WO2014154829A1 - Herbicidal compounds - Google Patents

Herbicidal compounds Download PDF

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Publication number
WO2014154829A1
WO2014154829A1 PCT/EP2014/056213 EP2014056213W WO2014154829A1 WO 2014154829 A1 WO2014154829 A1 WO 2014154829A1 EP 2014056213 W EP2014056213 W EP 2014056213W WO 2014154829 A1 WO2014154829 A1 WO 2014154829A1
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WIPO (PCT)
Prior art keywords
alkyl
alkoxy
group
cealkyl
aryl
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PCT/EP2014/056213
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French (fr)
Inventor
Steven GAULIER
William Guy Whittingham
Gordon Richard Munns
Glynn Mitchell
Paula Rocha RZEPA
Russell Colin Viner
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Syngenta Limited
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Publication of WO2014154829A1 publication Critical patent/WO2014154829A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel herbicidal triazinones, to processes for their preparation, to herbicidal compositions which comprise the novel compounds, and to their use for controlling weeds, in particular in crops of useful plants.
  • Herbicidal triazinones are known, for example, from WO 94/03454 and WOOO/08000.
  • the present invention provides improved herbicidal triazinones, which are characterised as having, for example, a N-hydroxy substituent.
  • R 1 is selected from the group consisting of hydrogen, Ci-C 6 alkyl, C 3 - C 6 cycloalkyl, C2-C 6 alkenyl, C2-C 6 alkynyl, Ci-C 6 haloalkyl, Ci-Cealkoxy-Ci- C 3 -alkyl and C 3 -C 6 CycloalkylCi-C 3 -alkyl-; selected from the group consisting of Al, A2, A3, A4 and A5
  • X 1 is N or CR 7 ;
  • X 2 is N or CR 8 ;
  • X 3 is N or CR 9 ;
  • X 4 is N or CR 6 ;
  • R 4 is selected from the group consisting of hydrogen, Ci-C 6 alkyl, Ci- C 6 cycloalkyl, Ci-Cehaloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, Ci-Cealkylcarbonyl-, aryl, arylcarbonyl-, Ci-Cealkoxycarbonyl-, Ci- C 6 alkoxycarbonyl-oxy-Ci-C 6 alkyl-, Ci-C 6 alkyl-S(0) p -, Ci-Cealkyl- S(0) p carbonyl- and aryl-S(0) p , wherein said aryl groups may be optionally substituted by one or more R 11 ;
  • R 5 is selected from the group consisting of hydroxyl, halogen, Ci-Cealkyl, Ci- C 6 cycloalkyl, Ci-Cehaloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, Ci-C 6 alkoxy-, C 2 -C6alkenyloxy-, C3-C6CycloalkylCi-C3-alkyl-, Ci-C 6 alkoxyCi-Csalkyl-, Ci-C 6 alkoxy-C 2 -Cealkoxy-, Ci-C 6 alkoxy-C 2 -Cealkoxy-, Ci-C 6 alkoxy-C 2 -Cealkoxy- Ci-C3alkyl-,Ci-C6 haloalkoxy-, Ci-C 6 haloalkoxy-Ci-C3alkyl-, Ci-Cealkyl- S(0)
  • R 6 and R 9 are independently selected from the group consisting of hydrogen, hydroxyl, halogen, Ci-Cealkyl, Ci-Cecycloalkyl, Ci-Cehaloalkyl, C 2 -Cealkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, Ci-C 6 alkoxy-, C 2 -C6 alkenyloxy-, C3- C6CycloalkylCi-C3-alkyl-, Ci-C 6 alkoxyCi-C3alkyl-, Ci-C 6 alkoxy-C 2 - C 6 alkoxy-, Ci-C 6 alkoxy-C2-C6alkoxy-Ci-C3alkyl-,Ci-C6 haloalkoxy-, Ci-C 6 haloalkoxy-Ci-C3alkyl-, Ci-C6alkyl-S(0) p -, Ci-C6haloalkyl-
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, halogen, C 1 -C3 alkyl-, C 1 -C3 alkoxy-, C 2 -C3alkenyl-, C 2 -C3alkynyl-, C 1 -C3 haloalkyl- and Ci-C3haloalkoxy-; and wherein R 5 and R 9 can together form a saturated or unsaturated 5- or 6- membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more nitrogen and/or oxygen heteroatoms, the 5- or 6-membered ring being optionally substituted by one or more R 12 ; or
  • R 6 and R 9 can together form a saturated or unsaturated 5- or 6-membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more heteroatoms selected from the group consisting of nitrogen, oxygen and S(0) 2 , the 5- or 6-membered ring being optionally substituted by one or more R 12 ; or
  • R 6 and R 8 can together form a saturated or unsaturated 5- or 6-membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more nitrogen heteroatoms, the 5- or 6-membered ring being optionally substituted by one or more R 13 ;
  • R 11 is selected from the group consisting of halo-, Ci-C3alkyl, C 1 -C3 haloalkyl and Ci-C 6 alkoxy;
  • R 12 is selected from the group of hydrogen, cyano, halo-, oxy-, Ci- C 3 alkylS(0)p-, d-C 3 alkyl, C 3 -C 6 cycloalkyl-, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, Ci-C 3 alkoxy and Ci-C 3 haloalkyl;
  • R 13 is selected from the group of hydrogen, cyano, halo-, Ci-C 3 alkylS(0)p-, Ci-C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, morpholinyl- and Ci-C 3 haloalkyl;
  • R 14 is selected from the group consisting of hydrogen, Ci-Cealkyl, Ci-
  • Ci-Cealkoxy-Ci-Cealkyl Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-
  • Alkyl groups having a chain length of from 1 to 6 carbon atoms include, for example, methyl (Me, CH 3 ), ethyl (Et, C 2 H 5 ), n-propyl (n-Pr), isopropyl (z-Pr), n- butyl (ft-Bu), isobutyl (z ' -Bu), sec-butyl and tert-butyl (t-Bu).
  • Alkynyl groups having a chain length of from 2 to 6 carbon atoms include, for example, -C ⁇ CH (ethynyl) and -CH 2 -C ⁇ CH (propargyl).
  • Cycloalkyl groups include c-propyl (c-Pr), c-butyl (c-Bu), c-pentyl and c- hexyl.
  • Halogen encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl or halophenyl.
  • Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3, 3-tetrafluoroethyl and 2,2,2- trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.
  • Haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine and especially fluorine or chlorine, for example 2,2-difluoro-l-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4- trifluorobut-2-en-l-yl.
  • Preferred C 2 -C 6 alkenyl radicals substituted once, twice or three times by halogen are those having a chain length of from 2 to 5 carbon atoms.
  • Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy.
  • Alkylcarbonyl is preferably acetyl or propionyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl, ethoxycarbonyl or tert -butoxycarbonyl.
  • two alkoxy substituents present on the same carbon atom may be joined to form a spiro group.
  • the methyl groups present in two methoxy substituents may be joined to form a spiro 1,3 dioxolane substituent, for example. Such a possibility is within the scope of the present invention.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
  • Alkylthio (alkyl- ⁇ * -) groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
  • Alkylsulfmyl (alkyl-SO-) is, for example, methylsulfmyl, ethylsulfmyl, propylsulfmyl, isopropylsulfmyl, n-butylsulfinyl, isobutylsulfmyl, sec-butylsulfmyl or tert-butylsulfinyl, preferably methylsulfmyl or ethylsulfmyl.
  • Alkylsulfonyl (alkyl-S(0) 2 -) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
  • Alkylamino (alkyl-NH-) is, for example, methylamino, ethylamino, n- propylamino, isopropylamino or a butylamino isomer.
  • Dialkylamino ((alkyl) 2 -N-) is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino.
  • Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms.
  • Cyclo alkylamino- or dicycloalkylamino- is for example cyclohexylamino or dicyclopropylamino.
  • Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxy ethyl.
  • Alkylthioalkyl (alkyl-S-alkyl) groups preferably have from 1 to 6 carbon atoms.
  • Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthio methyl, ethylthio ethyl, n-propylthio methyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthio butyl.
  • Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms and may be substituted by one or more methyl groups; they are preferably unsubstituted, for example cyclopropyl (c-Pr), cyclobutyl (c-Bu), cyclopentyl (c-pentyl) or cyclohexyl (c-hexyl).
  • Aryl includes benzyl, phenyl, including phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl, may be in mono- or poly-substituted form, in which case the substituents may, as desired, be in the ortho-, meta- and/or para-position(s).
  • the term also includes, for example, naphthalenyl.
  • Heterocyclyl includes, for example, morpholinyl, tetrahydrofuryl, isoxazolinyl, and heteroaryl.
  • Heteroaryl including heteroaryl as part of a substituent such as heteroaryloxy, means, for example, a five to ten (preferably five or six) member heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur.
  • heteroaryl thus includes, for example, benzofuranyl, benzimidazolyl, indolyl, isobenzofuranyl, furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, pyridonyl, triazolyl, napthyridinyl and napthyridinonyl.
  • the heteroaryl component may be optionally mono or poly substituted as previously defined.
  • R 1 is selected from the group consisting of Ci-C 4 alkyl (especially methyl or z ' so-propyl), cyclopropyl, methoxymethyl, trifluoromethyl, cyclopropylmethyl-, vinyl and propargyl with methyl being particularly preferred.
  • R 2 is selected from the group consisting of Al , A2, A3 and A4.
  • R 2 is selected from the group consisting of Ala, Alb, Ale, Aid, Ale, Alf, Alg, Alh, A2a, A2b, A3a, A3b and A3c:
  • R J , R , R', R°, R R 1Z and R 1J are as defined previously and n is 0, 1 ,
  • R 2 is selected from the group consisting of phenyl (e.g. Ala), 3-pyridyl (e.g. Ale), N-pyridonyl (e.g. A2a) and 3-linked [l,8]naphthyridinyl (e.g. Aid). Even more preferably R 2 is phenyl (e.g. Ala).
  • R 4 is preferably selected from the group consisting of hydrogen, Ci- Cealkylcarbonyl-, arylcarbonyl-, Ci-C 6 alkoxycarbonyl-, Ci-C 6 alkyl-S(0) p -, Ci-C 6 alkyl-S(0) p Carbonyl- and aryl-S(0) p - , wherein said aryl groups may be optionally substituted by one or more R 11 ;
  • R 4 is more preferably H.
