WO2020079078A1 - Herbicidal compounds - Google Patents

Herbicidal compounds Download PDF

Info

Publication number
WO2020079078A1
WO2020079078A1 PCT/EP2019/078080 EP2019078080W WO2020079078A1 WO 2020079078 A1 WO2020079078 A1 WO 2020079078A1 EP 2019078080 W EP2019078080 W EP 2019078080W WO 2020079078 A1 WO2020079078 A1 WO 2020079078A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
alkyl
mmol
formula
group
Prior art date
Application number
PCT/EP2019/078080
Other languages
French (fr)
Inventor
Paul Matthew BURTON
Katie EMERY
Katy Louise BRIDGWOOD
Glynn Mitchell
Original Assignee
Syngenta Crop Protection Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection Ag filed Critical Syngenta Crop Protection Ag
Publication of WO2020079078A1 publication Critical patent/WO2020079078A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • C07D401/12—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 linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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.
  • N-(tetrazol-5-yl)- arylcarboxamides are disclosed in, for example, WO2012/028579 and W02019/141071 .
  • the present invention relates to novel amidine substituted benzoyl compounds.
  • R 1 is Ci-C4alkyl- or Ci-C3-alkoxy-Ci-C3-alkyl-;
  • R 2 is selected from the group consisting of halogen, Ci-Ce alkyl, Cs-Ce-cycloalkyl, Ci-Ce haloalkyl and -S(0) p Ci-C6 alkyl;
  • R 3 is selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 haloalkyl and - S(0) p Ci-C6 alkyl;
  • R 4 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3- Ce cycloalkyl
  • R 5 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and C 3 - Ce-cycloalkyl
  • R 6 is selected from the group consisting of C 3 -C 6 cycloalkyl, Cs-Cecycloalkyl-Ci-Csalkyl-, Ci-Cealkoxy-, Ci-C 3 alkoxy-Ci-C 3 alkyl-, Ci-C 3 alkoxy-Ci-C 3 alkoxy-, C 2 -C 6 -alkynyl, C 2 - Cealkenyl, and -(CH 2 )-phenyl wherein the phenyl is optionally substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and C Ce alkoxy; or
  • R 5 and R 6 together are -C(R 7 ) 2 C(R 7 )2C(R 7 ) 2 C(R 7 )2-, -C(R 7 ) 2 C(R 7 )2C(R 7 )2C(R 7 ) 2 C(R 7 )2-, - CH 2 CH2S(0)pCH 2 CH2-, -CH 2 CH 2 N(R 8 )CH 2 CH 2 -; and each R 7 is independently selected from the group consisting of hydrogen and halogen, wherein at least one R 7 is halogen;
  • Ci-Cealkyl groups include, for example, methyl (Me, CH 3 ), ethyl (Et, C 2 H 5 ), n-propyl ( n - Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/- Bu), sec-butyl and ferf-butyl (f-Bu).
  • Cs-Cecycloalkyl- includes cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl).
  • C 2 -C 6 alkenyl can be in the form of straight or branched chains and, where appropriate, can be of either the (E)- or (Z)-configuration. Examples include vinyl & allyl.
  • C 2 -C 6 alkynyl can be in the form of straight or branched chains. Examples include ethynyl & propargyl.
  • Halogen encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
  • Ci-C 6 haloalkyl 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-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 -difluoro-2,2,2- trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl- and heptafluoro-n-propyl-.
  • Ci-C 6 alkyl-S- (alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n- butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
  • Ci-C 6 alkyl-S(0)- (alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or te rt-buty Isu Ifi ny I , preferably methylsulfinyl or ethylsulfinyl.
  • Ci-C 6 alkyl-S(0) 2 - is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert- butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
  • Ci-C6alkoxy- is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and ethoxy.
  • R 1 is selected from the group consisting of methyl, ethyl and n-propyl, most preferably methyl.
  • R 2 is selected from the group consisting of methyl, Cl, -CF 3 and -SC ⁇ methyl.
  • R 3 is selected from the group consisting of methyl, Cl, -CF 3 and -S0 2 methyl.
  • R 4 is hydrogen.
  • R 5 is methyl
  • R 6 is -allyl, c-propyl or methoxy-, preferably methoxy-.
  • R 5 is methyl and R 6 is methoxy-.
  • R 5 and R 6 together are - C(R 7 ) 2 C(R 7 )2C(R 7 )2C(R 7 )2-, -C(R 7 ) 2 C(R 7 )2C(R 7 )2C(R 7 ) 2 C(R 7 )2-, -CH 2 CH 2 S(0) P CH 2 CH 2 -, -
  • each R 7 is independently selected from the group consisting of hydrogen and fluorine, wherein at least one R 7 is fluorine.
  • R 5 and R 6 together are selected from the group consisting of -CH 2 CF 2 CH 2 CH 2 -, -CH 2 CH 2 CF 2 CH 2 CH 2 -, -CH 2 CH 2 SCH 2 CH 2 -, - CH 2 CH 2 S(0) 2 CH 2 CH 2 - and -CH 2 CH 2 N(S0 2 )CH 2 CH 2 -.
  • 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.
  • Formula (I) is intended to include all possible geometric isomeric forms and mixtures thereof.
  • 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 of the present invention 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 formula- tion 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) 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 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 Ce-C-io fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cycl
  • 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 (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- /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 acid
  • 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 herbicidal 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, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim,
  • 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.
  • the mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula (I) with the mixing partner).
  • the compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners.
  • 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, 16 th Edition (BCPC), 2012.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048.
  • the mixing ratio of compound of Formula (I) to safener is from 100: 1 to 1 :10, especially from 20:1 to 1 :1.
  • the 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,
  • HPPD-tolerant soybean transgenic “events” are known, and 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 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 ⁇ l27 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’).
  • 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.
  • Agrostis Alopecurus
  • Avena Brachiaria
  • Bromus Cenchrus
  • Cyperus Digitaria
  • Echinochloa Eleusine
  • Lolium Monochoria
  • 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 according to the following schemes.
  • the benzoic acid of formula (II) is treated with an amine of formula (III) in the presence of a suitable amide coupling reagent in a suitable solvent.
  • suitable amide coupling reagents are propylphosphonic anhydride (T3P) and 1 ,T-carbonyldiimidazole (CDI).
  • suitable solvents are dichloromethane, N,N-dimethylformamide and 1 ,4- dioxane.
  • Benzoic acids of formula (II) are prepared by treating an ester of formula VI with an alkoxide base, for example sodium hydroxide or lithium hydroxide and a suitable solvent as shown in Scheme 2.
  • an alkoxide base for example sodium hydroxide or lithium hydroxide and a suitable solvent as shown in Scheme 2.
  • Alk is defined as a C1-C6 alkyl group.
  • Two examples of a suitable solvent are: a 2: 1 mixture of ethanol : water or a 2: 1 mixture of tetrahydrofuran : water.
  • Esters of formula (VI) may be prepared from anilines of formula (VII) and Vilsmeier salts of formula (VIII) as shown in Scheme 3:
  • the amine of formula (VII) is treated with the Vilsmeier salt of formula (VIII) in a suitable solvent, for example tetrahydrofuran.
  • the Vilsmeier salt of formula (VIII) may be prepared from amides of formula (IX) as shown in Scheme 4.
  • amide of formula (IX) is treated with oxalyl chloride in a suitable solvent, for example dichloromethane.
  • Amides of formula (IX) may be commercially available or their preparation will be straightforward to the skilled person.
  • N-methylprop-2-en-1 -amine 210 mg, 2.9 mmol
  • ethyl formate 2.3 ml_
  • Seeds of a variety of test species are sown in standard soil in pots ( Lolium perenne (LOLPE), Amaranthus retoflexus (AMARE), Abutilon theophrasti (ABUTH), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE)).
  • LPE Lolium perenne
  • AMARE Amaranthus retoflexus
  • ABUTH Abutilon theophrasti
  • SETFA Setaria faberi
  • EHCG 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 RN 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

