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WO2025114019A1 - Composés herbicides - Google Patents

Composés herbicides Download PDF

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Publication number
WO2025114019A1
WO2025114019A1 PCT/EP2024/082313 EP2024082313W WO2025114019A1 WO 2025114019 A1 WO2025114019 A1 WO 2025114019A1 EP 2024082313 W EP2024082313 W EP 2024082313W WO 2025114019 A1 WO2025114019 A1 WO 2025114019A1
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WO
WIPO (PCT)
Prior art keywords
formula
compounds
compound
methyl
chloro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/082313
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English (en)
Inventor
Joseph Andrew TATE
Suzanna DALE
Nicholas Phillip Mulholland
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Publication of WO2025114019A1 publication Critical patent/WO2025114019A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring

Definitions

  • the present invention relates to herbicidal compounds, to processes for their preparation, to herbicidal compositions which comprise the herbicidal compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.
  • the present invention relates to novel methyl hydroxy amino oxo-propionate compounds, which demonstrate herbicidal activity.
  • a 1 is selected from the group consisting of CR 8 R 9 , C(0), O, S(0) p and N(R 10 );
  • a 2 is selected from the group consisting of CR 6 R 7 , C(0), O, S(0) p and N(R 10 );
  • X 1 is a halogen;
  • R 1 is hydrogen or Ci-C4alkyl;
  • R 2 and R 3 are both Ci-Csalkyl;
  • R 4 is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl and Ci- Cealkoxy-;
  • R 6 is selected from the group consisting of
  • a herbicidal composition comprising a compound of Formula (I) as described herein, and an agriculturally acceptable formulation adjuvant.
  • the invention provides the use of a compound of Formula (I) or a composition of the invention as a herbicide.
  • the invention provides a method of controlling weeds at a locus comprising applying to the locus a weed controlling amount of a compound of or composition as described herein.
  • Ci-Cealkyl- includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n- Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/-Bu), sec-butyl and tert-butyl (f-Bu).
  • C1- Csalkyl includes methyl (Me, CH3), ethyl (Et, C2H5) and propyl (Pr e.g /so-propyl and n- propyl).
  • Ci-C4alkyl includes methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/-Bu), sec-butyl and tert-butyl (f-Bu).
  • Halogen includes, for example, fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
  • Ci-Cehaloalkyl- includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2- fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1-difluoro-2,2,2-trichloroethyl, 2, 2,3,3- tetrafluoropropyl and 2,2,2-trichloroethyl and heptafluoro-n-propyl.
  • Ci-C2haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, or 1 ,1- difluoro-2,2,2-trichloroethyl.
  • Ci-Cealkoxy includes methoxy, ethoxy and iso-propoxy-.
  • Cs-Cecycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • a compound of Formula (I) may comprise any combination of said values.
  • values of any specified set of embodiments may be combined with values of any other set of embodiments where such combinations are not mutually exclusive.
  • X 1 is bromo, chloro or fluoro.
  • X 1 is bromo or chloro.
  • X 1 is preferably chloro.
  • a compound of Formula (I) wherein A 1 is selected from the group consisting of CH2, C(O), O, S and NH, preferably O.
  • a 2 is selected from the group consisting of CH2, C(O), O, S and NH, preferably O.
  • a compound of Formula (I) wherein (i) A 1 and A 2 are O; (ii) A 1 is NH and A 2 is O; (iii) A 1 is O and A 2 is NH; (iv) A 1 and A 2 are NH; (v) A 1 is CH2 and A 2 is O; (vi) A 1 is O and A 2 is CH2; (vii) A 1 is CH2 and A 2 is CH2; (viii) A 1 is O and A 2 is S; or (ix) A 1 is S and A 2 is O.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen and Ci-Cealkyl.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, methyl and fluoro.
  • R 4 and R 5 are halogen, preferably fluoro.
  • 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.
  • the present invention also provides agronomically acceptable salts of compounds of Formula (I), and in one embodiment, it is preferred that compounds of Formula (I) are in salt form. Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.
  • amines including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.
  • the compounds of Formula (I) 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 (SAA).
  • formulation adjuvants such as carriers, solvents and surface-active agents (SAA).
  • SAA surface-active agents
  • 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. These include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a microemulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (Sil), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP) and a soluble granule (SG).
  • 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).
  • Soluble powders may be prepared by mixing a compound of Formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • 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 Cs-C 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 SAAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of Formula (I) is present initially in either the water or the solvent/SAA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • 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 (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I).
  • wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltri methyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /sopropyl- and tri-/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
  • Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SAAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • the compounds of present invention can also be used in mixture with one or more additional herbicides and/or plant growth regulators.
  • additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen- sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac-sodium, bixlozone, broclozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin
  • 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, Nineteenth Edition, British Crop Protection Council, 2021.
  • 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 or mixtures of the present invention can also be used in combination with one or more herbicide safeners.