  • R 5 is preferably selected from the group consisting of hydroxyl, halo, Ci- C 6 alkyl, Ci-C 6 Cycloalkyl, Ci-C 6 haloalkyl, Ci-C 6 alkenyl, Ci-C 6 alkynyl, Ci-C 6 alkoxy, Ci-C 6 alkoxyCi-C 3 alkyl, Ci-C 6 alkoxy-C 2 -Cealkoxy, Ci-C 6 alkoxy-C 2 -C 6 alkoxy-Ci- C 3 alkyl, Ci-C 6 haloalkoxy, Ci-C 6 haloalkoxy-Ci-C 3 alkyl, Ci-C 6 alkyl-S(0) p -, d- C 6 haloalkyl-S(0) p -, aryl, aryloxy, heterocyclyl, heterocyclyl-Ci-C 3 alkoxy-Ci-C 3 alkyl, Ci-C 3 al
  • aryl and "heterocyclyl” are further defined above.
  • phenyl, benzyl, isoxazolinyl (e.g 4,5-dihydro-l,2-oxazol-3-yl), pyrimidinyl, morpholinyl, furyl and thiophenyl are particularly preferred.
  • R 5 is selected from the group consisting of chloro, fluoro, bromo, methyl, trifluoromethyl, 2-fluoroethyl-, methoxymethyl, methoxyethoxymethyl-, trifluoromethoxymethyl-, methylS(0) p -, aryl, isoxazolinyl, morpholinyl, methyl-S(0) p -dimethylamino-, cyano and nitro, wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of chloro, methyl and trifluoromethyl.
  • R 5 is selected from the group consisting of halogen, Ci- C 6 alkyl, Ci-C 6 haloalkyl, Ci-C 6 alkoxyCi-C 3 alkyl, Ci-C 6 alkoxy-C 2 -Cealkoxy-Ci- C 3 alkyl, Ci-C 6 alkyl-S(0) p - and nitro.
  • R 5 is selected from the group consisting of chloro, fluoro, bromo, methyl, methoxymethyl-, methoxyethoxymethyl-, methylS(0) p - and nitro.
  • R 6 is selected from the group consisting of hydrogen, halogen, Ci-
  • R 6 is selected from the group consisting of hydrogen, halogen (especially chlorine), Ci-Cealkyl (especially methyl), Ci-Cehaloalkyl (e.g trifluoromethyl-), Ci- C 6 alkyl-S(0) p - (e.g -S(0) 2 Me), C 2 -C 6 alkenyl, C 2 -C 6 alkynyl and cyano.
  • R 7 is selected from the group consisting of hydrogen, halogen and Ci-C 3 alkyl-, most preferably hydrogen.
  • R is selected from the group consisting of hydrogen, halogen and Ci-C 3 alkyl-, most preferably hydrogen.
  • R 9 is selected from the group consisting of hydrogen, halogen, Ci- Cealkyl, Ci-C 6 haloalkyl, Ci-C 6 alkyl-S(0) p -, Ci-C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 - C 6 haloalkenyl, C 2 -C6alkynyl, Ci-C 6 alkoxy-, Ci-C 6 haloalkoxy, Ci-Cehaloalkoxy-Ci- C 3 alkyl-, C 2 -C 6 alkenyloxy-, C 3 -C 6 CycloalkylCi-C 3 -alkyl-, Ci-C 6 alkoxyCi-C 3 alkyl-, Ci-C 6 alkoxy-C 2 -C6alkoxy-, nitro, isoxazolinyl, and phenyl wherein the phenyl may be optionally substituted by one or more substituents selected from the group consist
  • R 9 is selected from the group consisting of hydrogen, isoxazolinyl, Ci-C 6 haloalkoxy-Ci-C 3 alkyl- (e.g 2,2,2trifluoroethyloxymethyl-) and Ci-C 6 alkoxy-C 2 -C 6 alkoxy-Ci-C 3 alkyl- (e.g methoxyethoxymethyl-).
  • R 14 is selected from the group consisting of hydrogen, methyl and halogen.
  • Compounds of Formula I or II may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities.
  • compounds of Formula I or II may be in equilibrium with alternative hydroxyl tautomeric forms. It should be appreciated that all tautomeric forms (single tautomer or mixtures thereof), racemic mixtures and single isomers are included within the scope of the present invention.
  • the present invention also includes agronomically acceptable salts that the compounds of Formula I may form with amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • amines for example ammonia, dimethylamine and triethylamine
  • alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali metal and alkaline earth metal hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as salt formers emphasis is to be given to the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium, magnesium and calcium.
  • the corresponding trimethylsulfonium salt may also be used.
  • the compounds of Formula (I) or (II) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surface- active agents (SFAs).
  • formulation adjuvants such as carriers, solvents and surface- active agents (SFAs).
  • the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.
  • the composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • 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.
  • compositions can be chosen from a number of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).
  • Dustable powders may be prepared by mixing a compound of Formula (I) or (II) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of Formula (I) or (II) 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). Wettable powders (WP) may be prepared by mixing a compound of Formula (I) or (II) 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 dispers
  • Granules may be formed either by granulating a mixture of a compound of Formula (I) or (II) 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 (II) (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).
  • DC Dispersible Concentrates
  • a compound of Formula (I) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • 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 C 8 - Cio fatty acid dimethylamide) and chlorinated hydrocarbons.
  • 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) or (II) 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 SFAs, 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 may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of Formula (I) is present initially in either the water or the solvent/SFA 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.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I) or (II).
  • SCs may be prepared by ball or bead milling the solid compound of Formula (I) or (II) 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) or (II) 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) or (II) and a suitable propellant (for example n-butane).
  • a compound of Formula (I) or (II) 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) or (II) and they may be used for seed treatment.
  • a compound of Formula (I) or (II) 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) or (II).
  • additives include surface active agents (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I)) ⁇
  • Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs 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-z ' sopropyl- and tri-z ' sopropyl-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
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs 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); and lecithins.
  • 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
  • composition of the present may further comprise at least one additional pesticide.
  • additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures are (in which T represents a compound of Formula I or II).
  • the mixing partners of the compound of Formula (I) or (II) 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) or (II) 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) or (II) to the mixing partner is preferably from 1 : 100 to 1000: 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) or (II) with the mixing partner).
  • the compounds of Formula (I) or (II) according to the invention can also be used in combination with one or more safeners.
  • mixtures of a compound of Formula (I) or (II) according to the invention with one or more further herbicides can also be used in combination with one or more safeners.
  • the safeners can be AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31- 8), dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, N-isopropyl- 4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4).
  • Other possibilities include safener compounds disclosed in, for example, EP0365484 e.g N- (2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
  • the safeners of the compound of Formula (I) or (II) 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) or (II) 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) or (II) with the safener).
  • the present invention still further provides a method of selectively controlling weeds at a locus comprising 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 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) or (II) 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) or (II) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 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.
  • 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.
  • crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.
  • Maize, wheat and barley are particularly preferred.
  • 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 crop plant is rendered tolerant to HPPD- inhibitors via genetic engineering.
  • Methods of rending crop plants tolerant to HPPD- inhibitors are known, for example from WO0246387.
  • the crop plant is transgenic in respect of a polynucleotide comprising a DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more particularly, from a barley, maize, wheat, rice, Brachiaria, Chenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species.
  • 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.
  • turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod
  • ornamental plants such as flowers or bushes.
  • the compositions 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.
  • Weeds can also include plants which may be considered crop plants but which are growing outside a crop area ('escapes'), or which grow from seed left over from a previous planting of a different crop ('volunteers'). Such volunteers or escapes may be tolerant to certain other herbicides.
  • the compounds of the present invention can be prepared using the following schemes.
  • Example 1 4-Hvdroxy-6-isopropyl-3- [2-methylsulfonyl-4-f trifluoromethyl)- phenyll-l.,2,4-triazin-5-one (Compound 1.028)
  • Step 1 flE)-2-methylsulfonyl-4-ftrifluoromethyl)benzaldehyde oxime.
  • Step 2 flZ)-N-hydroxy-2-methylsulfonyl-4-ftrifluoromethyl)benzimidoyl chloride
  • reaction mixture is diluted with ether and washed with water (x2), passed through a phase separator and reduced under vacuum to give an off yellow solid, (lZ)-N-hydroxy-2-methylsulfonyl-4- (trifluoromethyl)benzimidoyl chloride (1.02g).
  • Steps 3-5 4-hydroxy-6-isopropyl-3-[2-methylsulfonyl-4-trifluoromethyl)phenyll- 1 ,2,4-triazin-5-one
  • ethyl 3-methyl-2-oxo-butanoate (0.96g) and zinc diperchlorate (0.0088g).
  • the reaction mixture is then stirred at room temperature for 30min during which a free flowing suspension is formed.
  • Two portions of ethyl 3- methyl-2-oxo-butanoate (each of 0.96g) are added to the reaction mixture and the precipitate on the sides of the flask washed down with ethanol ( ⁇ 5 ml). All the precipitate dissolved and a clear yellow solution formed.
  • Step 1 flZ)-N-hydroxy-2-methyl-propanimidoyl chloride
  • N,N-dimethylformamide 1.3 mL/mmol, 75 mL
  • N-chlorosuccinimide 8.8g, 66 mmol
  • reaction mixture is diluted with ether and washed with 1 : 1 water: brine (x2), passed through a phase separator and reduced under vacuum to give a colourless oil, (lZ)-N-hydroxy-2-methyl- propanimidoyl chloride (7.66g) that contains approximately 10% diethyl ether.
  • Step 2 N-amino-N'-hvdroxy-2-methyl-propanamidine
  • ⁇ , ⁇ -diethylethanamine 0.5 mL/mmol, 0.93 mL
  • the reaction mixture is cooled to 0°C and (lZ)-N- hydroxy-2-methyl-propanimidoyl chloride (0.25g) in ethanol (0.5 mL/mmol, 0.93 mL) is added via syringe pump over 1.5 hours.
  • the crude product is used directly in the next step.
  • Step 3 6-( 2,4-dichlorophenyl)-4-hvdroxy-3-isopropyl- 1 ,2,4-triazin-5-one
  • zinc diperchlorate (0.73g)
  • methyl 2-(2,4- dichlorophenyl)-2-oxo-acetate (0.45g)
  • the reaction mixture is allowed to warm up to room temperature slowly over 30 minutes.
  • the reaction mixture is then left to stand overnight at room temperature.
  • the reaction mixture is acidified with 1 M HC1, the layers separated and the organic washed with brine, passed through a phase separator and reduced under vacuum to give a yellow oil. This is then purified on the Fraction- lynx to give 6-(2,4-dichlorophenyl)-4-hydroxy-3-isopropyl-l,2,4-triazin-5-one as an off-white foam (0.02g)
  • Step 1 2-tetrahydrothiophen-l-ium-l-ylacetonitrile bromide To tetrahydrothiophene (8.49g) is added 2-bromoacetonitrile (10.5g). The reaction is stirred at room temperature for 16 hours. 150mL diethylether is added and the solid broken with a spatula. The suspension is stirred for 2 hours, occasionally breaking the lumps with a spatula to produce a suspension. The white solid is collected rapidly by filtration and put in a flask to dry on high vacuum for 3 hours. 2-tetrahydrothiophen- 1-ium-l-ylacetonitrile bromide (14.75g).
