WO2018036992A1 - Composés de triazolotriazinone herbicides - Google Patents

Composés de triazolotriazinone herbicides Download PDF

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Publication number
WO2018036992A1
WO2018036992A1 PCT/EP2017/071083 EP2017071083W WO2018036992A1 WO 2018036992 A1 WO2018036992 A1 WO 2018036992A1 EP 2017071083 W EP2017071083 W EP 2017071083W WO 2018036992 A1 WO2018036992 A1 WO 2018036992A1
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compound
formula
ethyl
group
methyl
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PCT/EP2017/071083
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English (en)
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Linda Hazel CURLEY
Glynn Mitchell
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to novel herbicidal compounds, 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, or for inhibiting plant growth.
  • Herbicidal 6-oxo-l,6-dihydropyrimidin-5-carboxamides are reported in EP-A- 2562174.
  • Herbicidal l,2,4-triazine-3,5-dione-6-carboxamides are disclosed, for example, in WO2014/053473.
  • Herbicidal oxopyrazine derivatives are disclosed in WO2009/016841.
  • the present invention relates to novel herbicidal triazolotriazinone compounds.
  • R 1 is selected from the group consisting of Ci-C4alkyl-, Ci-C4haloalkyl- and Ci-C6alkoxy-Ci-C3alkyl-;
  • R 2 is selected from the group consisting of Ci-C6alkyl-, Ci-C 6 haloalkyl, C 2 - C 6 alkenyl-, C 2 -C 6 haloalkenyl-, C 2 -C 6 alkynyl-, C 2 -C6haloalkynyl-, Ci-C 6 alkoxyCi-Csalkyl-, Ci-CehaloalkoxyCi-Csalkyl-, Ci-C6alkoxyC 2 -C3alkoxyCi- Csalkyl-, -(CH 2 ) n -C3-C6cycloalkyl, benzyl, phenyl and a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the benzyl, phenyl or heteroaryl may be optionally substituted by one or more substituents selected
  • Ci-C6alkyl and Ci-C4alkyl groups include, for example, methyl (Me, CH3), ethyl (Et, C 2 H 5 ), n-propyl (n-Pr), isopropyl (z-Pr), n-butyl (n- u), isobutyl (z-Bu), sec- butyl and tert-butyl (t-Bu).
  • C 2 -C6alkynyl- groups include, for example, -C ⁇ CH (ethynyl) and -CH 2 -C ⁇ CH (propargyl).
  • Halogen encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl, halkoalkenyl and haloalkynyl.
  • Ci-C 6 haloalkyl includes, 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-, 2,2,2-trichloroethyl-, heptafluoro -n-propyl and perfluoro-n-hexyl.
  • Ci-C4haloalkyl includes, for example, fluoromethyl-, difluoromethyl-, trifluoromethyl-, chloromethyl-, dichloromethyl-, trichloromethyl-, 2,2,2-trifluoroethyl-, 2-fluoroethyl-, 2-chloroethyl-, pentafluoroethyl-, 1,1-dif uoro- 2,2,2-trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl- and heptafluoro-n- propyl-.
  • Ci-C6alkoxy- includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy.
  • Ci-C6alkoxy-Ci-C3alkyl- groups include, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxy ethyl.
  • Ci-Cehaloalkoxy- is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2-dif uoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
  • Ci-C6haloalkoxy-Ci-C3alkyl- is, for example, 2,2,2-trifluoroethoxymethyl-.
  • Ci-C6alkoxyC2-C3alkoxyCi-C3alkyl- is, for example, methoxy ethoxymethyl-.
  • Ci-C6alkyl-S- (alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
  • Ci-C6alkyl-S(0)- (alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfmyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfmyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfmyl.
  • Ci-C6alkyl-S(0)2- (alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
  • C3-C6cycloalkyl groups include, for example, cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl) and may be substituted or unsubstituted as described.
  • Heteroaryl is, for example, furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, iso thiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl.
  • R 2 is selected from the group consisting of Ci-C 6 alkyl (e.g methyl, ethyl, n-propyl, n-butyl, z ' -pentyl) and Ci- C 6 haloalkyl (e.g 1 , 1 ,1 trifluorobutyl-).
  • Ci-C 6 alkyl e.g methyl, ethyl, n-propyl, n-butyl, z ' -pentyl
  • Ci- C 6 haloalkyl e.g 1 , 1 ,1 trifluorobutyl-
  • R 2 is phenyl or a heteroaryl selected from the group consisting of furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl all of which may be optionally substituted as described herein.