  • herbicide safeners include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.
  • mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen are particularly preferred.
  • 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, Nineteenth Edition, British Crop Protection Council, 2021.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048.
  • the mixing ratio of compound of Formula (I) to safener is from 100:1 to 1 :10, especially from 20: 1 to 1 : 1.
  • the present invention still further provides a method of controlling weeds at a locus said method comprising applying to the locus a weed controlling amount of a composition comprising a compound of Formula (I).
  • the present invention may further provide 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 compounds of the present invention show a much-improved selectivity compared to know, structurally similar compounds.
  • the plants to be controlled are unwanted plants (weeds).
  • Locus means the area in which the plants are growing or will grow.
  • the application may be applied to the locus pre-emergence and/or postemergence of the crop plant.
  • Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I).
  • Preferred crop plants include maize, wheat, barley soybean and rice.
  • the rates of application of compounds of Formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2500 g/ha, especially from 25 to 1000 g/ha, more especially from 25 to 250 g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS, GS, EPSPS, PPG, HPPD, PDS, SDPS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS, GS, EPSPS, PPG, HPPD, PDS, SDPS and ACCase-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®.
  • 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.
  • 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, Brachia ria, Bromus, Cenchrus, Cy perus, 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.
  • Agrostis Alopecurus
  • Avena Brachia ria
  • Bromus Cenchrus
  • Cy perus Digitaria
  • Echinochloa Eleusine
  • Compounds of formula (2) are treated with a suitable base, for example sodium hydroxide, in a suitable solvent, for example a water/methanol/2-methyltetrahydrofuran mixture.
  • a suitable base for example sodium hydroxide
  • a suitable solvent for example a water/methanol/2-methyltetrahydrofuran mixture.
  • Compounds of formula (2) may be prepared from compounds of formula (3).
  • R 2 and R 3 are methyl
  • compounds of formula (3) are treated with 2,2-dimethylmalonyl chloride and a suitable base, for example pyridine, in a suitable solvent, for example dichloromethane.
  • Compounds of formula (4) are treated with a suitable source of hydroxylamine, for example hydroxylamine hydrochloride, and optionally a suitable base, for example sodium acetate, in a suitable solvent, for example ethanol, to give compounds of formula (5).
  • a suitable reducing agent for example sodium cyanoborohydride
  • a suitable acid for example 4 M hydrochloric acid in 1 ,4-dioxane
  • a suitable solvent for example methanol
  • compounds of formula (3) may be prepared from compounds of formula (6), where LG represents a suitable leaving group (for example Br or Cl), according to the following scheme.
  • Compounds of formula (6) are treated with (terf-butoxycarbonylamino) terf-butyl carbonate (7), a suitable base, for example potassium carbonate, and optionally a suitable additive, for example 18-crown-6, in a suitable solvent, for example acetonitrile, to give compounds of formula (8).
  • Compounds of formula (8) are treated with a suitable acid, for example hydrochloric acid, in a suitable solvent, for example 1 ,4-dioxane, to give compounds of formula (3).
  • compounds of formula (2) may be prepared from compounds of formula (9).
  • Compounds of formula (9) are treated with a suitable oxidant system, for example a mixture of trichloroisocyanuric acid and a catalytic quantity of TEMPO in a suitable solvent, for example dichloromethane.
  • a suitable oxidant system for example a mixture of trichloroisocyanuric acid and a catalytic quantity of TEMPO in a suitable solvent, for example dichloromethane.
  • Compounds of formula (9) may be prepared from compounds of formula (10), where PG 1 represents a suitable protecting group, for example -CH 2 CH 2 (Si(CH3)3).
  • Compounds of formula (10) may be prepared from compounds of formula (6), where LG represents a suitable leaving group (for example Br or Cl), and compounds of formula (11), where PG 1 represents a suitable protecting group, for example -
  • Compounds of formula (6) are treated with compounds of formula (11), a carbonate base, for example potassium carbonate, and optionally a suitable additive, for example sodium iodide, in a suitable solvent, for example acetone.
  • a carbonate base for example potassium carbonate
  • a suitable additive for example sodium iodide
  • 3,3-Dichloro-2,2-dimethylpropanoic acid (12) is treated with a suitable chlorinating agent, for example thionyl chloride, to give 3,3-dichloro-2,2-dimethylpropanoyl chloride (13).
  • 3,3-Dichloro-2,2-dimethylpropanoyl chloride (13) is treated with a suitable source of hydroxylamine, for example hydroxylamine (50% in H2O), to give 3,3-dichloro-2,2- dimethyl-propanehydroxamic acid (14).
  • 3,3-Dichloro-2,2-dimethyl-propanehydroxamic acid (14) is treated with compounds of formula (15), where PG 1 represents a suitable protecting group, for example -CH 2 CH2(Si(CH 3 )3), and a suitable base, for example 1 ,8- diazabicyclo(5.4.0)undec-7-ene, to give compounds of formula (11).
  • PG 1 represents a suitable protecting group, for example -CH 2 CH2(Si(CH 3 )3)
  • a suitable base for example 1 ,8- diazabicyclo(5.4.0)undec-7-ene
  • compounds of formula (16) are treated with a chlorinating agent, for example thionyl chloride, either neat or in a suitable solvent, for example dichloromethane.
  • a chlorinating agent for example thionyl chloride
  • Compounds of formula (16) may be prepared from compounds of formula (17), where Z is H or O-alkyl.
  • compounds of formula (17) are treated with a reducing agent, for example sodium borohydride, in a suitable solvent, for example a tetra hy d rof u ra n/m eth an ol m ixtu re .
  • a reducing agent for example sodium borohydride
  • a suitable solvent for example a tetra hy d rof u ra n/m eth an ol m ixtu re .
  • synthesis routes used to access compounds of formula (17) will vary depending on the nature of Z, X 1 , A 1 , A 2 , R 4 and R 5 .
