EP4702009A1 - Dérivés herbicides - Google Patents

Dérivés herbicides

Info

Publication number
EP4702009A1
EP4702009A1 EP24721604.7A EP24721604A EP4702009A1 EP 4702009 A1 EP4702009 A1 EP 4702009A1 EP 24721604 A EP24721604 A EP 24721604A EP 4702009 A1 EP4702009 A1 EP 4702009A1
Authority
EP
European Patent Office
Prior art keywords
formula
ethyl
compound
dichlorophenyl
chloro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24721604.7A
Other languages
German (de)
English (en)
Inventor
James Alan Morris
Louisa WHALLEY
Abbie Louise KRISTOFFERSEN
Marco Michele MASTANDREA
Andrew GOMM
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of EP4702009A1 publication Critical patent/EP4702009A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • 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
    • 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
    • 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
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4

Definitions

  • the present invention relates to herbicidal pyridone derivatives, e.g., as active ingredients, which have herbicidal activity.
  • the invention also relates to agrochemical compositions which comprise at least one of the pyridone derivatives, to processes of preparation of these compounds and to uses of the pyridone derivatives or compositions in agriculture or horticulture for controlling weeds, in particular in crops of useful plants.
  • EP0239391, EP0127313, EP0040082, GB2182931, GB2328614, WO2022117445, WO2022117446, and WO 2023/110664 describe pyridone derivatives as herbicidal agents.
  • R 1 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxyC 1 -C 6 alkyl, or C 3 - C6cycloalkyl
  • R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 5 ;
  • R 3 is hydrogen or C1-C6alkyl;
  • R 4 is hydrogen or halogen;
  • R 5 is cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6
  • a problem with many current herbicides used to control unwanted vegetation before planting a crop is that they can cause damage to the following crop if it is planted soon after the herbicide is used. 82965-FF 2 A herbicide that is safe to crops when applied before they emerge, whilst providing good control on already emerged weeds, is therefore a major advantage over current herbicides.
  • novel compounds of Formula (I) not only have, for practical purposes, a very advantageous level of herbicidal activity, but they also shown no or low levels of damage to several major agricultural crops, such as corn (zea mays), when applied pre-emergence whilst providing exceptional control of unwanted vegetation (weeds and volunteer crops) when applied post-emergence, thus enabling them to be used successfully shortly before planting a new crop.
  • major agricultural crops such as corn (zea mays)
  • weeds and volunteer crops when applied post-emergence
  • an agrochemical composition comprising a herbicidally effective amount of a compound of Formula (I) according to the present invention.
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
  • a method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a composition comprising a compound of Formula (I).
  • a compound of Formula (I) as a herbicide.
  • 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 R 6 substituents.
  • C 1 -C 6 alkyl substituted by 1, 2 or 3 halogens may include, but not be limited to, -CH 2 Cl, -CHCl 2 , -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups.
  • C1-C6alkoxy substituted by 1, 2 or 3 halogens may include, but not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.
  • cyano means a -CN group.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).
  • nitro means an -NO2 group.
  • acetyl means a -C(O)CH 3 group.
  • C1-C6alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. “C1-C4alkyl” and “C1- 82965-FF 3 C3alkyl” are to be construed accordingly.
  • C1-C6alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, and the isomers thereof, for example, isopropyl.
  • a “C1-C6alkylene” group refers to the corresponding definition of C1-C6alkyl, except that such radical is attached to the rest of the molecule by two single bonds.
  • the term “C1-C2alkylene” is to be construed accordingly.
  • Examples of C1-C6alkylene include, but are not limited to, -CH 2 -, -CH 2 CH 2 - and -(CH 2 ) 3 -.
  • C1-C6haloalkyl refers a C1-C6alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C1-C4haloalkyl and “C1- C3haloalkyl”, are to be construed accordingly.
  • Examples of C1-C6haloalkyl include, but are not limited to trifluoromethyl.
  • C1-C6alkoxy refers to a radical of the formula -ORa where Ra is a C1- C6alkyl radical as generally defined above.
  • C1-C4alkoxy and “C1-C3alkoxy” are to be construed accordingly.
  • Examples of C1-C6alkoxy include, but are not limited to, methoxy, ethoxy, 1- methylethoxy (iso-propoxy), and propoxy.
  • C1-C6haloalkoxy refers to a C1-C6alkoxy radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C1-C4haloalkoxy and “C1-C3haloalkoxy” are to be construed accordingly.
  • C1-C6haloalkoxy examples include, but are not limited to trifluoromethoxy.
  • 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 (Z)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • C 2 -C 3 alkenyl is to be construed accordingly.
  • C2-C6alkenyl examples include, but are not limited to, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), but-1-enyl.