The present invention relates to compounds Formula (I): wherein R1, R2, R3, R4, R5 and R6 are as defined herein. The invention further relates to compositions comprising said compounds, and methods of controlling weeds using said compounds and/or compositions.

Description

HERBICIDAL COMPOUNDS
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.
N-(tetrazol-5-yl)- arylcarboxamides are disclosed in, for example, WO2012/028579 and W02019/141071 . The present invention relates to novel amidine substituted benzoyl compounds.
Thus, according to the present invention there is provided a compound of Formula (I):
Figure imgf000002_0001
or an agronomically acceptable salt thereof,
wherein:-
R1 is Ci-C4alkyl- or Ci-C3-alkoxy-Ci-C3-alkyl-;
R2 is selected from the group consisting of halogen, Ci-Ce alkyl, Cs-Ce-cycloalkyl, Ci-Ce haloalkyl and -S(0)pCi-C6 alkyl;
R3 is selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 haloalkyl and - S(0)pCi-C6 alkyl;
R4 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3- Ce cycloalkyl; R5 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3- Ce-cycloalkyl;
R6 is selected from the group consisting of C3-C6 cycloalkyl, Cs-Cecycloalkyl-Ci-Csalkyl-, Ci-Cealkoxy-, Ci-C3alkoxy-Ci-C3alkyl-, Ci-C3alkoxy-Ci-C3alkoxy-, C2-C6-alkynyl, C2- Cealkenyl, and -(CH2)-phenyl wherein the phenyl is optionally substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 haloalkyl and C Ce alkoxy; or
R5 and R6 together are -C(R7)2C(R7)2C(R7)2C(R7)2-, -C(R7)2C(R7)2C(R7)2C(R7)2C(R7)2-, - CH2CH2S(0)pCH2CH2-, -CH2CH2N(R8)CH2CH2-; and each R7 is independently selected from the group consisting of hydrogen and halogen, wherein at least one R7 is halogen;
R8 is selected from the group consisting of hydrogen, Ci-Ce alkyl, -S(0)pCi-C6alkyl, C1- Cealkoxy-; and p = 0, 1 or 2.
Ci-Cealkyl groups include, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl ( n - Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/- Bu), sec-butyl and ferf-butyl (f-Bu).
Cs-Cecycloalkyl- includes cyclopropyl (c-propyl (c-Pr)), cyclobutyl (c-butyl (c-Bu)), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl).
C2-C6alkenyl can be in the form of straight or branched chains and, where appropriate, can be of either the (E)- or (Z)-configuration. Examples include vinyl & allyl.
C2-C6alkynyl can be in the form of straight or branched chains. Examples include ethynyl & propargyl. Halogen (or halo) encompasses fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
Ci-C6haloalkyl 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-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 -difluoro-2,2,2- trichloroethyl-, 2,2,3,3-tetrafluoroethyl-, 2,2,2-trichloroethyl- and heptafluoro-n-propyl-.
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, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or te rt-buty Isu Ifi ny I , preferably methylsulfinyl or ethylsulfinyl.
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.
Ci-C6alkoxy- is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and ethoxy.
In a preferred embodiment of the present invention, R1 is selected from the group consisting of methyl, ethyl and n-propyl, most preferably methyl.
In a preferred embodiment of the present invention, R2 is selected from the group consisting of methyl, Cl, -CF3 and -SC^methyl.
In another preferred embodiment of the present invention, R3 is selected from the group consisting of methyl, Cl, -CF3 and -S02methyl. In another embodiment of the present invention, R4 is hydrogen.
In another embodiment of the present invention, R5 is methyl.
In another embodiment of the present invention, R6 is -allyl, c-propyl or methoxy-, preferably methoxy-.
In a preferred embodiment of the present invention R5 is methyl and R6 is methoxy-.
In another embodiment of the present invention, R5 and R6 together are - C(R7)2C(R7)2C(R7)2C(R7)2-, -C(R7)2C(R7)2C(R7)2C(R7)2C(R7)2-, -CH2CH2S(0)PCH2CH2-, -
CH2CH2N(R8)CH2CH2-; wherein each R7 is independently selected from the group consisting of hydrogen and fluorine, wherein at least one R7 is fluorine.
In another embodiment of the present invention, R5 and R6 together are selected from the group consisting of -CH2CF2CH2CH2-, -CH2CH2CF2CH2CH2-, -CH2CH2SCH2CH2-, - CH2CH2S(0)2CH2CH2- and -CH2CH2N(S02)CH2CH2-.
Compounds of Formula (I) (and certain intermediate compounds used to synthesise compound 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. Furthermore, Formula (I) is intended to include all possible geometric isomeric forms and mixtures thereof.