  • R 2 is phenyl which may be optionally substituted as described herein.
  • R 2 is phenyl optionally substituted by one or more (e.g one, two or three) substituents selected from the group consisting of halogen (especially fluorine and/or chlorine), Ci-C6alkyl- (especially methyl), Ci-Cehaloalkyl- (especially trifluoromethyl), Ci-C6alkoxy- (especially methoxy-), Ci-Cehaloalkoxy- (especially trifluoromethoxy-, Ci-C6alkyl-S(0)p- (especially -SC -methyl), cyano and nitro.
  • substituents selected from the group consisting of halogen (especially fluorine and/or chlorine), Ci-C6alkyl- (especially methyl), Ci-Cehaloalkyl- (especially trifluoromethyl), Ci-C6alkoxy- (especially methoxy-), Ci-Cehaloalkoxy- (especially trifluoromethoxy-, Ci-C6alkyl-S(0)p- (especially -SC -methyl),
  • R 3 is hydrogen
  • Compounds of Formula (I) 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) may be in equilibrium with alternative 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) 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.
  • dustable powders DP
  • SP soluble powders
  • SG water soluble granules
  • WP water dispersible granules
  • GR granules
  • SL
  • Dustable powders may be prepared by mixing a compound of Formula (I) 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) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from preformed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • Dispersible Concentrates may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N- methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as 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) 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).
  • SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane).
  • a compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment.
  • a compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • the composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I).
  • additives include surface active agents (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
  • 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 tetra
  • 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.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkylphenols such as octylphenol, nonyl
  • 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.
  • the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators.
  • the additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures are (in which T represents a compound of Formula I).
  • the mixing partners of the compound of Formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.
  • the compound of Formula I can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
  • the mixing ratio of the compound of Formula I to the mixing partner is preferably from 1 : 100 to 1000: 1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula I with the mixing partner).
  • the compounds of Formula I according to the invention can also be used in combination with one or more safeners.
  • mixtures of a compound of Formula I 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-me
  • the safeners of the compound of Formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16 th Edition (BCPC), 2012.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phos- phonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
  • the mixing ratio of compound of Formula I to safener is from 100: 1 to 1 : 10, especially from 20: 1 to 1 : 1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula I with the safener).
  • the present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I). Moreover, the present invention 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. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I).
  • tolerance may need to be engineered into the crop plant, for example by way of genetic engineering.
  • 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, Cenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species.
  • 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, Cenchrus, Lolium, Festuca, Setaria, Eleusine,
  • HPPD-tolerant soybean transgenic "events” include for example SYHT04R (WO2012/082542), SYHT0H2 (WO2012/082548) and FG72.
  • Crop plants in which the composition according to the invention can be used thus include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.
  • Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.
  • the rates of application of compounds of Formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post- emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of Formula I according to the invention are generally applied at a rate of from 10 to 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.
  • Crop plants are to be understood as also including those crop plants 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 PvOundupReady® and LibertyLink®.
  • Crop plants 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.
  • Crop plants are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • 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.
  • DMAP 4-(dimethylamino) pyridine
  • Et 3 N triethylamine
  • PPAA 1- propanephosphonic acid cyclic anhydride
  • the solvent is a non-protic organic solvent such as ethyl acetate, tetrahydofuran, 1,4-dioxane, dimethylformamide or dichloromethane, and the reaction may be subjected to heating by microwave irradiation.
  • R 1 is an optionally substituted alkyl or benzyl group
  • X is a leaving group such as chloro, bromo, iodo, 4-toluenesulfonyloxy or trifluoromethanesulfonyloxy
  • solvent is a non-protic organic solvent such as dimethylformamide (DMF) or acetonitrile
  • the base is an inorganic base such as caesium carbonate, potassium carbonate or calcium carbonate.
  • Step 1 A solution of compound El (20.0 g, 0.162 mol) in formic acid (lOOmL) was heated to 120°C and stirred for 6 hours. The reaction mixture was then cooled to room temperature, and cone. HCI (lOOmL) was added. The mixture was then heated to 120°C and stirred for a further 6 hours. The cooled mixture was then concentrated under reduced pressure, and the residue was triturated with methanol followed by diethyl ether to afford compound E2 (20.0 g).