  • 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-C3alkynyl is to be construed accordingly.
  • C2-C6alkynyl examples include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.
  • C2-C6alkenyloxy refers to a C2-C6alkenyl radical as generally defined above attached to the rest of the molecule through an oxygen atom.
  • C2-C6alkynyloxy refers to C2-C6alkynyl radical as generally defined above attached to the rest of the molecule through an oxygen atom.
  • C1-C6alkoxyC1-C6alkyl refers to a radical of the formula RbORa- wherein Rb is a C1-C6alkyl radical as generally defined above, and Ra is a C1-C6alkylene radical as generally defined above.
  • C1-C4alkoxyC1-C4alkyl is to be construed accordingly.
  • C1-C6alkoxyC1-C6alkoxy refers to a radical of the formula RbORaO- wherein Ra and Rb are each independently a C1-C6alkyl radical as generally defined above.
  • C 1 -C 4 alkoxyC 1 -C 4 alkoxy and “C 1 -C 3 alkoxyC 1 -C 3 alkoxy” are to be construed accordingly.
  • C3-C6cycloalkyl refers to a radical which is a monocyclic saturated ring system which contains 3 to 6 carbon atoms.
  • C3-C5cycloalkyl and “C3-C4cycloalkyl” are to be construed accordingly.
  • Examples of C3-C6cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • C3-C6cycloalkenyl refers to a radical which is a monocyclic unsaturated ring system, containing at least one double bond, and which contains 3 to 6 carbon atoms.
  • the terms "C3-C5cycloalkenyl” and “C3-C4cycloalkenyl” are to be construed accordingly.
  • Examples of C3- C6cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.
  • C3-C6cycloalkylC1-C6alkyl refers to a C3-C6cycloalkyl ring attached to the rest of the molecule by a C1-C6alkylene linker as defined above.
  • Examples of C3-C6cycloalkylC1- C6alkyl include, but are not limited to, cyclopropylmethyl.
  • C3-C6cycloalkylC1-C6alkoxy refers to a C3-C6cycloalkyl ring attached to the rest of the molecule by a C1-C6alkoxy linker as defined above.
  • C3-C6cycloalkylC1- C6alkoxy examples include, but are not limited to, cyclopropoxy.
  • C3-C6cycloalkylaminocarbonyl refers to a C3-C6cycloalkyl ring attached to the rest of the molecule through an -NHC(O)- linker.
  • Examples of C 3 -C 6 cycloalkylaminocarbonyl include, but are not limited to, cyclopropylcarbamoyl (i.e., cyclopropylaminocarbonyl).
  • C6-C10aryl 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.
  • C6-C10arylC1-C3alkyl refers to an aryl moiety as generally defined above, which is attached to the rest of the molecule by a C1-C3alkylene linker as defined above.
  • phenoxy refers to a phenyl ring attached to the rest of the molecule through an oxygen atom.
  • benzyloxy refers to a benzyl ring attached to the rest of the molecule through an oxygen atom.
  • heterocyclyl refers to a stable 4-, 5- or 6-membered non-aromatic monocyclic ring which comprises 1, 2 or 3 heteroatoms, wherein the heteroatoms are 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, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidnyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl and thiazolidinyl.
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur.
  • heteroaryl examples include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
  • C1-C6alkylcarbonyl refers to a radical of the formula -C(O)Ra, where Ra is a C1-C6alkyl radical as generally defined above.
  • C1-C6alkylcarbonyl examples include, but are not limited to, acetyl.
  • C 1 -C 6 alkoxycarbonyl refers to a radical of the formula -C(O)OR a , where Ra is a C1-C6alkyl radical as generally defined above.
  • C1-C6alkylaminocarbonyl refers to a radical of the formula -C(O)NHRa, wherein Ra is a C1-C6alkyl radical as generally defined above.
  • C1-C6alkylaminocarbonyl examples include, but are not limited to, ethylcarbamoyl (i.e., ethylaminocarbonyl). 82965-FF 5
  • N,N-di(C1-C4alkyl)aminocarbonyl“ refers to a radical of the formula - C(O)N(Ra)(Rb), wherein Ra and Rb are each individually a C1-C4alkyl radical as generally defined above.
  • the term “N,N-di(C1-C3alkyl)aminocarbonyl” is to be construed accordingly.
  • N,N-di(C1- C4alkyl)aminocarbonyl examples include, but are not limited to, dimethylcarbamoyl (i.e. N, N- di(methyl)aminocarbonyl).
  • N,N-di(C1-C4alkyl)aminosulfonyl“ refers to a radical of the formula - S(O)2N(Ra)(Rb), wherein Ra and Rb are each individually a C1-C4alkyl radical as generally defined above.