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) 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 of the present invention 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 formula- tion 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) 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) 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) 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) 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. 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 Ce-C-io 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 (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). 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. Alternatively, 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 (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) 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). 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- /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 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 herbicidal compounds of present invention can also be used in mixture with one or more additional herbicides and/or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop (including clodinafop- propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4- DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, diquat dibromide, diuron, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyraxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone- sodium), flufenacet, flumetsulam, flumioxazin, flupyrsulfuron (including flupyrsulfuron-methyl- sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron, glufosinate (including the ammonium salt thereof), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox, imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron- methyl, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimsulfuron, saflufenacil, sethoxydim, simazine, S-metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, 4-hydroxy-1 -methoxy-5-methyl-
3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-
2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2- pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one,
4-hydroxy-1 ,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5- tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 3-[2-(3,4- dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[2- (3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1 ,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1 ,3-dione, 2-[2- (3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1 ,3- dione, 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl- cyclohexane-1 ,3,5-trione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5- ethyl-cyclohexane-1 ,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]- 4,4,6,6-tetramethyl-cyclohexane-1 ,3-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo- pyridazine-4-carbonyl]-5-methyl-cyclohexane-1 ,3-dione, 3-[6-cyclopropyl-2-(3,4- dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[6-cyclopropyl- 2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1 ,3-dione, 6-[6- cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl- cyclohexane-1 ,3,5-trione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carbonyl]cyclohexane-1 ,3-dione, 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4- carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione and 4-[6-cyclopropyl-2-(3,4- dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione.
The mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 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. The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of Formula (I) with the mixing partner).
The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such 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.
Particularly preferred are mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen.
The safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16th Edition (BCPC), 2012. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048.
Preferably the mixing ratio of compound of Formula (I) to safener is from 100: 1 to 1 :10, especially from 20:1 to 1 :1.
The 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). However, in some instances tolerance may need to be engineered into the crop plant, for example by way of genetic engineering. Thus, it is possible that 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, Cenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species. Several HPPD-tolerant soybean transgenic “events” are known, and 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. 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®.
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). 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^l27 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.
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).
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 according to the following schemes.
As shown in Scheme 1 , the benzoic acid of formula (II) is treated with an amine of formula (III) in the presence of a suitable amide coupling reagent in a suitable solvent. Examples of suitable amide coupling reagents are propylphosphonic anhydride (T3P) and 1 ,T-carbonyldiimidazole (CDI). Examples of suitable solvents are dichloromethane, N,N-dimethylformamide and 1 ,4- dioxane.
Scheme 1
Figure imgf000015_0001
Benzoic acids of formula (II) are prepared by treating an ester of formula VI with an alkoxide base, for example sodium hydroxide or lithium hydroxide and a suitable solvent as shown in Scheme 2. “Aik” is defined as a C1-C6 alkyl group. Two examples of a suitable solvent are: a 2: 1 mixture of ethanol : water or a 2: 1 mixture of tetrahydrofuran : water.