  • aqueous layer is basified with a diluted solution of NaOH then carefully bleached to destroy any remaining cyanide.
  • the crude product is put onto a silica cartridge, eluting with iso-hexane: ethyl acetate as solvent system. Fractions containing the product were combined and concentrated in vacuo to yield ethyl 2-[2-(methoxymethyl)-6-(trifluoromethyl)-3-pyridyl]-2-oxo- acetate (1.17g) as a translucent oil.
  • the filtrate is concentrated and liquid- loaded onto a silica cartridge using iso-hexane: ethyl acetate as the solvent system.
  • the fractions containing the product are combined, added to the solid previously collected and concentrated in vacuo to yield ethyl (2E)-2-[2-(methoxymethyl)-6-(trifluoromethyl)-3-pyridyl]-2-(2- methylpropanoylhydrazono)acetate (0.430 g, 1.15 mmol, 22.2% yield) as a white solid.
  • NMR indicates the presence of the two regioisomers.
  • Step 5 Ethyl 2-[[l-fhvdroxyamino)-2-methyl-propylidenelhydrazonol-2-[2- fmethoxymethyl)-6-ftrifluoromethyl)-3-pyridyllacetate
  • Ethyl (2E)-2- [2-(methoxymethyl)-6-(trifluoromethyl)-3 -pyridy 1] -2-(2-methyl- propanoylhydrazono)acetate (1.08g) is dissolved in toluene (35mL) and the mixture heated to 100°C. Phosphorus oxychloride (0.552g) is added and the mixture is heated for 3 hours. 0.4eq OPCl ⁇ is added and the mixture stirred for another 3 hours and themixture was concentrated to about 5.0mL.
  • hydroxylamine hydrochloride (1.3g) is suspended in propan-2-ol (5.00 mL). Triethylamine (1.91g) is added followed by the toluene solution of ethyl (2E)-2-[(l -chloro-2-methyl-propylidene)hydrazono]-2-[2-(methoxymethyl)-6-
  • Step 6 4-hvdroxy-3-isopropyl-6- [2-( methoxymethyl)-6-( trifluoromethyl)-3- pyridyll - 1 ,2,4-triazin-5-one
  • Omg is diluted in 1,4-dioxane (7.50 mL) and DBU (0.56g) is then added. The reaction is heated to 90°C for 2h30.
  • the reaction is stopped, and poured into aqueous HC1 (25.0mL).
  • the product is extracted using 2 x 20.0mL ethyl acetate and the organic layers are combined, dried over sodium sulphate, filtered and concentrated in vacuo.
  • the residue is dry-loaded on a stacker of 2 x 24g columns, eluting with a mixture of water:ethanol:dioxane:triethylamine:toluene (0.5:2:4:2: 10).
  • the fractions containing the product are combined and concentrated in vacuo to give a dark orange oil.
  • reaction mixture is diluted with dichloromethane and purified by column chromatography on silica, eluting with ethyl acetate: iso hexane, to give [3-isopropyl-6-[2-methylsulfonyl-4- (trifluoromethyl)phenyl]-5-oxo-l,2,4-triazin-4-yl] benzoate (225 mg, 0.47 mmol, 88 % yield) as a white foamy solid.
  • Alopecurus myosuroides Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solarium nigrum (SOLNI), Amaranthus retoflexus (AMARE), Ipomoea hederacea (IPOHE)).
  • Alopecurus myosuroides Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solarium nigrum (SOLNI), Amaranthus retoflexus (AMARE), Ipomoea hederacea (IPOHE)).
  • the plants After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°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 R 9005-64-5). Compounds are applied at 1000 g/h. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily.

Abstract

The present invention provides a compound of Formula (I) or Formula (II): or an agronomically acceptable salt thereof, wherein :- R2 is selected from the group consisting of A1, A2, A3, A4 and A5 wherein X1 is N or CR7; X2 is N or CR8; X3 is N or CR9; X4 is N or CR6; R1, R4, R5 R6, R7, R8, R9, R12 and R14 are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) or Formula (II), and to their use for controlling weeds, in particular in crops of useful plants.

Description

HERBICIDAL COMPOUNDS
The present invention relates to novel herbicidal triazinones, to processes for their preparation, to herbicidal compositions which comprise the novel compounds, and to their use for controlling weeds, in particular in crops of useful plants.
Herbicidal triazinones are known, for example, from WO 94/03454 and WOOO/08000. The present invention provides improved herbicidal triazinones, which are characterised as having, for example, a N-hydroxy substituent.
Thus, according to the present invention there is provided a compound of Formula (I) or Formula (II):
Figure imgf000002_0001
or an agronomically acceptable salt thereof,
wherein :-
R1 is selected from the group consisting of hydrogen, Ci-C6alkyl, C3- C6cycloalkyl, C2-C6alkenyl, C2-C6alkynyl, Ci-C6haloalkyl, Ci-Cealkoxy-Ci- C3-alkyl and C3-C6CycloalkylCi-C3-alkyl-; selected from the group consisting of Al, A2, A3, A4 and A5
Figure imgf000002_0002
wherein X1 is N or CR7; X2 is N or CR8; X3 is N or CR9; X4 is N or CR6;
R4 is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci- C6cycloalkyl, Ci-Cehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-Cealkylcarbonyl-, aryl, arylcarbonyl-, Ci-Cealkoxycarbonyl-, Ci- C6alkoxycarbonyl-oxy-Ci-C6alkyl-, Ci-C6alkyl-S(0)p-, Ci-Cealkyl- S(0)pcarbonyl- and aryl-S(0)p- , wherein said aryl groups may be optionally substituted by one or more R11;
R5 is selected from the group consisting of hydroxyl, halogen, Ci-Cealkyl, Ci- C6cycloalkyl, Ci-Cehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C6 alkoxy-, C2-C6alkenyloxy-, C3-C6CycloalkylCi-C3-alkyl-, Ci-C6 alkoxyCi-Csalkyl-, Ci-C6 alkoxy-C2-Cealkoxy-, Ci-C6 alkoxy-C2-Cealkoxy- Ci-C3alkyl-,Ci-C6 haloalkoxy-, Ci-C6 haloalkoxy-Ci-C3alkyl-, Ci-Cealkyl- S(0)p-, Ci-C6haloalkyl-S(0)p-, aryl, aryl-S(0)p-, heterocyclyl, heterocyclyl- S(0)p-, aryloxy-, aryl-C2-C6alkyl-, aryl-Ci-Cealkoxy-, heterocyclyloxy-, heterocyclyl-Ci-C3alkoxy-Ci-C3alkyl-, hydroxycarbonyl, hydroxycarbonyl- C1-C3 alkoxy-, Ci-C3alkoxycarbonyl-, C1-C3 alkoxycarbonyl-Ci-C3 alkoxy-, Ci-C3alkylamino-, Ci-C3dialkylamino-, C1-C3 alkylamino-S(0)p-, C1-C3 alkylamino-S(0)p-Ci-C3alkyl-, C1-C3 dialkylamino-S(0)p-, C1-C3 dialkylamino-S(0)p-Ci-C3alkyl-, Ci-C3alkylaminocarbonyl-, Ci-
C3alkylaminocarbonyl-Ci-C3alkyl-, Ci-C3dialkylaminocarbonyl-, C1-C3 dialkylaminocarbonyl-Ci-C3alkyl-, Ci-C3alkylcarbonylamino-, C1-C3 alkyl- S(0)p-amino-, Ci-C3alkyl-S(0)p-Ci-C3alkylamino-, Ci-C3alkyl-S(0)p- aminoCi-C3alkyl-, cyano and nitro, wherein said heterocyclyls are five or six membered heterocyclyls containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-Cshaloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, Ci-Cealkyl- S(0)p-, phenyl, cyano and nitro;
R6 and R9 are independently selected from the group consisting of hydrogen, hydroxyl, halogen, Ci-Cealkyl, Ci-Cecycloalkyl, Ci-Cehaloalkyl, C2-Cealkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C6 alkoxy-, C2-C6 alkenyloxy-, C3- C6CycloalkylCi-C3-alkyl-, Ci-C6 alkoxyCi-C3alkyl-, Ci-C6 alkoxy-C2- C6alkoxy-, Ci-C6 alkoxy-C2-C6alkoxy-Ci-C3alkyl-,Ci-C6 haloalkoxy-, Ci-C6 haloalkoxy-Ci-C3alkyl-, Ci-C6alkyl-S(0)p-, Ci-C6haloalkyl-S(0)p-, aryl, aryl- S(0)p-, heterocyclyl, heterocyclyl- S(0)p-, aryloxy-, aryl-C2-Cealkyl-, aryl-Ci- C6alkoxy-, heterocyclyloxy-, heterocyclyl-Ci-C3alkoxy-Ci-C3alkyl-, hydroxycarbonyl, hydroxycarbonyl-Ci-C3alkoxy-, Ci-C3alkoxycarbonyl-, Ci- C3alkoxycarbonyl-Ci-C3 alkoxy-, Ci-C3alkylamino-, Ci-C3dialkylamino-, Ci- C3alkylamino-S(0)p-, Ci-C3alkylamino-S(0)p-Ci-C3alkyl-, C1-C3 dialkylamino-S(0)p-, Ci-C3dialkylamino-S(0)p-Ci-C3alkyl-, Ci-
C3alkylaminocarbonyl-, Ci-C3alkylaminocarbonyl-Ci-C3alkyl-, Ci- C3 dialky laminocarbony 1- , C 1 -C3 dialky laminocarbony 1- C 1 -C3 alky 1- , C 1 - C3alkylcarbonylamino-, Ci-C3alkyl-S(0)p-amino-, Ci-C3alkyl-S(0)p-Ci- C3alkylamino-, Ci-C3alkyl-S(0)p- aminoCi-C3alkyl-, cyano and nitro, wherein said heterocyclyls are five or six membered heterocyclyls containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, Ci-C6alkyl-S(0)p-, phenyl, cyano and nitro;
R7 and R8 are independently selected from the group consisting of hydrogen, halogen, C1-C3 alkyl-, C1-C3 alkoxy-, C2-C3alkenyl-, C2-C3alkynyl-, C1-C3 haloalkyl- and Ci-C3haloalkoxy-; and wherein R5 and R9 can together form a saturated or unsaturated 5- or 6- membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more nitrogen and/or oxygen heteroatoms, the 5- or 6-membered ring being optionally substituted by one or more R12; or
R6 and R9 can together form a saturated or unsaturated 5- or 6-membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more heteroatoms selected from the group consisting of nitrogen, oxygen and S(0)2, the 5- or 6-membered ring being optionally substituted by one or more R12; or
R6 and R8 can together form a saturated or unsaturated 5- or 6-membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more nitrogen heteroatoms, the 5- or 6-membered ring being optionally substituted by one or more R13; and
R11 is selected from the group consisting of halo-, Ci-C3alkyl, C1-C3 haloalkyl and Ci-C6alkoxy;
R12 is selected from the group of hydrogen, cyano, halo-, oxy-, Ci- C3alkylS(0)p-, d-C3 alkyl, C3-C6cycloalkyl-, C2-C3alkenyl, C2-C3alkynyl, Ci-C3 alkoxy and Ci-C3 haloalkyl;
R13 is selected from the group of hydrogen, cyano, halo-, Ci-C3alkylS(0)p-, Ci-C3 alkyl, C2-C3alkenyl, C2-C3alkynyl, morpholinyl- and Ci-C3 haloalkyl;
R14 is selected from the group consisting of hydrogen, Ci-Cealkyl, Ci-
C6haloalkyl, Ci-Cealkoxy-Ci-Cealkyl, Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-
C6alkoxy-Ci-C6alkoxy-Ci-C6alkyl, Ci-Cealkyl, C2-Cealkenyl, C2- C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl and C3-C6 cycloalkyl; and p = 0, 1 or 2 with the exception of compounds of Formula (II) wherein R2 = (Al), R4 = hydrogen, R5 = halogen, X1 = CH, X2 = CH, X3 = CH and X4 = -C-CN.