  • the term “N,N-di(C1-C3alkyl)aminosulfonyl” is to be construed accordingly.
  • N,N-di(C1- C4alkyl)aminosulfonyl examples include, but are not limited to, diethylsulfamoyl (i.e., N,N-di(methyl)aminosulfonyl).
  • C1-C6alkylsulfanyl refers to a radical of the formula -SRa, where Ra is a C1-C6alkyl radical as generally defined above.
  • the terms “C1-C4alkylsulfanyl” and “C1-C3alkylsulfanyl”, are to be construed accordingly.
  • C1-C6alkylsulfanyl examples include, but are not limited to methylsulfanyl.
  • C1-C6alkylsulfinyl refers to a radical of the formula -S(O)Ra, where Ra is a C1-C6alkyl radical as generally defined above.
  • the terms “C1-C4alkylsulfinyl” and “C1-C3alkylsulfinyl”, are to be construed accordingly.
  • Examples of C1-C6alkylsulfinyl include, but are not limited to methylsulfinyl.
  • C1-C6alkylsulfonyl refers to a radical of the formula -S(O)2Ra, where Ra is a C1-C6alkyl radical as generally defined above.
  • Examples of C1-C6alkylsolfanyl include, but are not limited to methylsulfonyl.
  • C1-C6alkylsulfonamido refers to a radical of the formula -NHS(O)2Ra, where Ra is a C1-C6alkyl radical as generally defined above.
  • Ra is a C1-C6alkyl radical as generally defined above.
  • the presence of one or more possible stereogenic elements in a compound of formula (I) means that the compounds may occur in optically 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.
  • the present invention includes all possible tautomeric forms for a compound of formula (I).
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, or in salt form, e.g., an agronomically usable salt form. Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.
  • the compounds of Formula (I) may form chloride or 2,2,2-trifluoroacetate salts.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton (1991). 82965-FF 6 The following list provides definitions, including preferred definitions, for substituents R 1 , R 2 , R 3 , R 4 , and R 5 , with reference to compounds of Formula (I).
  • R 1 is C1-C6alkyl, C1-C6alkoxy, C2-C6alkenyl, C2-C6alkynyl, C1-C6alkoxyC1-C6alkyl, or C3- C6cycloalkyl.
  • R 1 is C1-C4alkyl, C1-C4alkoxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkoxyC1- C4alkyl, or C3-C6cycloalkyl.
  • R 1 is C1-C3alkyl, C1-C3alkoxy, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxyC1-C3alkyl, or C3-C4cycloalkyl. More preferably still, R 1 is methyl, ethyl, n-propyl, methoxy, 2-methoxyethyl, ally, and prop-2-ynyl. In one set of embodiments, R 1 is C1-C3alkyl, preferably methyl or ethyl, and more preferably, ethyl.
  • R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1, 2, 3, or 4 groups, which may be the same or different, represented by R 5 .
  • R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1, 2, or 3 heteroatoms individually selected from N, O and S, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by R 5 .
  • R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1, 2, or 3 groups, which may be the same or different, represented by R 5 . More preferably still, R 2 is phenyl or heteroaryl, wherein the heteroaryl moiety is a 5- or 6- membered aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein each phenyl and heteroaryl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
  • R 2 is phenyl or pyridyl, wherein each phenyl and pyridyl moiety may be optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
  • R 2 is phenyl optionally substituted with 1 or 2 groups, which may be the same or different, represented by R 5 .
  • R 2 is phenyl optionally substituted with 2 groups, which may be the same or different, represented by R 5 .
  • R 2 is 3-chloro-4-cyanophenyl, 3,4-dichlorophenyl, or 3,4-difluorophenyl.
  • R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl. In a particularly preferred set of embodiments, R 2 is 3,4-dichlorophenyl.
  • R 3 is hydrogen or C1-C6alkyl. Preferably, R 3 is hydrogen or C1-C4alkyl, more preferably, hydrogen or C1-C3alkyl. More preferably still, R 3 is hydrogen, methyl, or ethyl. Even more preferably, R 3 is hydrogen or ethyl. Even more preferably still, R 3 is hydrogen. 82965-FF 7 R 4 is hydrogen or halogen. Preferably, R 4 is hydrogen, chloro, fluoro, or bromo.
  • R 4 is hydrogen or bromo. In one set of embodiments, R 4 is hydrogen.
  • R 5 is cyano, nitro, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, C1-C6haloalkoxy, C1- C 6 alkoxyC 1 -C 6 alkyl, C 1 -C 6 alkylsulfanyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfonamido, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, C3-C6cycloalkyl, C3- C6cycloalkylaminocarbonyl, or N,N-di(C1-C4alkyl)aminocarbonyl.