Scheme 2
Figure imgf000015_0002
Esters of formula (VI) may be prepared from anilines of formula (VII) and Vilsmeier salts of formula (VIII) as shown in Scheme 3:
Scheme 3
Figure imgf000015_0003
Following Scheme 3, the amine of formula (VII) is treated with the Vilsmeier salt of formula (VIII) in a suitable solvent, for example tetrahydrofuran. The Vilsmeier salt of formula (VIII) may be prepared from amides of formula (IX) as shown in Scheme 4.
Scheme 4 oxalyl chloride
solvent
Figure imgf000016_0002
(IX)
Figure imgf000016_0001
Following scheme 4, the amide of formula (IX) is treated with oxalyl chloride in a suitable solvent, for example dichloromethane.
Amides of formula (IX) may be commercially available or their preparation will be straightforward to the skilled person.
The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to the Table provided herein.
Preparative Example 1 : Compound 1.007
Figure imgf000016_0003
Thiomorpholine (0.43 g, 4.2 mmol) and ethyl formate (3.4 ml_, 42 mmol) were heated at 45 °C for 7 h. The reaction mixture was cooled to RT and then evaporated to remove ethyl formate and ethanol, leaving the desired product thiomorpholine-4-carbaldehyde (510 mg, 3.89 mmol, 93%) as a colourless oil.
Figure imgf000016_0004
Figure imgf000017_0002
To a solution of thiomorpholine-4-carbaldehyde (640 mg, 4.9 mmol) was added dichloromethane (3 mL) and oxalyl dichloride (0.85 ml_, 9.8 mmol) at RT and the reaction was stirred for 2 h (note: effervescence upon addition of oxalyl chloride). Then a solution of ethyl 3-amino-2-chloro-4- (trifluoromethyl)benzoate (650 mg, 2.4 mmol) in DCM (1 mL) was added dropwise and the reaction stirred for 2 h. LCMS suggest complete conversion. The reaction was poured into cold NaHC03 solution and stirred for 10 mins. The aqueous solution was then extracted with DCM and passed through a phase separator cartridge. The organic solution was concentrated and then purified by flash column chromatography to give ethyl 2-chloro-3-[(E)- thiomorpholinomethyleneamino]-4-(trifluoromethyl)benzoate (720 mg, 1.7 mmol, 71 %) as a colourless oil. 1 H NMR (400 MHz, chloroform) 1.40 (t, J=7.09 Hz, 3 H) 2.69 (br d, J=10.15 Hz, 4 H) 3.63 (br s, 2 H) 4.02 (br s, 2 H) 4.41 (q, J=7.17 Hz, 2 H) 7.27 - 7.37 (m, 2 H) 7.51 (d, J=8.07 Hz, 1 H).
Figure imgf000017_0001
To a solution of ethyl 2-chloro-3-[(E)-thiomorpholinomethyleneamino]-4-(trifluoromethyl)benzoate (610 mg, 1.6 mmol) in ethanol (9 mL) was added sodium hydroxide (1.6 mL, 1 .6 mmol, 1 mol/L) and water (2 mL) and the reaction stirred for 2 h at 40 °C. Analysis showed some starting material remaining so 400 uL NaOH 1 M solution was added and the reaction stirred for 2 h at 40 °C. The ethanol was removed under reduced pressure and the aqueous layer was adjusted to pH7 with 2M HCI and the aqueous layer was concentrated using a freeze dryer to give 2-chloro-3-[(E)- thiomorpholinomethyleneamino]-4-(trifluoromethyl)benzoic acid (616 mg, 1.57 mmol, 99%) as a white solid with a NaCI contaminant. The mixture was taken on to the next step without further purification. 1 H NMR (400 MHz, d4-methanol) 2.67 (br s, 4 H) 3.68 (brs, 2 H) 3.95 (brs, 2 H) 7.10 (dd, J=8.07, 0.61 Hz, 1 H) 7.42 (d, J=1.10 Hz, 1 H) 7.47 (d, J=8.07 Hz, 1 H).
Figure imgf000018_0001
To a solution of 2-chloro-3-[(E)-thiomorpholinomethyleneamino]-4-(trifluoromethyl)benzoic acid (620 mg, 1.6 mmol) in DMF (8 mL) in a carousel tube at 80 °C was added CDI (1.0 g, 6.4 mmol). After stirring for 16 h, two more batches of CDI (200 mg, 1.3 mmol) were added over a 1 h period.
To this solution was added DBU (0.29 mL, 1.9 mmol) and 1-methyltetrazol-5-amine (0.24 g, 2.4 mmol) and the reaction stirred at 80 °C for 2 h. Analysis showed some imidazole intermediate remaining so further portions of 1-methyltetrazol-5-amine (0.32 g, 3.2 mmol) and DBU (0.48 mL, 3.2 mmol) were added and the reaction stirred at 80°C for 16 h. The reaction was allowed to cool to RT and then concentrated. The crude residue was taken up in DCM (4 mL), and water (4 mL) was added. The aqueous layer was adjusted to pH 6-7 with 2M HCI. The biphasic mixture was passed through a phase separator and the organic phase concentrated and purified by reversed- phase prep HPLC to give 2-chloro-N-(1 -methyltetrazol-5-yl)-3-[(E)- thiomorpholinomethyleneamino]-4-(trifluoromethyl)benzamide (264 mg, 0.609 mmol) as a white solid. 1 H NMR (400 MHz, d4-methanol) 2.68 (br s, 4 H) 3.70 (br s, 2 H) 3.93 - 4.03 (m, 2 H) 4.06 (s, 3 H) 7.35 (d, J=7.95 Hz, 1 H) 7.48 (s, 1 H) 7.68 (d, J=8.07 Hz, 1 H).
Preparative Example 2: Compound 1.005
Figure imgf000019_0001
A solution of 4,4-difluoropiperidine (360 mg, 3.0 mmol) in ethyl formate (2.5 ml_, 30 mmol) was heated to 45 °C for 6 h. The solution was then concentrated to give 4,4-difluoropiperidine-1- carbaldehyde (435 mg, 2.92 mmol, 97% Yield) as a colourless oil.
Figure imgf000019_0002
