-C2alkyl. Even more preferably, R9 is Ci-C4alkyl. Even more preferably still, R9 is methyl.
R10 is hydrogen, Ci-Cealkyl, SO2R14. Preferably R10 is hydrogen or SO2R14, more preferably SO2R14.
R11 is hydrogen or Ci-Cealkyl. Preferably R11 is hydrogen.
Or R10 and R11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring.
R12 is hydrogen, Ci-C4alkyl, or Ci-C4alkylcarbonyl. Preferably R12 is hydrogen, Ci-C2alkyl or C1- C2alkylcarbonyl, more preferably hydrogen or methyl.
R13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl. Preferably R13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano or C1- C4alkylsulfonyl.
R14 is Ci-C4alkyl, Ci-C4haloalkyl, or Ci-C4alkyl(Ci-C4alkyl)amino. Preferably R14 is Ci-C4alkyl or C1- C4alkyl(Ci-C4alkyl)amino, more preferably methyl or isopropyl(methyl)amino.
R15 is hydrogen, halogen, Ci-C4alkyl, or Ci-C4haloalkyl. Preferably R15 is hydrogen, halogen or C1- C2alkyl, more preferably hydrogen or methyl, more preferably still, hydrogen.
R16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl. Preferably R16 is halogen, more preferably fluorine.
R17 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11. Preferably R17 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, most preferably hydrogen, fluorine, chlorine, methyl or tri fluoromethyl.
R18 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11. Preferably R18 hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, more preferably still, hydrogen, fluorine, chlorine, methyl or trifluoromethyl. Even more preferably, R18 is hydrogen.
R19 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11. Preferably R19 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably hydrogen, fluorine, chlorine, Ci-C2alkyl, or Ci-C2haloalkyl, more preferably still hydrogen, fluorine, chlorine, methyl, difluoromethyl, trifluoromethyl or 1 ,1 -difluoroethyl. Even more preferably, R19 is chlorine.
R20 and R21 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ci-C4alkoxy, or - CH2OR12. Preferably R20 and R21 are each independently hydrogen, Ci-C4alkyl or Ci-C2alkoxy, more preferably hydrogen or Ci-C2alkyl, more preferably still hydrogen or methyl.
In embodiments where two of X1, X2, X3, and X4 are nitrogen, preferably X2 or X3 is nitrogen. In embodiments where one of X1, X2, X3, and X4 is nitrogen, preferably X2 is nitrogen.
A preferred subset of compounds is one in which:
X1 is C-R1;
X2 is nitrogen;
X3 is C-R18;
X4 is C-R19;
Y is C-H;
B is O or NH; m is 0; n is 1 or 2;
R1 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl;
R2 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl;
R3 is hydrogen, chlorine or fluorine;
R4 is chlorine, bromine or cyano;
R6 and R7 are each independently hydrogen, halogen or Ci-C2alkyl;
R8 is OR9;
R9 is hydrogen, Ci-C4alkyl, Ci-C2alkoxyCi-C2alkyl or phenylCi-C2alkyl;
R18 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl;
R19 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl.
R20 and R21 are each independently hydrogen or Ci-C2alkyl. Another preferred subset of compounds is one in which:
X1 is C-R1;
X2 is C-R17;
X3 is nitrogen;
X4 is C-R19;
Y is C-H;
B is O or NH; m is 0; n is 1 or 2;
R1 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl;
R2 and R19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which contains one or two heteroatoms selected nitrogen, oxygen and sulfur and which is substituted with 1 to 4 groups represented by R16;
R3 is hydrogen, chlorine or fluorine;
R4 is chlorine, bromine or cyano;
R6 and R7 are independently hydrogen, halogen or Ci-C2alkyl;
R8 is OR9;
R9 is hydrogen, Ci-C4alkyl, Ci-C2alkoxyCi-C2alkyl or phenylCi-C2alkyl;
R16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano or Ci-C4alkylsulfonyl;
R17 is hydrogen, fluorine, chlorine, Ci-C2alkyl or Ci-C2haloalkyl.
R20 and R21 are each independently hydrogen or Ci-C2alkyl.
A more preferred subset of compounds is one in which:
X1 is C-R1;
X2 is nitrogen;
X3 is C-R18;
X4 is C-R19;
Y is C-H;
B is O or NH; m is 0; n is 2;
R1 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
R2 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
R3 is hydrogen or fluorine;
R4 is chlorine or bromine;
R6 and R7 are each independently hydrogen, chlorine or methyl;
R8 is OR9;
R9 is hydrogen, Ci-C4alkyl or phenylCi-C2alkyl;
R18 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
R19 is hydrogen, fluorine, chlorine, methyl, difluoromethyl, trifluoromethyl or 1 ,1 -difluoroethyl.
R20 and R21 are each independently hydrogen or methyl. Another more preferred subset of compounds is one in which:
X1 is C-R1;
X2 is C-R17;
X3 is nitrogen;
X4 is C-R19;
Y is C-H;
B is O or NH; m is 0; n is 2;
R1 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
R2 and R19 together with the carbon atoms to which they are attached form a saturated 5-membered ring, which contains one or two oxygen atoms and which is substituted with 1 to 3 groups represented by R16;
R3 is hydrogen or fluorine;
R4 is chlorine or bromine;
R6 and R7 are each independently hydrogen, chlorine or methyl;
R8 is OR9;
R9 is hydrogen, Ci-C4alkyl or phenylCi-C2alkyl;
R16 is halogen;
R17 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl; and
R20 and R21 are each independently hydrogen or methyl.