  • R 5 is cyano, nitro, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C1-C4haloalkoxy, C1-C4alkoxyC1-C3alkyl, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkylsulfonamido, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylaminocarbonyl, C3-C6cycloalkyl, C3- C6cycloalkylaminocarbonyl, or N,N-di(C1-C3alkyl)aminocarbonyl.
  • R 5 is cyano, nitro, halogen, C1-C3alkyl, C1-C3alkoxy, C1-C3haloalkyl, C1- C 3 haloalkoxy, C 1 -C 3 alkoxyC 1 -C 3 alkyl, C 1 -C 3 alkylsulfanyl, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 - C3alkylsulfonamido, C1-C3alkylcarbonyl, C1-C3alkoxycarbonyl, C1-C3alkylaminocarbonyl, C3- C6cycloalkyl, C3-C6cycloalkylaminocarbonyl, or N,N-di(C1-C3alkyl)aminocarbonyl.
  • R 5 is cyano, nitro, halogen, C1-C3alkyl, C1-C3alkoxy, C1-C3haloalkyl, C1- C3haloalkoxy, C1-C3alkoxyC1-C3alkyl, C1-C3alkylcarbonyl, or C3-C6cycloalkyl.
  • R5 is cyano, nitro, chloro, fluoro, methyl, isopropyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2-difluoroethoxy, methoxymethyl, acetyl, or cyclopropyl.
  • R 5 is cyano or halogen, preferably halogen, and more preferably R 5 is cyano or chloro, and more preferably still, R 5 is chloro.
  • X is halogen.
  • X is chloro, fluoro, or iodo. More preferably, X is chloro or fluoro.
  • R 1 is C1-C3alkyl
  • R 2 is phenyl substituted with 2 groups, which may be the same or different, represented by R 5
  • R 3 is C1-C3alkyl
  • R 4 is hydrogen or halogen
  • R 5 is cyano or halogen
  • X is halogen.
  • R 1 is C1-C3alkyl
  • R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl
  • R 3 is hydrogen, methyl, or ethyl
  • R 4 is hydrogen or halogen
  • X is halogen.
  • R 1 is C1-C3alkyl; R 2 is 3,4-dichlorophenyl; R 3 is hydrogen or ethyl; 82965-FF 8 R 4 is hydrogen; and X is chloro, fluoro, or iodo.
  • R 1 is ethyl; R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl; R 3 is hydrogen, methyl, or ethyl; R 4 is hydrogen or halogen; and X is halogen.
  • R 1 is ethyl
  • R 2 is 3-chloro-4-cyanophenyl or 3,4-dichlorophenyl
  • R 3 is hydrogen
  • R 4 is hydrogen
  • X is chloro
  • the compound of Formula (I) is selected from 6-chloro-2-(3,4- dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 2), and 6-chloro-2-(4-chloro-3- cyano-phenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 6).
  • a compound of Formula (I) wherein R 3 is hydrogen may be prepared by hydrolysis of a compound of Formula (A) where R 3 is C1-C6alkyl, with a suitable base (such as sodium hydroxide or lithium hydroxide), or with a suitable Bronsted acid (such as trifluoroacetic acid, hydrochloric acid, or sulfuric acid), or with a suitable Lewis acid (such as scandium triflate or zinc triflate) in a suitable solvent (such as dichloromethane, chloroform, ethyl acetate or tetrahydrofuran) with an optional co-solvent (such as 82965-FF 9 water).
  • a suitable base such as sodium hydroxide or lithium hydroxide
  • a suitable Bronsted acid such as trifluoroacetic acid, hydrochloric acid, or sulfuric acid
  • a suitable Lewis acid such as scandium triflate or zinc triflate
  • a suitable solvent such as dichloromethane, chloroform, ethyl
  • a compound of Formula (B) wherein R 3 is C1-C6alkyl and X is chloride may be converted to a compound of Formula (A) wherein R 3 is C1-C6alkyl and X is bromide or fluoride by a halogen exchange reaction with a suitable halide source (such as trimethylsilyl bromide or tetramethylammonium;fluoride) in analogy to literature conditions.
  • a suitable halide source such as trimethylsilyl bromide or tetramethylammonium;fluoride
  • a suitable solvent such as dimethylformamide or dichloromethane
  • reaction is performed by the reaction of a compound of Formula (C) in the presence of a suitable oxidant (such as sodium nitrite or isoamyl nitrite), with a suitable halogen source (such as copper (I) chloride) with a suitable acid (such as hydrogen chloride) in a suitable solvent (such as acetonitrile or dichloromethane) with an optional co-solvent (such as water) at elevated temperature.