To 4,4-difluoropiperidine-1 -carbaldehyde (440 mg, 2.9 mmol) was added CH2CI2 (1.5 mL) and oxalyl dichloride (0.28 mL, 3.2 mmol) at RT and the reaction stirred for 2 h (note: effervescence upon addition of oxalyl chloride). Then a solution of ethyl 3-amino-2-chloro-4- (trifluoromethyl)benzoate (520 mg, 1.9 mmol) in DCM (1 mL) was added at RT and the reaction stirred for 2 h. The reaction was poured into cold NaHCC>3 solution and stirred for 10 mins. The aqueous solution was then extracted with DCM and the DCM layer was separated, concentrated and purified by flash chromatography to give ethyl 2-chloro-3-[(E)-(4,4-difluoro-1- piperidyl)methyleneamino]-4-(trifluoromethyl)benzoate (600 mg, 1.35 mmol) as a colourless oil. 1 H NMR (400 MHz, chloroform) 1.40 (t, J=7.09 Hz, 3 H) 2.05 (s, 4 H) 3.48 (br s, 2 H) 3.83 (br s,
2 H) 4.41 (q, J=7.13 Hz, 2 H) 7.29 - 7.39 (m, 2 H) 7.52 (d, J=8.19 Hz, 1 H).
Figure imgf000020_0001
To a solution of ethyl 2-chloro-3-[(E)-(4,4-difluoro-1-piperidyl)methyleneamino]-4- (trifluoromethyl)benzoate (540 mg, 1.4 mmol) in ethanol (8 mL) was added sodium hydroxide (1.4 ml_, 1.4 mmol, 1 mol/L) and water (2 mL) and the reaction stirred for 2 h at 40 °C. The ethanol was removed under reduced pressure and the remaining aqueous solution taken to pH7 with 2M HCI. The solution was evaporated using a freeze dryer to give 2-chloro-3-[(E)-(4,4-difluoro-1- piperidyl)methyleneamino]-4-(trifluoromethyl)benzoic acid (518 mg, 1.26 mmol) as a white solid. 1 H NMR (400 MHz, d4-methanol) d ppm 1.90 - 2.15 (m, 4 H) 3.46 - 3.60 (m, 2 H) 3.78 (br d, J=6.97 Hz, 2 H) 7.10 (dd, J=8.01 , 0.67 Hz, 1 H) 7.42 - 7.52 (m, 2 H).
Figure imgf000020_0002
To a solution of 2-chloro-3-[(E)-(4,4-difluoro-1-piperidyl)methyleneamino]-4- (trifluoromethyl)benzoic acid (200 mg, 0.54 mmol) in DMF (3 mL) at 80 °C was added CDI (0.35 g, 2.2 mmol) in portions over 1 h. The reaction mixture was stirred for a further 16 h at 80 °C. After analysis showed incomplete conversion, two more batches of CDI (200 mg, 1.3 mmol) were then added a 1 h period. To this solution was then added DBU (0.099 mL, 0.65 mmol) and 1- methyltetrazol-5-amine (80 mg, 0.81 mmol) and the reaction stirred at 80 °C for 2 h. Analysis showed some intermediate remaining so further portions of 1-methyltetrazol-5-amine (106 mg, 1.08 mmol) and DBU (0.12 ml_, 0.54 mmol) were added and the reaction stirred at 80°C for a further 16 h. The reaction mixture was then cooled and concentrated. The crude residue was taken up in DCM (4 ml_), and water (4 mL) was added. The aqueous layer was made to pH 6-7 by the addition of 2M HCI. The reaction mixture was passed through a phase separator and the organic phase was evaporated and then purified by reverse-phase prep-HPLC to give 2-chloro- 3-[(E)-(4,4-difluoro-1-piperidyl)methyleneamino]-N-(1-methyltetrazol-5-yl)-4- (trifluoromethyl)benzamide (37 mg, 0.082 mmol) as a white solid. 1 H NMR (400 MHz, methanol) d ppm 1.99 - 2.10 (m, 4 H) 3.57 (br d, J=1.22 Hz, 2 H) 3.77 - 3.88 (m, 2 H) 4.04 (s, 3 H) 7.35 (d, J=8.19 Hz, 1 H) 7.52 (s, 1 H) 7.67 (d, J=8.07 Hz, 1 H)
Preparative Example 3: Compound 1.007
Figure imgf000021_0001
N-methylprop-2-en-1 -amine (210 mg, 2.9 mmol) and ethyl formate (2.3 ml_) were heated at 45 °C for 7 h and then concentrated under reduced pressure to give N-allyl-N-methyl-formamide (290 mg, 2.9 mmol) as a colourless oil.
Figure imgf000021_0002
To the solution of N-allyl-N-methyl-formamide in dichloromethane (2.5 mL) was added oxalyl dichloride (0.87 mL, 9.9 mmol) at RT and the reaction mixture was stirred for 2h (note: effervescence upon addition of oxalyl chloride). Then a solution of ethyl 3-amino-2-chloro-4- (trifluoromethyl)benzoate (670 mg, 2.5 mmol) in DCM (1 mL) was added at RT and the reaction stirred for 2 h. The reaction mixture was poured into cold NaHCC>3 solution and stirred for 10 mins. The aqueous solution was then extracted with DCM and passed through a phase separator cartridge. The DCM layer was concentrated to give an orange oil which was purified by flash chromatography to give ethyl 3-[(E)-[allyl(methyl)amino]methyleneamino]-2-chloro-4- (trifluoromethyl)benzoate (780 mg, 1 .8 mmol, 72%) as a colourless oil. 1 H NMR (400 MHz, chloroform) d ppm 1.39 - 1 .42 (m, 3 H) 3.04 (s, 2 H) 3.84 (br d, J=5.14 Hz, 1 H) 4.38 - 4.45 (m, 2 H) 5.18 - 5.32 (m, 2 H) 5.74 - 5.96 (m, 1 H) 7.28 - 7.37 (m, 2 H) 7.51 (d, J=8.07 Hz, 1 H).
Figure imgf000022_0001
To a solution of ethyl 3-[(E)-[allyl(methyl)amino]methyleneamino]-2-chloro-4- (trifluoromethyl)benzoate (410 mg, 1.1 mmol) in ethanol (6 mL) was added sodium hydroxide (1 M, 1.1 mL, 1.1 mmol) and water (1.5 mL) and the reaction stirred for 2 h at 40 °C. Further NaOH 1 M solution (0.5 mL) was added and the reaction stirred for 2 h at 40 °C. The ethanol was removed under reduced pressure and the remaining aqueous solution was adjusted to pH7 with 2M HCI solution. This was then concentrated in a freeze-dryer to give 3-[(E)- [allyl(methyl)amino]methyleneamino]-2-chloro-4-(trifluoromethyl)benzoic acid (432 mg) with NaCI as a byproduct. The mixture was taken on to the next step without further purification. 1 H NMR (400 MHz, methanol) d ppm 3.00 (s, 3 H) 3.83 - 4.15 (m, 1 H) 3.92 (br d, J=4.77 Hz, 1 H) 5.15 - 5.35 (m, 2 H) 5.74 - 5.99 (m, 1 H) 7.1 1 (br d, J=7.70 Hz, 1 H) 7.38 - 7.53 (m, 2 H).