A further more more preferred subset of compounds is one in which:
X1 is C-R1;
X2 is nitrogen;
X3 is C-R18;
X4 is C-R19;
Y is C-H;
B is O or NH; m is 0; n is 2;
R1 is halogen;
R2 is hydrogen;
R3 is halogen;
R4 is halogen;
R6 and R7 are both hydrogen;
R8 is OR9;
R9 is Ci-C3alkyl;
R18 is hydrogen;
R19 is halogen; and R20 and R21 are each independently hydrogen or methyl.
A particularly preferred subset of compounds is one in which:
X1 is C-R1;
X2 is nitrogen;
X3 is C-R18;
X4 is C-R19;
Y is C-H;
B is O or NH; m is 0; n is 2;
R1 is chlorine;
R2 is hydrogen;
R3 is fluorine;
R4 is chlorine;
R6 and R7 are both hydrogen;
R8 is OR9;
R9 is methyl;
R18 is hydrogen;
R19 is chlorine; and
R20 and R21 are each independently hydrogen or methyl.
Tables of Examples
Table 1 below discloses 1140 specific compounds of formula (I), designated compounds 1-1 to 1-1140 respectively, wherein R3 is hydrogen, R4 is chlorine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is oxygen.
Table 1
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
‘W erein X4 is C-R19, and R2 and R19 together with the carbon atoms to which they are attached form a saturated 5-membered ring comprising two oxygen atoms, and which is substituted with 2 groups represented by R16, wherein both R16 groups are fluoro. 1140 compounds of formula (I), wherein R3 is fluorine, R4 is chlorine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 2-1 to 2-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is chlorine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 3-1 to 3-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is bromine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 4-1 to 4-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is bromine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 5-1 to 5-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is bromine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 6-1 to 6-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is chlorine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 7-1 to 7-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is chlorine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 8-1 to 8-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is chlorine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 9-1 to 9-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is bromine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 10-1 to 10-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is bromine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 11-1 to 11-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is bromine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 12-1 to 12-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is chlorine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 13-1 to 13-1140 respectively. 1140 compounds of formula (I), wherein R3 is fluorine, R4 is chlorine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 14-1 to 14-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is chlorine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 15-1 to 15-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is bromine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 16-1 to 16-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is bromine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 17-1 to 17-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is bromine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is oxygen, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 18-1 to 18-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is chlorine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 19-1 to 19-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is chlorine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 20-1 to 20-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is chlorine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 21-1 to 21-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is bromine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 22-1 to 22-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is bromine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 23-1 to 23-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is bromine, R20 is hydrogen, R21 is hydrogen, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 24-1 to 24-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is chlorine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 25-1 to 25-1140 respectively. 1140 compounds of formula (I), wherein R3 is fluorine, R4 is chlorine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 26-1 to 26-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is chlorine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 27-1 to 27-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is bromine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 28-1 to 28-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is bromine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 29-1 to 29-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is bromine, R20 is hydrogen, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 30-1 to 30-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is chlorine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 31-1 to 31-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is chlorine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 32-1 to 32-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is chlorine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 33-1 to 33-1140 respectively.
1140 compounds of formula (I), wherein R3 is hydrogen, R4 is bromine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 34-1 to 34-1140 respectively.
1140 compounds of formula (I), wherein R3 is fluorine, R4 is bromine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 35-1 to 35-1140 respectively.
1140 compounds of formula (I), wherein R3 is chlorine, R4 is bromine, R20 is methyl, R21 is methyl, m is 0, Y is C-H and B is N-H, and the values of X1, X2, X3, X4, R2, D and R8 are as given in Table 1 for compounds 1-1 to 1-1140, are designated as compound numbers 36-1 to 36-1140 respectively.
Compounds of the invention may be prepared by techniques known to the person skilled in the art of organic chemistry. General methods for the production of compounds of formula (I) are described below. Unless otherwise stated in the text, the substituents X1, X2, X3, X4, m, Y, B, D, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20 and R21 are as defined hereinbefore. The starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods. The starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.
Compounds of formula (I) may be prepared from compounds of formula (A) and compounds of formula (B) as shown in reaction scheme 1 .
Reaction Scheme 1
Figure imgf000048_0001
For example, a mixture of a compound of formula (A) and a compound of formula (B), wherein Hal represents a halogen atom, for example a chlorine, bromine or iodine atom, may be treated with a metal catalyst, such as palladium acetate, optionally in the presence of a suitable ligand, such as a phosphine ligand, for example S-Phos, or a preformed complex of a metal and a ligand, such as dppf palladium dichloride, and a base, such as potassium acetate, in a suitable solvent such as dioxane.
Boronic acids (or the corresponding boronate esters) of formula (A) are available or may be prepared by methods well known in the literature.
Compounds of formula (B) may be prepared from anilines of formula (C) as shown in reaction scheme 2.
Reaction Scheme 2
Figure imgf000048_0002
For example, a compound of formula (C) may be treated with a metal halide, such as potassium iodide, and a nitrosylating reagent, such as sodium nitrite and toluene sulphonic acid, in a suitable solvent, such as a mixture of water and acetontrile.
Anilines of formula (C) may be prepared from nitro compounds of formula (D) as shown in reaction scheme 3.