  • compounds of formula (4) may be prepared from compounds of formula (18).
  • compounds of formula (16) may be prepared from compounds of formula (19).
  • Compounds of formula (19) may be prepared from compounds of formula (20), where Z is H or O-alkyl.
  • compounds of formula (20) are treated with a reducing agent, for example sodium borohydride, in a suitable solvent, for example water.
  • a reducing agent for example sodium borohydride
  • compounds of formula (16) may be prepared from compounds of formula (21) and compounds of formula (22) where PG 2 represents a suitable protecting group, for example -CH2CH2(Si(CH3)3), according to the following scheme.
  • PG 2 represents a suitable protecting group, for example -CH2CH2(Si(CH3)3), according to the following scheme.
  • Compounds of formula (22) are available from commercial sources.
  • Compounds of formula (24) are treated with a suitable halogenating agent, for example /V-chlorosuccinimide, in a suitable solvent, for example acetonitrile.
  • a suitable halogenating agent for example /V-chlorosuccinimide
  • Compounds of formula (17), formula (18), formula (19), formula (20), formula (21) and formula (24) may be commercially available. Alternatively, they may be prepared utilising ring synthesis strategies known in the literature. The synthetic route adopted will vary depending on the nature of Z, X 1 , A 1 , A 2 , R 4 and R 5 .
  • compounds of formula (25) may be prepared from compounds of formula (26) according to the following scheme.
  • Compounds of formula (26) are available from commercial sources or may be prepared according to strategies known in the literature.
  • Compounds of formula (2) are treated with a metal alkoxide, for example sodium methoxide, in a suitable solvent, for example methanol.
  • a metal alkoxide for example sodium methoxide
  • a suitable solvent for example methanol
  • compounds of formula (29) where R 1 is Ci-C4alkyl may be prepared from compounds of formula (3) and compounds of formula (30).
  • Compounds of formula (30) are available from commercial sources.
  • Compounds of formula (30) are activated by converting the -OH of the carboxylic acid into a good leaving group such as -Cl, for example by treatment with a suitable chlorinating agent, for example thionyl chloride, and optionally a suitable base, for example triethylamine, either neat or in a suitable solvent, for example dichloromethane.
  • a suitable chlorinating agent for example thionyl chloride
  • a suitable base for example triethylamine
  • a suitable solvent for example dichloromethane
  • compounds of formula (30) are reacted with compounds of formula (3) under suitable amide coupling conditions, for example by treatment with a carboxylic acid activating agent, for example 2,4,6-tripropyl- 1 ,3,5,2A 5 ,4A 5 ,6A 5 -trioxatriphosphinane 2,4,6-trioxide, and a suitable base, for example triethylamine, in a suitable solvent, for example dichloromethane.
  • a carboxylic acid activating agent for example 2,4,6-tripropyl- 1 ,3,5,2A 5 ,4A 5 ,6A 5 -trioxatriphosphinane 2,4,6-trioxide
  • a suitable base for example triethylamine
  • reaction mixture was stirred at room temperature for 3 h, during which time the reaction mixture was kept acidic by the addition of small amounts of hydrochloric acid (4 M solution in 1 ,4-dioxane). Subsequently, further hydrochloric acid (4 M solution in 1 ,4-dioxane, 0.26 mL, 1.05 mmol) and sodium cyanoborohydride (0.066 g, 1.05 mmol) in methanol (3.0 mL) were added. The reaction mixture was allowed to stand overnight and was then concentrated. The resulting residue was diluted in dichloromethane and water and the pH of the aqueous phase was adjusted to pH 9 through the dropwise addition of concentrated sodium hydroxide.
  • Step 5 Preparation of 2-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl]-4,4-dimethyl- isoxazolidine-3, 5-dione
  • Step 6 Preparation of sodium 3-[(6-chloro-2,3-dihydrobenzofuran-5-yl)methyl-hydroxy- amino]-2,2-dimethyl-3-oxo-propanoate
  • Step 1 Preparation of 6-chloro-2,2-dimethyl-1 ,3-benzodioxole-5-carbaldehyde
  • Step 2 Preparation of 6-chloro-2,2-dimethyl-1 ,3-benzodioxole-5-carbaldehyde oxime
  • Step 3 Preparation of N-[(6-chloro-2,2-dimethyl-1,3-benzodioxol-5- yl)methyl]hydroxylamine
  • reaction mixture was stirred at room temperature for 30 min, during which time the reaction mixture was kept acidic by the addition of small amounts of hydrochloric acid (4 M solution in 1 ,4-dioxane).
  • hydrochloric acid 4 M solution in 1 ,4-dioxane
  • the reaction mixture was cooled to 0 °C and the pH adjusted to 9.4 through the dropwise addition of concentrated sodium hydroxide.
  • the reaction mixture was concentrated then ethyl acetate (25 mL) and water (50 mL) were added and the layers separated.
  • Step 4 Preparation of 2-[(6-chloro-2,2-dimethyl-1,3-benzodioxol-5-yl)methyl]-4,4- dimethyl-isoxazolidine-3, 5-dione
  • 2,2-Dimethylpropanedioyl dichloride (1.22 g, 0.96 mL, 7.23 mmol) in dichloromethane (10 mL) was added dropwise over 15 min to a solution of / ⁇ /-[(6-chloro- 2,2-dimethyl-1,3-benzodioxol-5-yl)methyl]hydroxylamine (1.66 g, 7.23 mmol) and pyridine (1.16 g, 1.18 mL, 14.5 mmol) in dichloromethane (10 mL) at O °C. The reaction was stirred at room temperature for 2 h and left to stand overnight.
  • Step 5 Preparation of sodium 3-[(6-chloro-2,2-dimethyl-1,3-benzodioxol-5-yl)methyl- hydroxy-amino]-2,2-dimethyl-3-oxo-propanoate
  • AMAPA Amaranthus palmeri
  • AMARE Amaranthus retoflexus
  • SETFA Setaria faberi
  • Echinochloa crus-galli Echinochloa crus-galli
  • IPHE Ipomoea hederacea
  • aqueous spray solution derived from either i) the formulation of the technical active ingredient in acetone I water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5) or ii) the dissolution of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM + 44.44% N- methylpyrrolidone + 44.44% Dowanol DPM glycol ether), which was then diluted to required concentration using 0.2% Genapol XO80 (CAS No.9043-30-5) in water, as the diluent.
  • 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 damage caused to the plant.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des dérivés d'acide hydroxamique de formule (I) ou un sel agronomiquement acceptable de ceux-ci, des compositions herbicides les comprenant et leur utilisation pour lutter contre les mauvaises herbes, en particulier dans des cultures de plantes utiles.
PCT/EP2024/082313 2023-11-27 2024-11-14 Composés herbicides Pending WO2025114019A1 (fr)