  • a suitable oxidant such as sodium nitrite or isoamyl nitrite
  • a suitable halogen source such as copper (I) chloride
  • a suitable acid such as hydrogen chloride
  • a suitable solvent such as acetonitrile or dichloromethane
  • an optional co-solvent such as water
  • a compound of Formula (A) may be prepared by the decarboxylation and subsequent halogenation of compounds of Formula (G) with a halogenating agent (such as iodine) optionally in the presence of base (such as potassium phosphate) in a suitable solvent (such as dimethyl sulfoxide or acetonitrile) at elevated temperatures.
  • a halogenating agent such as iodine
  • base such as potassium phosphate
  • suitable solvent such as dimethyl sulfoxide or acetonitrile
  • a compound of Formula (G) may be prepared by the oxidation of compounds of Formula (H) where R is an aldehyde or alcohol, for example via a Pinnick oxidation, with a suitable oxidising agent (such as sodium chlorite) in the presence of base (such as monosodium phosphate) in a suitable solvent (such as tert-butanol or 2-methylbut-2-ene), and optionally in the presence of water.
  • a suitable oxidising agent such as sodium chlorite
  • base such as monosodium phosphate
  • a suitable solvent such as tert-butanol or 2-methylbut-2-ene
  • Scheme 8 Compounds of Formula (i) where R is an aldehyde, alcohol or carboxylic acid may be prepared by treatment of compounds of Formula (J), with a suitable oxidising agent (such as 4-methyl-4-oxido- morpholin-4-ium), and optionally in the presence of base (such as N-ethyl-N-isopropyl-propan-2-amine) in a suitable solvent (such as acetonitrile). This is shown above in Scheme 8.
  • Scheme 9 Compounds of Formula (J) may be prepared by reacting a compound of Formula (K), with a compound of Formula (E), optionally in the presence of a solvent (such as xylene), at an elevated temperature (for 82965-FF 12 example 140 °C).
  • amine salts may be reacted with compounds of Formula (M) in a suitable solvent (such as toluene or tetrahydrofuran) in the presence of an acid (such as acetic acid) and a drying agent (such as 4 ⁇ molecular sieves).
  • a suitable solvent such as toluene or tetrahydrofuran
  • an acid such as acetic acid
  • a drying agent such as 4 ⁇ molecular sieves
  • Scheme 11 Formula (O) Formula (N) Formula (M)
  • Compounds of Formula (M) may be prepared by treatment of carboxylic acids of Formula (O), wherein A is hydroxy or Cl, with an optional coupling agent (such as 1,1'-carbonyldiimidazole) in a suitable solvent (such as tetrahydrofuran) at ambient temperature.
  • an optional coupling agent such as 1,1'-carbonyldiimidazole
  • a suitable solvent such as tetrahydrofuran
  • the intermediate can subsequently be reacted with compounds of Formula (N) (such as potassium 3-methoxy-3-oxopropanoate) in the presence of an inorganic salt (such as magnesium chloride) in a suitable solvent (such as tetrahydrofuran or acetonitrile) at elevated temperatures.
  • an inorganic salt such as magnesium chloride
  • suitable solvent such as tetrahydrofuran or acetonitrile
  • the present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I). Moreover, the present invention may further provide a method of selectively controlling weeds at a locus comprising useful (crop) plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention.
  • Controlling means killing, reducing or retarding growth or preventing or reducing germination.
  • the compounds of the present invention show a much improved selectivity compared to know, structurally similar compounds.
  • the plants to be controlled are unwanted plants (weeds).
  • Locus means the area in which the plants are growing or will grow. The application may be applied to the locus pre-emergence and/or postemergence of the crop plant. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I).
  • 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- or post-emergence; seed dressing; 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 2500 g/ha, especially from 25 to 1000 g/ha, more especially from 25 to 250 g/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 is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as, for example, 4- Hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyrovyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen-oxidase (PPO) inhibitors as a result of conventional methods of breeding or genetic engineering.
  • HPPD 4- Hydroxyphenylpyruvate dioxygenase
  • ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
  • 5-enol-pyrovyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors glutamine syntheta
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I ⁇ and LibertyLink®.
  • useful plants is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard ⁇ (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm ⁇ (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus ⁇ (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink ⁇ (maize variety that expresses a Cry9(c) toxin); Herculex I ⁇ (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ⁇ (cotton variety that expresses a CryIA(c) toxin); Bollgard I ⁇ (cotton variety that expresses a CryIA(c) toxin); Bollgard
  • 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.
  • Crop plants 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.
  • the compounds of Formula (I) can be used to control unwanted plants (collectively, ‘weeds’).