Alkyl groups having a chain length of from 1 to 6 carbon atoms include, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (z-Pr), n- butyl (ft-Bu), isobutyl (z'-Bu), sec-butyl and tert-butyl (t-Bu).
Alkenyl groups having a chain length of from 2 to 6 carbon atoms include, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).
Alkynyl groups having a chain length of from 2 to 6 carbon atoms include, for example, -C≡CH (ethynyl) and -CH2-C≡CH (propargyl).
Cycloalkyl groups include c-propyl (c-Pr), c-butyl (c-Bu), c-pentyl and c- hexyl.
Halogen (halo) encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl or halophenyl.
Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3, 3-tetrafluoroethyl and 2,2,2- trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.
Haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine and especially fluorine or chlorine, for example 2,2-difluoro-l-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4- trifluorobut-2-en-l-yl. Preferred C2-C6alkenyl radicals substituted once, twice or three times by halogen are those having a chain length of from 2 to 5 carbon atoms. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl, ethoxycarbonyl or tert -butoxycarbonyl. It should also be appreciated that two alkoxy substituents present on the same carbon atom may be joined to form a spiro group. Thus, the methyl groups present in two methoxy substituents may be joined to form a spiro 1,3 dioxolane substituent, for example. Such a possibility is within the scope of the present invention.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
Alkylthio (alkyl-^*-) groups preferably have a chain length of from 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
Alkylsulfmyl (alkyl-SO-) is, for example, methylsulfmyl, ethylsulfmyl, propylsulfmyl, isopropylsulfmyl, n-butylsulfinyl, isobutylsulfmyl, sec-butylsulfmyl or tert-butylsulfinyl, preferably methylsulfmyl or ethylsulfmyl.
Alkylsulfonyl (alkyl-S(0)2-) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
Alkylamino (alkyl-NH-) is, for example, methylamino, ethylamino, n- propylamino, isopropylamino or a butylamino isomer. Dialkylamino ((alkyl)2-N-) is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms.
Cyclo alkylamino- or dicycloalkylamino- is for example cyclohexylamino or dicyclopropylamino.
Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxy ethyl.
Alkylthioalkyl (alkyl-S-alkyl) groups preferably have from 1 to 6 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthio methyl, ethylthio ethyl, n-propylthio methyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthio butyl.
Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms and may be substituted by one or more methyl groups; they are preferably unsubstituted, for example cyclopropyl (c-Pr), cyclobutyl (c-Bu), cyclopentyl (c-pentyl) or cyclohexyl (c-hexyl).
Aryl includes benzyl, phenyl, including phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl, may be in mono- or poly-substituted form, in which case the substituents may, as desired, be in the ortho-, meta- and/or para-position(s). The term also includes, for example, naphthalenyl.
Heterocyclyl, includes, for example, morpholinyl, tetrahydrofuryl, isoxazolinyl, and heteroaryl.
Heteroaryl, including heteroaryl as part of a substituent such as heteroaryloxy, means, for example, a five to ten (preferably five or six) member heteroaryl containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur. The term heteroaryl thus includes, for example, benzofuranyl, benzimidazolyl, indolyl, isobenzofuranyl, furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, pyridonyl, triazolyl, napthyridinyl and napthyridinonyl. The heteroaryl component may be optionally mono or poly substituted as previously defined.
Preferably, R1 is selected from the group consisting of Ci-C4alkyl (especially methyl or z'so-propyl), cyclopropyl, methoxymethyl, trifluoromethyl, cyclopropylmethyl-, vinyl and propargyl with methyl being particularly preferred.
Preferably, R2 is selected from the group consisting of Al , A2, A3 and A4.
Figure imgf000009_0001
More preferably R2 is selected from the group consisting of Ala, Alb, Ale, Aid, Ale, Alf, Alg, Alh, A2a, A2b, A3a, A3b and A3c:
Figure imgf000010_0001
Figure imgf000010_0002
5 6 7 8 9 12 13
wherein RJ, R , R', R°, R R1Z and R1J are as defined previously and n is 0, 1 ,
2 or 3.
More preferably, R2 is selected from the group consisting of phenyl (e.g. Ala), 3-pyridyl (e.g. Ale), N-pyridonyl (e.g. A2a) and 3-linked [l,8]naphthyridinyl (e.g. Aid). Even more preferably R2 is phenyl (e.g. Ala).
R4 is preferably selected from the group consisting of hydrogen, Ci- Cealkylcarbonyl-, arylcarbonyl-, Ci-C6alkoxycarbonyl-, Ci-C6alkyl-S(0)p-, Ci-C6alkyl-S(0)pCarbonyl- and aryl-S(0)p- , wherein said aryl groups may be optionally substituted by one or more R11;
R4 is more preferably H. R5 is preferably selected from the group consisting of hydroxyl, halo, Ci- C6alkyl, Ci-C6Cycloalkyl, Ci-C6haloalkyl, Ci-C6alkenyl, Ci-C6alkynyl, Ci-C6 alkoxy, Ci-C6 alkoxyCi-C3alkyl, Ci-C6 alkoxy-C2-Cealkoxy, Ci-C6 alkoxy-C2-C6alkoxy-Ci- C3alkyl, Ci-C6 haloalkoxy, Ci-C6 haloalkoxy-Ci-C3alkyl, Ci-C6alkyl-S(0)p-, d- C6haloalkyl-S(0)p-, aryl, aryloxy, heterocyclyl, heterocyclyl-Ci-C3alkoxy-Ci-C3alkyl, Ci-C3alkylamino-, Ci-C3dialkylamino-, Ci-C3 alkylamino-S(0)p-, Ci-C3 alkylamino- S(0)p-Ci-C3alkyl-, Ci-C3 dialkylamino-S(0)p-, d-C3 dialkylamino-S(0)p-Ci-C3alkyl-, Ci-C3alkylaminocarbonyl-, Ci-C3dialkylaminocarbonyl-, Ci-C3 dialkylaminocarbonyl-Ci-C3alkyl-, Ci-C3alkylcarbonylamino-, Ci-C3 alkyl-S(0)p- amino-, cyano and nitro, wherein said heterocyclyls are five or six membered heterocyclyls containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3 alkoxy, Ci-C3 haloalkoxy, cyano and nitro.
The terms "aryl" and "heterocyclyl" are further defined above. However, in the context of R5 phenyl, benzyl, isoxazolinyl (e.g 4,5-dihydro-l,2-oxazol-3-yl), pyrimidinyl, morpholinyl, furyl and thiophenyl are particularly preferred.
More preferably, R5 is selected from the group consisting of chloro, fluoro, bromo, methyl, trifluoromethyl, 2-fluoroethyl-, methoxymethyl, methoxyethoxymethyl-, trifluoromethoxymethyl-, methylS(0)p-, aryl, isoxazolinyl, morpholinyl, methyl-S(0)p-dimethylamino-, cyano and nitro, wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of chloro, methyl and trifluoromethyl.
More preferably, R5 is selected from the group consisting of halogen, Ci- C6alkyl, Ci-C6haloalkyl, Ci-C6 alkoxyCi-C3alkyl, Ci-C6 alkoxy-C2-Cealkoxy-Ci- C3alkyl, Ci-C6alkyl-S(0)p- and nitro. Even more preferably, R5 is selected from the group consisting of chloro, fluoro, bromo, methyl, methoxymethyl-, methoxyethoxymethyl-, methylS(0)p- and nitro. Preferably, R6 is selected from the group consisting of hydrogen, halogen, Ci-
Cealkyl, Ci-C6haloalkyl, Ci-C6alkyl-S(0)p-, Ci-C6cycloalkyl, C2-C6alkenyl, C2- C6haloalkenyl, C2-C6alkynyl, Ci-C6 alkoxy-, Ci-C6haloalkoxy, C2-C6alkenyloxy-, C3- C6CycloalkylCi-C3-alkyl-, Ci-C6 alkoxyCi-C3alkyl-, Ci-C6 alkoxy-C2-C6alkoxy-, nitro and phenyl wherein the phenyl may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3 alkoxy, Ci-C3 haloalkoxy, Ci-C6alkyl-S(0)p-, phenyl, cyano and nitro. More preferably, R6 is selected from the group consisting of hydrogen, halogen (especially chlorine), Ci-Cealkyl (especially methyl), Ci-Cehaloalkyl (e.g trifluoromethyl-), Ci- C6alkyl-S(0)p- (e.g -S(0)2Me), C2-C6alkenyl, C2-C6alkynyl and cyano.
Preferably, R7 is selected from the group consisting of hydrogen, halogen and Ci-C3 alkyl-, most preferably hydrogen.
Preferably, R is selected from the group consisting of hydrogen, halogen and Ci-C3 alkyl-, most preferably hydrogen.