Reaction Scheme 3
Figure imgf000049_0001
(D) (C)
For example, a compound of formula (D) can be treated with a reducing agent, such as iron and ammonium chloride, in a suitable solvent, such as a mixture of water and ethanol.
Nitro compounds of formula (D) in which m is 0 may be prepared from thiols of formula (E) and compounds of formula (F), in which LG represents a leaving group, for example a halogen atom, such as a chlorine atom, as shown in reaction scheme 4.
Reaction Scheme 4
Figure imgf000049_0002
For example, a nitro compound of formula (E) may be treated with a compound of formula (F) in the presence of a base, such as triethylamine, in a suitable solvent such as acetonitrile.
Nitro compounds of formula (E) are available or may be prepared by methods well known in the literature.
Compounds of formula (F) may be prepared from alcohols or amines of formula (G) and acids of formula (H) as shown in reaction scheme 5.
Reaction Scheme 5
Figure imgf000049_0003
For example, an acid of formula (H) may be treated with an activating agent such as oxalyl chloride in a suitable solvent, such as dichloromethane and dimethylformamide, and the resulting intermediate then treated with an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane.
Alcohols and amines of formula (G) and acids of formula (H) are available or may be prepared by methods well known in the literature. Alternatively compounds of formula (l-A), which are compounds of formula (I) in which m = 0, may be prepared from compounds of formula (F) and thiols of formula (J) as shown in reaction scheme 6.
Reaction Scheme 6
Figure imgf000050_0001
For example, a thiol of formula (J) may be treated with a compound of formula (F) in the presence of a base, such as triethylamine, in a suitable solvent such as acetonitrile.
Thiols of formula (J) may be prepared from sulphonyl chlorides of formula (K) as shown in reaction scheme 7.
Reaction Scheme 7
Figure imgf000050_0002
For example, a sulphonyl chloride of formula (K) may be treated with a reducing agent, such as tin dichloride, in a suitable solvent, such as a mixture of water and acetic acid.
Sulphonyl chlorides of formula (K) can be prepared from compounds of formula (L) as shown in reaction scheme 8.
Reaction Scheme 8
Figure imgf000050_0003
For example, a compound of formula (L) may be treated with a sulphonylating agent, such as chlorosulphonic acid.
Compounds of formula (L) can be prepared from compounds of formula (M) and compounds of formula (A) as shown in reaction scheme 9. Reaction Scheme 9
Figure imgf000051_0001
For example, a mixture of a compound of formula (A) and a compound of formula (M), wherein Hal represents a halogen atom, for example a chlorine, bromine or iodine atom, may be treated with a metal catalyst, such as palladium acetate, optionally in the presence of a suitable ligand, such as a phosphine ligand, for example S-Phos, or a preformed complex of a metal and a ligand, such as dppf palladium dichloride, and a base, such as potassium acetate, in a suitable solvent such as dioxane.
Boronic acids (or the corresponding boronate esters) of formula (A) are available or may be prepared by methods well known in the literature. Compounds of formula (M) are available or may be prepared from anilines of formula (N) as shown in reaction scheme 10.
Reaction Scheme 10
Figure imgf000051_0002
For example, a compound of formula (N) may be treated with a metal halide, such as potassium iodide, and a nitrosylating reagent, such as sodium nitrite and toluene sulphonic acid, in a suitable solvent, such as a mixture of water and acetontrile.
Compounds of formula (I) may also be prepared from acids of formula (P) and alcohols or amines of formula (G) as shown in reaction scheme 11 .
Reaction Scheme 11
Figure imgf000052_0001
For example, an acid of formula (P) may be treated with an activating agent such as oxalyl chloride in a suitable solvent, such as dichloromethane and dimethylformamide, and the resulting intermediate then treated with an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane.
Acids of formula (P) may be prepared from esters of formula (Q), in which R represents an alkyl or similar group, as shown in reaction scheme 12.
Reaction Scheme 12
Figure imgf000052_0002
For example, a compound of formula (Q) may be treated with hydrochloric acid in a suitable solvent, such as dioxane.
Esters of formula (Q) in which m is 0 may be prepared from thiols of formula (J) and esters of formula (R), in which LG represents a leaving group, for example a halogen atom, such as a chlorine atom, and R represents an alkyl or similar group, as shown in reaction scheme 13. Reaction Scheme 13
Figure imgf000052_0003
For example, a thiol of formula (J) may be treated with a compound of formula (R) in the presence of a base, such as triethylamine, in a suitable solvent such as acetonitrile. Esters of formula (R) are available or may be prepared by methods well known in the literature.
Compounds of formula (l-B), which are compounds of formula (I) in which m is 1 or 2, may be prepared from compounds of formula (l-A), which are compounds of formula (I) in which m is 0, as shown in reaction scheme 14.
Reaction Scheme 14
Figure imgf000053_0001
For example, a compound of formula (l-A) may be treated with an oxidising agent, for example oxone or metachloroperbenzoic acid, in a suitable solvent, such as acetonitrile or dichloromethane.
Compounds of formula (l-C), which are compounds of formula (I) in which R8 is an OH group, may be prepared from compounds of formula (l-D), which are compounds of formula (I) in which R8 is OR9, as shown in reaction scheme 15.
Reaction Scheme 15
Figure imgf000053_0002
For example, a compound of formula (l-D) may be treated with hydrochloric acid in a suitable solvent, such as dioxane.
Compounds of formula (l-E), which are compounds of formula (I) in which R8 is NR10R11, may be prepared from compounds of formula (l-C) as shown in reaction scheme 16.