  • the weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
  • monocotyledonous species for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Sci
  • Compounds of Formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation to provide herbicidal compositions, using formulation adjuvants, such as carriers, solvents and surface-active agents (SAA).
  • formulation adjuvants such as carriers, solvents and surface-active agents (SAA).
  • SAA surface-active agents
  • the invention therefore further provides a herbicidal composition, comprising at least one compound Formula (I) and an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art.
  • 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 compositions can be chosen from a number of formulation types.
  • emulsion concentrate EC
  • SC suspension concentrate
  • SE suspo-emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • EG emulsifiable granule
  • EO oil in oil
  • EW oil in water
  • ME micro-emulsion
  • OD oil dispersion
  • OF oil miscible flowable
  • OLED oil miscible liquid
  • SL soluble concentrate
  • SU ultra-low volume suspension
  • UL ultra-low volume liquid
  • TK technical concentrate
  • TK dispersible concentrate
  • DC soluble powder
  • SP soluble powder
  • WP wettable powder
  • SG soluble granule
  • Soluble powders may be prepared by mixing a compound of Formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • Dispersible Concentrates may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-C10 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cyclo
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SAAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of Formula (I) is present initially in either the water or the solvent/SAA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • 82965-FF 16 Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I). SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane).
  • a compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non- pressurised, hand-actuated spray pumps.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment.
  • a compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • the composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I).
  • additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).
  • SAAs surface active agents
  • spray additives based on oils for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).
  • SAAs of the cationic, anionic, ampho
  • Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid
  • Suitable SAAs of the amphoteric type include betaines, propionates and glycinates. 82965-FF 17 Suitable SAAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite.
  • the compounds of the present invention can also be used in mixture with one or more additional herbicides and/or plant growth regulators.
  • herbicides or plant growth regulators examples include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac-sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron- ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop (
  • 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, Sixteenth Edition, British Crop Protection Council, 2012.
  • 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).
  • the compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners.
  • safeners examples include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr- diethyl), metcamifen and oxabetrinil.
  • Particularly preferred are mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen.
  • 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, 16 th Edition (BCPC), 2012.
  • 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.
  • 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 compounds of Formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
  • Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion.
  • plant propagation material is understood to denote seeds.
  • Pesticidal agents referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
  • the compounds of formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation.
  • compositions may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants e.g., for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of Formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be, e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation. 82965-FF 20
  • the compound of Formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.
  • Table A-2 provides 26 compounds A-2.001 to A.2.026 of Formula (I) wherein R 1 is ethyl, X is bromo, R 3 and R 4 are both hydrogen, and R 2 is defined in Table 1.
  • Table A-3 provides 26 compounds A-3.001 to A.3.026 of Formula (I) wherein R 1 is ethyl, X is chloro, R 3 is hydrogen, R 4 is bromo, and R 2 is defined in Table 1.
  • Table A-4 provides 26 compounds A-4.001 to A.4.026 of Formula (I) wherein R 1 is ethyl, X is chloro, R 3 is ethyl, R 4 is hydrogen, and R 2 is defined in Table 1.
  • Table A-5 provides 26 compounds A-5.001 to A.5.026 of Formula (I) wherein R 1 is ethyl, X is chloro, R 3 is methyl, R 4 is hydrogen, and R 2 is defined in Table 1.
  • 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 water to 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 %
  • 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.
  • 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 % 82965-FF 23 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.
  • 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. Examples The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in Table 2 below. 82965-FF 24 Throughout this description, temperatures are given in degrees Celsius (°C) and “m.p.” means melting point.
  • Example 1 Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3- carboxylate (Compound 1)
  • Step 1 Synthesis of ethyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate
  • 1-(3,4-dichlorophenyl)ethanone 5.00 g, 26.5 mmol
  • dimethyl carbonate 40 mL, 466 mmol
  • reaction mixture Overnight the reaction mixture became a solid paste which was not possible to stir. More dimethyl carbonate (10 mL) was added in an attempt to create a mobile slurry for quenching.
  • the reaction mixture was cooled to 0 °C and quenched by addition of water (25 mL).
  • the reaction mixture was acidified to pH3 by addition of 2M aqueous hydrochloric acid and then extracted into ethyl acetate. The organic extract was dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure.
  • Step 2 Synthesis of ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate
  • ethyl 3-(3,4-dichlorophenyl)-3-oxo-propanoate (1.65 g, 6.32 mmol) in toluene (11 mL)
  • ethylammonium;acetate (19.0 mmol) and acetic acid (6.32 mmol) The orange 82965-FF 25 reaction mixture was heated at reflux for 6 hours.
  • the cooled reaction mixture was diluted with ethyl acetate and was washed with saturated aqueous sodium bicarbonate solution.