Preferably, R9 is selected from the group consisting of hydrogen, halogen, Ci- Cealkyl, Ci-C6haloalkyl, Ci-C6alkyl-S(0)p-, Ci-C6cycloalkyl, C2-C6alkenyl, C2- C6haloalkenyl, C2-C6alkynyl, Ci-C6 alkoxy-, Ci-C6haloalkoxy, Ci-Cehaloalkoxy-Ci- C3alkyl-, C2-C6alkenyloxy-, C3-C6CycloalkylCi-C3-alkyl-, Ci-C6 alkoxyCi-C3alkyl-, Ci-C6 alkoxy-C2-C6alkoxy-, nitro, isoxazolinyl, and phenyl wherein the phenyl may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-C3halo alkyl, Ci-C3 alkoxy, Ci-C3 haloalkoxy, Ci- C6alkyl-S(0)p-, phenyl, cyano and nitro.
More preferably, R9 is selected from the group consisting of hydrogen, isoxazolinyl, Ci-C6haloalkoxy-Ci-C3alkyl- (e.g 2,2,2trifluoroethyloxymethyl-) and Ci-C6alkoxy-C2-C6alkoxy-Ci-C3alkyl- (e.g methoxyethoxymethyl-). Preferably, R14 is selected from the group consisting of hydrogen, methyl and halogen. Compounds of Formula I or II may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities.
Similarly, where there are disubstituted alkenes, these may be present in E or Z form or as mixtures of both in any proportion.
Furthermore, compounds of Formula I or II may be in equilibrium with alternative hydroxyl tautomeric forms. It should be appreciated that all tautomeric forms (single tautomer or mixtures thereof), racemic mixtures and single isomers are included within the scope of the present invention.
The present invention also includes agronomically acceptable salts that the compounds of Formula I may form with amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as salt formers, emphasis is to be given to the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium, magnesium and calcium. The corresponding trimethylsulfonium salt may also be used.
The compounds of Formula (I) or (II) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surface- active agents (SFAs). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. The composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
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, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).
Dustable powders (DP) may be prepared by mixing a compound of Formula (I) or (II) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder. Soluble powders (SP) may be prepared by mixing a compound of Formula (I) or (II) 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). Wettable powders (WP) may be prepared by mixing a compound of Formula
(I) or (II) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) or (II) 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 (II) (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. 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). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) 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 (EC) 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- Cio fatty acid dimethylamide) and chlorinated hydrocarbons. 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) or (II) 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 SFAs, 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 SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SFA 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.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I) or (II). SCs may be prepared by ball or bead milling the solid compound of Formula (I) or (II) 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. Alternatively, a compound of Formula (I) or (II) 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) or (II) and a suitable propellant (for example n-butane). A compound of Formula (I) or (II) 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 (CS) 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) or (II) and they may be used for seed treatment. A compound of Formula (I) or (II) 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) or (II). Such additives include surface active agents (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I))·
Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts. Suitable anionic SFAs 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-z'sopropyl- and tri-z'sopropyl-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 (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.
Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs 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); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
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. Examples of such mixtures are (in which T represents a compound of Formula I or II). I + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + ametryn, I + amicarbazone, I + amidosulfuron, I + aminopyralid, I + amitrole, I + anilofos, I + asulam, I + atrazine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bromobutide, I + bromoxynil, I + butachlor, I + butamifos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, I + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + cyanazine, I + cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop, I + cyhalofop-butyl,, I + 2,4-D, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + I + desmedipham, I + dicamba, I + dichlobenil, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclofop- methyl, I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + dimethachlor, I + dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + endothal, I + EPTC, I + esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron-methyl, I + ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I + fenoxaprop-P, I + fenoxaprop-P-ethyl, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop-butyl, I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone- sodium, I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I + flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumiclorac- pentyl, I + flumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I + fluorogly co fen-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I + fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinate- ammonium, I + glyphosate, I + halauxifen, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-P, I + hexazinone, I + imazamethabenz, I + imazamethabenz-methyl, I + imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I + imazosulfuron, I + indanofan, I + indaziflam, I + iodomethane, I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron, I + metazachlor, I + methabenzthiazuron, I + methazole, I + methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, I + metolachlor, I + S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I + metsulfuron-methyl, I + molinate, I + mono linuron, I + naproanilide, I + napropamide, I + naptalam, I + neburon, I + nicosulfuron, I + n-methyl glyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, I + pendimethalin, I + penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + pethoxamid, I + phenmedipham, I + picloram, I + picolinafen, I + pinoxaden, I + piperophos, I + pretilachlor, I + primisulfuron, I + primisulfuron- methyl, I + prodiamine, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I + propisochlor, I + propoxycarbazone, I + propoxycarbazone-sodium, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen-ethyl, I + pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + pyridate, I + pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac, I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxsulam, I + quinclorac, I + quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + rimsulfuron, I + saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I + terbutryn, I + thenylchlor, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + topramezone, I + tralkoxydim, I + tri-allate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trihydroxytriazine, I + trinexapac-ethyl, I + tritosulfuron, I + [3-[2-chloro-4-fluoro-5- (l-methyl-6-trifluoromethyl-2,4-dioxo-l,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2- pyridyloxy] acetic acid ethyl ester (CAS R 353292-31-6). The compounds of the present invention may also be combined with herbicidal compounds disclosed in WO06/024820 and/or WO07/096576.
The mixing partners of the compound of Formula (I) or (II) 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) or (II) 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) or (II) 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) or (II) with the mixing partner).
The compounds of Formula (I) or (II) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of Formula (I) or (II) according to the invention with one or more further herbicides can also be used in combination with one or more safeners. The safeners can be AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31- 8), dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, N-isopropyl- 4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4). Other possibilities include safener compounds disclosed in, for example, EP0365484 e.g N- (2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Particularly preferred are mixtures of a compound of Formula (I) of (II) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or N-(2-methoxybenzoyl)- 4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.
The safeners of the compound of Formula (I) or (II) 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) or (II) 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) or (II) with the safener).
The present invention still further provides a method of selectively controlling weeds at a locus comprising 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. 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) or (II) 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) or (II) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 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 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. Maize, wheat and barley are particularly preferred.
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®.
In a preferred embodiment the crop plant is rendered tolerant to HPPD- inhibitors via genetic engineering. Methods of rending crop plants tolerant to HPPD- inhibitors are known, for example from WO0246387. Thus in an even more preferred embodiment the crop plant is transgenic in respect of a polynucleotide comprising a DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more particularly, from a barley, maize, wheat, rice, Brachiaria, Chenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species.
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.
The compositions 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. Weeds can also include plants which may be considered crop plants but which are growing outside a crop area ('escapes'), or which grow from seed left over from a previous planting of a different crop ('volunteers'). Such volunteers or escapes may be tolerant to certain other herbicides.
The compounds of the present invention can be prepared using the following schemes.
Scheme 1: Preparation of Compounds of Formula (I), wherein R is hydrogen.
Figure imgf000025_0001
Scheme 2: Preparation of Compounds of Formula (II), wherein R is hydrogen.
Figure imgf000025_0002
Scheme 3: Preparation of Compounds of Formula (I), wherein R4 is hydrogen.
PCI5, toluene, 40°C
Figure imgf000026_0001
or POCI3, toluene, 110°C
Zn(CI04)2
NEt3 iPrOH, 80°C
Figure imgf000026_0002
Scheme 4: Preparation of Compounds of Formula (II), wherein R is hydrogen.
Figure imgf000026_0003
-A Y' PCI5, toluene, 40°C
EtOH, -78°C * H,CT°Y^ or POCI3, toluene, 1 10°C
Zn(CI04)2 iPrOH, 80°C
NEt3
Figure imgf000026_0004
Ύ
Scheme 5: Preparation of Compounds of Formula (I), wherein R is not H
Figure imgf000026_0005
base e.g. K2CO3 , Et3N
solvent e.g. DMF or dichloromethane Scheme 6: Preparation of Compounds of Formula (II), wherein R4 is not H
Figure imgf000027_0001
base e.g. K2C03 , Et3N
solvent e.g. DMF or dichloromethane
Example 1 : 4-Hvdroxy-6-isopropyl-3- [2-methylsulfonyl-4-f trifluoromethyl)- phenyll-l.,2,4-triazin-5-one (Compound 1.028)
Step 1: flE)-2-methylsulfonyl-4-ftrifluoromethyl)benzaldehyde oxime.
To a stirred solution of 2-methylsulfonyl-4-(trifluoromethyl)benzaldehyde (10. Og) in pyridine (50.0 mL) and ethanol (50.0mL) is added hydroxylamine hydrochloride (2.76g) and the reaction is refluxed overnight. The reaction mixture is then diluted with ethyl acetate, washed with water (2x), then aqueous FeS04, then 1M HCl and the organic phase is passed through a phase separator and concentrated in vacuo to yield an off white solid, (lE)-2-methylsulfonyl-4-(trifluoromethyl)benzaldehyde oxime (9-72g).
iH NMR (400 MHz, Methanol) δ ppm 8.93 (s, 1 H) 8.30 (t, J=4.0 Hz, 2 H) 7.97 - 8.11 (m, 1 H) 3.24 (s, 3 H)
Step 2: flZ)-N-hydroxy-2-methylsulfonyl-4-ftrifluoromethyl)benzimidoyl chloride
To a solution of (lE)-2-methylsulfonyl-4-(trifluoromethyl)benzaldehyde oxime (1.0 g) in Ν,Ν-dimethylformamide (8.8g), cooled in an ice/brine bath, is added drop wise tert-butyl hypochlorite (0.6 lg) over 5 minutes. The colourless solution turns bright yellow and is stirred with cooling for 15 minutes before allowing slowly to attain ambient temperature and then stirred for lh. The reaction mixture is diluted with ether and washed with water (x2), passed through a phase separator and reduced under vacuum to give an off yellow solid, (lZ)-N-hydroxy-2-methylsulfonyl-4- (trifluoromethyl)benzimidoyl chloride (1.02g).
Steps 3-5: 4-hydroxy-6-isopropyl-3-[2-methylsulfonyl-4-trifluoromethyl)phenyll- 1 ,2,4-triazin-5-one
Step 3
To a solution of hydrazine hydrate (0.50g) in ethanol (5mL) at 0 C is slowly added a suspension of (1 Z)-N-hydroxy-2-methylsulfonyl-4-(trifluoromethyl)-benzimidoyl chloride (1.0 g) in ethanol (5mL) over 5 min. During the addition a white precipitate formed and remained. The reaction mixture is stirred at 0°C for 1 h 10 min.