Reaction Scheme 16
Figure imgf000053_0003
For example, a compound of formual (l-C) may be treated with a halogenating reagent, such as oxalyl chloride, in a suitable solvent, such as dichloromethane, to form an acyl halide which may be treated with a reagent HNR10R11 in the presence of a base, such as triethylamine, in a suitable solvent, such as dichloromethane. One skilled in the art will realise that it is often possible to alter the order in which the transformations described above are conducted, or to combine them in alternative ways to prepare a wide range of compounds of formula (I). Multiple steps may also be combined in a single reaction. All such variations are contemplated within the scope of the invention.
The skilled person will also be aware that some reagents will be incompatible with certain values or combinations of the substituents X1, X2, X3, X4, m, Y, B, D, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20 and R21 as defined herein, and any additional steps, such as protection and/or deprotection steps, which are necessary to achieve the desired transformation will be clear to the skilled person.
The compounds according to the invention can be used as herbicidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). For water-soluble compounds, soluble liquids, water-soluble concentrates or water soluble granules are preferred. Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated. The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, /V,/V-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).
Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.
The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
Preferred formulations can have the following compositions (weight %):
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The composition of the present may further comprise at least one additional pesticide. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment the additional pesticide is a herbicide and/or herbicide safener.
Thus, compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures. Specific examples of such mixtures include (wherein “I” represents a compound of formula (I)):- 1 + acetochlor; I + acifluorfen (including acifluorfen-sodium); I + aclonifen; I + alachlor; I + alloxydim; I + ametryn; I + amicarbazone; I + amidosulfuron; I + aminocyclopyrachlor ; I + aminopyralid; I + amitrole; I + asulam; I + atrazine; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bilanafos; I + bifenox; I + bispyribac-sodium; I + bixlozone; I + bromacil; I + bromoxynil; I + butachlor; I + butafenacil; I + cafenstrole; I + carfentrazone (including carfentrazone-ethyl); cloransulam (including cloransulam-methyl); I + chlorimuron (including chlorimuron-ethyl); I + chlorotoluron; I + cinosulfuron; I + chlorsulfuron; I + cinmethylin; I + clacyfos; I + clethodim; I + clodinafop (including clodinafop-propargyl); I + clomazone; I + clopyralid; I + cyclopyranil; I + cyclopyrimorate; I + cyclosulfamuron; I + cyhalofop (including cyhalofop-butyl); I + 2,4-D (including the choline salt and 2-ethylhexyl ester thereof); I + 2,4-DB; I + daimuron; I + desmedipham; I + dicamba (including the aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof); I + diclofop-methyl; I + diclosulam; I + diflufenican; I + difenzoquat; I + diflufenican; I + diflufenzopyr; I + dimethachlor; I + dimethenamid-P; I + diquat dibromide; I + diuron; I + esprocarb; I + ethalfluralin; I + ethofumesate; I + fenoxaprop (including fenoxaprop-P-ethyl); I + fenoxasulfone; I + fenquinotrione; I + fentrazamide; I + flazasulfuron; I + florasulam; I + florpyrauxifen; I + fluazifop (including fluazifop-P-butyl); I + flucarbazone (including flucarbazone-sodium); I + flufenacet; I + flumetralin; I + flumetsulam; I + flumioxazin; I + flupyrsulfuron (including flupyrsulfuron-methyl-sodium); I + fluroxypyr (including fluroxypyr-meptyl);; I + fluthiacet-methyl; I + fomesafen; I + foramsulfuron; I + glufosinate (including the ammonium salt thereof); I + glyphosate (including the diammonium, isopropylammonium and potassium salts thereof); I + halauxifen (including halauxifen-methyl); I + halosulfuron-methyl; I + haloxyfop (including haloxyfop- methyl); I + hexazinone; I + hydantocidin; I + imazamox; I + imazapic; I + imazapyr; I + imazaquin; I + imazethapyr; I + indaziflam; I + iodosulfuron (including iodosulfuron-methyl-sodium); I + iofensulfuron; I + iofensulfuron-sodium; I + ioxynil; I + ipfencarbazone; I + isoproturon; I + isoxaben; I + isoxaflutole; I + lactofen; I + lancotrione; I + linuron; I + MCPA; I + MCPB; I + mecoprop-P; I + mefenacet; I + mesosulfuron; I + mesosulfuron-methyl; I + mesotrione; I + metamitron; I + metazachlor; I + methiozolin; I + metobromuron; I + metolachlor; I + metosulam; I + metoxuron; I + metribuzin; I + metsulfuron; I + molinate; I + napropamide; I + nicosulfuron; I + norflurazon; I + orthosulfamuron; I + oxadiargyl; I + oxadiazon; I + oxasulfuron; I + oxyfluorfen; I + paraquat dichloride; I + pendimethalin; I + penoxsulam; I + phenmedipham; I + picloram; I + picolinafen; I + pinoxaden; I + pretilachlor; I + primisulfuron-methyl; I + prodiamine; I + prometryn; I + propachlor; I + propanil; I + propaquizafop; I + propham; I + propyrisulfuron, I + propyzamide; I + prosulfocarb; I + prosulfuron; I + pyraclonil; I + pyraflufen (including pyraflufen-ethyl): I + pyrasulfotole; I + pyrazolynate, I + pyrazosulfuron-ethyl; I + pyribenzoxim; I + pyridate; I + pyriftalid; I + pyrimisulfan, I + pyrithiobac-sodium; I + pyroxasulfone; I + pyroxsulam ; I + quinclorac; I + quinmerac; I + quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl),; I + rimsulfuron; I + saflufenacil; I + sethoxydim; I + simazine; I + S-metolachlor; I + sulcotrione; I + sulfentrazone; I + sulfosulfuron; I + tebuthiuron; I + tefuryltrione; I + tembotrione; I + terbuthylazine; I + terbutryn; I + thiencarbazone; I + thifensulfuron; I + tiafenacil; I + tolpyralate; I + topramezone; I + tralkoxydim; I + triafamone; I + triallate; I + triasulfuron; I + tribenuron (including tribenuron-methyl); I + triclopyr; I + trifloxysulfuron (including trifloxysulfuron-sodium); I + trifludimoxazin; I + trifluralin; I + triflusulfuron; I + tritosulfuron; I + 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one; I + 4-hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1- methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1 ,5-dimethyl-3-[1-methyl-5- (trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one; I + (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-