  • Step 2 A stirred solution of compound E2 (20.0 g, 0.148 mol) in ethanol (200 ml) was treated with sodium acetate (20.0 g, 0.222 mol) followed by diethyl ketomalonate (45mL, 0.296 mol). The reaction mixture was then heated to 90°C and stirred for 16 hours. The cooled solution was then concentrated under reduced pressure to leave a yellow gummy solid, which was stirred with water (200 mL) for 30 min. The solid was then filtered off, washed with diethyl ether and dried under high vacuum to afford compound E3 (12.0 g). lH nmr (d6-DMSO): 1.30 (3H, t); 4.36 (2H, q); 9.13 (1H, s); 14.23 (lH. br s)
  • Step 3 A stirred solution of compound E3 (5.0 g, 23.9 mmol) and phenylboronic acid (5.8 g, 47.8 mmol) in tetrahydrofuran (THF; 200mL) was treated with triethylamine (10.0 mL, 71.7 mmol), pyridine (6 mL, 71.7 mmol) and copper (II) acetate (8.6 g, 47.8 mmol). The reaction mixture was heated to 60°C and stirred for 4 hours. The cooled mixture was then filtered, the solid material was washed twice with dihloromethane and the combined filtrates were evaporated under reduced pressure.
  • THF tetrahydrofuran
  • Step 4 A mixture of compound E4 (0.50 g, 1.75 mmol) and 2M hydrochloric acid (lOmL) was stirred at 100°C for 16 hours. After completion of the reaction, the cooled reaction mixture was concentrated under reduced pressure, and the residue was triturated with methanol and diethyl ether to afford compound E5 (0.41 g).
  • Step 5 A stirred solution of compound E5 (0.065 g, 0.252 mmol) and 2-amino-5- methyl-l,3,4-oxadiazole (0.026 g, 0.262 mmol) in dichloromethane (10 mL) was treated with 4-(dimethylamino)pyridine (DMAP: 0.062 g, 0.492 mmol). After stirring for a further 3 hours, 1-propanephosphonic acid cyclic anhydride (PPAA: [50% in ethyl acetate (0.32 mL, 0.54 mmol)]) was added. Stirring was continued for a further 2 hours, and the mixture was then left to stand overnight.
  • DMAP 4-(dimethylamino)pyridine
  • Step 1 By a method analogous to that described in Preparative Example 1, Step 3, but using compound E3 (1.324 g, 6.330 mmol), 2-methylphenylboronic acid (1.723 g, 12.67 mmol), powdered molecular sieves (4A), pyridine (2.10 mL), copper (II) acetate (2.336 g, 12.72 mmol), a mixture of ethyl acetate (100 mL) and dichloromethane (100 mL) as solvent, and conducting the reaction at room temperature for 68 hours, compound E6 (0.165 g) was obtained as a white solid.
  • Step 2 A stirred solution of compound E6 (165 mg, 0.5513 mmol) in acetic acid (4 mL) was treated with cone, hydrochloric acid (1 mL), and the mixture was heated to 70°C for 2 hours, then cooled to room temperature and allowed to stand overnight. The mixture was evaporated to dryness under reduced pressure, using toluene to azeotrope out remaining water, to afford compound E7 as an off white solid (133 mg).
  • lHnmr(d6-DMSO) 9.49(s, 1H), 7.52-7.38(m, 4H), 2.23(s, 3H)
  • Step 3 A stirred solution of compound E7 (86 mg, 0.317 mmol) and 2-amino-5- methyl-l,3,4-oxadiazole (32 mg, 0.323 mmol) in dichloromethane (10 mL) was treated with 4-(dimethylamino)pyridine (DMAP: 78 mg, 0.620 mmol). After stirring for a further 30 minutes, 1-propanephosphonic acid cyclic anhydride (PPAA: [50% in ethyl acetate (0.40 mL, 0.67 mmol)]) was added. Stirring was continued for a further 10 minutes, and the mixture was then left to stand overnight. Water was added, and the organic layer was separated.
  • DMAP 4-(dimethylamino)pyridine
  • Step 1 A stirred solution of compound E3 (180 mg, 0.861 mmol) in dimethylformamide (DMF: 3 mL) was treated with caesium carbonate (281 mg, 0.862 mmol) followed by benzyl bromide (0.20 mL, 2.0 mmol). The reaction mixture was heated to 70°C for 30 minutes under microwave irradiation, then cooled. The mixture was filtered and the residual solid was washed with a little ethyl acetate.
  • DMF dimethylformamide
  • Step 2 A stirred solution of compound E8 (68 mg, 0.227 mmol) in acetic acid (3 mL) was treated with cone, hydrochloric acid (0.5 mL). The mixture was stirred for 2 hours, then heated to 70°C under microwave irradiation for 30 minutes, then heated to 100°C under microwave irradiation for 30 minutes. The mixture was cooled, then evaporated to dryness under reduced pressure, using toluene to azeotrope out remaining water, to afford compound E9 (46 mg).