  • Step 3 Synthesis of ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo- butanoate
  • ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (5.10 g, 17.7 mmol) and 2- cyanoacetic acid (1.51 g, 17.7 mmol) in acetic anhydride (16 mL) was heated with stirring at 105 oC for 0.25 hours. The cooled reaction mixture was evaporated to dryness under reduced pressure. To the residue was added water (20 mL).
  • Step 4 Synthesis of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate
  • ethyl (2E)-4-cyano-2-[(3,4-dichlorophenyl)-(ethylamino)methylene]-3-oxo- butanoate (4.50 g, 12.67 mmol) in ethanol (80 mL) at 0 oC was added sodium ethoxide (4.11 g, 12.7 mmol).
  • the reaction mixture was heated at 50 oC for 2 hours.
  • Step 5 Synthesis of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate To a suspension of ethyl 6-amino-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (0.500 g, 1.41 mmol) in a mixture of acetonitrile (12 mL) and aqueous hydrogen chloride solution (2M, 1.8 mL) was added copper (I) chloride (0.167 g, 1.69 mmol).
  • the resultant reaction mixture was heated to 75 oC after which a solution of sodium nitrite (0.126 g, 1.83 mmol) water (1 mL) was added dropwise. The reaction mixture was heated with stirring at 75 oC for 0.25 hours. The cooled reaction mixture was poured into saturated aqueous ammonium chloride solution (30 mL) and extracted into ethyl acetate (2 x 50 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness under reduced pressure.
  • Example 2 Synthesis of 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 2)
  • Compound 2 A mixture of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (0.200 g, 0.53 mmol) and tris(trifluoromethylsulfonyloxy)scandium (0.276 g, 0.56 mmol) in water (2 mL) and tetrahydrofuran (2 mL) was heated under microwave irradiation at 120 oC for 0.5 hours.
  • Example 3 Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3- carboxylate (Compound 3) 82965-FF 27
  • Step 1 Synthesis of 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one
  • a stirring solution of 2,2,6-trimethyl-1,3-dioxin-4-one (4.88 g, 34.3 mmol) and N-bromosuccinimide (7.94 g, 44.6 mmol) in dichloromethane (120 mL) was irradiated with 450 nm light for 12 hours at room temperature.
  • Step 2 Synthesis of ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3- carboxylate
  • ethyl (Z)-3-(3,4-dichlorophenyl)-3-(ethylamino)prop-2-enoate (2.00 g, 6.94 mmol) in xylene (20.0 mL) was added 6-(bromomethyl)-2,2-dimethyl-1,3-dioxin-4-one (2.30 g, 10.4 mmol).
  • the resultant reaction mixture was heated with stirring at 140 °C for 5 minutes.
  • Step 3 Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate To a stirring solution of ethyl 6-(bromomethyl)-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3- carboxylate (6.99 g, 16.1 mmol) and N-ethyl-N-isopropyl-propan-2-amine (3.67 mL, 21.0 mmol) in acetonitrile (140 mL) at 0 °C was added 4-methyl-4-oxido-morpholin-4-ium (2.92 g, 24.2 mmol) portion- wise.
  • reaction mixture was stirred at 25 °C for 2.5 hours.
  • the reaction mixture was diluted with water and ethyl acetate and the phases were separated.
  • the organic phase was washed with brine, dried over magnesium sulfate and evaporated to dryness under reduced pressure to give ethyl 2-(3,4- dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate a yellow solid.
  • Step 4 Synthesis of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-2- carboxylic acid
  • ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-formyl-4-oxo-pyridine-3-carboxylate 5.67 g, 15.4 mmol
  • tert-butanol 77 mL
  • 2-methylbut-2-ene 77 mL
  • the reaction mixture was cooled to 0 °C and sodium chlorite (4.22 g, 46.2 mmol) was added portion-wise.
  • the reaction mixture was warmed to room temperature and stirred for 2.5 hours.
  • the resultant yellow solution was diluted with brine, methanol and 2M aqueous hydrochloric acid before extraction into ethyl acetate.
  • the organic extract was extracted into saturated sodium metabisulfite solution.
  • the aqueous phase was acidified to pH 1 by addition of 2M aqueous hydrochloric acid and extracted into dichloromethane.
  • Step 5 Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-iodo-4-oxo-pyridine-3-carboxylate To a stirring solution of 6-(3,4-dichlorophenyl)-5-ethoxycarbonyl-1-ethyl-4-oxo-pyridine-2-carboxylic acid (1.42 g, 3.69 mmol) in methylsulfinylmethane (37 mL) was added iodine (0.281 g, 1.11 mmol). The reaction mixture was heated at 120 °C for 1.5 hours before being quenched with saturated sodium thiosulfate solution and extracted into dichloromethane.