3-methyl-imidazolidin-2-one; I + 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carbonyl]bicyclo[3.2.1]octane-2, 4-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carbonyl]-5-methyl-cyclohexane-1 ,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-
4-carbonyl]cyclohexane-1 ,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carbonyl]-5,5-dimethyl-cyclohexane-1 ,3-dione; I + 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo- pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1 ,3,5-trione; I + 2-[2-(3,4-dimethoxyphenyl)-6- methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1 ,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6- methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1 ,3-dione; I + 2-[6-cyclopropyl-2- (3, 4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1 ,3-dione; I + 3-[6- cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2, 4-dione; I + 2- [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1 ,3- dione; I + 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl- cyclohexane-1 ,3,5-trione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carbonyl]cyclohexane-1 ,3-dione; I + 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]- 2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione and I + 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo- pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione.
The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.
The compound of formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1. The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner).
Compounds of formula (I) of the present invention may also be combined with herbicide safeners. Preferred combinations (wherein “I” represents a compound of formula (I)) include:- I + benoxacor, I + cloquintocet (including cloquintocet-mexyl); I + cyprosulfamide; I + dichlormid; I + fenchlorazole (including fenchlorazole-ethyl); I + fenclorim; I + fluxofenim; l+ furilazole I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including mefenpyr-diethyl); I + metcamifen; I + N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino] benzenesulfonamide and I + oxabetrinil.
Particularly preferred are mixtures of a compound of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen-ethyl), cloquintocet (including cloquintocet-mexyl) and/or N-(2-methoxybenzoyl)-4- [(methyl-aminocarbonyl)amino]benzenesulfonamide.
The safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
Preferably the mixing ratio of compound of formula (I) to safener is from 100:1 to 1 :10, especially from 20:1 to 1 :1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the safener).
The compounds of formula (I) of this invention are useful as herbicides. The present invention therefore further comprises a method for controlling unwanted plants comprising applying to the said plants or a locus comprising them, an effective amount of a compound of the invention or a herbicidal composition containing said compound. ‘Controlling’ means killing, reducing or retarding growth or preventing or reducing germination. Generally the plants to be controlled are unwanted plants (weeds). ‘Locus’ means the area in which the plants are growing or will grow.
The rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha. A preferred range is 10-200g/ha.
The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
Useful plants in which the composition according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf. Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
The compounds of the present invention can be used in methods of controlling undesired vegetation in crop plants which are tolerant to protoporphyrinogen oxidase (PPO) inhibitors. Such plants can be obtained, for example, by transforming crop plants with nucleic acids which encode a suitable protoporphyrinogen oxidase, which may contain a mutation in order to make it more resistant to the PPO inhibitor. Examples of such nucleic acids and crop plants are disclosed in WO95/34659, WO97/32011 , W02007/024739, WO2012/080975, WO2013/189984, WO2015/022636,
WO2015/022640, WO2015/092706, WO2016/099153, WO2017/023778, WO2017/039969, WO2017/217793, WO2017/217794, WO2018/114759, WO2019/117578, WO2019/117579 and WO2019/118726.
Thus the present invention also provides a method for controlling undesired vegetation at a plant cultivation site, the method comprising the steps of: a) providing, at said site, a plant that comprises at least one nucleic acid comprising a nucleotide sequence encoding a protoporphyrinogen oxidase (PPO) polypeptide which is resistant or tolerant to a "PPO inhibiting herbicide"; b) applying to said site an effective amount of said herbicide, wherein the PPO inhibiting herbicide is a compound of formula (I) as herein defined.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour). Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes.
Compounds of formula (I) and compositions of the invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium.
Unwanted plants are to be understood as also including those weeds that have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD- inhibitors) by evolution, by conventional methods of breeding or by genetic engineering. Examples include Amaranthus palmeri that has evolved resistance to glyphosate and/or acetolactate synthase (ALS) inhibiting herbicides.
The compounds of the present invention can be used in methods of controlling unwanted plants or weeds which are resistant to protoporphyrinogen oxidase (PPO) inhibitors. For example, Amaranthus palmeri and Amaranthus tuberculatus populations have evolved as PPO-resistant weeds e.g. due to amino acid substitutions in PPX2L such as those occurring at amino acids R128 (also referred to as R98) and G399, or a codon (glycine) deletion in PPX2L at codon 210 (A210), the codon numbering being based on NCBI reference DQ3861 14. The compounds of the present invention can be used in methods of controlling Amaranthus palmeri and/or Amaranthus tuberculatus with mutations or deletions at the previously mentioned codons or equivalents, and it would be obvious to try the compounds to control unwanted plants or weeds with other mutations conferring tolerance or resistance to PPO inhibitors that may arise.