Step 4
To the reaction mixture is added ethyl 3-methyl-2-oxo-butanoate (0.96g) and zinc diperchlorate (0.0088g). The reaction mixture is then stirred at room temperature for 30min during which a free flowing suspension is formed. Two portions of ethyl 3- methyl-2-oxo-butanoate (each of 0.96g) are added to the reaction mixture and the precipitate on the sides of the flask washed down with ethanol (~ 5 ml). All the precipitate dissolved and a clear yellow solution formed.
Ste S
To the remaining solution is added iso propylamine (2.9g) and the reaction mixture is stirred at room temperature overnight. LCMS shows conversion of all the Z hydrazone to the desired product. The reaction mixture is acidified with 1 M HC1, the layers separated and the organic washed with brine, passed through a phase separator and reduced under vacuum to give a yellow solid. This is then purified to give a yellow so lid, 4-hydroxy-6-isopropyl-3 - [2-methylsulfonyl-4-(trifluoromethyl)phenyl] - l,2,4-triazin-5-one (0.22g) Example 2 : 6-( 2,4-dichlorophenyl)-4-hvdroxy-3-isopropyl- 1 ,2,4-triazin-5-one (Compound 2.027)
Step 1: flZ)-N-hydroxy-2-methyl-propanimidoyl chloride To a solution of (lE)-2-methylpropanal oxime (5.0g) in N,N-dimethylformamide (1.3 mL/mmol, 75 mL), cooled in an ice/brine bath, is added N-chlorosuccinimide (8.8g, 66 mmol) over 10 minutes. The colourless solution is warmed up to room temperature slowly and left to stand at room temperature overnight. The reaction mixture is diluted with ether and washed with 1 : 1 water: brine (x2), passed through a phase separator and reduced under vacuum to give a colourless oil, (lZ)-N-hydroxy-2-methyl- propanimidoyl chloride (7.66g) that contains approximately 10% diethyl ether.
Step 2: N-amino-N'-hvdroxy-2-methyl-propanamidine To a solution of hydrazine hydrate (O. lg) in ethanol (0.5 mL/mmol, 0.93 mL) is added Ν,Ν-diethylethanamine (0.19g). The reaction mixture is cooled to 0°C and (lZ)-N- hydroxy-2-methyl-propanimidoyl chloride (0.25g) in ethanol (0.5 mL/mmol, 0.93 mL) is added via syringe pump over 1.5 hours. The crude product is used directly in the next step.
Step 3 : 6-( 2,4-dichlorophenyl)-4-hvdroxy-3-isopropyl- 1 ,2,4-triazin-5-one To the reaction mixture is added zinc diperchlorate (0.73g) and methyl 2-(2,4- dichlorophenyl)-2-oxo-acetate (0.45g) and the reaction mixture is allowed to warm up to room temperature slowly over 30 minutes. The reaction mixture is then left to stand overnight at room temperature. The reaction mixture is acidified with 1 M HC1, the layers separated and the organic washed with brine, passed through a phase separator and reduced under vacuum to give a yellow oil. This is then purified on the Fraction- lynx to give 6-(2,4-dichlorophenyl)-4-hydroxy-3-isopropyl-l,2,4-triazin-5-one as an off-white foam (0.02g)
Example 3:
4-hvdroxy-3-isopropyl-6-[2-fmethoxymethyl)-6-ftrifluoromethyl)-3-pyridyll- l,2,4-triazin-5-one (Compound 4.001)
Step 1: 2-tetrahydrothiophen-l-ium-l-ylacetonitrile bromide To tetrahydrothiophene (8.49g) is added 2-bromoacetonitrile (10.5g). The reaction is stirred at room temperature for 16 hours. 150mL diethylether is added and the solid broken with a spatula. The suspension is stirred for 2 hours, occasionally breaking the lumps with a spatula to produce a suspension. The white solid is collected rapidly by filtration and put in a flask to dry on high vacuum for 3 hours. 2-tetrahydrothiophen- 1-ium-l-ylacetonitrile bromide (14.75g). lU NMR (400 MHz, MeOD, δ ppm = 2.35 - 2.46 (m, 2 H) 2.48 - 2.57 (m, 2 H) 3.75 (dt, J=13.09, 6.46 Hz, 2 H) 3.86 (dt, J=13.57, 6.93 Hz, 2 H) Step 2: 3-[2-fmethoxymethyl)-6-ftrifluoromethyl)-3-pyridyll-3-oxo-2-fthiolan-l- ylidene)propanenitrile 2-(methoxymethyl)-6-(trifluoromethyl)pyridine-3-carboxylic acid (3.85 g) and HATU (9.53g) are suspended in dichloromethane (120.0 mL). 2-tetrahydrothiophen-l-ium-l- ylacetonitrile bromide (5.68g) followed by N-ethyl-N-isopropyl-propan-2-amine (6.35g) are added and the mixture is stirred at room temperature for 8 hours. The reaction is stopped and then washed with 2 x 40mL aqueous saturated ammonium chloride. The dichloromethane layer is separated using a separation cartridge and concentrated in vacuo.
The crude product is purified on a silica cartridge using dichloromethane: methanol. Fractions containing the product are combined and concentrated in vacuo to yield 3- [2-(methoxymethyl)-6-(trifluoromethyl)-3 -pyridyl] -3 -oxo-2-(thio lan- 1 - ylidene)propanenitrile (8.0g). lU NMR (400 MHz, Chloroform) δ ppm = 2.17 (dd, J=10.66, 5.54 Hz, 2 H) 2.67 (dd, J=9.69, 6.08 Hz,
2 H) 3.34 (s, 3 H) 3.46 - 3.53 (m, 2 H) 3.53 - 3.59 (m, 2 H) 4.79 (s, 2 H) 7.64 (d, J=7.89 Hz, 1 H) 7.88 (d, =7.89 Hz, 1 H)
Step 3: Ethyl 2-[2-fmethoxymethyl)-6-ftrifluoromethyl)-3-pyridyll-2-oxo-acetate
3 - [2-(methoxymethyl)-6-(trifluoromethyl)-3 -pyridyl] -3 -oxo-2-(thiolan- 1 - ylidene)propanenitrile (8.00g) is suspended in tetrahydrofuran (90.0 mL), ethanol (90.0 mL) and water (90.0 mL). Oxone (28.6g) is added in one portion and the mixture is stirred at room temperature for 30 minutes. The reaction is stopped and a solution of saturated sodium bicarbonate is added carefully to the mixture. The aqueous layer is extracted with 2 x 75.0mL dichloromethane and then the organic layer is dried over sodium sulphate, filtered and concentrated in vacuo. The aqueous layer is basified with a diluted solution of NaOH then carefully bleached to destroy any remaining cyanide. The crude product is put onto a silica cartridge, eluting with iso-hexane: ethyl acetate as solvent system. Fractions containing the product were combined and concentrated in vacuo to yield ethyl 2-[2-(methoxymethyl)-6-(trifluoromethyl)-3-pyridyl]-2-oxo- acetate (1.17g) as a translucent oil. lU NMR (500 MHz, Chloroform) δ ppm = 1.41 (t, J=7.15 Hz, 3 H) 3.32 (s, 3 H) 4.40 (q, J=7.09 Hz, 2 H) 4.77 (s, 2 H) 7.69 (d, J=8.07 Hz, 1 H) 7.99 (d, J=7.95 Hz, 1 H)
Step4:Ethyl-2-r2-(methoxymethyl)-6-(trifluoromethyl)-3-pyridyll-2-q- methylpropanoylhydrazono)acetate
Ethyl 2-[2-(methoxymethyl)-6-(trifluoromethyl)-3-pyridyl]-2-oxo-acetate (1.50g mmol) is dissolved in dioxane (50.0mL) and heated to 90°C. 2- methylpropanehydrazide (0.552g) is added portion wise and the mixture stirred for 9 hours. The reaction mixture is concentrated in vacuo and the residue suspended in 15.0mL diethylether. The resulting solid is collected by filtration to give the clean product as a white solid (420. Omg). lR NMR (400 MHz, Chloroform) δ ppm = 1.22 (br. s., 6 H) 1.33 (t, J=6.91 Hz, 3 H) 3.32 (s, 3 H) 3.54 (br. s., 1 H) 4.33 (q, J=6.97 Hz, 2 H) 4.55 (s, 2 H) 7.68 - 7.78 (m, 2 H) 8.08 (br. s., 1 H)
The filtrate is concentrated and liquid- loaded onto a silica cartridge using iso-hexane: ethyl acetate as the solvent system. The fractions containing the product are combined, added to the solid previously collected and concentrated in vacuo to yield ethyl (2E)-2-[2-(methoxymethyl)-6-(trifluoromethyl)-3-pyridyl]-2-(2- methylpropanoylhydrazono)acetate (0.430 g, 1.15 mmol, 22.2% yield) as a white solid. NMR indicates the presence of the two regioisomers. lR NMR (400 MHz, Chloroform) δ ppm = 1.21 (d, J=6.60 Hz, 6 H) 1.33 (t, J=7.09 Hz, 3 H) 3.31 (s, 3 H) 3.53 (br. s., 1 H) 4.27 - 4.38 (m, 2 H) 4.54 (s, 2 H) 7.68 - 7.78 (m, 2 H) 8.15 (br. s., 1 H)
Step 5: Ethyl 2-[[l-fhvdroxyamino)-2-methyl-propylidenelhydrazonol-2-[2- fmethoxymethyl)-6-ftrifluoromethyl)-3-pyridyllacetate Ethyl (2E)-2- [2-(methoxymethyl)-6-(trifluoromethyl)-3 -pyridy 1] -2-(2-methyl- propanoylhydrazono)acetate (1.08g) is dissolved in toluene (35mL) and the mixture heated to 100°C. Phosphorus oxychloride (0.552g) is added and the mixture is heated for 3 hours. 0.4eq OPCl^ is added and the mixture stirred for another 3 hours and themixture was concentrated to about 5.0mL.
In another flask, hydroxylamine hydrochloride (1.3g) is suspended in propan-2-ol (5.00 mL). Triethylamine (1.91g) is added followed by the toluene solution of ethyl (2E)-2-[(l -chloro-2-methyl-propylidene)hydrazono]-2-[2-(methoxymethyl)-6-
(trifluoromethyl)-3-pyridyl] acetate (1.13g). The flask is rinsed with 2 x 5.0mL dioxane. The mixture is stirred at 80°C for 60 minutes. LC indicated complete conversion to the two desired regioisomers. The reaction is stopped and concentrated in vacuo. The crude product is diluted with 40 mL ethyl acetate and washed with 2 x 40mL water. The aqueous extract is extracted again with 40mL ethyl acetate and the organic layers are combined, dried over sodium sulphate, filtered and concentrated in vacuo.