  • Example 4 Synthesis of ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-fluoro-4-oxo-pyridine-3- carboxylate (Compound 7)
  • Compound 7 A suspension of ethyl 6-chloro-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (0.600 g, 1.60 mmol) and tetramethylammonium;fluoride (0.448 g, 4.80 mmol) in N,N-dimethylformamide (8 mL) was heated with stirring at 40 °C for 40 hours.
  • the cooled reaction mixture was diluted with ethyl acetate and washed sequentially with water and brine.
  • the organic extract was dried over anhydrous sodium sulfate, filtered and evaporated to dryness under reduced pressure.
  • the crude product was purified by flash chromatography on C-18 silica to give ethyl 2-(3,4-dichlorophenyl)-1-ethyl-6-fluoro-4-oxo-pyridine- 3-carboxylate as a white solid.
  • Example 6 Synthesis of 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylic acid (Compound 8) Ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (40 mg, 0.10 mmol) and scandium triflate (49 mg, 0.10 mmol) were dissolved in a mixture of tetrahydrofuran (0.3 mL) and water (0.3 mL). The reaction mixture was then heated to 120 degrees for 45 minutes. The reaction mixture was then diluted with water and 2 M HCl solution and then extracted with dichloromethane.
  • Compound 8 Ethyl 6-bromo-2-(3,4-dichlorophenyl)-1-ethyl-4-oxo-pyridine-3-carboxylate (40 mg, 0.10 mmol) and scandium triflate (49 mg, 0.
  • the plants After 8 days cultivation under controlled conditions in a glasshouse (at 24 °C /16 °C, day/night; 14 hours light; 65 % humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 250 g/ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24 °C/16 °C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test is evaluated for the percentage damage caused to the plant.

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  • Life Sciences & Earth Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne des composés de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1. L'invention concerne en outre des compositions herbicides qui comprennent un composé de formule (I) et l'utilisation de composés de formule (I) pour lutter contre les mauvaises herbes, en particulier dans des cultures de plantes utiles.
EP24721604.7A 2023-04-27 2024-04-23 Dérivés herbicides Pending EP4702009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23170466 2023-04-27
PCT/EP2024/060993 WO2024223510A1 (fr) 2023-04-27 2024-04-23 Dérivés herbicides

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EP4702009A1 true EP4702009A1 (fr) 2026-03-04

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EP (1) EP4702009A1 (fr)
KR (1) KR20260004377A (fr)
CN (1) CN121001990A (fr)
AR (1) AR132501A1 (fr)
AU (1) AU2024263972A1 (fr)
CL (1) CL2025003194A1 (fr)
IL (1) IL323815A (fr)
MX (1) MX2025011982A (fr)
PY (1) PY2430925A (fr)
UY (1) UY40723A (fr)
WO (1) WO2024223510A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA813029B (en) 1980-05-12 1982-05-26 Rohm & Haas Novel substituted oxonicotinates,their use as plant growth regulators and plant growth regulating compositions containing them
CA1236700A (fr) 1983-04-26 1988-05-17 Samuel E. Sherba Angiospermes haploides et diploides
US4844732A (en) 1985-10-24 1989-07-04 Daicel Chemical Industries Ltd. Pyridine-3-carboxamide derivatives
CA1317599C (fr) 1986-03-26 1993-05-11 Yukio Nezu Derives, 1,2,6-triphenyl-4(1h)pyridinone, leur production et leur utilisation
PT888359E (pt) 1996-03-11 2002-10-31 Syngenta Participations Ag Derivados de pirimidin-4-ona como pesticida
GB9718375D0 (en) 1997-08-29 1997-11-05 Zeneca Ltd Herbicidal method
AR031027A1 (es) 2000-10-23 2003-09-03 Syngenta Participations Ag Composiciones agroquimicas
GB202018994D0 (en) 2020-12-02 2021-01-13 Syngenta Crop Protection Ag Herbicidal derivatives
GB202018996D0 (en) 2020-12-02 2021-01-13 Syngenta Crop Protection Ag Herbicidal derivatives
MX2024007176A (es) 2021-12-17 2024-06-26 Syngenta Crop Protection Ag Derivados herbicidas de piridona.

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MX2025011982A (es) 2025-11-03
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PY2430925A (es) 2025-01-23
AU2024263972A1 (en) 2025-09-18
KR20260004377A (ko) 2026-01-08
WO2024223510A1 (fr) 2024-10-31
CN121001990A (zh) 2025-11-21
UY40723A (es) 2024-11-29
CL2025003194A1 (es) 2026-01-16

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