Figure imgf000023_0001
To a solution of 3-[(E)-[allyl(methyl)amino]methyleneamino]-2-chloro-4-(trifluoromethyl)benzoic acid (430 mg, 1.1 mmol) in DMF (3 mL) at 80 °C was added CDI (0.70 g, 4.3 mmol). The reaction mixture was stirred overnight at 80 °C. The following day, further CDI (200 mg, 1 .23 mmol) was added. After stirring for 1 h, DBU (0.20 mL, 1.3 mmol) and 1-methyltetrazol-5-amine (0.16 g, 1.6 mmol) were then added and the reaction stirred at 80 °C for 2 h. Further 1-methyltetrazol-5-amine (0.20 g, 2.0 mmol) and DBU (0.31 mL, 2.0 mmol) were added and the reaction stirred at 80°C overnight. The reaction mixture was allowed to cool and then it was concentrated under reduced pressure to remove DMF. The crude residue was taken up in DCM (4 mL), and water (4 mL) was added. The material was made to pH 6-7 with 2M HCI. The reaction mixture was passed through a phase separator and the organic phase was concentrated under reduced pressure, then purified by reversed phase prep-HPLC to give 3-[(E)-[allyl(methyl)amino]methyleneamino]-2-chloro-N-(1- methyltetrazol-5-yl)-4-(trifluoromethyl)benzamide (153 mg, 0.381 mmol) as a white solid. 1 H NMR (400 MHz, d4-methanol) d ppm 3.03 (s, 3 H) 3.95 (br d, J=5.38 Hz, 1 H) 4.06 (s, 3 H) 4.13 (br d, J=5.75 Hz, 1 H) 5.21 - 5.36 (m, 2 H) 5.79 - 5.98 (m, 1 H) 7.30 - 7.41 (m, 1 H) 7.45 - 7.56 (m, 1 H)
7.63 - 7.73 (m, 1 H).
Preparative Example 4: Compound 1.015
Figure imgf000023_0002
To a solution of N-methoxy-N-methyl-formamide (290 mg, 3.3 mmol) in dichloromethane (2 mL) was added and oxalyl dichloride (0.1 1 mL, 3.6 mmol) at RT and the reaction stirred for 2 h (note: effervescence upon addition of oxalyl chloride). Then a solution of ethyl 3-amino-2-chloro-4- (trifluoromethyl)benzoate (595 mg, 2.22 mmol) in DCM (2 mL) was added at RT and the reaction stirred for 5 min. The reaction was poured into cold NaHC03 solution and stirred for 2 min. The aqueous solution was then extracted with DCM and passed through a phase separator cartridge and concentrated. The residue was purified by flash chromatography to give ethyl 2-chloro-3-[(E)- [methoxy(methyl)amino]methyleneamino]-4-(trifluoromethyl)benzoate (687 mg, 1.83 mmol) as a colourless oil. 1 H NMR (400 MHz, chloroform) 1.40 (t, J=7.15 Hz, 3 H) 3.27 (s, 3 H) 3.77 (s, 3 H) 4.41 (q, J=7.21 Hz, 2 H) 7.31 - 7.41 (m, 1 H) 7.53 (d, J=8.19 Hz, 1 H) 7.60 (s, 1 H).
Figure imgf000024_0001
To a solution of ethyl 2-chloro-3-[(E)-[methoxy(methyl)amino]methyleneamino]-4- (trifluoromethyl)benzoate (680 mg, 2.0 mmol) in ethanol (11 mL) was added sodium hydroxide solution (2.0 mL, 2.0 mmol, 1 mol/L) and water (3 mL) and the reaction stirred for 2 h at rt. The ethanol was removed under reduced pressure and the remaining aqueous solution was adjusted to pH6-7 with 2M HCI and then concentrated on a freeze-dryer to give 2-chloro-3-[(E)- [methoxy(methyl)amino]methyleneamino]-4-(trifluoromethyl)benzoic acid (650 mg, 2.1 mmol) as a white solid with NaCI contaminant. It was taken on to the next step without further purification. 1 H NMR (400 MHz, d4-methanol) d ppm 3.25 (s, 3 H) 3.77 (s, 3 H) 7.10 - 7.21 (m, 1 H) 7.50 (d, J=8.07 Hz, 1 H) 7.62 (s, 1 H).
Figure imgf000025_0001
To a solution of 2-chloro-3-[(E)-[methoxy(methyl)amino]methyleneamino]-4- (trifluoromethyl)benzoic acid (350 mg, 1 .1 mmol) in DMF (5 mL) at 90 °C was added CDI (0.37 g, 2.3 mmol). After stirring for 4 h, 1-methyltetrazol-5-amine (0.45 g, 4.5 mmol) and DBU (0.21 mL, 1.4 mmol) and the reaction stirred at 90 °C overnight. The reaction mixture was then concentrated in a Genevac. The crude residue was taken up in DCM (4 mL), and water (4 mL) was added. The aqueous layer was adjusted to pH 6-7 with 2M HCI. The reaction mixture was passed through a phase separator and the organic phase was concentrated, then purified by reversed phase HPLC to give 2-chloro-3-[(E)-[methoxy(methyl)amino]methyleneamino]-N-(1-methyltetrazol-5-yl)-4- (trifluoromethyl)benzamide (39 mg, 0.10 mmol) as a white solid. 1 H NMR (400 MHz, d4-methanol) d ppm 3.28 (s, 3 H) 3.79 (s, 3 H) 4.06 (s, 3 H) 7.41 (d, J=8.07 Hz, 1 H) 7.66 - 7.73 (m, 2 H).
TABLE 1 - Examples of herbicidal compounds of the present invention.
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Biological Examples
Seeds of a variety of test species are sown in standard soil in pots ( Lolium perenne (LOLPE), Amaranthus retoflexus (AMARE), Abutilon theophrasti (ABUTH), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), 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 RN 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. After 13 days for pre and post-emergence, the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following tables on a five point scale (5 = 80-100%; 4 = 60-79%; 3=40-59%; 2=20-39%; 1=0- 19%). TABLE B1: Application pre-emergence
Figure imgf000032_0001
Table B2: Application post-emergence
Figure imgf000033_0001
*Applied at 250g/ha