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EP23212463.6 2023-11-27
EP23212463 2023-11-27

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WO2025114019A1 true WO2025114019A1 (fr) 2025-06-05

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2080289A (en) * 1980-06-02 1982-02-03 Fmc Corp Herbicidal 3-isoxazolidinones and hydroxamic acid intermediates
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO2002034048A1 (fr) 2000-10-23 2002-05-02 Syngenta Participations Ag Compositions agrochimiques avec des phytoprotecteurs a base de quinoline
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2015000353A1 (fr) * 2013-07-03 2015-01-08 Rotam Agrochem International Co. Ltd Procédé de préparation de clomazone, nouvelle forme et son utilisation
WO2023247293A1 (fr) * 2022-06-20 2023-12-28 Syngenta Crop Protection Ag Dérivés d'isoxalidine utilisés comme composés hericides

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2080289A (en) * 1980-06-02 1982-02-03 Fmc Corp Herbicidal 3-isoxazolidinones and hydroxamic acid intermediates
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO2002034048A1 (fr) 2000-10-23 2002-05-02 Syngenta Participations Ag Compositions agrochimiques avec des phytoprotecteurs a base de quinoline
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2015000353A1 (fr) * 2013-07-03 2015-01-08 Rotam Agrochem International Co. Ltd Procédé de préparation de clomazone, nouvelle forme et son utilisation
WO2023247293A1 (fr) * 2022-06-20 2023-12-28 Syngenta Crop Protection Ag Dérivés d'isoxalidine utilisés comme composés hericides

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