The compounds of formula (I) are also useful for pre-harvest desiccation in crops, for example, but not limited to, potatoes, soybean, sunflowers and cotton. Pre-harvest desiccation is used to desiccate crop foliage without significant damage to the crop itself to aid harvesting.
Compounds/compositions of the invention are particularly useful in non-selective burn-down applications, and as such may also be used to control volunteer or escape crop plants.
Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.
EXAMPLES
The Examples which follow serve to illustrate, but do not limit, the invention.
SYNTHESIS EXAMPLES Example 1 : Preparation of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4- fluoro-phenyl]sulfanylpropanoate (Compound 8-374)
Step 1 : Synthesis of 3,5-dichloro-2-(4-chloro-2-fluoro-phenyl)pyridine
Figure imgf000062_0001
Palladium(dppf) dichloride (1 .5 g, 1 .8 mmol) was added to a stirred mixture of (4-chloro-2-fluoro-phenyl)- boronic acid (3.2 g, 18 mmol), 2-bromo-3,5-dichloro-pyridine (4.0 g, 18 mmol), caesium carbonate (17.4 g, 53 mmol), water (12 ml) and toluene (60 ml). The resulting mixture was heated at 100 °C for 2 hours, then allowed to cool and ethyl acetate (70 ml) and water (20 ml) added. The phases were separated and the aqueous phase extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to leave a residue which was purified by column chromatography to provide 3,5-dichloro-2-(4-chloro-2-fluoro-phenyl)pyridine (4.1 g) as a solid. 1H NMR (400 MHz, CDCb) 6 8.6 (d,1 H), 7.85 (d,1 H), 7.4 (t,1 H), 7.25 (dd,1 H), 7.2 (dd,1 H) ppm.
Step 2: Synthesis of 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenesulfonyl chloride
Figure imgf000062_0002
Chlorosulphonic acid (1 .8 ml, 27 mmol) was added to 3,5-dichloro-2-(4-chloro-2-fluoro-phenyl)pyridine (1.5 g, 5.4 mmol) and the resulting mixture heated to 140 °C for 3 hours. The mixture was allowed to cool then added to iced water and the resulting mixture extracted with ethyl acetate (2 x 80 ml) added. The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to provide 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenesulfonyl chloride (1.8 g) as a solid. 1H NMR (400 MHz, CDCb) 6 8.6 (d,1 H), 8.3 (d,1 H), 7.9 (d,1 H), 7.5 (d,1 H) ppm.
Step 3: Synthesis of 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenethiol
Figure imgf000062_0003
Triphenylphosphine (4.0 g, 15 mmol) was added portionwise to a stirred solution of 2-chloro-5-(3,5- dichloro-2-pyridyl)-4-fluoro-benzenesulfonyl chloride (1 .8 g, 4.3 mmol) in tetra hydrofuran (22 ml) at room temperature. Water (3.6 ml) was added and the resulting mixture stirred at ambient temperature for 18 hours. Water (40 ml) and ethyl acetate (90 ml) were added and the phases separated. The aqueous phase was extracted with ethyl acetate (50 ml) and the combined organic phases dried over sodium sulphate, filtered and evaporated under reduced pressure to leave a residue which was purified by column chromatography to provide 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenethiol (1.75 g) as a gum. 1H NMR (400 MHz, CDCh) 6 8.55 (d,1 H), 7.85 (d,1 H), 7.45 (d,1 H), 7.35 (d,1 H), 3.9 (s,1 H) ppm.
Step 4: Synthesis of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro- phenyl]sulfanylpropanoate (Compound 8-374)
Figure imgf000063_0001
(3-Methoxy-3-oxo-propyl) 2-bromopropanoate (prepared as described in example 2; 130 mg, 0.53 mmol) was added to a stirred mixture of 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenethiol (200 mg, 0.49 mmol), caesium carbonate (160 mg, 0.50 mmol) and acetonitrile (14 ml) and the resulting mixture stirred at ambient temperature for 2 hours. Ethyl acetate (50 ml) was added and the resulting mixture washed with water (2 x 20 ml), dried over sodium sulphate, filtered and evaporated to leave a residue which was purified by column chromatography to provide (3-methoxy-3-oxo-propyl) 2-[2-chloro- 5-(3,5-dichloro-2-pyridyl)-4-fluoro-phenyl]sulfanylpropanoate (Compound 8-374) (44 mg) as an oil. 1H NMR (400 MHz, CDCh) 6 8.6 (d,1 H), 7.9 (d,1 H), 7.7 (d,1 H), 7.35 (d, 1 H), 4.35 (m, 2H), 3.9 (q, 1 H), 3.7 (s, 3H), 2.6 (m, 2H), 1.55 (d, 3H) ppm.