Claims

Claims
1. A compound of Formula (I):
Figure imgf000034_0001
or an agronomically acceptable salt thereof,
wherein:-
R1 is Ci-C4alkyl- or CrC3-alkoxy-Ci-C3-alkyl-;
R2 is selected from the group consisting of halogen, Ci-Ce alkyl, Cs-Ce-cycloalkyl, Ci-Ce haloalkyl and -S(0)pCi-C6 alkyl;
R3 is selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 haloalkyl and - S(0)pCi-C6 alkyl;
R4 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3- Ce cycloalkyl;
R5 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3- Ce-cycloalkyl;
R6 is selected from the group consisting of C3-C6 cycloalkyl, Cs-Cecycloalkyl-Ci-Csalkyl-, Ci-Cealkoxy-, Ci-C3alkoxy-CrC3alkyl-, Ci-C3alkoxy-Ci-C3alkoxy-, C2-C6-alkynyl, C2- Cealkenyl, and -(CH2)-phenyl wherein the phenyl is optionally substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 haloalkyl and C Ce alkoxy; or
R5 and R6 together are -C(R7)2C(R7)2C(R7)2C(R7)2-, -C(R7)2C(R7)2C(R7)2C(R7)2C(R7)2-, - CH2CH2S(0)pCH2CH2-, -CH2CH2N(R8)CH2CH2-; and each R7 is independently selected from the group consisting of hydrogen and halogen, wherein at least one R7 is halogen;
R8 is selected from the group consisting of hydrogen, Ci-Ce alkyl, -S(0)pCi-C6alkyl, Ci- Cealkoxy-; and p = 0, 1 or 2.
2. A compound according to claim 1 , wherein R2 is selected from the group consisting of methyl, Cl, -CF3 and -S02methyl.
3. A compound according to claim 1 , wherein R3 is selected from the group consisting of methyl, Cl, -CF3 and -S02methyl.
4 A compound according to any one of the previous claims, wherein R1 is selected from the group consisting of methyl, ethyl and n-propyl.
5. A compound according to any one of the previous claims, wherein R1 is methyl.
6. A compound according to any one of the previous claims, wherein R4 is hydrogen.
7. A compound according to any one of the previous claims, wherein R5 is methyl.
8. A compound according to any one of the previous claims, wherein R6 is methoxy-.
9. A compound according to any one of claims 1 to 6, wherein R5 and R6 together are - C(R7)2C(R7)2C(R7)2C(R7)2C(R7)2-,
10. A compound according to claim 9, wherein R5 and R6 together are -CH2CH2CF2CH2CH2-.
1 1 . A herbicidal composition comprising a compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.
12. A herbicidal composition according to claim 1 1 , further comprising at least one additional pesticide.
13. A herbicidal composition according to claim 12, wherein the additional pesticide is a herbicide or herbicide safener.
14. 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 1 1 to 13.
15. Use of a compound of Formula (I) as defined in claim 1 as a herbicide.
PCT/EP2019/078080 2018-10-17 2019-10-16 Herbicidal compounds WO2020079078A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1816931.8 2018-10-17
GBGB1816931.8A GB201816931D0 (en) 2018-10-17 2018-10-17 Improvements in or relating to organic compounds