The residue is liquid-loaded onto a silica cartridge eluting with dichloromethane: ethyl acetate. Fractions containing the product are combined and concentrated in vacuo to yield a yellow oil. LC and TLC showed an impurity that could be removed using another solvent system, so the crude product is liquid loaded onto a silica cartridge eluting with iso-hexane: ethyl acetate. The fractions containing the product are combined and concentrated in vacuo to give ethyl 2-[[l-(hydroxyamino)-2-methyl- propylidene]hydrazono]-2-[2-(methoxymethyl)-6-(trif uoromethyl)-3-pyridyl]acetate (560. Omg) as a pale yellow oil). NMR and LC indicated presence of the two hydrazone isomers (9: 1 to 8:2 ratio).
Step 6 : 4-hvdroxy-3-isopropyl-6- [2-( methoxymethyl)-6-( trifluoromethyl)-3- pyridyll - 1 ,2,4-triazin-5-one Ethyl 2-[(Z)-[ 1 -(hydroxyamino)-2-methyl-propylidene]hydrazono]-2-[2-(methoxy- methyl)-6-(trifluoromethyl)-3-pyridyl] acetate (560. Omg) is diluted in 1,4-dioxane (7.50 mL) and DBU (0.56g) is then added. The reaction is heated to 90°C for 2h30. The reaction is stopped, and poured into aqueous HC1 (25.0mL). The product is extracted using 2 x 20.0mL ethyl acetate and the organic layers are combined, dried over sodium sulphate, filtered and concentrated in vacuo. The residue is dry-loaded on a stacker of 2 x 24g columns, eluting with a mixture of water:ethanol:dioxane:triethylamine:toluene (0.5:2:4:2: 10). The fractions containing the product are combined and concentrated in vacuo to give a dark orange oil. This is partitioned between ethyl acetate and HC1 (2.0M) and the organic is then collected, dried over sodium sulphate, filtered and concentrated in vacuo to give a pale brown foam solid (230. Omg). The residue is taken up in lO.OmL iso-hexane and sonicated for 5 minutes until a fine suspension is obtained. The resulting solid is collected by filtration and dried under suction for 2 hours to yield 4-hydroxy-3-isopropyl-6-[2- (methoxymethyl)-6-(trifluoromethyl)-3-pyridyl]-l,2,4-triazin-5-one as a pale brown solid (198.0 mg). NMR (400 MHz, Chloroform) δ ppm = 1.50 (d, J=6.80 Hz, 6 H) 3.09 (s, 3 H) 3.47 - 3.55 (m, 1 H) 4.88 (s, 2 H) 7.74 (d, J=7.97 Hz, 1 H) 8.10 (d, J=7.97 Hz, 1 H)
Example 4. Synthesis of [3-isopropyl-6-[2-methylsulfonyl-4- (trifluoromethyl)phenyll -5-oxo- l,2,4-triazin-4-yll benzoate ( CSCZ173713) as example of a procide
4- hydroxy-3-isopropyl-6-[2-methylsulfonyl-4-(trifluoromethyl)phenyl]-l,2,4-triazin-
5- one (200 mg, 0.53 mmol) is suspended in dichloromethane (5 mL, 77.8 mmol) in a 25ml round-bottomed flask with ice-bath cooling. Triethylamine (0.2 mL, 1 mmol) is added drop wise and the solid material slowly dissolved giving a yellow solution. Benzoyl chloride (0.15 mL, 1.3 mmol) is added. After 1 hour with ice-bath cooling, LCMS showed complete conversion to the desired product. The reaction mixture is diluted with dichloromethane and purified by column chromatography on silica, eluting with ethyl acetate: iso hexane, to give [3-isopropyl-6-[2-methylsulfonyl-4- (trifluoromethyl)phenyl]-5-oxo-l,2,4-triazin-4-yl] benzoate (225 mg, 0.47 mmol, 88 % yield) as a white foamy solid.
4- hydroxy-3-isopropyl-6-[2-methylsulfonyl-4-(trifluoromethyl)phenyl]-l ,2,4-triazin-
5- one is prepared from ethyl 2-[2-methylsulfonyl-4-(trifiuoromethyl)phenyl]-2-oxo- acetate analogously to the synthesis of compound 4.001 (Example 3).
TABLE CI - Examples of herbicidal compounds of the present invention.
12.76 (br. J=1.2 H (m, 2 H) 2.38
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
(s, 1 H)
Hz, 1 H)7.93 1 H)3.44 1 H)3.29 J=6.8Hz, 6
(d, J=8.2 J=8.2Hz, 1 H)4.60 2 H) 3.21 3H) 1.37 6 H) 8.12 (d, 8.01 (dd, 1 H) ,7.79 1 H) , 3.43 (s, 3 H), 1.33 6 H) (d, J=6.85 2 H) 3.49- 4.07 (d, 5.42 (s, 2 Hz, 1 H) Hz, 1 H)
ppm 8.11 1 H) 7.52 3 H) 2.69
Figure imgf000039_0001
TABLE C2 - Examples of herbicidal compounds of the present invention.
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
(s, 3 H) 3.32
J=8.07 Hz, 1 H) H) 8.51 (d, H)
(d, J=6.85 Hz, H) 2.67 (s, 3 1 H) 7.54 (d, 7.68 (s, 1 H) Hz, 1 H) (d, J=6.85 Hz, 3.22 (s, 3 H) 3.54 (dt, 1 H) 4.60 (t, 7.73 (d, J=8.19 1
- 1.35 (m, 6 J=6.12 J=5.96 Hz, 1 Hz, 1 H) 8.43
- 1.38 (m, 4 1 H) 3.32 (s, 1 H) 1 H) 8.40 (s,
(s, 1 H) 8.05 1 H) 3.32 (s, 3 (m, 1H) H) 0.38 - 0.44
(s, 3 H) 3.32 J=8.07 Hz, 1 H) 1 H) 8.41 (s,
(d, J=6.85 Hz, 3.54 (s, 1 H) 2 H) 5.42 (s, 1 H) Hz, 1 H)
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
TABLE C3 - Examples of herbicidal compounds of the present invention.
Figure imgf000049_0001
TABLE C4 - Examples of herbicidal compounds of the present invention.
Compound
Structure NMR Number
CDC13: ppm 1.50 (d, J=6.80 Hz, 6 H) 3.09 (s, 3 H) 3.47 - 3.55
4.001 (m, 1 H) 4.88 (s, 2 H) 7.74 (d,
J=7.97 Hz, 1 H) 8.10 (d, J=7.97 Hz, 1 H)
4.002
Biological Examples
Seeds of a variety of test species are sown in standard soil in pots (Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solarium nigrum (SOLNI), Amaranthus retoflexus (AMARE), Ipomoea hederacea (IPOHE)). After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°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 R 9005-64-5). Compounds are applied at 1000 g/h. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days for pre and post-emergence, the test is evaluated for the percentage herbicidal damage caused to the plant. The biological activities are shown in the following table on a five point scale (5 = 80-100% damage; 4 = 60-79% damage; 3 = 40-59% damage; 2 = 20-39% damage; 1 = 0-19% damage).
TABLE Bl
Compound POST Application PRE A jplication
SOLNI AMARE SETFA ALOMY ECHCG EPOHE SOLNI AMARE SETFA ALOMY ECHCG EPOHE
1.001 5 5 4 4 5 5 5 5 5 4 5 4
1.025 5 4 1 1 4 3 1 5 1 1 1 2
1.027 5 5 4 5 5 4 5 5 5 4 5 4
1.028 5 5 5 5 5 5 5 5 5 5 5 5
1.029 5 5 5 5 5 5 5 5 4 3 3 4
1.030 5 5 5 4 5 4 5 5 4 3 0 4
1.031 5 5 5 5 5 5 5 5 4 4 2 5
1.032 5 5 5 5 5 5 5 5 5 5 5 5
2.027 5 5 5 5 5 5 5 5 5 5 5 5
2.028 5 5 5 5 5 5 5 5 5 5 5 5
2.030 5 5 5 4 5 5 5 5 4 2 5 5
2.031 5 5 5 5 5 5 5 5 4 4 5 4
2.032 5 5 5 5 5 5 5 5 5 5 5 5
2.033 5 5 5 3 5 5 5 5 4 3 5 5
2.034 5 5 5 5 5 5 4 5 5 5 5 5
2.035 5 5 5 5 5 5 5 5 5 5 5 5
2.036 5 5 4 2 4 5 5 5 1 1 2 5
2.037 5 5 5 5 5 5 5 5 5 5 5 5
2.038 5 5 2 2 5 5 5 5 2 1 4 4
2.039 5 5 5 5 5 5 5 5 5 5 5 5
2.040 5 5 5 5 5 5 5 5 5 5 5 5
2.041 5 5 5 5 5 5 5 5 5 5 5 5
2.042 5 5 5 5 5 5 5 5 5 5 5 5
2.043 5 4 5 5 5 5 5 5 5 5 5 5
2.044 5 5 5 5 5 5 5 5 5 5 5 5
2.045 5 5 5 5 5 5 5 5 5 5 5 5
2.046 5 5 5 5 5 5 5 5 5 5 5 5
2.047 5 5 5 5 5 5 5 5 5 5 5 5
2.048 5 5 5 3 4 3 5 5 3 1 1 3
2.049 5 5 5 5 5 5 5 5 5 5 5 5
2.055 5 5 5 5 5 5 5 5 5 5 Compound POST Application PRE A jplication
SOLNI AMARE SETFA ALOMY ECHCG IPOHE SOLNI AMARE SETFA ALOMY ECHCG EPOHE
2.059 5 5 5 5 5 5 5 2 5 5
2.060 5 5 5 5 5 5 5 5 5 5
2.064 5 5 5 4 5 5 5 5 3 1 4 5
3.001 5 5 5 5 5 5 5 5 5 5 5 5
3.002 5 5 5 5 5 5 5 5 4 4 4 4
4.001 5 5 5 5 5 5 5 5 5 5 5 5

Claims

Claims
1. A compound of Formula (I) or Formula (II):
Figure imgf000053_0001
or an agronomically acceptable salt thereof,
wherein :-
R1 is selected from the group consisting of hydrogen, Ci-C6alkyl, C3- C6cycloalkyl, C2-C6alkenyl, C2-C6alkynyl, Ci-C6haloalkyl, Ci-Cealkoxy-Ci- C3-alkyl and C3-C6CycloalkylCi-C3-alkyl-; selected from the group consisting of Al , A2, A3, A4 and A5
Figure imgf000053_0002
wherein X1 is N or CR7; X2 is N or CR8; X3 is N or CR9; X4 is N or CR6; R4 is selected from the group consisting of hydrogen, Ci-Cealkyl, Ci- C6cycloalkyl, Ci-Cehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-Cealkylcarbonyl-, aryl-, arylcarbonyl-, Ci-Cealkoxycarbonyl-, Ci- C6alkoxycarbonyl-oxy-Ci-C6alkyl-, Ci-C6alkyl-S(0)p-, Ci-Cealkyl- S(0)pcarbonyl- and aryl-S(0)p- , wherein said aryl groups may be optionally substituted by one or more R11;