Example 2: Preparation of (3-methoxy-3-oxo-propyl) 2-bromopropanoate
Figure imgf000063_0002
Triethylamine (1.3 ml, 9.1 mmol) and methyl 3-hydroxy propanoate (0.48 ml, 5.0 mmol) were added dropwise to a stirred solution of 2-bromopropanoyl bromide (0.49 ml, 4,5 mmol) in acetonitrile (15 ml) at 0 °C. The resulting mixture was stirred at 0 °C for 1 hour, then ambient temperature for 2 hours. Water (20 ml) and ethyl acetate (60 ml) were added, the phases separated and the aqueous phase extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to leave an oil, which was purified by column chromatography to provide (3-methoxy-3-oxo-propyl) 2-bromopropanoate (440 mg) as an oil. 1H NMR (400 MHz, CDCh) 5 4.45 (m, 2H), 4.35 (m, 1 H), 3.75 (s, 3H), 2.7 (t, 2H), 1.8 (d, 3H) ppm. Example 3: Preparation of methyl 3-[2-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro- phenyl]sulfanylpropanoylamino]propanoate (Compound 26-374)
Step 1 : Synthesis of methyl 3-(2-bromopropanoylamino)propanoate
Figure imgf000064_0001
Triethylamine (2.6 ml, 9.1 mmol) and 2-bromopropanoyl bromide (0.97 ml, 9.1 mmol) were added to a stirred mixture of (3-methoxy-3-oxo-propyl)ammonium chloride (1.42 g, 10 mmol) in acetonitrile (30 ml) at 0 °C. The resulting mixture was stirred at 0 °C for 1 hour, then ambient temperature for 2 hours. Water (20 ml) and ethyl acetate (60 ml) were added, the phases separated and the aqueous phase extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to leave an oil, which was purified by column chromatography to provide methyl 3-(2-bromopropanoylamino)propanoate (560 mg) as a solid. 1H NMR (400 MHz, CDCb) 6 6.95 (br s, 1 H), 4.4 (q, 1 H), 3.75 (s, 3H), 3.55 (m, 2H), 2.6 (m, 2H), 1.85 (d, 3H) ppm.
Step 2: Synthesis of methyl 3-[2-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro- phenyl]sulfanylpropanoylamino]propanoate (Compound 26-374)
Figure imgf000064_0002
Methyl 3-(2-bromopropanoylamino)propanoate (130 mg, 0.53 mmol) was added to a stirred mixture of 2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzenethiol (prepared as described in Example 1 , Step 3; 200 mg, 0.49 mmol), caesium carbonate (160 mg, 0.50 mmol) and acetonitrile (4 ml) and the resulting mixture stirred at ambient temperature for 1 hour. Ethyl acetate (50 ml) was added and the resulting mixture washed with water (2 x 20 ml), dried over sodium sulphate, filtered and evaporated to leave a residue which was purified by column chromatography to provide methyl 3-[2-[2-chloro-5-(3,5-dichloro- 2-pyridyl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (Compound 26-374) (36 mg). 1H NMR (400 MHz, CDCb) 6 8.55 (d,1 H), 7.85 (d,1 H), 7.45 (d,1 H), 7.3 (d, 1 H), 7.05 (br t, 1 H), 3.85 (q, 1 H), 3.6 (s, 3H), 3.5 (m, 1 H), 3.45 (m, 1 H), 2.45 (t, 2H), 1.55 (d, 3H) ppm.
FORMULATION EXAMPLES
Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with waterto give suspensions of the desired concentration.
Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %
Kaolin 65 % 40 %
Talcum 20 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
Cyclohexanone 30 % xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Dusts a) b) c)
Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
Kaolin 94 % mineral filler 96 % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruder granules
Active ingredient [compound of formula (I)] 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 %
Kaolin 82 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
The mixture is extruded and then dried in a stream of air.
Coated granules
Active ingredient [compound of formula (I)] 8 % polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %
Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
Water 45.3 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow Release Capsule Suspension
28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1 .2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
BIOLOGICAL EXAMPLES
Pre-emergence biological efficacy
Seeds of weeds and/or crops were sown in standard soil in pots (Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Euphorbia heterophylla (EPHHL), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG),).. After cultivation for one day under controlled conditions in a glasshouse (at 24/19°C, day/night; 16 hours light), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether), to create a 50g/l solution which was then diluted using 0.2% Genapol XO80 as diluent to give the desired final dose of test compound.
The test plants were then grown under controlled conditions in the glasshouse (at 24/18°C, day/night; 15 hours light; 50 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). The results are shown in Table 2 below.
Table 2
Figure imgf000067_0001
Post-emergence biological efficacy
Seeds of weeds and/or crops were sown in standard soil in pots (Amaranthus palmeri (AMAPA), Chenopodium album (CHEAL), Euphorbia heterophylla (EPHHL), Ipomoea hederacea (IPOHE), Eleusine indica (ELEIN), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG)).. After cultivation for 14 days under controlled conditions in a glasshouse (at 24/19°C, day/night; 16 hours light), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether), to create a 50g/l solution which was then diluted using 0.2% Genapol XO80 as diluent to give the desired final dose of test compound.