Publications (1)

Publication Number Publication Date
WO2020079078A1 true WO2020079078A1 (en) 2020-04-23

Family

ID=64397537

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/078080 WO2020079078A1 (en) 2018-10-17 2019-10-16 Herbicidal compounds

Country Status (4)

Country Link
AR (1) AR116706A1 (en)
GB (1) GB201816931D0 (en)
UY (1) UY38421A (en)
WO (1) WO2020079078A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022238178A1 (en) * 2021-05-10 2022-11-17 Syngenta Crop Protection Ag Substituted benzamides as herbicides

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2002046387A2 (en) 2000-12-07 2002-06-13 Syngenta Limited Plant derived hydroxy phenyl pyruvate dioxygenases (hppd) resistant against triketone herbicides and transgenic plants containing these dioxygenases
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2012028579A1 (en) 2010-09-01 2012-03-08 Bayer Cropscience Ag N-(tetrazol-5-yl)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides
WO2012082548A2 (en) 2010-12-15 2012-06-21 Syngenta Participations Ag Soybean event syht0h2 and compositions and methods for detection thereof
WO2012082542A2 (en) 2010-12-15 2012-06-21 Syngenta Participations Ag Soybean event syht04r and compositions and methods for detection thereof
WO2019141071A1 (en) 2018-01-17 2019-07-25 广东格林精密部件股份有限公司 Structure modularization intelligent assembly flexible production line
WO2019141740A1 (en) * 2018-01-19 2019-07-25 Syngenta Participations Ag Amidine substituted benzoyl derivatives useful as herbicides

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2002046387A2 (en) 2000-12-07 2002-06-13 Syngenta Limited Plant derived hydroxy phenyl pyruvate dioxygenases (hppd) resistant against triketone herbicides and transgenic plants containing these dioxygenases
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2012028579A1 (en) 2010-09-01 2012-03-08 Bayer Cropscience Ag N-(tetrazol-5-yl)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides
WO2012082548A2 (en) 2010-12-15 2012-06-21 Syngenta Participations Ag Soybean event syht0h2 and compositions and methods for detection thereof
WO2012082542A2 (en) 2010-12-15 2012-06-21 Syngenta Participations Ag Soybean event syht04r and compositions and methods for detection thereof
WO2019141071A1 (en) 2018-01-17 2019-07-25 广东格林精密部件股份有限公司 Structure modularization intelligent assembly flexible production line
WO2019141740A1 (en) * 2018-01-19 2019-07-25 Syngenta Participations Ag Amidine substituted benzoyl derivatives useful as herbicides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Manual on Development and Use of FAO Specifications for Plant Protection Products", 1999
"The Pesticide Manual", 2012, BRITISH CROP PROTECTION COUNCIL
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. RN 9005-64-5

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022238178A1 (en) * 2021-05-10 2022-11-17 Syngenta Crop Protection Ag Substituted benzamides as herbicides

Also Published As

Publication number Publication date
AR116706A1 (en) 2021-06-02
GB201816931D0 (en) 2018-11-28
UY38421A (en) 2020-05-29

Similar Documents

Publication Publication Date Title
AU2017251378B2 (en) Herbicidal pyridazinone compounds
JP6524207B2 (en) Herbicidal pyridazinone derivatives
WO2021204706A1 (en) 5-haloalkoxy-pyrimidine compounds as herbicides
EP3237421A1 (en) Thiazolopyridinones as herbicides
EP4058438B1 (en) Herbicidal compounds
CA2926552A1 (en) Herbicidal 3-(2-benzyloxyphenyl)-2,4-dihydroxy-1,8-naphthyridine derivatives
EP4136080B1 (en) Herbicidal compounds
WO2020079078A1 (en) Herbicidal compounds
WO2021028316A1 (en) 2-phenoxy-pyrimidine derivatives as herbicidal compounds
WO2022233727A1 (en) Herbicidal compounds
WO2023066784A1 (en) Substituted benzamides as herbicides
EP4337651A1 (en) Substituted benzamides as herbicides
EP4263510A1 (en) Herbicidal tetrazole compounds
EP4337644A1 (en) Herbicidal compounds
WO2024017762A1 (en) Herbicidal compounds
WO2022207482A1 (en) Herbicidal compounds
WO2020193322A1 (en) Sulfonamides and their use as herbicides
WO2023247293A1 (en) Isoxalidine derivatives as hericidal compounds
GB2620577A (en) Improvements in or relating to organic compounds
WO2021074325A1 (en) Herbicidal compounds
CA3155860A1 (en) Fluorinated phenylacetic acid derivatives in a weed control method
WO2017001408A1 (en) Pyridazinones as herbicidal compounds

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19798174

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19798174

Country of ref document: EP

Kind code of ref document: A1