R5 is selected from the group consisting of hydroxyl, halogen, Ci-Cealkyl, Ci- C6cycloalkyl, Ci-Cehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C6 alkoxy-, C2-C6 alkenyloxy-, C3-C6CycloalkylCi-C3-alkyl-, Ci-C6 alkoxyCi-Csalkyl-, Ci-C6 alkoxy-C2-C6alkoxy-, Ci-C6 alkoxy-C2-C6alkoxy- Ci-C3alkyl-,Ci-C6 haloalkoxy-, Ci-C6 haloalkoxy-Ci-C3alkyl-, Ci-Cealkyl- S(0)p-, Ci-C6haloalkyl-S(0)p-, aryl, aryl-S(0)p-, heterocyclyl, heterocyclyl- S(0)p-, aryloxy-, aryl-C2-Cealkyl-, aryl-Ci-Cealkoxy-, heterocyclyloxy-, heterocyclyl-Ci-C3alkoxy-Ci-C3alkyl-, hydroxycarbonyl, hydroxycarbonyl- C1-C3 alkoxy-, C1-C3 alkoxycarbonyl-, C1-C3 alkoxycarbonyl-Ci-C3 alkoxy-, Ci-C3alkylamino-, Ci-C3dialkylamino-, C1-C3 alkylamino-S(0)p-, C1-C3 alkylamino-S(0)p-Ci-C3alkyl-, Ci-C3dialkylamino-S(0)p-, C1-C3 dialkylamino-S(0)p-Ci-C3alkyl-, Ci-C3alkylaminocarbonyl-, Ci-
C3alkylaminocarbonyl-Ci-C3alkyl-, Ci-C3dialkylaminocarbonyl-, C1-C3 dialkylaminocarbonyl-Ci-C3alkyl-, Ci-C3alkylcarbonylamino-, C1-C3 alkyl- S(0)p-amino-, Ci-C3alkyl-S(0)p-Ci-C3alkylamino-, Ci-C3alkyl-S(0)p- aminoCi-C3alkyl-, cyano and nitro, wherein said heterocyclyls are five or six membered heterocyclyls containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, Ci-Cealkyl- S(0)p-, phenyl, cyano and nitro;
R6 and R9 are independently selected from the group consisting of hydrogen, hydroxyl, halogen, Ci-Cealkyl, Ci-Cecycloalkyl, Ci-Cehaloalkyl, C2-Cealkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-Cealkoxy-, C2-C6alkenyloxy-, C3- C6CycloalkylCi-C3-alkyl-, Ci-C6alkoxyCi-C3alkyl-, Ci-C6alkoxy-C2- C6alkoxy-, Ci-C6alkoxy-C2-C6alkoxy-Ci-C3alkyl-, Ci-Cehaloalkoxy-, Ci-C6 haloalkoxy-Ci-C3alkyl-, Ci-C6alkyl-S(0)p-, Ci-C6haloalkyl-S(0)p-, aryl, aryl- S(0)p-, heterocyclyl, heterocyclyl-S(0)p-, aryloxy-, aryl-C2-C6alkyl-, aryl-Ci- C6alkoxy-, heterocyclyloxy-, heterocyclyl-Ci-C3alkoxy-Ci-C3alkyl-, hydroxycarbonyl, hydroxycarbonyl-Ci-C3alkoxy-, Ci-C3alkoxycarbonyl-, Ci- C3alkoxycarbonyl-Ci-C3alkoxy-, Ci-C3alkylamino-, Ci-C3dialkylamino-, Ci- C3alkylamino-S(0)p-, Ci-C3alkylamino-S(0)p-Ci-C3alkyl-, C1-C3 dialkylamino-S(0)p-, Ci-C3dialkylamino-S(0)p-Ci-C3alkyl-, Ci- C3alkylaminocarbonyl-, Ci-C3alkylaminocarbonyl-Ci-C3alkyl-, Ci-
C3 dialky laminocarbony 1- , C 1 -C3 dialky laminocarbony 1- C 1 -C3 alky 1- , C 1 - C3alkylcarbonylamino-, Ci-C3alkyl-S(0)p-amino-, Ci-C3alkyl-S(0)p-Ci- C3alkylamino-, Ci-C3alkyl-S(0)p- aminoCi-C3alkyl-, cyano and nitro, wherein said heterocyclyls are five or six membered heterocyclyls containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heterocyclyl components may be optionally substituted by one or more substituents selected from the group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, Ci-C6alkyl-S(0)p-, phenyl, cyano and nitro;
R7 and R8 are independently selected from the group consisting of hydrogen, halogen, Ci-C3alkyl-, Ci-C3alkoxy-, C2-C3alkenyl-, C2-C3alkynyl-, C1-C3 haloalkyl- and Ci-C3haloalkoxy-; and wherein R5 and R9 can together form a saturated or unsaturated 5- or 6- membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more nitrogen and/or oxygen heteroatoms, the 5- or 6-membered ring being optionally substituted by one or more R12; or
R6 and R9 can together form a saturated or unsaturated 5- or 6-membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more hetereoatoms selected from the group consisting of nitrogen, oxygen and S(0)2, the 5- or 6-membered ring being optionally substituted by one or more R12; or
R6 and R8 can together form a saturated or unsaturated 5- or 6-membered carbocyclic or heterocyclic ring, said heterocyclic ring comprising one or more nitrogen heteroatoms, the 5- or 6-membered ring being optionally substituted by one or more R13; and
R11 is selected from the group consisting of halo-, Ci-C3alkyl, C1-C3 haloalkyl and Ci-C6alkoxy;
R12 is selected from the group of hydrogen, cyano, halo-, oxy-, Ci- C3alkylS(0)p-, C1-C3 alkyl, C3-C6cycloalkyl-, C2-C3alkenyl, C2-C3alkynyl, C1-C3 alkoxy and C1-C3 haloalkyl;
R13 is selected from the group of hydrogen, cyano, halo-, Ci-C3alkylS(0)p-, C1-C3 alkyl, C2-C3alkenyl, C2-C3alkynyl, morpholinyl- and C1-C3 haloalkyl;
R14 is selected from the group consisting of hydrogen, Ci-Cealkyl, Ci- C6haloalkyl, Ci-Cealkoxy-Ci-Cealkyl, Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-
C6alkoxy-Ci-C6alkoxy-Ci-C6alkyl, Ci-Cealkyl, C2-C6alkenyl, C2- C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl and C3-C6 cycloalkyl; and p = 0, 1 or 2 with the exception of compounds of Formula (II) wherein R2 = (Al), R4 = hydrogen, R5 = halogen, X1 = CH, X2 = CH, X3 = CH and X4 = -C-CN.
A compound according to claim 1, wherein R1 is selected from the group consisting of hydrogen, Ci-Cealkyl, C3-C6Cycloalkyl, Ci-Cealkoxy-, C3- Cecyclolkyl- C3-C6alkyl-.
3. A compound according to claim 1 or claim 2, wherein R2 is selected from the group consisting of Ala, Alb, Ale, Aid, Ale, Alf, Alg, Alh, A2a, A2b, A3a, A3b and A3c:
Figure imgf000057_0001
5 6 7 8 9 12 13
wherein RJ, R°, R', R°, R Rlz and R1J are as defined previously and n is 0, 1, 2 or 3.
A compound according to claim 3, wherein R2 is Ala.
A compound according to any one of the previous claims, wherein R5 is selected from the group consisting of, halogen, Ci-Cealkyl, Ci-C6haloalkyl, Ci-C6alkoxyCi-C3alkyl-, Ci-C6alkoxy-C2-C6alkoxy-Ci-C3alkyl-, Ci-Cealkyl- S(0)p- and nitro.
6. A compound according to claim 5, wherein R5 is selected from the group consisting of chloro, fluoro, bromo, methyl, methoxymethyl, methoxyethoxymethyl-, methylS(0)p- and nitro.
7. A compound according to any one of the previous claims, wherein R6 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci- C6haloalkyl, Ci-C6alkyl-S(0)p-, C2-C6alkenyl and C2-C6alkynyl.
8. A compound according to any one of the previous claims, wherein R7 and R8 are independently selected from the group consisting of hydrogen, halogen and Ci-C3alkyk
9. A compound according to any one of the previous claims, wherein R9 is selected from the group consisting of hydrogen, isoxazolinyl, Ci- C6haloalkoxy-Ci-C3alkyl- and Ci-C6alkoxy-C2-C6alkoxy-Ci-C3alkyl-.
10. A herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.
11. A herbicidal composition according to claim 10, further comprising at least one additional pesticide.
12. A herbicidal composition according to claim 11, wherein the additional pesticide is a herbicide or herbicide safener.
13. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to any one of claims 10 to 12.
14. Use of a compound of Formula (I) of Formula (II) as defined in claim 1 as a herbicide.
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WO2017042259A1 (en) 2015-09-11 2017-03-16 Bayer Cropscience Aktiengesellschaft Hppd variants and methods of use
WO2018050631A1 (en) 2016-09-13 2018-03-22 Haplogen Gmbh Antiviral compounds
WO2019068841A1 (en) 2017-10-05 2019-04-11 Haplogen Gmbh Antiviral compounds
US11180770B2 (en) 2017-03-07 2021-11-23 BASF Agricultural Solutions Seed US LLC HPPD variants and methods of use
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Publication number Priority date Publication date Assignee Title
WO2017042259A1 (en) 2015-09-11 2017-03-16 Bayer Cropscience Aktiengesellschaft Hppd variants and methods of use
WO2018050631A1 (en) 2016-09-13 2018-03-22 Haplogen Gmbh Antiviral compounds
US11091428B2 (en) 2016-09-13 2021-08-17 Haplogen Gmbh Antiviral compounds
US11180770B2 (en) 2017-03-07 2021-11-23 BASF Agricultural Solutions Seed US LLC HPPD variants and methods of use
US11344029B2 (en) * 2017-06-01 2022-05-31 Sumitomo Chemical Company, Limited Heterocyclic compound and composition containing same
WO2019068841A1 (en) 2017-10-05 2019-04-11 Haplogen Gmbh Antiviral compounds
US11180479B2 (en) 2017-10-05 2021-11-23 Haplogen Gmbh Antiviral compounds

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