The test plants were then grown under controlled conditions in the glasshouse (at 24/18°C, day/night; 15 hours light; 50 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). The results are shown in Table 3 below. Table 3
Figure imgf000068_0001

Claims

CLAIMS:
1 . A compound of formula (I) or an agronomically acceptable salt thereof:
Figure imgf000069_0001
X1 is C-R1, nitrogen, or N+-O_;
X2 is C-R17 or nitrogen;
X3 is C-R18 or nitrogen;
X4 is C-R19 or nitrogen; with the proviso that a maximum of two of X1, X2, X3 and X4 are nitrogen, and X3 and X4 are not both nitrogen;
Y is C-H or nitrogen;
B is O, S, or NR5;
D is -[C(Re)(R7)]n- ; m is an integer from 0 to 2; n is an integer from 1 to 4;
R1 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1- C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R2 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, CO2R9, or CONR10R11; or
R1 and R2 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R16; or R2 and R19 together with the carbon atoms to which they are attached form a 5- or 6-membered ring, which may be saturated or partially or fully unsaturated, and which may optionally contain one or two heteroatoms selected from nitrogen, oxygen and sulfur, and which may be substituted with 1 to 4 groups represented by R16;
R3 is hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, or Ci-C4alkylsulfonyl;
R4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, or Ci-C4alkylsulfonyl;
R5 is hydrogen, hydroxy, Ci-Cealkyl, or Ci-C4alkoxy;
R6 and R7 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, hydroxy, Ci-C4alkoxy, Ci-C4alkoxycarbonyl, or -CH2OR12; provided that R6 and R7 are not both hydroxy on the same carbon atom; or two R6 and R7 groups, on the same or different carbon atoms, together form a Ci-Csalkylene chain, which contain 0, 1 or 2 oxygen atoms, substituted by 1 to 3 groups represented by R15; or two R6 and R7 groups, on the same carbon atom, together form a C2-C3alkene;
R8 is OR9, SR9, or NR10R11;
R9 is hydrogen, Ci-Cwalkyl, Ci-Cwhaloalkyl, Cs-Cealkenyl, Cs-Cehaloalkenyl, Cs-Cealkynyl, C1- C4alkoxyCi-C6alkyl, Ci-C4haloalkoxyCi-C6alkyl, Ce-CwarylCi-Csalkyl, Ce-CwarylCi-Csalkyl substituted by 1 to 4 groups represented by R13, heteroarylCi-Csalkyl, or heteroarylCi-Csalkyl substituted by 1 to 3 groups represented by R13;
R10 is hydrogen, Ci-Cealkyl, SO2R14;
R11 is hydrogen or Ci-Cealkyl; or
R10 and R11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring;
R12 is hydrogen, Ci-C4alkyl, or Ci-C4alkylcarbonyl;
R13 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl;
R14 is Ci-C4alkyl, Ci-C4haloalkyl, or Ci-C4alkyl(Ci-C4alkyl)amino;
R15 is hydrogen, halogen, Ci-C4alkyl, or Ci-C4haloalkyl;
R16 is halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, cyano, or Ci-C4alkylsulfonyl; R17 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-C6alkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, Ci- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, Ci- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, Ci-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R18 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R19 is hydrogen, halogen, cyano, nitro, Ci-C4alkyl, Ci-C4haloalkyl, Cs-Cecycloalkyl, Ci-C4alkoxyCi- Cealkyl, Ci-C4haloalkoxyCi-Cealkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkoxyCi-C4alkoxy, C1- C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C1- C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, amino, Ci-C4alkylamino, di(Ci- C4alkyl)amino, Ci-C4alkylcarbonylamino, Ci-C4alkylcarbonyl(Ci-C4alkyl)amino, C1- C4alkoxycarbonylamino, aminocarbonylamino, Ci-C4alkylaminocarbonylamino, C1-
C4alkylsulfonylamino, Ci-C4haloalkylsulfonylamino, -CO2R9, or -CONR10R11;
R20 and R21 are each independently hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Ci-C4alkoxy, or - CH2OR12; or two R20 and R21 groups together with the carbon atom to which they are attached form a C2-Csalkylene chain, wherein said C2-Csalkylene chain comprise 0, 1 or 2 oxygen atoms, and wherein said C2- Csalkylene chain is substituted by 1 to 3 groups represented by R15; or two R20 and R21 groups together with the carbon atom to which they are attached form a C2-C3alkene; and with the proviso that R1, R2, R17, R18 and R19 are not all hydrogen.
2. A compound as claimed in claim 1 in which X1 is C-R1.
3. A compound as claimed in claim 1 or claims 2 in which X2 is nitrogen.
4. A compound as claimed in any previous claim in which X3 is C-R18.
5. A compound as claimed in any previous claim in which X4 is C-R19.
6. A compound as claimed in any previous claim in which Y is C-H.
7. A compound as claimed in any previous claim in which B is O, NH and NCH3.
8. A compound as claimed in any previous claim in which n is 2.
9. A compound as claimed in any previous claim in which R2 is hydrogen, fluorine, chlorine, methyl or trifluoromethyl.
10. A compound as claimed in any previous claim in which R3 is hydrogen, chlorine or fluorine.
11. A compound as claimed in any previous claim in which R4 is hydrogen, chlorine, bromine, cyano or aminothiocarbonyl, preferably chlorine, bromine or cyano.
12. A compound as claimed in any previous claim in which R8 is OR9.
13. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) as defined in any of claims 1 to 12 and an agrochemically-acceptable diluent or carrier.
14. A method of controlling or preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12, or a composition according to claim 13, is applied to the plants, to parts thereof or to the locus thereof.
15. A method for controlling undesired vegetation at a plant cultivation site, the method comprising the steps of: a) providing, at said site, a plant that comprises at least one nucleic acid comprising a nucleotide sequence encoding a protoporphyrinogen oxidase (PPO) polypeptide which is resistant or tolerant to a "PPO inhibiting herbicide"; b) applying to said site an effective amount of said herbicide, wherein the PPO inhibiting herbicide is a compound as claimed in any previous claim.
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