  • Step 3 A stirred solution of compound E9 (50 mg, 0.0.184 mmol) in dimethylformamide (2 mL) was treated at room temperature with 2-amino-5-methyl- 1,3,4-oxadiazole (21 mg, 0.212 mmol), then triethylamine (0.13 mL, 0.93 mmol) and then 1-propanephosphonic acid cyclic anhydride (PPAA: [ 50 % in ethyl acetate] 0.57 mL, 0.96 mmol). The reaction mixture was stirred for 2 hours, then left to stand overnight.
  • 2-amino-5-methyl- 1,3,4-oxadiazole 21 mg, 0.212 mmol
  • PPAA 1-propanephosphonic acid cyclic anhydride
  • Step 1 By a method analogous to that described in Preparative Example 4, Step 1, but using propargyl bromide in place of benzyl bromide, compound E10 was obtained.
  • Step 2 By a method analogous to that described in Preparative Example 4, Step 2, but using compound E10 in place of E8, compound El l was obtained as a white solid.
  • Step 3 By a method analogous to that described in Preparative Example 1, Step 5, but using compound El l in place of E5 and a mixture of tetrahydrofuran and dichloromethane as solvent, compound 1.073 was obtained as an off- white solid.
  • lHnmr(d4-MeOH) 9.12 (s, 1H), 5.08 (s, 2H), 3.00 (s, 1H), 2.54 (s, 3H) (all signals were broad)
  • Step 1 By a method analogous to that described in Preparative Example 4, Step 1, but using allyl iodide in place of benzyl bromide, compound E12 was obtained.
  • Step 2 By a method analogous to that described in Preparative Example 4, Step 2, but using compound E12 in place of E8, compound El 3 was obtained as a white solid.
  • lHnmr(dMeOH) 9.05 (s, 1H), 6.08-5.99 (m, 1H), 5.39-5.33 (m, 2H), 4.80 (dt, 2H)
  • Step 3 By a method analogous to that described in Preparative Example 2, Step 3, but using compound E13 in place of E7, compound 1.074 was obtained as an off- white solid.
  • Lolium perenne Lolium perenne
  • AMARE Amaranthus retoflexus
  • ABUTH Abutilon theophrasti
  • SETFA Setaria faberi
  • Echinochloa crus-galli Echinochloa crus-galli
  • IPHE Ipomoea hederacea
  • 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 500 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

La présente invention concerne des composés de formule (I), dans laquelle: Q, R2 et R3 sont tels que définis dans la description ou un sel agronomiquement acceptable desdits composés. L'invention concerne en outre des compositions herbicides comportant un composé de formule (I), leur utilisation pour la lutte contre les mauvaises herbes, en particulier dans des cultures de plantes utiles, ainsi que des intermédiaires pour la synthèse desdits composés.
PCT/EP2017/071083 2016-08-24 2017-08-22 Composés de triazolotriazinone herbicides WO2018036992A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943936A (zh) * 2020-09-11 2020-11-17 西北大学 一种亚甲基桥连富氮双杂环化合物及其衍生物、制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014053473A1 (fr) * 2012-10-04 2014-04-10 Bayer Cropscience Ag 1,2,4-triazine-3,5-dione-6-carboxamides et leur utilisation comme herbicides
EP3006444A1 (fr) * 2013-05-31 2016-04-13 Nissan Chemical Industries, Ltd. Composé amide hétérocyclique
WO2016135196A1 (fr) * 2015-02-27 2016-09-01 Syngenta Participations Ag Dérivés de triazolotriazinone présentant une activité en tant qu'herbicides
WO2017032786A1 (fr) * 2015-08-26 2017-03-02 Syngenta Participations Ag Composés herbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014053473A1 (fr) * 2012-10-04 2014-04-10 Bayer Cropscience Ag 1,2,4-triazine-3,5-dione-6-carboxamides et leur utilisation comme herbicides
EP3006444A1 (fr) * 2013-05-31 2016-04-13 Nissan Chemical Industries, Ltd. Composé amide hétérocyclique
WO2016135196A1 (fr) * 2015-02-27 2016-09-01 Syngenta Participations Ag Dérivés de triazolotriazinone présentant une activité en tant qu'herbicides
WO2017032786A1 (fr) * 2015-08-26 2017-03-02 Syngenta Participations Ag Composés herbicides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943936A (zh) * 2020-09-11 2020-11-17 西北大学 一种亚甲基桥连富氮双杂环化合物及其衍生物、制备方法

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